a process for the preparation of indanones of the formula II from, indanones of the formula I or of indanones of the formula IIa from indanones of the formula Ia

The present invention relates to a simple and economically interesting process for preparing substituted indanones.
Substituted indanones are important intermediates for preparing active compounds in the fields of pharmacy and crop protection (cf. S. J. deSolms et al., J. Med. Chem., 1978, 21, 437) and for preparing metallocene complexes (cf. Chemie in unserer Zeit, 1994, 28, 204, 205). In particular, substituted indanones can be used to prepare bridged chiral metallocenes which are of great importance as highly active catalysts in olefin polymerization (cf. EP-A 129 368). The catalyst properties can be influenced in a targeted manner by variation of the ligand system, eg. by substitution. This makes it possible to achieve the desired degree of change in the polymer yield, the tacticity or the melting point of the polymers (New J. Chem., 1990, 14, 499; Organomet., 1990, 9, 3098; Angew. Chem., 1990, 102, 339; EP-A 316 155; EP-A 351 392). Bridged zirconocenes containing, as xcfx80 ligands, substituted indenyl radicals which bear the bridge in: position 1, preferably a hydrocarbon radical in position 2 and a hydrocarbon radical, preferably an aryl radical, in position 4 have been found to be particularly active and stereoselective catalyst systems (EP 0 576 970 A1; EP 0 629 632 A2). The ligand systems used for these highly active metallocenes are prepared from the corresponding indenes which are in turn obtained from indanones which are substituted in the appropriate positions (EP 0 576 970 A1; EP 0 629 632 A2). These indanones are synthesized from commercially available precursors or precursors known in the literature, for example as follows:
EP 0 576 970 A1:
The 2-methyl-4-phenylindanone is converted into the corresponding indene, for example by reduction of the ketone function to the alcohol and subsequent dehydration.
The three synthetic routes shown by way of example go through 2-, 4-substituted indanones which have in each case been obtained by Friedel-Crafts cyclization of the corresponding 3-arylpropionic acids. The syntheses are multistage processes in which relatively expensive starting compounds are used. Furthermore, in the syntheses disclosed in EP 0 629 632, the introduction of a protective group cannot be avoided. The processes shown are thus very costly routes.
It is therefore an object of the present invention to find a simple, flexible, inexpensive process for preparing substituted indanones which are important intermediates for preparing active compounds and metallocene complexes.
We have now surprisingly found that substituted indanones which contain a leaving group can be used to prepare, in a simple manner, other indanones which can be used, inter alia, for preparing active compounds and metallocene complexes.
The present invention accordingly provides a process for the preparation of indanones of the formula II from indanones of the Formula I or of indanones of the formula IIa from indanones of the formula Ia
which comprises reacting an indanone of the formula I or Ia with a coupling component, where, in the formulae I, Ia, II and IIa,
R1 is a C1-C40-group such as a C1-C40-hydrocarbon group which is bound via a carbon atom and may bear one or more identical or different heteroatom-containing radicals as substituents, eg. a linear, branched or cyclic C1-C20-alkyl group which may bear one or more identical or different halogen, OH, OR2, SR2NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C6-C22-aryl group which may bear one or more identical or different halogen, OH, OR2, SR2NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C7-C20-alkylaryl group or a C7-C20-arylalkyl group, where the alkyl part may bear one or more identical or different halogen, OH, OR2, SR2NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents and the aryl part may bear one or more identical or different halogen, OH, OR2, SR2NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C2-C10-alkenyl group which may bear one or more identical or different halogen, OH, OR2, SR2NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C2-C20-alkynyl group which may bear one or more identical or different halogen, OH, OR2, SR2NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C8-C12-arylalkenyl group, where the alkenyl part may bear one or, more identical or different halogen, OH, OR2, SR2NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents and the aryl part may bear one or more identical or different halogen, OH, OR2, SR2NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents,
or R1 is an OR2, SR2, NR22, PR22, SiR23 or OSiR23 group, where R2 are identical or different and are each a C1-C20-hydrocarbon group such as a C1-C10-alkyl group or C6-C14-aryl group which may each bear one or more identical or different halogen, OH, OR2, SR2NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents or two radicals R2 may be joined to form a ring system, or R1 is a C1-C20-heterocyclic group which is bound via a carbon atom and may in turn bear C1-C20-radicals or heteroatoms as substituents,
x is a leaving group such as a diazonium group, a halogen atom or a C1-C40-, preferably C1-C10-group which is bound via a heteroatom such as an atom of Group 13, 14, 15 or 16 of the Periodic Table of the Elements, eg. boron, silicon, tin, oxygen or sulfur, for example C1-C40-alkylsulfonate, C1-C40-haloalkylsulfonate, C6-C40-arylsulfonate, C6-C40-haloarylsulfonate, C7-C40-arylalkysulfonate, C7-C40-haloarylalkylsulfonate, C1-C40-alkylcarboxylate, C1-C40-haloalkylcarboxylate, C6-C40-arylcarboxylate, C6-C40-haloarylcarboxylate, C7-C40-arylalkylcarboxylate, C7-C40-haloarylalkylcarboxylate, formate, C1-C40-alkyl carbonate, C1-C40-haloalkyl carbonate, C6-C40-aryl carbonate, C6-C40-haloaryl carbonate, C7-C40-arylalkyl carbonate, C7-C40-haloarylalkyl carbonate, C1-C40-alkyl phosphonate, C1-C40-haloalkyl phosphonate, C6-C40-aryl phosphonate, C6-C40-haloaryl phosphonate, C7-C40-arylalkyl phosphonate or C7-C40-haloarylalkyl phosphonate,
R3 is a C1-C40-hydrocarbon group which is bound via a carbon atom and may bear one or more identical or different heteroatom-containing radicals as substituents, for example a linear, branched or cyclic C1-C20-alkyl group which may bear one or more identical or different halogen, OH, OR2, SR2, NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C6-C22-aryl group which may bear one or more identical or different halogen, OR2, SR2, NR22xe2x80x94, NH2, xe2x80x94N2H3, NO2, CN, CO2R2, CHO, COR2, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C7-C15-alkylaryl group or C7-C15-arylalkyl group, where the alkyl part may bear one or more identical or different halogen, OH, OR2, SR2NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents and the aryl part may bear one or more identical or different halogen, OR2, SR2NR22xe2x80x94, NH2, xe2x80x94N2H3, NO2, CN, CO2R2, CHO, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C2-C10-alkenyl group which may bear one or more identical or different halogen, OR, OR2, CO2R2, COR2, SR2, NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C2-C10-alkynyl group which may bear one or more identical or different halogen, OH, OR2, SR2, NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C8-C12-arylalkenyl group which may bear one or more identical or different halogen, OH, OR2, SR2, NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents,
or R3 is a halogen atom or a PR22, B(OR2)2, SiR23 or SnR23 group, where R2 are identical or different and are each a C1-C20-hydrocarbon group, eg. a C1-C10-alkyl group or C6-C14-aryl group which may each bear one or more identical or different halogen, OH, OR2, SR2NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, or two radicals R2 may be joined to form a ring system, or R3 is a C1-C20-heterocyclic group which is bound via a carbon atom and may in turn bear C1-C20-radicals or heteroatoms as substituents,
Y1, Y2 and Y3 are identical or different and are each a hydrogen atom or are as defined for X or R3, and
Y4, Y5 and Y6 are identical or different and are each a hydrogen atom or are as defined for R3.
In the process of the present invention, the indanones of the formula I or Ia are converted directly into the indanones of the formula II or IIa in one reaction step by reaction with the coupling component. In this reaction, no use is made of protective groups for the carbonyl function of the indanone of the formula I or Ia.
For the purposes of this application, the term xe2x80x9cheteroatomxe2x80x9d refers to any atom of the Periodic Table of the Elements with the exception of carbon and hydrogen. A heteroatom is preferably an atom of Group 14, 15 or 16 of the Periodic Table of the Elements with the exception of carbon. The term xe2x80x9cheterocyclic groupxe2x80x9d refers to a heteroatom-containing cyclic group.
In the process of the present invention, particular preference is given to using indanones of the formula I or Ia in which X is chlorine, bromine, iodine, triflate, nonaflate, mesylate, ethylsulfonate, benzenesulfonate, tosylate, triisopropylbenzenesulfonate, formate, acetate, trifluoroacetate, nitrobenzoate, halogenated arylcarboxylates, in particular fluorinated benzoate, methyl carbonate, ethyl carbonate, benzyl carbonate, tert-butyl carbonate, dimethyl phosphonate, diethyl phosphonate, diphenyl phosphonate or diazonium,
R1 is a linear, branched or cyclic C1-C8-alkyl group which may bear one or more identical or different fluorine, chlorine, OR2, PR22xe2x80x94, NR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C6-C10-aryl group which may bear one or more identical or different fluorine, chlorine, OR2, SR2, NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C7-C12-alkylaryl or arylalkyl group, where the alkyl part may bear one or more identical or different fluorine, chlorine, OR2, SR2NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents and the aryl part may bear one or more identical or different fluorine, chlorine, OR2, SR2, NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C2-C8-alkenyl group or a C2-C8-alkynyl group which may each bear one or more identical or different fluorine, chlorine, OR2 or NR22 substituents, a C8-C12-arylalkenyl group which may bear one or more identical or different fluorine, chlorine, OR2 or NR22 substituents, or R1 is an OR2, PR22, NR22, xe2x80x94SiR23 or xe2x80x94OSiR23 group, where R2 are identical or different and are each a C1-C4-alkyl group or C6-C10-aryl group, where the alkyl group may bear one or more identical or different fluorine, chlorine, OR2, SR2, NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents and the aryl group may bear one or more identical or different fluorine, chlorine, OR2, SR2, NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, or R1 is a C1-C20-heterocyclic group, with preferred heteroatoms being oxygen, nitrogen, sulfur, phosphorus and silicon, which may in turn bear C1-C20-radicals or heteroatoms as substituents,
R3 is a C1-C20-group such as a linear, branched or cyclic C1-10-alkyl group which may bear one or more identical or different fluorine, OR2, NR22xe2x80x94 or xe2x80x94OSiR23 substituents, a C1-C4-aryl group which may bear fluorine, chlorine, OR2, SR2, NR22, NH2, NO2, CN, COR2 or CO2R2 substituents, a C7-C15-alkylaryl group or C7-C15-arylalkyl group, where the alkyl part may bear one or more identical or different fluorine, OR2, NR22xe2x80x94 or OSiR23 substituents, and the aryl part may bear fluorine, chlorine, OR2, SR2, NR22xe2x80x94, NH2, NO2, CN, COR2 or CO2R2 substituents, a C2-C10-alkenyl group which may bear one or more identical or different fluorine, OR2, CO2R2, COR2, NR22xe2x80x94 or OSiR23 substituents, a C2-C10-alkynyl group which may bear one or more identical or different fluorine, OR2, NR22xe2x80x94 or OSiR23 substituents, a C8-C12-arylalkenyl group, a PR22, B(OR2)2 or SnR23 group, where R2 are identical or different and are each a C1-C4-alkyl group or, C6-aryl group, where the alkyl group may bear one or more identical or different fluorine, chlorine, OR2 or NR22 substituents and the aryl group may bear fluorine, chlorine, OR2 or NR22 substituents and, in addition, two radicals R2 may be joined to one another to form a ring system, a C1-C14-heterocyclic group, where preferred heteroatoms are oxygen, nitrogen or sulfur and the group may in turn bear C1-C6-radicals or heteroatoms as substituents,
Y1, Y2 and Y3 are identical or different and are each a hydrogen atom or are as defined for R3 or X and at least one of the radicals Y1, Y2 and Y3, preferably Y3, is a hydrogen atom,
Y4, Y5 and Y6 are identical or different and are each a hydrogen atom or are as defined for R3 and at least one of the radicals Y4,
Y5 and Y6, preferably Y6, is a hydrogen atom.
Very particular preference is given to indanones of the formula I or Ia in which X is chlorine, bromine, iodine, triflate, nonaflate, mesylate, tosylate or diazonium,
R1 is a linear, branched or cyclic C1-C8-alkyl group which may bear one or more identical or different fluorine, chlorine, OR2 or NR22 substituents, a phenyl group which may bear one or more identical or different fluorine, chlorine, OR2 or NR22 substituents, a C7-C12-alkylaryl or arylalkyl group, where the alkyl part may bear one or more identical or different fluorine, chlorine, OR2 or NR22 substituents and the aryl part may bear one or more identical or different fluorine, chlorine, OR2 or NR22 substituents, a C2-C8-alkenyl group or a C2-C8-alkynyl group which may each bear one or more identical or different fluorine, chlorine, OR2 or NR22 substituents, a C8-C12-arylalkenyl group which may bear one or more identical or different fluorine, chlorine, OR2 or NR22 substituents, or R1 is an OR2, SiR23 or xe2x80x94OSiR23 group, where R2 are identical or different and are each a C1-4-alkyl group or phenyl group, where the alkyl group may bear one or more identical or different fluorine, chlorine, OR2 or NR22 substituents and the aryl group may bear one or more identical or different fluorine, chlorine, OR2 or NR22 substituents, or R1 is a C1-C16-heterocyclic group, where preferred heteroatoms are oxygen, nitrogen, sulfur and silicon and the group may in turn bear C1-C10-radicals or heteroatoms as substituents,
Y1, Y2 or Y3 are identical or different and are each a hydrogen atom, chlorine, bromine, iodine, triflate, nanoflate, mesylate, tosylate or diazonium, or Y1, Y2 or Y3 are each a linear, branched or cyclic C1-C8-alkyl group which may bear one or more identical or different halogen, OH, OR2, SR2NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C6-C14-aryl group which may bear one or more identical or different halogen, OR2, SR2NR22xe2x80x94, NH2, xe2x80x94N2H3, NO2, CN, CO2R2, CHO, COR2, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C7-C15-alkylaryl group or C7-C15-arylalkyl group, where the alkyl part may bear one or more identical or different halogen, OH, OR2, SR2NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents and the aryl part may bear one or more identical or different halogen, OR2, SR2NR22xe2x80x94, NH2, xe2x80x94N2H3, NO2, CN, CO2R2, CHO, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C2-C10-alkenyl group which may bear one or more identical or different halogen, OH, OR2, SR2, NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C2-C8-alkynyl group which may bear one or more identical or different halogen, OH, OR2, SR2, NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C8-C12-arylalkenyl group which may bear one or more identical or different halogen, OH, OR2, SR2, NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents,
or Y1, Y2 or Y3 are each a halogen atom or an NR22, PR22, B(OR2)2, SiR23 or SnR23 group, where R2 are identical or different and are each a C1-C20-hydrocarbon group, eg. a C1-C10-alkyl group or C6-C14-aryl group which may each bear one or more identical or different halogen, OH, OR2, SR2, NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, or two radicals R2 may be joined to form a ring system, or Y1, Y2 or Y3 are each a C1-C20-heterocyclic group which is bound via a carbon atom and may in turn bear C1-C20-radicals or heteroatoms as substituents, and at least two of the radicals Y1, Y2 and Y3 are each a hydrogen atom, preferably Y1 and Y3.
R3 is a C1-C4-group such as a linear, branched or cyclic C1-C8-alkyl group which may bear one or more identical or different fluorine, OR2a, NR2a2xe2x80x94 or OSiR2a3 substituents, a C6-C14-aryl group which may bear fluorine, chlorine, R2, OR2a or NR2a2 substituents, a C7-C10-alkylaryl group or C7-C10-arylalkyl group, where the alkyl part may bear one or more identical or different fluorine, OR2a, NR2a2xe2x80x94 or OSiR2a3 substituents and the aryl part may bear one or more identical or different fluorine, chlorine, OR2a or NR2a2 substituents, a C2-C8-alkenyl group which may bear one or more identical or different fluorine, OR2a, CO2R2a or NR2a2 substituents, a C2-C8-alkynyl group which may bear one or more identical or different fluorine, OR2a or NR2a2 substituents, a C8-C12-arylalkenyl group, a PR2a2, B(OR2a)2 or SnR2a3 group, where R2a are identical or different and are each a linear or branched C1-C4-alkyl group which may bear one or more fluorine substituents, or a phenyl group which may bear one or more identical or different fluorine or OR2a substituents, and, in addition, two radicals R2a may be joined to one another to form a ring system, a C1-C4-heterocyclic group, where preferred heteroatoms are oxygen, nitrogen or sulfur and the group may in turn bear C1-C4-radicals or heteroatoms as substituents, and Y4, Y5 and Y6 are identical or different and are each a hydrogen atom or R3 and at least two of the radicals Y4, Y5 and Y6 are hydrogen, preferably Y4 and Y6.
Illustrative examples of indanones of the formula I, which do not, however, restrict the scope of the invention, are:
2-methyl-7-chloro-1-indanone 2-methyl-7-bromo-1-indanone 2-methyl-7-iodo-1-indanone 2-methyl-7-trifluoroacetoxy-1-indanone 2-methyl-7-trifluoromethanesulfonoxy-1-indanone 2-methyl-7-methanesulfonoxy-1-indanone 2-methyl-7-ethanesulfonoxy-1-indanone 2-methyl-7-(p-toluenesulfonoxy)-1-indanone 2-methyl-7-benzenesulfonoxy-1-indanone 2-methyl-7-(2,4,6-triisopropylbenzenesulfonoxy)-1-indanone 2-methyl-7-pentafluorobenzenesulfonoxy-1-indanone 2-methyl-7-nonafluorobutanesulfonoxy-1-indanone 2-methyl-7-acetoxy-1-indanone 2-methyl-7-formyloxy-1-indanone 2-methyl-7-pentafluorobenzoyloxy-1-indanone 2-methyl-7-(p-nitrobenzoyloxy)-1-indanone 2-methyl-7-methoxycarbonyloxy-1-indanone 2-methyl-7-tert-butyloxycarbonyloxy-1-indanone 2-methyl-7-ethoxycarbonyloxy-1-indanone 2-methyl-7-benzyloxycarbonyloxy-1-indanone 2-methyl-7-dimethylphosphonoxy-1-indanone 2-methyl-7-diethylphosphonoxy-1-indanone 2-methyl-7-diphenylphosphonoxy-1-indanone 2-methyl-7-diazonium-1-indanone chloride 2-methyl-7-diazonium-1-indanone tetrafluoroborate 2-methyl-7-diazonium-1-indanone sulfate 2-methyl-4-vinyl-7-bromo-1-indanone 2-methyl-5-butyl-7-bromo-1-indanone 2-methyl-5-fluoro-7-bromo-1-indanone 2-methyl-4-isopropyl-7-bromo-1-indanone 2-methyl-5,7-dibromo-1-indanone 2-methyl-5,7-dichloro-1-indanone 2-methyl-6,7-dichloro-1-indanone 2-methyl-5-chloro-7-bromo-1-indanone 2-methyl-4-phenyl-7-diazonium-1-indanone chloride 2-methyl-4-cyclohexyl-7-diazonium-1-indanone tetrafluoroborate 2,5-dimethyl-7-chloro-1-indanone 2,4-dimethyl-7-bromo-1-indanone 2,6-dimethyl-7-chloro-1-indanone 2-methyl-5-butyl-7-chloro-1-indanone 2-methyl-5-isopropyl-7-trifluoromethanesulfonoxy-1-indanone 2-methyl-5-tert-butyl-7-methanesulfonoxy-1-indanone 2-methyl-5-phenyl-7-bromo-1-indanone 2-methyl-5-(3,5-dimethoxyphenyl)-7-iodo-1-indanone 2-methyl-5-benzyl-7-chloro-1-indanone 2-methyl-5-methoxy-7-chloro-1-indanone 2-methyl-5-phenoxy-7-chloro-1-indanone 2-methyl-6-methoxy-7-chloro-1-indanone 2-methyl-6-isopropoxy-7-bromo-1-indanone 2-methyl-6-trimethylsilyloxy-7-bromo-1-indanone 2-methyl-5-vinyl-7-(p-toluenesulfonoxy)-1-indanone 2-methyl-6-bromo-7-trifluoroacetoxy-1-indanone 2-methyl-6-phenyl-7-bromo-1-indanone 2-methyl-4-methoxy-7-chloro-1-indanone 2-methyl-4-diisopropylamino-7-chloro-1-indanone 2-trifluoromethyl-7-chloro-1-indanone 2-trifluoromethyl-7-bromo-1-indanone 2-trifluoromethyl-4-methyl-7-chloro-1-indanone 2-trifluoromethyl-5-isobutyl-7-trifluoromethanesulfonoxy-1-indanone 2-ethyl-7-chloro-1-indanone 2-ethyl-7-bromo-1-indanone 2-ethyl-7-diazonium-1-indanone tetrafluoroborate 2-ethyl-7-methanesulfonoxy-1-indanone 2-ethyl-4-trimethylsilyloxy-7-trifluoromethanesulfonoxy-1-indanone 2-ethyl-5-methyl-7-bromo-1-indanone 2-ethyl-4-benzyl-7-bromo-1-indanone 2-ethyl-7-diazonium-1-indanone tetrafluoroborate 2-n-propyl-7-chloro-1-indanone 2-n-propyl-7-bromo-1-indanone 2-n-propyl-5,7-dichloro-1-indanone 2-n-propyl-7-trifluoromethanesulfonoxy-1-indanone 2,6-diethyl-7-diazonium-1-indanone chloride 2-butyl-7-chloro-1-indanone 2-butyl-5-fluoro-7-chloro-1-indanone 2-butyl-5,7-dichloro-1-indanone 2-isopropyl-7-chloro-1-indanone 2-isopropyl-7-bromo-1-indanone 2-isopropyl-7-iodo-1-indanone 2-isopropyl-5-diphenylphosphino-7-nonafluorobutanesulfonoxy-1-indanone 2-phenyl-4-dimethylamino-7-bromo-1-indanone 2-phenyl-7-chloro-1-indanone 2-(2-pyridyl)-7-bromo-1-indanone 2-(2-furyl)-7-iodo-1-indanone 2-cyclohexyl-7-chloro-1-indanone 2-cyclohexyl-7-bromo-1-indanone 2-cyclohexyl-7-trifluoromethanesulfonoxy-1-indanone 2-isobutyl-7-chloro-1-indanone 2-isobutyl-7-bromo-1-indanone 2-tert-butyl-7-chloro-1-indanone 2-tert-butyl-7-iodo-1-indanone 2-benzyl-7-chloro-1-indanone 2-allyl-7-chloro-1-indanone 2-vinyl-7-trifluoromethanesulfonoxy-1-indanone 2-(2-trimethylsilylethyn-1-yl)-6-benzyl-7-chloroindanone 2-(hex-1-ynyl)-7-trifluoromethanesulfonoxy-1-indanone 2-trimethylsilyl-7-bromo-1-indanone 2-trimethylsilyloxy-7-bromo-1-indanone 2-dimethylamino-7-trifluoromethanesulfonoxy-1-indanone 2-N-pyrrolidino-7-chloro-1-indanone 2-diphenylphosphino-5-isopropyl-7-bromo-1-indanone 2-methoxy-6-allyl-7-chloro-1-indanone 2,6-dimethoxy-7-bromo-1-indanone 2-phenoxy-5-dimethylamino-7-trifluoromethanesulfonoxy-1-indanone 2-(2-methoxyethyl)-7-chloro-1-indanone 2-(3-chloropropyl)-7-chloro-1-indanone 2,4,5,6-tetramethyl-7-chloro-1-indanone 2-methyl-4-phenyl-5-methoxy-7-bromo-1-indanone 2-butyl-5-benzyl-6-bromo-7-trifluoromethanesulfonoxy-1-indanone 2-trimethylsilyloxy-4-methoxy-5-allyl-7-diazonium-1-indanone tetrafluoroborate 2-N-piperidino-4-fluoro-5,7-dibromo-1-indanone 2-isopropyl-4-cyclohexyl-5-methyl-7-trimethylstannyl-1-indanone 2,5-dimethoxy-4-bromo-6-trifluoromethyl-7-iodo-1-indanone 2-ethyl-4-dimethylamino-5-trimethylsilyl-7-chloroindanone 2-trifluoroethoxy-4-thiomethoxy-6-butyl-7-bromo-1-indanone 2-triethylsilyl-5,6-difluoro-7-methanesulfonoxy-1-indanone 2,5-diphenyl-7-bromo-1-indanone
Illustrative examples of indanones of the formula Ia, which, however, do not restrict the scope of the invention, are:
2-methyl-4-chloro-1-indanone 2-methyl-4-bromo-1-indanone 2-methyl-4-iodo-1-indanone 2-methyl-4-trifluoroacetoxy-1-indanone 2-methyl-4-trifluoromethanesulfonoxy-1-indanone 2-methyl-4-methanesulfonoxy-1-indanone 2-methyl-4-ethanesulfonoxy-1-indanone 2-methyl-4-(p-toluenesulfonoxy)-1-indanone 2-methyl-4-benzenesulfonoxy-1-indanone 2-methyl-4-(2,4,6-triisopropylbenzenesulfonoxy)-1-indanone 2-methyl-4-pentafluorobenzenesulfonoxy-1-indanone 2-methyl-4-nonafluorobutanesulfonoxy-1-indanone 2-methyl-4-acetoxy-1-indanone 2-methyl-4-formyloxy-1-indanone 2-methyl-4-pentafluorobenzoyloxy-1-indanone 2-methyl-4-(p-nitrobenzoyloxy)-1-indanone 2-methyl-4-methoxycarbonyloxy-1-indanone 2-methyl-4-tert-butyloxycarbonyloxy-1-indanone 2-methyl-4-ethoxycarbonyloxy-1-indanone 2-methyl-4-benzyloxycarbonyloxy-1-indanone 2-methyl-4-dimethylphosphonoxy-1-indanone 2-methyl-4-diethylphosphonoxy-1-indanone 2-methyl-4-diphenylphosphonoxy-1-indanone 2-methyl-4-diazonium-1-indanone chloride 2-methyl-4-diazonium-1-indanone tetrafluoroborate 2-methyl-4-diazonium-1-indanone sulfate 2-methyl-7-vinyl-4-bromo-1-indanone 2-methyl-5-butyl-4-bromo-1-indanone 2-methyl-6-fluoro-4-bromo-1-indanone 2-methyl-7-isopropyl-4-bromo-1-indanone 2-methyl-4,7-dibromo-1-indanone 2-methyl-5,4-dichloro-1-indanone 2-methyl-6,4-dichloro-1-indanone 2-methyl-4,7-dichloro-1-indanone 2-methyl-5-chloro-4-bromo-1-indanone 2-methyl-7-phenyl-4-diazonium-1-indanone chloride 2-methyl-7-cyclohexyl-4-diazonium-1-indanone tetrafluoroborate 2,5-dimethyl-4-chloro-1-indanone 2,7-dimethyl-4-bromo-1-indanone 2,6-dimethyl-4-chloro-1-indanone 2-methyl-5-butyl-4-chloro-1-indanone 2-methyl-5-isopropyl-4-trifluoromethanesulfonoxy-1-indanone 2-methyl-5-tert-butyl-4-methanesulfonoxy-1-indanone 2-methyl-5-phenyl-4-bromo-1-indanone 2-methyl-5-(3,5-dimethoxyphenyl)-4-iodo-1-indanone 2-methyl-6-benzyl-4-chloro-1-indanone 2-methyl-6-methoxy-4-chloro-1-indanone 2-methyl-5-phenoxy-4-chloro-1-indanone 2-methyl-6-methoxy-4-chloro-1-indanone 2-methyl-6-isopropoxy-4-bromo-1-indanone 2-methyl-6-trimethylsilyloxy-4-bromo-1-indanone 2-methyl-5-vinyl-4-(p-toluenesulfonoxy)-1-indanone 2-methyl-6-bromo-4-trifluoroacetoxy-1-indanone 2-methyl-6-phenyl-4-bromo-1-indanone 2-methyl-7-methoxy-4-chloro-1-indanone 2-methyl-7-diisopropylamino-4-chloro-1-indanone 2-trifluoromethyl-4-chloro-1-indanone 2-trifluoromethyl-4-bromo-1-indanone 2-trifluoromethyl-4-methyl-4-chloro-1-indanone 2-trifluoromethyl-5-isobutyl-4-trifluoromethanesulfonoxy-1-indanone 2-ethyl-4-chloro-1-indanone 2-ethyl-4-bromo-1-indanone 2-ethyl-4-diazonium-1-indanone tetrafluoroborate 2-ethyl-4-methanesulfonoxy-1-indanone 2-ethyl-5-trimethylsilyloxy-4-trifluoromethanesulfonoxy-1-indanone 2-ethyl-5-methyl-4-bromo-1-indanone 2-ethyl-7-benzyl-4-bromo-1-indanone 2-ethyl-4-diazonium-1-indanone tetrafluoroborate 2,6-diethyl-4-diazonium-1-indanone chloride 2-n-propyl-4-chloro-1-indanone 2-n-propyl-4-bromo-1-indanone 2-n-propyl-4,6-dichloro-1-indanone 2-n-propyl-7-trifluoromethanesulfonoxy-1-indanone 2-butyl-4-chloro-1-indanone 2-butyl-4-bromo-1-indanone 2-butyl-5-fluoro-4-chloro-1-indanone 2-butyl-4,5-dichloro-1-indanone 2-isopropyl-4-chloro-1-indanone 2-isopropyl-4-bromo-1-indanone 2-isopropyl-4-iodo-1-indanone 2-isopropyl-5-diphenylphosphino-4-nonafluorobutanesulfonoxy-1-indanone 2-phenyl-7-dimethylamino-4-bromo-1-indanone 2-phenyl-4-chloro-1-indanone 2-(2-pyridyl)-4-bromo-1-indanone 2-(2-furyl)-4-iodo-1-indanone 2-cyclohexyl-4-chloro-1-indanone 2-cyclohexyl-4-bromo-1-indanone 2-cyclohexyl-4-trifluoromethanesulfonoxy-1-indanone 2-isobutyl-4-chloro-1-indanone 2-isobutyl-4-bromo-1-indanone 2-tert-butyl-4-chloro-1-indanone 2-tert-butyl-4-iodo-1-indanone 2-benzyl-4-chloro-1-indanone 2-allyl-4-chloro-1-indanone 2-vinyl-4-trifluoromethanesulfonoxy-1-indanone 2-(2-trimethylsilylethyn-1-yl)-6-benzyl-4-chloroindanone 2-(hex-1-ynyl)-4-trifluoromethanesulfonoxy-1-indanone 2-trimethylsilyl-4-bromo-1-indanone 2-trimethylsilyloxy-4-bromo-1-indanone 2-dimethylamino-4-trifluoromethanesulfonoxy-1-indanone 2-N-pyrrolidino-4-chloro-1-indanone 2-diphenylphosphino-5-isopropyl-4-bromo-1-indanone 2-methoxy-6-allyl-4-chloro-1-indanone 2,6-dimethoxy-4-bromo-1-indanone 2-phenoxy-5-dimethylamino-4-trifluoromethanesulfonoxy-1-indanone 2-(2-methoxyethyl)-4-chloro-1-indanone 2-(3-chloropropyl)-4-chloro-1-indanone 2,5,6,7-tetramethyl-4-chloro-1-indanone 2-methyl-7-phenyl-5-methoxy-4-bromo-1-indanone 2-butyl-5-benzyl-6-bromo-4-trifluoromethanesulfonoxy-1-indanone 2-trimethylsilyloxy-7-methoxy-5-allyl-4-diazonium-1-indanone tetrafluoroborate 2-N-piperidino-7-fluoro-5,4-dibromo-1-indanone 2-isopropyl-7-cyclohexyl-5-methyl-4-trimethylstannyl-1-indanone 2,5-dimethoxy-7-bromo-6-trifluoromethyl-4-iodo-1-indanone 2-ethyl-7-dimethylamino-5-trimethylsilyl-4-chloroindanone 2-trifluoroethoxy-7-thiomethoxy-6-butyl-4-bromo-1-indanone 2-triethylsilyl-5,6-difluoro-4-methanesulfonoxy-1-indanone 2,5-diphenyl-4-bromo-1-indanone
Illustrative examples of indanones of the formula II, which, however, do not restrict the scope of the invention, are:
2-methyl-7-phenyl-1-indanone 2-methyl-7-(1-naphthyl)-1-indanone 2-methyl-6-(2-naphthyl)-1-indanone 2-methyl-7-(2-methyl-1-naphthyl)-1-indanone 2-methyl-7-(4-methyl-1-naphthyl)-1-indanone 2-methyl-7-(4-methoxy-1-naphthyl)-1-indanone 2-methyl-7-(6-methoxy-2-naphthyl)-1-indanone 2-methyl-7-(4-methylphenyl)-1-indanone 2-methyl-7-(3-methylphenyl)-1-indanone 2-methyl-7-(2-methylphenyl-1-indanone 2-methyl-7-(3,5-dimethylphenyl)-1-indanone 2-methyl-7-(2,3-dimethylphenyl)-1-indanone 2-methyl-7-(2,4-dimethylphenyl)-1-indanone 2-methyl-7-(2,5-dimethylphenyl)-1-indanone 2-methyl-7-(3-butylphenyl)-1-indanone 2-methyl-7-(4-tert-butylphenyl)-1-indanone 2-methyl-7-(4-ethylphenyl)-1-indanone 2-methyl-7-(4-isopropylphenyl)-1-indanone 2-methyl-7-(3,5-di-tert-butylphenyl)-1-indanone 2-methyl-7-mesityl-1-indanone 2-methyl-7-(4-biphenyl)-1-indanone 2-methyl-7-(3-biphenyl)-1-indanone 2-methyl-7-(2-biphenyl)-1-indanone 2-methyl-7-(3,5-diphenylphenyl)-1-indanone 2-methyl-7-(4-styryl)-1-indanone 2-methyl-7-(3-styryl)-1-indanone 2-methyl-7-(2-styryl)-1-indanone 2-methyl-7-(9-anthracenyl)-1-indanone 2-methyl-7-(9-phenanthrenyl)-1-indanone 2-methyl-7-(2-hydroxyphenyl)-1-indanone 2-methyl-7-(4-hydroxyphenyl)-1-indanone 2-methyl-7-(3-hydroxyphenyl)-1-indanone 2-methyl-7-(2,4-dihydroxyphenyl)-1-indanone 2-methyl-7-(3,5-dihydroxyphenyl)-1-indanone 2-methyl-7-(4-methoxyphenyl)-1-indanone 2-methyl-7-(3-methoxyphenyl)-1-indanone 2-methyl-7-(2-methoxyphenyl)-1-indanone 2-methyl-7-(2,4-dimethoxyphenyl)-1-indanone 2-methyl-7-(3,5-dimethoxyphenyl)-1-indanone 2-methyl-7-(3,4,5-trimethoxyphenyl)-1-indanone 2-methyl-7-(4-phenoxyphenyl)-1-indanone 2-methyl-7-(3,4-methylenedioxyphenyl)-1-indanone 2-methyl-7-(4-thioanisyl)-1-indanone 2-methyl-7-(3-thioanisyl)-1-indanone 2-methyl-7-(4-nitrophenyl)-1-indanone 2-methyl-7-(3-nitrophenyl)-1-indanone 2-methyl-7-(2-nitrophenyl)-1-indanone 2-methyl-7-(4-methyl-3-nitrophenyl)-1-indanone 2-methyl-7-(4-methoxycarbonylphenyl)-1-indanone 2-methyl-7-(3-methoxycarbonylphenyl)-1-indanone 2-methyl-7-(2-methoxycarbonylphenyl)-1-indanone 2-methyl-7-(4-carboxyphenyl)-1-indanone 2-methyl-7-(2-carboxyphenyl)-1-indanone 2-methyl-7-(4-formylphenyl)-1-indanone 2-methyl-7-(4-acetylphenyl)-1-indanone 2-methyl-7-(4-pivaloylphenyl)-1-indanone 2-methyl-7-(4-aminophenyl)-1-indanone 2-methyl-7-(3-aminophenyl)-1-indanone 2-methyl-7-(2-aminophenyl)-1-indanone 2-methyl-7-(4-dimethylaminophenyl)-1-indanone 2-methyl-7-(3-dimethylaminophenyl)-1-indanone 2-methyl-7-(4-(1-pyrrolidino)phenyl)-1-indanone 2-methyl-7-(4-hydrazinophenyl)-1-indanone 2-methyl-7-(4-cyanophenyl)-1-indanone 2-methyl-7-(3-cyanophenyl)-1-indanone 2-methyl-7-(2-cyanophenyl)-1-indanone 2-methyl-7-(4-trifluoromethoxyphenyl)-1-indanone 2-methyl-7-(4-fluorophenyl)-1-indanone 2-methyl-7-(4-bromophenyl)-1-indanone 2-methyl-7-(2,4-difluorophenyl)-1-indanone 2-methyl-7-(4-chlorophenyl)-1-indanone 2-methyl-7-(3,5-dichlorophenyl)-1-indanone 2-methyl-7-(4-trifluoromethylphenyl)-1-indanone 2-methyl-7-(3-trifluoromethylphenyl)-1-indanone 2-methyl-7-(3,5-bis(trifluoromethyl)phenyl)-1-indanone 2-methyl-7-(2,4-bis(trifluoromethyl)phenyl)-1-indanone 2-methyl-7-(2-furyl)-1-indanone 2-methyl-7-(3-furyl)-1-indanone 2-methyl-7-(5-methyl-2-furyl)-1-indanone 2-methyl-7-(benzofuryl)-1-indanone 2-methyl-7-(2-thiophenyl)-1-indanone 2-methyl-7-(5-methyl-2-thiophenyl)-1-indanone 2-methyl-7-(3-thiophenyl)-1-indanone 2-methyl-7-(5-isobutyl-2-thiophenyl)-1-indanone 2-methyl-7-(benzothiophenyl)-1-indanone 2-methyl-7-(N-methyl-2-pyrrolyl)-1-indanone 2-methyl-7-(N-methyl-3-pyrrolyl)-1-indanone 2-methyl-7-(2-pyridyl)-1-indanone 2-methyl-7-(3-pyridyl)-1-indanone 2-methyl-7-(4-pyridyl)-1-indanone 2-methyl-7-(2-pyrimidyl)-1-indanone 2-methyl-7-(2-quinolyl)-1-indanone 2-methyl-7-(3-quinolyl)-1-indanone 2-methyl-7-(4-isoquinolyl)-1-indanone 2-methyl-7-(2-thiazolyl)-1-indanone 2-methyl-7-(2-benzothiazolyl)-1-indanone 2-methyl-7-(2-N-methylimidazolyl)-1-indanone 2-methyl-7-(2-N-methylbenzoimidazolyl)-1-indanone 2-methyl-7-(2-oxazolyl)-1-indanone 2-methyl-7-(N-methyltriazolyl)-1-indanone 2-methyl-7-butyl-1-indanone 2-methyl-7-cyclohexyl-1-indanone 2-methyl-7-isopropyl-1-indanone 2-methyl-7-benzyl-1-indanone 2-methyl-7-(hex-1-en-6-yl)-1-indanone 2-methyl-7-(hex-1-en-1-yl)-1-indanone 2-methyl-7-vinyl-1-indanone 2-methyl-7-(2-trimethylsilylethen-1-yl)-1-indanone 2-methyl-7-(2-phenylethyn-1-yl)-1-indanone 2-methyl-7-(2-tert-butylethyn-1-yl)-1-indanone 2-methyl-7-allyl-1-indanone 2-methyl-7-(2-trimethylsilylethyn-1-yl)-1-indanone 2-methyl-7-(2-phenylethen-1-yl)-1-indanone 2-methyl-7-trimethylstannyl-1-indanone 2-methyl-7-tributylstannyl-1-indanone 2-methyl-7-triphenylstannyl-1-indanone 2-methyl-7-(boronic acid pinacol ester)-1-indanone 2-methyl-7-(boronic acid trimethylene glycol ester)-1-indanone 2-methyl-7-(B-catecholborane)-1-indanone 2-methyl-7-diphenylphosphino-1-indanone 2-methyl-7-dibutylphosphino-1-indanone 2-methyl-7-(methoxyphenylmethylphosphino)-1-indanone 2-ethyl-7-phenyl-1-indanone 2-ethyl-7-(4-tolyl)-1-indanone 2-ethyl-7-naphthyl-1-indanone 2-ethyl-7-(2-furyl)-1-indanone 2-ethyl-7-cyclohexyl-1-indanone 2-ethyl-7-(4-tert-butylphenyl)-1-indanone 2-n-propyl-7-phenyl-1-indanone 2-n-propyl-7-naphthyl-1-indanone 2-n-propyl-7-(4-tert-butylphenyl)-1-indanone 2-n-propyl-7-(4-methylphenyl)-1-indanone 2-n-butyl-7-phenyl-1-indanone 2-n-butyl-7-naphthyl-1-indanone 2-n-butyl-7-(4-tert-butylphenyl)-1-indanone 2-n-butyl-7-(4-methylphenyl)-1-indanone 2-isopropyl-7-(2-pyrridyl)-1-indanone 2-isopropyl-7-phenyl-1-indanone 2-isopropyl-7-naphthyl-1-indanone 2-isobutyl-7-phenyl-1-indanone 2-isobutyl-7-naphthyl-1-indanone 2-cyclohexyl-7-phenyl-1-indanone 2-trifluoromethyl-7-phenyl-1-indanone 2-trifluoromethyl-7-(4-tolyl)-1-indanone 2-trifluoromethyl-7-naphthyl-1-indanone 2-trifluoromethyl-7-(4-methoxyphenyl)-1-indanone 2-trifluoromethyl-7-(3,5-bis(trifluoromethyl)phenyl)-1-indanone 2,4-dimethyl-7-phenyl-1-indanone 2-methyl-4-methoxy-7-phenyl-1-indanone 2,6-dimethyl-7-phenyl-1-indanone 2,5-dimethyl-7-phenyl-1-indanone 2,5-dimethyl-7-p-tolyl-1-indanone 2,5-dimethyl-7-(2-thiophenyl)-1-indanone 2,4-methyl-7-naphthyl-1-indanone 2-methyl-5-phenyl-7-naphthyl-1-indanone 2-methyl-5,7-diphenyl-1-indanone 2-methyl-7-(4-fluorophenyl)-1-indanone 2-methyl-5-diphenylphosphino-7-(4-nitrophenyl)-1-indanone 2-methyl-5-chloro-7-phenyl-1-indanone 2,6-dimethyl-7-(4-methoxyphenyl)-1-indanone 2-ethyl-4-methyl-7-(3,5-bis(trifluoromethyl)phenyl)-1-indanone 2-ethyl-5-vinyl-7-(2-furyl)-1-indanone 2-isopropyl-5-trifluoromethyl-7-phenyl-1-indanone 2-cyclohexyl-5-methyl-7-(2-pyridyl)-1-indanone 2-trifluoromethyl-4-butyl-7-naphthyl-1-indanone 2,5-trifluoromethyl-7-butyl-1-indanone 2-trimethylsilyl-5-isopropyl-7-(boronic acid pinacol ester)-1-indanone 2-dimethylamino-6-cyclohexyl-7-trimethylstannyl-1-indanone 2,4,5,6-tetramethyl-7-phenyl-1-indanone 2-methyl-4-phenyl-5-methoxy-7-naphthyl-1-indanone 2-butyl-5-benzyl-6-bromo-7-(4-methoxyphenyl)-1-indanone 2-trimethylsilyloxy-4-methoxy-5-allyl-7-(2-pyridyl)-1-indanone 2-N-piperidino-4-fluoro-5,7-diphenyl-1-indanone 2-isopropyl-4-cyclohexyl-5-methyl-7-trimethylstannyl-1-indanone 2,5-dimethoxy-4-bromo-6-trifluoromethyl-7-furyl-1-indanone 2-ethyl-5-trimethylsilyl-7-(2-tert-butylethyn-1-yl)-1-indanone 2-trifluoroethoxy-4-thiomethoxy-6-butyl-7-vinyl-1-indanone 2-triethylsilyl-5,6-difluoro-7-(3-cyanophenyl)-1-indanone 2,5-diphenyl-7-fluoro-1-indanone
Illustrative examples of indanones of the formula IIa, which, however, do not restrict the scope of the invention, are:
2-methyl-4-phenyl-1-indanone 2-methyl-4-(1-naphthyl)-1-indanone 2-methyl-4-(2-naphthyl)-1-indanone 2-methyl-4-(2-methyl-1-naphthyl)-1-indanone 2-methyl-4-(4-methyl-1-naphthyl)-1-indanone 2-methyl-4-(4-methoxy-1-naphthyl)-1-indanone 2-methyl-4-(6-methoxy-2-naphthyl)-1-indanone 2-methyl-4-(4-methylphenyl)-1-indanone 2-methyl-4-(3-methylphenyl)-1-indanone 2-methyl-4-(2-methylphenyl)-1-indanone 2-methyl-4-(3,5-dimethylphenyl)-1-indanone 2-methyl-4-(2,3-dimethylphenyl)-1-indanone 2-methyl-4-(2,4-dimethylphenyl)-1-indanone 2-methyl-4-(2,5-dimethylphenyl)-1-indanone 2-methyl-4-(3-butylphenyl)-1-indanone 2-methyl-4-(4-tert-butylphenyl)-1-indanone 2-methyl-4-(3,5-di-tert-butylphenyl)-1-indanone 2-methyl-4-mesityl-1-indanone 2-methyl-4-(4-biphenyl)-1-indanone 2-methyl-4-(3-biphenyl)-1-indanone 2-methyl-4-(2-biphenyl)-1-indanone 2-methyl-4-(3,5-diphenylphenyl)-1-indanone 2-methyl-4-(4-styryl)-1-indanone 2-methyl-4-(3-styryl)-1-indanone 2-methyl-4-(2-styryl)-1-indanone 2-methyl-4-(9-anthracenyl-1-indanone 2-methyl-4-(9-phenanthrenyl)-1-indanone 2-methyl-4-(2-hydroxyphenyl)-1-indanone 2-methyl-4-(4-hydroxyphenyl)-1-indanone 2-methyl-4-(3-hydroxyphenyl)-1-indanone 2-methyl-4-(2,4-dihydroxyphenyl)-1-indanone 2-methyl-4-(3,5-dihydroxyphenyl)-1-indanone 2-methyl-4-(4-methoxyphenyl)-1-indanone 2-methyl-4-(3-methoxyphenyl)-1-indanone 2-methyl-4-(2-methoxyphenyl)-1-indanone 2-methyl-4-(2,4-dimethoxyphenyl)-1-indanone 2-methyl-4-(3,5-dimethoxyphenyl)-1-indanone 2-methyl-4-(3,4,5-trimethoxyphenyl)-1-indanone 2-methyl-4-(4-phenoxyphenyl)-1-indanone 2-methyl-4-(3,4-methylenedioxyphenyl)-1-indanone 2-methyl-4-(4-thioanisyl)-1-indanone 2-methyl-4-(3-thioanisyl)-1-indanone 2-methyl-4-(4-nitrophenyl)-1-indanone 2-methyl-4-(3-nitrophenyl)-1-indanone 2-methyl-4-(2-nitrophenyl)-1-indanone 2-methyl-4-(4-methyl-3-nitrophenyl)-1-indanone 2-methyl-4-(4-methoxycarbonylphenyl)-1-indanone 2-methyl-4-(3-methoxycarbonylphenyl)-1-indanone 2-methyl-4-(2-methoxycarbonylphenyl)-1-indanone 2-methyl-4-(4-carboxylphenyl)-1-indanone 2-methyl-4-(2-carboxylphenyl)-1-indanone 2-methyl-4-(4-formylphenyl)-1-indanone 2-methyl-4-(4-acetylphenyl)-1-indanone 2-methyl-4-(4-pivaloylphenyl)-1-indanone 2-methyl-4-(4-aminophenyl)-1-indanone 2-methyl-4-(3-aminophenyl)-1-indanone 2-methyl-4-(2-aminophenyl)-1-indanone 2-methyl-4-(4-dimethylaminophenyl)-1-indanone 2-methyl-4-(3-dimethylaminophenyl)-1-indanone 2-methyl-4-(4-(1-pyrrolidino)phenyl)-1-indanone 2-methyl-4-(4-hydrazinophenyl)-1-indanone 2-methyl-4-(4-cyanophenyl)-1-indanone 2-methyl-4-(3-cyanophenyl)-1-indanone 2-methyl-4-(2-cyanophenyl)-1-indanone 2-methyl-4-(4-trifluoromethoxyphenyl)-1-indanone 2-methyl-4-(4-fluorophenyl)-1-indanone 2-methyl-4-(4-bromophenyl)-1-indanone 2-methyl-4-(2,4-difluorophenyl)-1-indanone 2-methyl-4-(4-chlorophenyl)-1-indanone 2-methyl-4-(3,5-dichlorophenyl)-1-indanone 2-methyl-4-(4-trifluoromethylphenyl)-1-indanone 2-methyl-4-(3-trifluoromethylphenyl)-1-indanone 2-methyl-4-(3,5-bis(trifluoromethyl)phenyl)-1-indanone 2-methyl-4-(2,4-bis(trifluoromethyl)phenyl)-1-indanone 2-methyl-4-(2-furyl)-1-indanone 2-methyl-4-(3-furyl)-1-indanone 2-methyl-4-(5-methyl-2-furyl)-1-indanone 2-methyl-4-(benzofuryl)-1-indanone 2-methyl-4-(2-thiophenyl)-1-indanone 2-methyl-4-(5-methyl-2-thiophenyl)-1-indanone 2-methyl-4-(3-thiophenyl)-1-indanone 2-methyl-4-(5-isobutyl-2-thiophenyl)-1-indanone 2-methyl-4-(benzothiophenyl)-1-indanone 2-methyl-4-(N-methyl-2-pyrrolyl)-1-indanone 2-methyl-4-(N-methyl-3-pyrrolyl)-1-indanone 2-methyl-4-(2-pyridyl)-1-indanone 2-methyl-4-(3-pyridyl)-1-indanone 2-methyl-4-(4-pyridyl)-1-indanone 2-methyl-4-(2-pyrimidyl)-1-indanone 2-methyl-4-(2-quinolyl)-1-indanone 2-methyl-4-(3-quinolyl)-1-indanone 2-methyl-4-(4-isoquinolyl)-1-indanone 2-methyl-4-(2-thiazolyl)-1-indanone 2-methyl-4-(2-benzothioazolyl)-1-indanone 2-methyl-4-(2-N-methylimidazolyl)-1-indanone 2-methyl-4-(2-N-methylbenzoimidazolyl)-1-indanone 2-methyl-4-(2-oxazolyl)-1-indanone 2-methyl-4-(N-methyltriazolyl)-1-indanone 2-methyl-4-butyl-1-indanone 2-methyl-4-cyclohexyl-1-indanone 2-methyl-4-isopropyl-1-indanone 2-methyl-4-benzyl-1-indanone 2-methyl-4-(hex-1-en-6-yl)-1-indanone 2-methyl-4-(hex-1-en-1-yl)-1-indanone 2-methyl-4-vinyl-1-indanone 2-methyl-4-(2-trimethylsilylethen-1-yl)-1-indanone 2-methyl-4-(2-phenylethyn-1-yl)-1-indanone 2-methyl-4-(2-tert-butylethyn-1-yl)-1-indanone 2-methyl-4-allyl-1-indanone 2-methyl-4-(2-trimethylsilylethyn-1-yl)-1-indanone 2-methyl-4-(2-phenylethen-1-yl)-1-indanone 2-methyl-4-trimethylstannyl-1-indanone 2-methyl-4-tributylstannyl-1-indanone 2-methyl-4-triphenylstannyl-1-indanone 2-methyl-4-(boronic acid pinacol ester)-1-indanone 2-methyl-4-(boronic acid trimethylene glycol ester)-1-indanone 2-methyl-4-(B-catecholborane)-1-indanone 2-methyl-4-diphenylphosphino-1-indanone 2-methyl-4-dibutylphosphino-1-indanone 2-methyl-4-(methoxyphenyl-methyl-phosphino)-1-indanone 2-ethyl-4-phenyl-1-indanone 2-ethyl-4-(4-tolyl)-1-indanone 2-ethyl-4-naphthyl-1-indanone 2-ethyl-4-(2-furyl)-1-indanone 2-ethyl-4-cyclohexyl-1-indanone 2-ethyl-4-butyl-1-indanone 2-n-propyl-4-phenyl-1-indanone 2-n-propyl-4-naphthyl-1-indanone 2-n-propyl-7-(4-tert-butylphenyl)-1-indanone 2-n-propyl-7-(4-methylphenyl)-1-indanone 2-n-butyl-7-phenyl-1-indanone 2-n-butyl-7-naphthyl-1-indanone 2-n-butyl-7-(4-tert-butylphenyl)-1-indanone 2-n-butyl-7-(4-methylphenyl)-1-indanone 2-isopropyl-4-(2-pyrridyl)-1-indanone 2-isopropyl-4-phenyl-1-indanone 2-isopropyl-4-naphthyl-1-indanone 2-isobutyl-4-phenyl-1-indanone 2-isobutyl-4-naphthyl-1-indanone 2-cyclohexyl-4-phenyl-1-indanone 25 2-trifluoromethyl-4-phenyl-1-indanone 2-trifluoromethyl-4-(4-tolyl)-1-indanone 2-trifluoromethyl-4-naphthyl-1-indanone 2-trifluoromethyl-4-(4-methoxyphenyl)-1-indanone 2-trifluoromethyl-4-(3,5-bis(trifluoromethyl)phenyl)-1-indanone 2,7-dimethyl-4-phenyl-1-indanone 2-methyl-7-methoxy-4-phenyl-1-indanone 2,6-dimethyl-4-phenyl-1-indanone 2,5-dimethyl-4-phenyl-1-indanone 2,5-dimethyl-4-p-tolyl-1-indanone 2,5-dimethyl-4-(2-thiophenyl)-1-indanone 2,7-methyl-4-naphthyl-1-indanone 2-methyl-5-phenyl-4-naphthyl-1-indanone 2-methyl-5,4-diphenyl-1-indanone 2-methyl-4-(4-fluorophenyl)-1-indanone 2-methyl-5-diphenylphosphino-4-(4-nitrophenyl)-1-indanone 2-methyl-5-chloro-4-phenyl-1-indanone 2,6-dimethyl-4-(4-methoxyphenyl)-1-indanone 2-ethyl-7-methyl-4-(3,5-bis(trifluoromethyl)phenyl)-1-indanone 2-ethyl-5-vinyl-4-(2-furyl)-1-indanone 2-isopropyl-5-trifluoromethyl-4-phenyl-1-indanone 2-cyclohexyl-5-methyl-4-(2-pyridyl)-1-indanone 2-trifluoromethyl-7-butyl-4-naphthyl-1-indanone 2,5-trifluoromethyl-4-butyl-1-indanone 2-trimethylsilyl-5-isopropyl-4-(boronic acid pinacol ester)-1-indanone 2-dimethylamino-6-cyclohexyl-4-trimethylstannyl-1-indanone 2,5,6,7-tetramethyl-4-phenyl-1-indanone 2-methyl-7-phenyl-5-methoxy-4-naphthyl-1-indanone 2-butyl-5-benzyl-6-bromo-4-(4-methoxyphenyl)-1-indanone 2-trimethylsilyloxy-7-methoxy-5-allyl-4-(2-pyridyl)-1-indanone 2-N-piperidino-7-fluoro-5,4-diphenyl-1-indanone 2-isopropyl-7-cyclohexyl-5-methyl-4-trimethylstannyl-1-indanone 2,5-dimethoxy-7-bromo-6-trifluoromethyl-4-furyl-1-indanone 2-trifluoroethoxy-7-thiomethoxy-6-butyl-4-vinyl-1-indanone 2-triethylsilyl-5,6-difluoro-4-(3-cyanophenyl)-1-indanone 2,5-diphenyl-7-fluoro-1-indanone
In the process of the present invention, at least one indanone of the formula I or Ia is reacted with at least one coupling component, forming the indanones of the formulae II and IIa. In this reaction, the coupling component serves to introduce the radical R3. It is also possible for the coupling component to convert one or more of the radicals Y1, Y2 and Y3 which are as defined for X into radicals Y4, Y5 and Y6 which are as defined for R3.
The coupling components are preferably compounds containing elements of Groups 13-17 of the Periodic Table of the Elements. The coupling components are preferably compounds containing boron, carbon, silicon, germanium, tin, phosphorus or fluorine. The coupling components are particularly preferably compounds containing boron, carbon, silicon, tin or phosphorus.
Preferred boron-containing coupling components are boronic acids and boronic esters, for example of the type
R4xe2x80x94B(OR5)2,
where R4 is a C1-C40-group such as a linear, branched or cyclic C1-C20-alkyl group which may bear one or more identical or different halogen, OH, OR2, SR2, NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C6-C22-aryl group which may bear one or more identical or different halogen, OR2, SR2, NR22xe2x80x94, NH2, xe2x80x94N2H3, NO2, CN, CO2R2, COR24, CHO, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C7-C15-alkylaryl group or C7-C15-arylalkyl group, where the alkyl group may bear one or more identical or different halogen, OH, OR2, SR2, NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents and the aryl group may bear one or more identical or different halogen, OR2, SR2, NR22xe2x80x94, NH2, xe2x80x94N2H3, NO2, CN, CO2R2, COR2, CHO, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C2-C10-alkenyl group which may bear one or more identical or different halogen, OH, OR2, SR2, NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C2-C10-alkynyl group which may bear one or more identical or different halogen, OH, OR2, SR2, NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C8-C12-arylalkenyl group which may bear one or more identical or different halogen, OH, OR2, SR2, NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, or R4 is a C1-C20-heterocyclic group which may in turn bear C1-C20-radicals or heteroatoms as substituents, and
R5 are identical or different and may each be a hydrogen atom, a linear, branched or cyclic C1-C40-group, for example a C1-20-alkyl group or a C6-C14-aryl group, or form a ring system. Also preferred are condensation products of the abovementioned boronic acids and boronic esters.
Preferred boron-containing coupling components are, furthermore, boranes, for example of the type R6xe2x80x94B(R7)2, where R6 is a linear, branched or cyclic C1-C20-alkyl group or a C6-C14-aryl group, which may each bear one or more identical or different halogen, OR2, SR2, NR22xe2x80x94, NH2, xe2x80x94N2H3, NO2, CN, CO2R2, COR2, CHO, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, and R7 are identical or different and are each halogen, a linear, branched or cyclic C1-C40-group, for example a C1-C20-alkyl group or a C6-C14-aryl group, or R7 form a ring system.
Also preferred are diboranes, for example of the type
where R5 is as defined above, in particular the compounds
Examples of carbon-containing coupling components are alkenes and alkynes. Particular preference is given to alkenes and alkynes of the formula
R, Rxe2x80x2 and Rxe2x80x3 are identical or different and are each H or a C1-C10-alkyl group, where one or more of the CH2 groups may be replaced by identical or different O, S, NR2, xe2x80x94COxe2x80x94, xe2x80x94OCxe2x95x90Oxe2x80x94, C(O)O, xe2x80x94CONR2, C6-C14-arylene xe2x80x94CH2xe2x95x90CH2xe2x80x94, xe2x80x94Cxe2x89xa1Cxe2x80x94 or xe2x80x94SiR2 groups and one or more H of R may be replaced by identical or different C1-C4-alkyl, OH, SiR32, halogen, xe2x80x94Cxe2x89xa1Nxe2x80x94, xe2x80x94N3, NR22, COOH, xe2x80x94CO2R2 or xe2x80x94OC(O)R2 substituents, where R, Rxe2x80x2 and Rxe2x80x3 may form one or more ring systems and R2 is as defined in formula I.
Very particular preference is given to alkenes and alkynes in which R, Rxe2x80x2 are identical or different and are each H or a C1-C6-alkyl group, where one or two CH2 groups may be replaced by identical or different xe2x80x94COxe2x80x94, xe2x80x94C(O)Oxe2x80x94, CONR2 and phenylene groups and from 1 to 3 H of R may be replaced by identical or different SiR32, OH, F, Cl, CN and CO2R2 substituents, and in which Rxe2x80x3 is H and R2 is as defined above.
Examples of silicon-containing coupling components are compounds of the type R4xe2x80x94Si(R7)3 with the abovementioned definitions for R4 and R7.
Examples of tin-containing coupling components are stannanes, for example of the type R4xe2x80x94Sn(R7)3, and also distannanes of the type (R7)3Snxe2x80x94Sn(R7)3 with the abovementioned definitions for R4 and R7.
Examples of phosphorus-containing coupling components are compounds of the type (R5)2Pxe2x80x94R8, where the radical R8 is H, Sn(R7)3 or Si(R7)3 and R5 and R7 are as defined above.
Examples of fluorine-containing coupling components are fluoride salts in which the cation is an element of groups 1-3 of the Periodic Table of the Elements or, particularly preferably, is a bulky peralkylated ammonium, sulfonium, amidosulfonium, phosphonium, amidophosphonium or guanidinium cation.
The coupling components described are illustrated by the following examples which do not restrict the scope of the invention.
Examples of boronic acids and boronic esters are:
phenylboronic acid p-tolylboronic acid m-tolylboronic acid o-tolylboronic acid 2,3-dimethylphenylboronic acid 2,4-dimethylphenylboronic acid 2,6-dimethylphenylboronic acid 3,5-dimethylphenylboronic acid mesitylboronic acid tetramethylphenylboronic acid butylphenylboronic acid 4-tert-butylphenylboronic acid 4-ethylphenylboronic acid tert-butylphenylboronic acid isopropylphenylboronic acid cyclohexylphenylboronic acid 4-(hex-5-en-1-yl)phenylboronic acid triisopropylsilylphenylboronic acid p-methoxyphenylboronic acid m-methoxyphenylboronic acid o-methoxyphenylboronic acid 2,4-dimethoxyphenylboronic acid 2,5-dimethoxyphenylboronic acid 3,5-dimethoxyphenylboronic acid 2,3,4-trimethoxyphenylboronic acid 2,4,6-trimethoxyphenylboronic acid 3,4,5-trimethoxyphenylboronic acid p-phenoxyphenylboronic acid p-ethoxyphenylboronic acid 2-(3xe2x80x2-phenylboronic acid)-1,3-dioxolane 3,4-(methylenedioxy)phenylboronic acid 3,4-(isopropylidenedioxy)phenylboronic acid p-thioanisylboronic acid m-thioanisylboronic acid o-thioanisylboronic acid p-nitrophenylboronic acid o-nitrophenylboronic acid m-nitrophenylboronic acid 3-nitro-4-methylphenylboronic acid 3-nitro-4-bromophenylboronic acid 4-(methoxycarbonyl)phenylboronic acid 3-(methoxycarbonyl)phenylboronic acid 2-(methoxycarbonyl)phenylboronic acid 4-carboxylphenylboronic acid 3-carboxylphenylboronic acid 2-carboxylphenylboronic acid formylphenylboronic acid acetylphenylboronic acid pivaloylphenylboronic acid o-fluorophenylboronic acid m-fluorophenylboronic acid p-fluorophenylboronic acid 2,3-difluorophenylboronic acid 2,4-difluorophenylboronic acid 3,5-difluorophenylboronic acid 2,3,4-trifluorophenylboronic acid 2,4,6-trifluorophenylboronic acid tetrafluorophenylboronic acid pentafluorophenylboronic acid o-chlorophenylboronic acid m-chlorophenylboronic acid p-chlorophenylboronic acid 3,5-dichlorophenylboronic acid 2,4,6-trichlorophenylboronic acid p-bromophenylboronic acid p-trifluoromethylphenylboronic acid m-trifluoromethylboronic acid o-trifluoromethylboronic acid 2,6-bis(trifluoromethyl)phenylboronic acid 3,5-bis(trifluoromethyl)phenylboronic acid p-trifluoromethyltetrafluorophenylboronic acid trifluoromethoxyphenylboronic acid o-cyanophenylboronic acid m-cyanophenylboronic acid p-cyanophenylboronic acid tetrafluorocyanophenylboronic acid m-aminophenylboronic acid p-aminophenylboronic acid tetrafluoro-4-aminophenylboronic acid 3-amino-4-methylphenylboronic acid p-dimethylaminophenylboronic acid m-dimethylaminophenylboronic acid o-dimethylaminophenylboronic acid hydrazylphenylboronic acid p-hydroxyphenylboronic acid m-hydroxyphenylboronic acid o-hydroxyphenylboronic acid 3-hydroxy-4-phenylboronic acid 2,4-dihydroxyphenylboronic acid 3,5-dihydroxyphenylboronic acid 1-naphthylboronic acid 2-naphthylboronic acid 2-methyl-1-naphthylboronic acid 4-methyl-1-naphthylboronic acid 4-methoxy-1-naphthylboronic acid 6-methoxy-2-naphthylboronic acid 2-biphenylboronic acid 3-biphenylboronic acid 4-biphenylboronic acid 3,5-diphenylphenylboronic acid p-styrylboronic acid m-styrylboronic acid o-styrylboronic acid 9-anthraceneboronic acid 9-phenanthreneboronic acid 2-furanboronic acid 3-furanboronic acid 5-methyl-2-furanboronic acid benzofuranboronic acid 2-thiopheneboronic acid 3-thiopheneboronic acid 5-methyl-2-thiopheneboronic acid benzothiopheneboronic acid N-methyl-2-pyrroleboronic acid N-methyl-3-pyrroleboronic acid 2-pyridineboronic acid 3-pyridineboronic acid 4-pyridineboronic acid pyrimidineboronic acid 2-quinolineboronic acid 3-quinolineboronic acid 4-isoquinolineboronic acid tetrafluoropyridineboronic acid vinylboronic acid but-2-en-2-ylboronic acid hexenylboronic acid cyclohexenylboronic acid 2-phenylethenylboronic acid 6-methoxyhex-1-ene-1-boronic acid allylboronic acid benzylboronic acid p-methoxybenzylboronic acid ethynylboronic acid 2-trimethylsilylethynylboronic acid 2-phenylethynylboronic acid hex-1-yne-1-boronic acid tert-butylacetyleneboronic acid n-butylboronic acid cyclohexylboronic acid isopropylboronic acid phenylboronic acid dimethyl ester phenylboronic acid diethyl ester phenylboronic acid dibutyl ester phenylboronic acid diisopropyl ester phenylboronic acid dicyclohexyl ester phenylboronic acid di-tert-butyl ester phenylboronic acid diphenyl ester p-tolylboronic acid dimethyl ester p-tolylboronic acid diethyl ester p-tolylboronic acid diisopropyl ester 3,5-dimethylphenylboronic acid dibutyl ester 3,5-bis(trifluoromethyl)phenylboronic acid methyl ester 1-naphthylboronic acid dimethyl ester 1-naphthylboronic acid diethyl ester 1-naphthylboronic acid dibutyl ester 1-naphthylboronic acid diisopropyl ester 1-naphthylboronic acid diphenyl ester 2-naphthylboronic acid dimethyl ester 2-naphthylboronic acid diisopropyl ester 2-furanboronic acid dimethyl ester 3-furanboronic acid diisopropyl ester 2-thiopheneboronic acid dimethyl ester n-methylpyrrole-2-boronic acid diisopropyl ester pyridineboronic acid dimethyl ester pyridineboronic acid diisopropyl ester B-n-butylcatecholborane B-(1-hexenyl)catecholborane B-cyclohexylcatecholborane B-phenylcatecholborane B-(1-naphthyl)catecholborane B-(2-naphthyl)catecholborane B-ethynylcatecholborane B-(2-trimethylsilylethynyl)catecholborane B-(2-phenylethynyl)catecholborane B-(hex-1-yn-1-yl)catecholborane B-(tert-butylethynyl)catecholborane phenylboronic acid pinacol ester phenylboronic acid cyclohexanediol ester phenylboronic acid trimethylene glycol ester phenylboronic acid glycol ester phenylboronic acid 2xe2x80x2,2xe2x80x2-dimethylpropanediol ester 1-naphthylboronic acid cyclohexanediol ester 1-naphthylboronic acid trimethylene glycol ester 1-naphthylboronic acid pinacol ester 1-naphthylboronic acid glycol ester 2-naphthylboronic acid trimethylene glycol ester 2-naphthylboronic acid pinacol ester methoxyphenylboronic acid dimethyl ester aminophenylboronic acid tributyl ester nitrophenylboronic acid pinacol ester fluorophenylboronic acid trimethylene glycol ester chlorophenylboronic acid diisopropyl ester bromophenylboronic acid pinacol ester cyanophenylboronic acid pinacol ester 4-(methoxycarbonyl)phenylboronic acid pinacol ester 4-(methoxycarbonyl)phenylboronic acid trimethylene glycol ester vinylboronic acid dimethyl ester B-vinylcatecholborane vinylboronic acid trimethylene glycol ester hex-1-en-1-ylboronic acid diisopropyl ester B-hexenylcatecholborane cyclohexenylboronic acid diethyl ester B-cyclohexenylcatecholborane 2-phenylethenylboronic acid diphenyl ester 2-phenylethenylcatecholborane 6-methoxyhex-1-ene-1-boronic acid dimethyl ester allylboronic acid diisopropyl ester allylboronic acid pinacol ester allylcatecholborane benzylboronic acid diisopropyl ester p-methoxybenzylboronic acid trimethylene glycol ester ethynylboronic acid diisopropyl ester 2-trimethylsilylethynylboronic acid diisopropyl ester 2-trimethylsilylethynylboronic acid trimethylene glycol ester 2-phenylethynylboronic acid pinacol ester 2-phenylethynylboronic acid diisopropyl ester hex-1-yn-1-boronic acid diisopropyl ester hex-1-yn-1-boronic acid dibutyl ester tert-butylacetyleneboronic acid diisopropyl ester tert-butylacetyleneboronic acid pinacol ester n-butylboronic acid dimethyl ester n-butylboronic acid diisopropyl ester B-n-butylcatecholborane n-butylboronic acid trimethylene glycol ester n-butylboronic acid pinacol ester cyclohexylboronic acid dimethyl ester B-cyclohexylcatecholborane cyclohexylboronic acid trimethylene glycol ester isopropylboronic acid diethyl ester B-isopropylcatecholborane isopropylboronic acid pinacol ester
Examples of above-described boranes are:
B-n-butyl-9-borabicyclo[3.3.1]nonane=B-n-butyl-9-BBN B-isoamyl-9-BBN B-(hex-1-en-1-yl)-9-BBN B-vinyl-9-BBN B-cyclohexyl-9-BBN B-(2-trimethylsilylethen-1-yl)-9-BBN B-phenyl-9-BBN B-(1-naphthyl)-9-BBN B-(2-naphthyl)-9-BBN B-(3,5-bis(trifluoromethyl)phenyl)-9-BBN B-(2-phenylethyn-1-yl)-9-BBN B-(2-phenylethen-1-yl)-9-BBN B-benzyl-9-BBN B-allyl-9-BBN ethyldisiamylborane n-butyldisiamylborane amyldisiamylborane cyclohexyldisiamylborane vinyldisiamylborane hex-1-en-1-yldisiamylborane 2-phenylethen-1-yldisiamylborane 2-trimethylsilylethen-1-yldisiamylborane phenyldisiamylborane naphthyldisiamylborane benzyldisiamylborane 2-trimethylsilylethyn-1-yldisiamylborane tributylborane cyclohexyldibutylborane vinyldibutylborane hex-1-en-1-yldibutylborane 2-phenylethen-1-yldibutylborane 2-trimethylsilylethen-1-yldibutylborane phenyldibutylborane naphthyldibutylborane benzyldibutylborane 2-trimethylsilylethyn-1-yldibutylborane ethyldicyclohexylborane n-butyldicyclohexylborane amyldicyclohexylborane vinyldicyclohexylborane hex-1-en-1-yldicyclohexylborane 2-phenylethen-1-yldicyclohexylborane 2-trimethylsilylethen-1-yldicyclohexylborane phenyldicyclohexylborane naphthyldicyclohexylborane benzyldicyclohexylborane 2-trimethylsilylethyn-1-yldicyclohexylborane di-n-butylthexylborane divinylthexylborane dihex-1-en-1-ylthexylborane diphenylthexylborane dinaphthylthexylborane bis-(2-trimethylsilylethen-1-yl)thexylborane n-butyldibromoborane n-butyldichloroborane amyldibromoborane cyclohexyldibromoborane vinyldibromoborane vinyldichloroborane hex-1-en-1-yldibromoborane 2-phenylethen-1-yldibromoborane 2-phenylethen-1-yldichloroborane 2-trimethylsilylethen-1-yldifluoroborane phenyldibromoborane phenyldichloroborane naphthyldibromoborane benzyldibromoborane 2-trimethylsilylethyn-1-yldibromoborane tert-butylethynyldifluoroborane butyldiisopinocamphenylborane vinyldiisopinocamphenylborane hex-1-en-1-yldiisopinocamphenylborane phenyldiisopinocamphenylborane naphthyldiisopinocamphenylborane 2-trimethylsilylethen-1-yldiisopinocamphenylborane
Examples of above-described stannanes and distannanes are:
phenyltrimethylstannane phenyltributylstannane tetraphenylstannane p-tolyltrimethylstannane m-tolyltributylstannane o-tolyltrimethylstannane 2,3-dimethylphenyltrimethylstannane 2,4-dimethylphenyltributylstannane 2,6-dimethylphenyltrimethylstannane 3,5-dimethylphenyltrimethylstannane mesityltrimethylstannane tetramethylphenyltrimethylstannane butylphenyltrimethylstannane tert-butylphenyltributylstannane isopropylphenyltrimethylstannane cyclohexylphenyltrimethylstannane 4-(hex-5-en-1-yl)phenyltrimethylstannane triisopropylsilylphenyltrimethylstannane p-methoxyphenyltrimethylstannane m-methoxyphenyltributylstannane o-methoxyphenyltrimethylstannane 2,4-dimethoxyphenyltrimethylstannane 2,5-dimethoxyphenyltrimethylstannane 3,5-dimethoxyphenyltributylstannane 2,3,4-trimethoxyphenyltrimethylstannane 2,4,6-trimethoxyphenyltrimethylstannane 3,4,5-trimethoxyphenyltributylstannane p-phenoxyphenyltrimethylstannane p-ethoxyphenyltrimethylstannane 2-(3xe2x80x2-phenyltrimethylstannane)-1,3-dioxolane 3,4-(methylenedioxy)phenyltrimethylstannane 3,4-(isopropylidenedioxy)phenyltrimethylstannane p-thioanisyltributylstannane m-thoianisyltrimethylstannane o-thioanisyltrimethylstannane p-nitrophenyltrimethylstannane o-nitrophenyltributylstannane m-nitrophenyltrimethylstannane 3-nitro-4-methylphenyltrimethylstannane 3-nitro-4-bromophenyltrimethylstannane 4-(methoxycarbonyl)phenyltributylstannane 3-(methoxycarbonyl)phenyltrimethylstannane 2-(methoxycarbonyl)phenyltrimethylstannane 4-carboxylphenyltrimethylstannane 3-carboxylphenyltributylstannane 2-carboxylphenyltrimethylstannane formylphenyltrimethylstannane acetylphenyltrimethylstannane pivaloylphenyltrimethylstannane o-fluorophenyltrimethylstannane m-fluorophenyltrimethylstannane p-fluorophenyltributylstannane 2,3-difluorophenyltrimethylstannane 2,4-difluorophenyltrimethylstannane 3,5-difluorophenyltriethylstannane 2,3,4-trifluorophenyltrimethylstannane 2,4,6-trifluorophenyltrimethylstannane tetrafluorophenyltriethylstannane pentafluorophenyltrimethylstannane o-chlorophenyltrimethylstannane m-chlorophenyltributylstannane p-chlorophenyltrimethylstannane 3,5-dichlorophenyltrimethylstannane 2,4,6-trichlorophenyltrimethylstannane p-bromophenyltrimethylstannane p-trifluoromethylphenyltrimethylstannane m-trifluoromethyltributylstannane o-trifluoromethyltrimethylstannane 2,6-bis(trifluoromethyl)phenyltrimethylstannane 3,5-bis(trifluoromethyl)phenyltributylstannane p-trifluoromethyltetrafluorophenyltrimethylstannane trifluoromethoxyphenyltrimethylstannane o-cyanophenyltrimethylstannane m-cyanophenyltributylstannane p-cyanophenyltrimethylstannane tetrafluorocyanophenyltrimethylstannane m-aminophenyltrimethylstannane p-aminophenyltrimethylstannane tetrafluoro-4-aminophenyltrimethylstannane 3-amino-4-methylphenyltrimethylstannane p-dimethylaminophenyltrimethylstannane m-dimethylaminophenyltriethylstannane o-dimethylaminophenyltrimethylstannane hydrazylphenyltrimethylstannane p-hydroxyphenyltrimethylstannane m-hydroxyphenyltributylstannane o-hydroxyphenyltrimethylstannane 3-hydroxy-4-phenyltrimethylstannane 2,4-dihydroxyphenyltrimethylstannane 3,5-dihydroxyphenyltrimethylstannane 1-naphthyltrimethylstannane 1-naphthyltributylstannane 2-naphthyltrimethylstannane 2-methyl-1-naphthyltrimethylstannane 4-methyl-1-naphthyltrimethylstannane 4-methoxy-1-naphthyltrimethylstannane 6-methoxy-2-naphthyltrimethylstannane 2-biphenyltrimethylstannane 3-biphenyltrimethylstannane 4-biphenyltrimethylstannane 3,5-diphenylphenyltrimethylstannane p-styryltrimethylstannane m-styryltrimethylstannane o-styryltrimethylstannane 9-anthracenetrimethylstannane 9-phenanthrenetrimethylstannane 2-furantrimethylstannane 3-furantrimethylstannane benzofurantrimethylstannane 2-thiophenetrimethylstannane 3-thiophenetrimethylstannane benzothiophenetrimethylstannane N-methyl-2-pyrroletrimethylstannane N-methyl-3-pyrroletrimethylstannane thiazoletributylstannane N-methylimidazoletrimethylstannane N-methylbenzoimidazoletrimethylstannane oxazoletributylstannane benzothiazoletrimethylstannane N-methyltriazoletributylstannane 2-pyridinetrimethylstannane 3-pyridinetrimethylstannane 4-pyridinetrimethylstannane pyrimidinetrimethylstannane 2-quinolinetrimethylstannane 3-quinolinetrimethylstannane 4-isoquinolinetrimethylstannane tetrafluoropyridinetrimethylstannane vinyltrimethylstannane 2-trimethylsilylethene-1-tributylstannane but-2-en-2-yltrimethylstannane methyl 3-tributylstannyl acrylate hexenyltrimethylstannane cyclohexenyltrimethylstannane 2-phenylethenyltrimethylstannane 6-methoxyhex-1-ene-1-trimethylstannane allyltrimethylstannane benzyltrimethylstannane p-methoxybenzyltrimethylstannane ethynyltrimethylstannane 2-trimethylsilylethynyltrimethylstannane 2-phenylethynyltrimethylstannane hex-1-ynyl-1-trimethylstannane tert-butylacetylenetrimethylstannane n-butyltrimethylstannane cyclohexyltrimethylstannane isopropyltrimethylstannane hexamethyldistannane hexaethyldistannane hexabutyldistannane hexaphenyldistannane
Examples of the above-described alkenes and alkynes are:
ethylene, styrene, xcex1-methylstyrene, p-methylstyrene, 2,4,6-trimethylstyrene, p-methoxystyrene, p-vinylstyrene, p-dimethylaminostyrene, p-chlorostyrene, p-aminostyrene, vinylnaphthalene, p-hydroxystyrene, methyl acrylate, ethyl acrylate, butyl acrylate, octadecyl acrylate, t-butyl acrylate, dimethylaminoethyl acrylate, hydroxyethyl acrylate, acrylamide, N,N-dimethylacrylamide, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octadecyl methacrylate, t-butyl methacrylate, dimethylaminoethyl methacrylate, hydroxyethyl methacrylate, N,N-diethylmethacrylamide acrylonitrile, methacrylonitrile vinylpyridines, butadiene, isoprene, phenylbutadiene, cyclohexene, cyclopentene, methyl vinyl ketone, cyclohexenone, cyclopentenone, acrolein, acetylene, propyne, hexyne, phenylacetylene, t-butylacetylene, trimethylsilylacetylene, propargyl alcohol, methyl propynoate, propargyl aldehyde, vinylacetylene, dihydrofuran, dihydropyran.
Examples of above-described silicon compounds are:
phenyltrimethylsilane phenyltrifluorosilane naphthyltrimethylsilane naphthyltrifluorosilane 2-pyridyltrimethylsilane p-methoxyphenyltriethylsilane trifluoromethylphenyltrimethylsilane vinyltrifluorosilane vinyltrimethylsilane hex-1-en-1-yltrimethylsilane ethynyltrimethylsilane ethynyltrichlorosilane tert-butylethynyltrifluorosilane
Examples of above-described phosphorus compounds are:
diphenylphosphine di(o-tolyl)phosphine di(bis(trifluoromethyl)phenylphosphine) trimethylstannyldi(p-methoxyphenyl)phosphine trimethylsilyldiphenylphosphine trimethylstannyldiphenylphosphine dibutylphosphine dimethylphosphine triethylsilyldimethylphosphine dicyclohexylphosphine trimethylsilyldicyclohexylphosphine trimethylstannylcyclohexylbutylphosphine
The process of the present invention for preparing indanones of the formula II or IIa can be carried out, for example, by reacting the indanones of the formula I or Ia with the above-described coupling components such as boron-, carbon-, tin-, silicon- or phosphorus-containing compounds in a solvent, eg. a nonpolar, polar aprotic or polar protic solvent or any mixtures of components of these solvent classes.
Solvents which can be used are, for example, hydrocarbons, halogenated hydrocarbons, ethers, polyethers, ketones, esters, amides, amines, ureas, sulfoxides, sulfones, phosphoramides, alcohols, polyalcohols, water and mixtures of these.
Preferred solvents are aromatics such as benzene, toluene, xylene, mesitylene, ethylbenzene, ethers such as diethyl ether, MTBE, THF, dioxane, anisole, di-n-butyl ether, DME, diglyme, triglyme, acetone, ethyl methyl ketone, isobutyl methyl ketone, ethyl acetate, DMF, dimethylacetamide, NMP, EMPA, acetonitrile, triethylamine, water, methanol, ethanol, isopropanol, isobutanol, ethylene glycol, diethylene glycol, glycerol, triethylene glycol and mixtures of these.
Particular preference is given to toluene, xylene, diethyl ether, MTBE, THF, DME, diglyme, acetone, DMF, NMP, water, ethylene glycol and mixtures of these.
The process of the present invention can be carried out, if desired, in the presence of a catalyst and, if desired, in the presence of a base, a salt-like additive or a phase transfer catalyst.
The catalysts which can be used in the process of the present invention comprise transition metal components such as transition metals or transition metal compounds and, if desired, cocatalyst components which can act as ligands.
As transition metal components, preference is given to using transition metals of groups 6 to 12 of the Periodic Table of the Elements or compounds of these transition metals.
Particularly preferred transition metal components are transition metals of groups 8 to 10 of the Periodic Table of the Elements.
Preferred transition metal components are nickel, palladium and platinum and also compounds of these transition metals, in particular nickel and palladium and also their compounds (J. Tsuji, Palladium-Reagents and Catalysts, Wiley 1995; M. Beller et al., Angew. Chem., 107, 1995, pp. 1992-1993), which can, if desired, be used in the presence of one or more cocatalysts.
Illustrative examples of catalysts, which, however, do not restrict the Scope of the invention, are Ni(CO4), NiCl2(PPh3)2, NiCl2(PBu3)2, Ni(PF3)4, Ni(COD)2, Ni(PPh3)4, Ni(acac)2, Ni(dppe)Cl2, Ni(dppp)Cl2, Ni(dppf)Cl2, NiCl2(PMe3)2, Pd(OAc)2/PPh3, Pd(OAc)2/P(MeOPh)3, Pd(OAc)2/PBu3, Pd(OAc)2/AsPh3, Pd(OAc)2/SbPh3, Pd(OAc)2/dppe, Pd(OAc)2/dppp, Pd(OAc)2/dppf, Pd(OAc)2/P(o-tolyl)3, Pd(OAc)2/tris(m-PhSO3Na)phosphine, Pd(PPh3)4, Pd2(dba)3*CHCl3, PdCl2/PPh3, PdCl2/P(o-tolyl)3, PdCl2(PPh3)2, PdCl2(MeCN)2, PdCl2(PhCN)2, Pd(acac)2, [(allyl)PdCl]2, PdCl2(dppp), PdCl2(dppe), PdCl2(COD), PdCl2(dppf), Pd on carbon/PPh3, Pd(OAc)2/P(OMe)3 and mononuclear and polynuclear palladacycles.
Very particularly preferred catalysts are NiCl2(PPh3)2, Ni(dppe)Cl2, Ni(dppp)Cl2, Ni(dppf)Cl2, Pd(OAc)2/PPh3, Pd(OAc)2/P(o-tolyl)3, Pd(PPh3)4, PdCl2(PPh3)2, PdCl2/PPh3, PdCl2(dppp), PdCl2(dppe), PdCl2(dppf), Pd(OAc)2/tris(m-PhSO3Na)phosphine, and
The amount of catalyst used is generally from 100 mol % to 10xe2x88x926 mol %, preferably from 10 mol % to 10xe2x88x925 mol %, particularly preferably from 5 mol % to 10xe2x88x924 mol %, in each case based on the indanone of the formula I or Ia.
If desired, the process of the present invention is carried out in the presence of bases and/or phase transfer catalysts.
Illustrative examples of bases, which do not, however, restrict the scope of the invention, are hydroxides, alkoxides, carboxylates, carbonates and hydrogen carbonates, oxides, fluorides, phosphates and amines.
Preferred bases are Li2CO3, Na2CO3, NaHCO3, K2CO3, Cs2CO3, LiOH, NaOH, KOH, CsOH, NaOMe, KOtBu, K3PO4, LiF, NaF, KF, CsF, NaOAc, KOAc, Ca(OAc)2, R(t-BuCO2), CaO, BaO, Ca(OH)2, Ba(OH)2, MgCO3, CaCO3, BaCO3, TlOH, Tl2CO3, Ag2O, ZnCO3, Bu4NF, [(Et2N)3S]Me3SiF2, DBU or amines such as triethylamine, diisopropylethylamine, dicyclohexylethylamine or dimethylaniline.
Phase transfer catalysts which can be used are ammonium or phosphonium salts and also crown ethers. Illustrative examples of phase transfer catalysts, which do not, however, restrict the scope of the invention are Bu4NCl, Bu4NBr, Bu4NI, BU4NHSO4, Et3BnNBr, Me3BnNCl, aliquot, Ph4PBr, Ph4PCl, 18-crow-6, 15-crown-5, 12-crown-4, dibenzo-18-crown-6.
If desired, the reaction can be carried out in the presence of one or more salt-like additives. Illustrative examples of salt-like additives, which do not, however, restrict the scope of the invention, are LiCl, LiBr, LiF, Li, LiBF4, LiPF6, LiClO4, LiCF3CO2, lithium triflate, LiNTf2, AgNO3, AgBF4, AgCF3CO2, silver triflate, AgPF6, CuCl, CuBr, CuJ, CuCN, Li2CU(CN)Cl2, ZnCl2, ZnBr2, ZnI2, zinc triflate and Zn(CF3CO2)2.
The process of the present invention is generally carried out at from xe2x88x92100xc2x0 C. to +600xc2x0 C., preferably from xe2x88x9278xc2x0 C. to +350xc2x0 C., particularly preferably at from 0xc2x0 C. to 180xc2x0 C.
The reaction generally takes place at a pressure of from 10 mbar to 1000 bar, preferably from 0.5 bar to 100 bar.
The reaction can be carried out in a single-phase system or in a multiphase system.
The concentration of indanone of the formula I or Ia in the reaction mixture is generally in the range from 0.0001 mol/l to 8 mol/l, preferably from 0.01 mol/l to 3 mol/l, particularly preferably from 0.1 mol/l to 2 mol/l.
The molar ratio of coupling component to indanone of the formula I or Ia is generally from 0.1 to 10, preferably from 0.5 to 3.
The molar ratio of base to indanone of the formula I or Ia is generally from 0 to 50.
The molar ratio of phase transfer catalyst to indanone of the formula I or Ia is generally from 0 to 2, preferably from 0 to 0.1.
The molar ratio of salt-like additives to indanone of the formula I or Ia is generally from 0 to 10.
The time of the reaction of indanones of the formula I or Ia with above-described coupling components to give indanones of the formula II or IIa is generally from 5 minutes to 1 week, preferably from 15 minutes to 48 hours.
The reaction of an indanone of the formula I or Ia with a boronic acid is preferably carried out under conditions in which the transition metal component used is a compound of a transition metal of groups 8 to 10 of the Periodic Table of the Elements, a base such as an alkoxide, hydroxide, carbonate, carboxylate, hydrogencarbonate, oxide, fluoride, phosphate or amine is used and a solvent such as a hydrocarbon, ether, polyether, alcohol, polyalcohol or water or any mixture of these is used and the reaction temperature is from xe2x88x92100xc2x0 to 500xc2x0 C.
Particular preference is given to conditions in which the transition metal component used is a compound of the transition metals Ni, Pd or Pt, the base used is an alkoxide, hydroxide, hydrogencarbonate, carbonate, carboxylate or phosphate, the solvent used is an aromatic hydrocarbon, ether, polyether, alcohol, polyalcohol or water or any mixture of these and the reaction temperature is from xe2x88x9278 to 300xc2x0 C.
Very particular preference is given to conditions in which the transition metal component used is a palladium compound, the base is an alkali metal or alkaline earth metal alkoxide, hydroxide, carbonate, carboxylate or orthophosphate, the solvent is toluene, xylene, mesitylene, ethylbenzene, THF, dioxane, DME, diglyme, butanol, ethylene glycol, glycerol or water or any mixture of these and the reaction temperature is from xe2x88x9230xc2x0 to 200xc2x0 C.
Extraordinary preference is given to conditions in which the transition metal compound is a palladium compound, the base is an alkali metal or alkaline earth metal carbonate, hydroxide or orthophosphate, the solvent is toluene, xylene, THF, DME, diglyme, ethylene glycol or water or any mixture of these and the reaction temperature is from 0xc2x0 C. to 160xc2x0 C.
Illustrative examples of reaction conditions in the reaction of an indanone of the formula I or Ia with a boronic acid, which do not, however, restrict the scope of the invention, are:
X (in formula I or Ia)=Br; catalyst: 0.01-5 mol % of Pd(P(Ph3)4); base: aqueous sodium carbonate solution; solvent: toluene; reaction temperature: reflux; reaction time: 1-24 h.
X (in formula I or Ia)=Cl; catalyst: 0.01-15 mol % of NiCl2(dppf); base: K3PO4; solvent: dioxane; reaction temperature: 80xc2x0 C.; reaction time: 1-24 h.
X (in formula I or Ia)=Br; catalyst: 0.01-5 mol % of Pd(OAc)2/PPh3; base: aqueous potassium carbonate solution; solvent: xylene; reaction temperature: reflux; reaction time: 1-24 h.
X (in formula I or Ia)=Cl or Br; catalyst: 0.01-5 mol % of
(OAc)2/P(m-HSO3xe2x80x94Ph)3; base: aqueous sodium carbonate solution; solvent: xylene/ethylene glycol; reaction temperature: reflux; reaction time: 1-24 h.
X (in formula I or Ia)=I or trifluoromethanesulfonate; catalyst: 0.01-1 mol % of PdCl2(NCxe2x80x94Ph)2; base: sodium carbonate; solvent: DME; additive: 5 mol % of tetrabutylammonium bromide; reaction temperature: reflux; reaction time: 1-24 h.
X (in formula I or Ia)=Br; catalyst: 0.01-5 mol % of Pd(OAc)2/P(o-tol)3; base: triethylamine; solvent: dimethylformamide (DMF); reaction temperature: 100xc2x0 C.; reaction time: 1-24 h.
Preference is given to carrying out the reaction of an indanone of the formula I or Ia with a stannane to give indanones of the formula II or IIa, where
R3 is preferably an aryl, heteroaryl or alkenyl group, the transition metal compound is a compound of a transition metal of groups. 8-10 of the Periodic Table of the Elements,
the solvent is a hydrocarbon, ether, polyether, amide or nitrile, the additive is a lithium salt, a zinc salt, a copper salt, a silver salt or a fluoride salt and
the reaction temperature is from xe2x88x9278xc2x0 C. to 300xc2x0 C. and the reaction time is from 5 minutes to 1 week.
In the reaction with a stannane, particular preference is given to conditions in which
R3 is preferably an aryl, heteroaryl (with the heteroatoms N, O and S) or alkenyl group, and in which the transition metal component is a palladium compound,
the solvent is an aromatic hydrocarbon, ether, THF, dioxane, DME, DMF, HMPA, NMP or acetonitrile,
the additive is a lithium or copper(I) salt and
the reaction temperature is from xe2x88x9230 to 200xc2x0 C. and the reaction time is from 10 minutes to 48 hours.
Illustrative examples of reaction conditions in the reaction of an indanone of the formula I or Ia with a stannane, which do not, however, restrict the scope of the invention, are:
X (in formula I or Ia)=I; catalyst: 0.1-5 mol % of PdCl2(PPh3)2; solvent: DME; additive: lithium chloride; temperature: 85xc2x0 C.; reaction time: 12-24 h.
X (in formula I or Ia)=Br; catalyst: 0.5-10 mol % of Pd(OAc)2/P(o-tolyl)3; solvent: xylene; additive: CuI; temperature: 135xc2x0 C.; reaction time: 3-6 h.
The reaction of an indanone of the formula I and Ia with an olefin is preferably carried out under conditions in which the transition metal component is a compound of a transition metal of groups 8-10 of the Period Table of the Elements,
the base is an amine or carboxylate,
the solvent is an amide, amine, urea, nitrile, alcohol or water and the reaction temperature is from xe2x88x9278 to 250xc2x0 C.
Particular preference is given to conditions in which the transition metal component is a palladium compound,
the base is a tertiary amine, carboxylate or DBU,
the solvent is an amide, nitrile or alcohol and the reaction temperature is from 0 to 200xc2x0 C.
Illustrative examples of reaction conditions in the reaction of an indanone of the formula I or Ia with an olefin, which do not, however, restrict the scope of the invention, are:
X (in formula I or Ia)=Br; olefin: butyl acrylate; catalyst: 0.01-5 mol % of Pd(OAc)2/PPh3; base: triethylamine; solvent: dimethylformamide; temperature 130xc2x0 C.
X (in formula I or Ia)=trifluoromethanesulfonate; olefin: methyl methacrylate; catalyst: 0.01-5 mol % of Pd/C/PPh3; base: diisopropylethylamine; solvent: dimethylacetamide; temperature: 130xc2x0 C.
X (in formula I or Ia)=Cl; olefin: acrylonitrile; catalyst: 0.01-1 mol % of [(o-tolyl)2P-(o-benzyl)Pd]2(OAc)2; base: sodium acetate; solvent: acetonitrile; temperature: 100xc2x0 C.
The present invention also provides substituted indanones of the formula III,
where
R1xe2x80x2 is a C1-C40-hydrocarbon group which is bound via a carbon atom and may bear one or more identical or different heteroatom-containing radicals, except for nitrogen-containing radicals, as substituents, eg. a linear, branched or cyclic C1-C20-alkyl group which may bear one or more identical or different halogen, OH, OR2, SR2, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C6-C22-aryl group which may bear one or more identical or different halogen, OH, OR2, SR2, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C7-C20-alkylaryl group or a C7-C20-arylalkyl group, where the alkyl part may bear one or more identical or different halogen, OH, OR2, SR2, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents and the aryl part may bear one or more identical or different halogen, OH, OR2, SR2, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C2-C10-alkenyl group which may bear one or more identical or different halogen, OH, OR2, SR2, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C2-C20-alkynyl group which may bear one or more identical or different halogen, OH, OR2, SR2, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C8-C12-arylalkenyl group, where the alkenyl part may bear one or more identical or different halogen, OH, OR2, SR2, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents and the aryl part may bear one or more identical or different halogen, OH, OR2, SR2, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, or
R1xe2x80x2 is an OR2, SR2, NR22, PR22, SiR23 or OSiR23 group, where R2 are identical or different and are each a C1-C20-hydrocarbon group such as a C1-C10-alkyl or C6-C14-aryl group which may each bear one or more identical or different halogen, OH, OR2, SR2, NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, or two radicals R2 may be joined to form a ring system or
R1xe2x80x2 is a C1-C20xe2x80x94, preferably C2-C20-heterocyclic group which is bound via a carbon atom and may in turn bear C1-C20-radicals or heteroatoms as substituents,
Xxe2x80x2 is a leaving group, preferably a diazonium group, a halogen atom such as chlorine, bromine or iodine, or C1-C40-alkylsulfonate, C1-C40-haloalkylsulfonate, C6-C40-arylsulfonate, C6-C40-haloarylsulfonate, C7-C40-arylalkylsulfonate, C7-C40-haloarylalkylsulfonate, C1-C40-alkylcarboxylate, C1-C40-haloalkylcarboxylate, C6-C40-arylcarboxylate, C6-C40-haloarylcarboxylate, C7-C40-arylalkylcarboxylate, C7-C40-haloarylalkylcarboxylate, formate, C1-C40-alkyl carbonate, C1-C40-haloalkyl carbonate, C6-C40-aryl carbonate, C6-C40-haloaryl carbonate, C7-C40-arylalkyl carbonate, C7-C40-haloarylalkyl carbonate, C1-C40-alkyl phosphonate, C1-C40-haloalkyl phosphonate, C6-C40-aryl phosphonate, C6-C40-haloaryl phosphonate, C7-C40-arylalkyl phosphonate or C7-C40-haloarylalkyl phosphonate,
Y7 and Y8 are identical or different and are each a hydrogen atom or are as defined for Xxe2x80x2 or are a C2-C40-hydrocarbon group which is bound via a carbon atom and may bear one or more identical or different heteroatom-containing radicals as substituents, eg. a linear, branched or cyclic C2-C20-alkyl group which may bear one or more identical or different halogen, OH, OR2, SR2, NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C6-C22-aryl group which may bear one or more identical or different halogen, OR2, SR2, NR22xe2x80x94, NH2, xe2x80x94N2H3, NO2, CN, CO2R2, CHO, COR2, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C7-C15-alkylaryl group or C7-C15-arylalkyl group, where the alkyl part may bear one or more identical or different halogen, OH, OR2, SR2, NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents and the aryl part may bear one or more identical or different halogen, OR2, SR2, NR22xe2x80x94, NH2, xe2x80x94N2H3, NO2, CN, CO2R2, CHO, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C2-C10-alkenyl group which may bear one or more identical or different halogen, OH, OR2, SR2, NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C2-C10-alkynyl group which may bear one or more identical or different halogen, OH, OR2, SR2, NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C8-C12-arylalkenyl group which may bear one or more identical or different halogen, OH, OR2, SR2, NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, or
Y7 and Y8 are each a halogen atom, a NR22, PR22, B(OR2)2, SiR23 or SnR23 group, where R2 are identical or different and are each a C1-C20-hydrocarbon group, eg. a C1-C10-alkyl group or C6-C14-aryl group which may bear one or more identical or different halogen, OH, OR2, SR2, NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, or two radicals R2 may be joined to form a ring system, or
Y7 and Y8 are each a C1-C20-heterocyclic group which is bound via a carbon atom and may in turn bear C1-C20-radicals or heteroatoms as substituents, and
in formula III, at least one of the radicals Y7 and Y8, preferably Y7, is a hydrogen atom and Y9 is a hydrogen atom.
Particular preference is given to indanones of the formula III in which
Xxe2x80x2 is chlorine, bromine, iodine, triflate, nonaflate, mesylate, ethylsulfonate, benzenesulfonate, tosylate, triisopropylbenzenesulfonate, formate, acetate, trifluoroacetate, nitrobenzoate, halogenated arylcarboxylates, in particular fluorinated benzoate, methyl carbonate, ethyl carbonate, benzyl carbonate, tert-butyl carbonate, dimethyl phosphonate, diethyl phosphonate, diphenyl phosphonate or diazonium,
R1xe2x80x2 is a linear, branched or cyclic C1-C8-alkyl group which may bear one or more identical or different fluorine, chlorine, OR2, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C6-C10-aryl group which may bear one or more identical or different fluorine, chlorine, OR2, SR2, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C7-C12-alkylaryl or arylalkyl group, where the alkyl part may bear one or more identical or different fluorine, chlorine, OR2, SR2, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents and the aryl part may bear one or more identical or different fluorine, chlorine, OR2, SR2, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C2-C8-alkenyl group, C2-C8-alkynyl group, a C8-C12-arylalkenyl group, an OR2, xe2x80x94SiR23 or xe2x80x94OSiR23 group, where R2 are identical or different and are each a C1-C4-alkyl or C6-C10-aryl group, or
R1xe2x80x2 is a C1-C20-heterocyclic group, where preferred heteroatoms are oxygen and sulfur, which may in turn bear C1-C20-hydrocarbon radicals as substituents.
Very particular preference is given to indanones of the formula III in which
Xxe2x80x2 is chlorine, bromine, iodine, triflate or mesylate, R1xe2x80x2 is a linear, branched or cyclic C1-C8-alkyl group which may bear one or more fluorine substituents, a C6-aryl group which may bear one or more identical or different fluorine, chlorine or OR2 substituents, a C7-C10-alkylaryl or arylalkyl group, where the alkyl part may bear one or more identical or different fluorine, chlorine or OR2 substituents and the aryl part may bear one or more identical or different fluorine, chlorine or OR2 substituents, a C2-C8-alkenyl group or C2-C8-alkynyl group which may each bear one or more identical or different fluorine or OR2 substituents, a C8-C12-arylalkenyl group, an OR2, SiR23 or xe2x80x94OSiR23 group, where R2 are identical or different and are each a C1-C4-alkyl or C6-aryl group, or R1xe2x80x2 is a C1-C16-heterocyclic group, where preferred heteroatoms are oxygen and sulfur, and Y7 is a hydrogen atom and Y8 is a hydrogen atom or is as defined for Xxe2x80x2 or Y8 is a linear, branched or cyclic C2-C6-alkyl group which may bear one or more fluorine substituents, a C6-C10-aryl group which may bear one or more fluorine substituents, a C7-C12-alkylaryl group or C7-C12-arylalkyl group, where the alkyl part may bear one or more fluorine substituents and the aryl part may bear one or more fluorine substituents, a C2-C8-alkenyl group, a C2-C8-alkynyl group, a C8-C10-arylalkenyl group or
Y8 is a C1-C9-heterocyclic group which is bound via a carbon atom and may in turn bear C1-C6-radicals or heteroatoms as substituents; preferably, Y8 is as defined for Xxe2x80x2 or is a C6-C14-aryl group.
Extraordinary preference is given to indanones of the formula III in which
Xxe2x80x2 is chlorine, bromine or triflate,
R1xe2x80x2 is a linear, branched or cyclic C1-C6-alkyl group, a C7-C10-alkylaryl or arylalkyl group, a C2-C6-alkenyl group or C2-C6-alkynyl group or a C8-C10-arylalkenyl group and
Y7, Y8 and Y9 are each a hydrogen atom.
Illustrative examples of indanones of the formula III, which do not, however, restrict the scope of the invention, are:
2-methyl-7-chloro-1-indanone 2-methyl-7-bromo-1-indanone 2-methyl-7-iodo-1-indanone 2-methyl-7-trifluoroacetoxy-1-indanone 2-methyl-7-trifluoromethanesulfonoxy-1-indanone 2-methyl-7-methanesulfonoxy-1-indanone 2-methyl-7-ethanesulfonoxy-1-indanone 2-methyl-7-(p-toluenesulfonoxy)-1-indanone 2-methyl-7-bezenesulfonoxy)-1-indanone 2-methyl-7-(2,4,6-triisopropylbenzenesulfonoxy)-1-indanone 2-methyl-7-pentafluorobenzenesulfonoxy-1-indanone 2-methyl-7-nonafluorobutanesulfonoxy-1-indanone 2-methyl-7-acetoxy-1-indanone 2-methyl-7-formyloxy-1-indanone 2-methyl-7-pentafluorobenzoyloxy-1-indanone 2-methyl-7-(p-nitrobenzoyloxy)-1-indanone 2-methyl-7-methoxycarbonyloxy-1-indanone 2-methyl-7-tert-butyloxycarbonyloxy-1-indanone 2-methyl-7-ethoxycarbonyloxy-1-indanone 2-methyl-7-benzyloxycarbonyloxy-1-indanone 2-methyl-7-dimethylphosphonoxy-1-indanone 2-methyl-7-diethylphosphonoxy-1-indanone 2-methyl-7-diphenylphosphonoxy-1-indanone 2-methyl-7-diazonium-1-indanone chloride 2-methyl-7-diazonium-1-indanone tetrafluoroborate 2-methyl-7-diazonium-1-indanone sulfate 2-methyl-5-butyl-7-bromo-1-indanone 2-methyl-5-fluoro-7-bromo-1-indanone 2-methyl-5,7-dibromo-1-indanone 2-methyl-5,7-dichloro-1-indanone 2-methyl-6,7-dichloro-1-indanone 2-methyl-5-chloro-7-bromo-1-indanone 2,6-dimethyl-7-chloro-1-indanone 2-methyl-5-butyl-7-chloro-1-indanone 2-methyl-5-isopropyl-7-trifluoromethanesulfonoxy-1-indanone 2-methyl-5-tert-butyl-7-methanesulfonoxy-1-indanone 2-methyl-5-phenyl-7-bromo-1-indanone 2-methyl-5-(3,5-dimethoxyphenyl)-7-iodo-1-indanone 2-methyl-5-benzyl-7-chloro-1-indanone 2-methyl-5-vinyl-7-(p-toluenesulfonoxy)-1-indanone 2-methyl-6-bromo-7-trifluoroacetoxy-1-indanone 2-methyl-6-phenyl-7-bromo-1-indanone 2-trifluoromethyl-7-chloro-1-indanone 2-trifluoromethyl-7-bromo-1-indanone 2-trifluoromethyl-5-isobutyl-7-trifluoromethanesulfonoxy-1-indanone 2-ethyl-7-chloro-1-indanone 2-ethyl-7-bromo-1-indanone 2-ethyl-7-diazonium-1-indanone tetrafluoroborate 2-ethyl-7-methanesulfonoxy-1-indanone 2-ethyl-5-methyl-7-bromo-1-indanone 2-ethyl-7-diazonium-1-indanone tetrafluoroborate 2,6-diethyl-7-diazonium-1-indanone chloride 2-butyl-7-chloro-1-indanone 2-butyl-5-fluoro-7-chloro-1-indanone 2-n-propyl-7-chloro-1-indanone 2-n-propyl-7-bromo-1-indanone 2-butyl-5,7-dichloro-1-indanone 2-isopropyl-7-chloro-1-indanone 2-isopropyl-7-bromo-1-indanone 2-isopropyl-7-iodo-1-indanone 2-isopropyl-5-diphenylphosphino-7-nonafluorobutanesulfonoxy-1-indanone 2-phenyl-7-chloro-1-indanone 2-(2-pyridyl)-7-bromo-1-indanone 2-(2-furyl)-7-iodo-1-indanone 2-cyclohexyl-7-chloro-1-indanone 2-cyclohexyl-7-bromo-1-indanone 2-cyclohexyl-7-trifluoromethanesulfonoxy-1-indanone 2-isobutyl-7-chloro-1-indanone 2-isobutyl-7-bromo-1-indanone 2-tert-butyl-7-chloro-1-indanone 2-tert-butyl-7-iodo-1-indanone 2-benzyl-7-chloro-1-indanone 2-allyl-7-chloro-1-indanone 2-vinyl-7-trifluoromethanesulfonoxy-1-indanone 2-(2-trimethylsilylethyn-1-yl)-6-benzyl-7-chloroindanone 2-(hex-1-ynyl)-7-trifluoromethanesulfonoxy-1-indanone 2-trimethylsilyl-7-bromo-1-indanone 2-trimethylsilyloxy-7-bromo-1-indanone 2-dimethylamino-7-trifluoromethanesulfonoxy-1-indanone 2-N-pyrrolidino-7-chloro-1-indanone 2-diphenylphosphino-5-isopropyl-7-bromo-1-indanone 2-methoxy-6-allyl-7-chloro-1-indanone 2,6-dimethoxy-7-bromo-1-indanone 2-phenoxy-5-dimethylamino-7-trifluoromethanesulfonoxy-1-indanone 2-(2-methoxyethyl)-7-chloro-1-indanone 2-(3-chloropropyl)-7-chloro-1-indanone
The indanones of the formula I or Ia can be prepared by methods similar to those known from the literature (eg. U.S. Pat. No. 5,489,712; U.S. Pat. No. 4,070,539; S. J. desolms et al., J. Med. Chem., 1978, 21, 437). To prepare indanones of the formula I, for example, an aryl alkyl ketone of the formula (A) can be methylenated and subsequently. subjected to a Nazarov cyclization.
R1, X, Y1, Y2 and Y3 in the formulae A, B and I are as defined: above for formula I.
In the case of an aryl alkyl ketone, the methylene group can, for example, be introduced by an aldol condensation with formaldehyde as methylene source or by a Mannich reaction, in which, for example, N,N,Nxe2x80x2,Nxe2x80x2-tetramethyldiaminomethane, Eschenmoser""s salt or urotropien/acetic anhydride can be used as methylene source. It is indicated in the literature (U.S. Pat. No. 5,489,712) that the aldol condensation of formaldehyde, which is the most inexpensive methylene source, and aryl alkyl ketones proceeds in poor yields and the management of the reaction is said to be complicated. M. M. Curzu et al. in Synthesis (1984) 339 state that in the aldol condensation of formaldehyde and certain aryl alkyl ketones, considerable amounts of starting material remain unreacted and undesirable by-products such as the primary aldol product containing a hydroxymethyl group are present in the end product.
It has surprisingly been found that the aldol condensation (ie. the introduction of the methylene group) of aryl alkyl ketones proceeds virtually quantitatively under basic conditions using formaldehyde, and the primary aldol product containing a hydroxymethyl group cannot be observed spectroscopically. Here, preferred aryl alkyl ketones of the formula A are those in which X is a halogen.
The aldol condensation is carried out using a formaldehyde source, preferably aqueous formalin solution, and a base, preferably an alkali metal carbonate or alkaline earth metal carbonate or an alkali metal hydroxide or alkaline earth metal hydroxide, particularly preferably an aqueous sodium hydroxide solution, at 0-100xc2x0 C., preferably 20-60xc2x0 C.
The molar ratio of base to aryl alkyl ketone is in the range from 0.01 to 5, preferably in the range from 0.1 to 2.
The molar ratio of formaldehyde to aryl alkyl ketone is in the range from 0.5 to 1.5, preferably in the range from 0.9 to 1.2. The concentration of the aryl alkyl ketone in the reaction mixture (total volume) is in the range from 0.01 to 6 mol/l, preferably from 0.1 to 2 mol/l. The aryl alkyl ketone can be diluted with inert solvents such as ethers, hydrocarbons or halogenated hydrocarbons. The reaction can be carried out in a single-phase or multiphase system.
In the case of multiphase reaction mixtures, phase transfer catalysts can be added to accelerate the reaction.
The reaction time is usually from 15 minutes to 12 hours or longer.
The reaction can also be carried out in an inert gas atmosphere and the pressure in the reaction vessel can be either below or above atmospheric pressure.
The subsequent cyclization to form the indanone is carried out by literature methods (J. H. Burckhalter, R. C. Fuson, J. Amer. Chem. Soc., 1948, 70, 4184; E. D. Thorsett, F. R. Stermitz, Synth. Commun., 1972, 2, 375; Synth. Commun., A. Bhattacharya, B. Segmuller, A. Ybarra, 1996, 26, 1775; U.S. Pat. No. 5,489,712). The cyclization is preferably carried out under acid conditions. As cyclization reagent, it is possible to use acids such as protic acids (eg. sulfuric acid, polyphosphoric acid, methanesulfonic acid) or Lewis acids (eg. aluminum trichloride, boron trifluoride). The reaction product from the aldol condensation can be diluted with an inert solvent before addition to the cyclization reagent, or can be added in undiluted form.
To prepare indanones of the formula I and Ia in which X is an oxygen-containing leaving group, for example a triflate group, the starting materials used are preferably hydroxyindanones, some of which are known from the literature (eg. Bringmann et al., Liebigs Ann. Chem., 1985, 2116-2125), and the hydroxy group is converted by literature methods into an oxygen-containing leaving group X, eg. triflate (eg.: P. J. Stang, Synthesis, 1982, 85; V. Percec, J. Org. Chem., 1995, 60, 176; Autorenkollektiv, Organikum, VEB Deutscher Verlag der Wissenschaften, 1976).
Some of the aryl alkyl ketones are known from the literature or they can easily be prepared by literature methods (eg.: R. C. Larock, Comprehensive Organic Transformations, VCH, 1989).
The invention further provides substituted indanones of the formula IV
where
R1xe2x80x3 is a C1-C40-group such as a C1-C40-hydrocarbon group which is bound via a carbon atom and may bear one or more identical or different heteroatom-containing radicals as substituents, eg. a linear, branched or cyclic C1-C20-alkyl group which may bear one or more identical or different halogen, OH, OR2, SR2NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C6-C22-aryl group which may bear one or more identical or different halogen, OH, OR2, SR2NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C7-C20-alkylaryl group or a C7-C20-arylalkyl group, where the alkyl part may bear one or more identical or different halogen, OH, OR2, SR2NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents and the aryl part may bear one or more identical or different halogen, OH, OR2, SR2, NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C2-C10-alkenyl group which may bear one or more identical or different halogen, OH, OR2, SR2NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C2-C20-alkynyl group which may bear one or more identical or different halogen, OH, OR2, SR2NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C8-C12-arylalkenyl group, where the alkenyl part may bear one or more identical or different halogen, OH, OR2, SR2NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents and the aryl part may bear one or more identical or different halogen, OH, OR2, SR2NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, or
R1xe2x80x3 is an OR2, SR2, NR22, PR22, SiR23 or OSiR23 group, where R2 are identical or different and are each a C1-C20-hydrocarbon group such as a C1-C10-alkyl or C6-C14-aryl group which may each bear one or more identical or different halogen, OH, OR2, SR2NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, or two radicals R2 may be joined to form a ring system, or
R1xe2x80x3 is a C1-C20-heterocyclic group which is bound via a carbon atom and may in turn bear C1-C20-radicals or heteroatoms as substituents,
R3xe2x80x2 is an unsaturated C2-C40-group such as an unsaturated C2-C40-hydrocarbon group which is bound via a carbon atom and may bear one or more identical or different heteroatom-containing radicals as substituents, eg. a C6-C22-aryl group which may bear one or more identical or different halogen, OR2, SR2NR22xe2x80x94, NH2, xe2x80x94N2H3, NO2, CN, CO2R2, CHO, COR2, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C7-C15-alkylaryl group or C7-C15-arylalkyl group, where the alkyl part may bear one or more identical or different halogen, OH, OR2, SR2NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents and the aryl part may bear one or more identical or different halogen, OR2, SR2NR22xe2x80x94, NH2, xe2x80x94N2H3, NO2, CN, CO2R2, CHO, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C2-C10-alkenyl group which may bear one or more identical or different halogen, OH, OR2, CO2R2, COR2, SR2, NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C2-C10-alkynyl group which may bear one or more identical or different halogen, OH, OR2, SR2, NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C8-C12-arylalkenyl group, which may bear one or more identical or different halogen, OH, OR2, CO2R2, COR2, SR2, NR22, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, or
R3xe2x80x2 is fluorine, a PR22, B(OR2)2, SiR23 or SnR23 group, where R2 are identical or different and are each a C1-C20-hydrocarbon group, eg. a C1-C10-alkyl group or C6-C14-aryl group which may each bear one or more identical or different halogen, OH, OR2, SR2NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, or two radicals R2 may be joined to form a ring system, or
R3xe2x80x2 is a C1-C20-heterocyclic group which is bound via a carbon atom and may in turn bear C1-C20-radicals or heteroatoms as substituents, and
Y10 and Y11 are identical or different and are each a hydrogen atom or are as defined for R3 in formula II, ie. are a C1-C40-hydrocarbon group which is bound via a carbon atom and may bear one or more identical or different heteroatom-containing radicals as substituents, eg. a linear, branched or cyclic C1-C20-alkyl group which may bear one or more identical or different halogen, OH, OR2, SR2, NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C6-C22-aryl group which may bear one or more identical or different halogen, OR2, SR2NR22xe2x80x94, NH2, xe2x80x94N2H3, NO2, CN, CO2R2, CHO, COR2, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C7-C15-alkylaryl group or C7-C15-arylalkyl group, where the alkyl part may bear one or more identical or different halogen, OH, OR2, SR2NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents and the aryl part may bear one or more identical or different halogen, OR2, SR2NR22xe2x80x94, NH2, xe2x80x94N2H3, NO2, CN, CO2R2, CHO, PR22xe2x80x94, xe2x80x94SiR23 CHO, PR22xe2x80x94or xe2x80x94OSiR23 substituents, a C2-C10-alkenyl group which may bear one or more identical or different halogen, OH, OR2, SR2, NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C2-C10-alkynyl group which may bear one or more identical or different halogen, OH, OR2, SR2, NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C8-C12-arylalkenyl group, which may bear one or more identical or different halogen, OH, OR2, CO2R2, COR2, SR2, NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, or
Y10 or Y11 are a halogen atom, a PR22, B(OR2)2, SiR23 or SnR23 group, where R2 are identical or different and are each a C1-C20-hydrocarbon group, eg. a C1-C10-alkyl group or C6-C14-aryl group which may each bear one or more identical or different halogen, OH, OR2, SR2NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, or two radicals R2 may be joined to form a ring system, or
Y10 or Y11 are each a C1-C20-heterocyclic group which is bound via a carbon atom and may in turn bear C1-C20-radicals or heteroatoms as substituents;
in formula IV, at least one of the radicals Y10 and Y11, preferably Y10, is a hydrogen atom and Y12 is a hydrogen atom.
Preference is given to indanones of the formula IV in which R1 is a linear, branched or cyclic C1-C8-alkyl group which may bear ,one or more identical or different fluorine, chlorine, OR2, PR22xe2x80x94, NR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C6-C10-aryl group which may bear one or more identical or different fluorine, chlorine, OR2, SR2, NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C7-C12-alkylaryl or arylalkyl group, where the alkyl part may bear one or more identical or different fluorine, chlorine, OR2, SR2, NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents and the aryl part may bear one or more identical or different fluorine, chlorine, OR2, SR2NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C2-C6-alkenyl group, C2-C6-alkynyl group, a C8-C12-arylalkenyl group, an OR2, PR22xe2x80x94, NR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 group where R2 are identical or different and are each a C1-C4-alkyl or C6-C10-aryl group, where the alkyl group may bear one or more identical or different fluorine, chlorine, OR2, SR2, NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents and the aryl group may bear 1-3 substituents such as fluorine, chlorine, OR2, SR2, NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23, or a C1-C20-heterocyclic group, where preferred heteroatoms are oxygen, nitrogen, sulfur, phosphorus and silicon, which may in turn bear C1-C10 radicals or heteroatoms as substituents, and
R3xe2x80x2 is an unsaturated C2-C20-group, a C6-C14-aryl group which may each bear one or more identical or different fluorine, chlorine, OR2, SR2, NR2, NH2, xe2x80x94N2H3, NO2, CN, CO2R2, COR2, CHO, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C7-C15-alkylaryl group or C7-C15-arylalkyl group, where the alkyl part may bear one or more identical or different fluorine, chlorine, OR2, CO2R2, COR2, NR22xe2x80x94 or xe2x80x94OSiR23 substituents and the aryl part may bear one or more identical or different fluorine, chlorine, OR2, SR2, NR22xe2x80x94, NH2, xe2x80x94N2H3, NO2, CN, CO2R2, COR2, CHO, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, a C2-C10-alkenyl group which may bear one or more identical or different fluorine, chlorine, OR2, CO2R2, COR2, NR22xe2x80x94 or xe2x80x94OSiR23 substituents, a C2-C10-alkynyl group which may bear one or more identical or different fluorine, chlorine, OR2, CO2R2, CONR22xe2x80x94 or xe2x80x94OSiR23 substituents, a C8-C12-arylalkenyl group which may bear one or more identical or different fluorine, chlorine, CO2R2, COR2, OR2, NR22xe2x80x94 or xe2x80x94OSiR23 substituents, a PR22, B(OR2)2, SiR23 or SnR23 group where R2 are identical or different and are each a C1-C4-alkyl or C6-C10-aryl group, where the alkyl group may bear one or more identical or different fluorine, chlorine, OR2, SR2, NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents and the aryl group may bear one or more identical or different fluorine, chlorine, OR2, SR2, NR22xe2x80x94, PR22xe2x80x94, xe2x80x94SiR23 or xe2x80x94OSiR23 substituents, and, in addition, two radicals R2 may be joined to one another to form a ring system, a C2-C20-heterocyclic group, where preferred heteroatoms are oxygen, nitrogen, sulfur, phosphorus and silicon, which may in turn bear C1-C10 radicals or heteroatoms as substituents.
Particular preference is given to indanones of the formula IV in which
R1xe2x80x3 is a linear, branched or cyclic C1-C8-alkyl group which may bear one or more identical or different fluorine, chlorine, OR2 or NR22 substituents, a C6-C10-aryl group which may bear one or more identical or different fluorine, chlorine, OR2 or NR22 substituents, a C7-C12-alkylaryl or arylalkyl group, where the alkyl part may bear one or more identical or different fluorine, chlorine, OR2 or NR22 substituents and the aryl part may bear fluorine, chlorine, OR2 or NR22 substituents, a C2-C8-alkenyl group or C2-C8-alkynyl group which may each bear one or more identical or different fluorine, chlorine, OR2 or NR22 substituents, a C8-C12-arylalkenyl group which may bear one or more identical or different fluorine, chlorine, OR2 or NR22 substituents, a OR2, SiR23 or xe2x80x94OSiR23 group, where R2 are identical or different and are each a C1-C4-alkyl or phenyl group, where the alkyl group may bear one or more identical or different fluorine, chlorine, OR2 or NR22 substituents and the aryl group may bear fluorine, chlorine, OR2 or NR22 substituents, a C2-C16-heterocyclic group, where preferred heteroatoms are oxygen, nitrogen, sulfur and silicon, which may in turn bear C1-C10-radicals or heteroatoms as substituents, and
R3xe2x80x2 is an unsaturated C2-C20-group such as a C6-C14-aryl group which may bear fluorine, chlorine, OR2, SR2, NR22, NH2, NO2, CN, COR2 or CO2R2 substituents, a C7-C15-alkylaryl group or C7-C15-arylalkyl group, where the alkyl part may bear one or more identical or different fluorine, OR2, NR22xe2x80x94 or xe2x80x94OSiR23 substituents and the aryl part may bear fluorine, chlorine, OR2, SR2, NR22xe2x80x94, NH2, NO2, CN, COR2 or CO2R2 substituents, a C2-C10-alkenyl group which may bear one or more identical or different fluorine, OR2, CO2R2, COR2, NR22xe2x80x94or xe2x80x94OSiR23 substituents, a C2-C10-alkynyl group which may bear one or more identical or different fluorine, OR2, NR22xe2x80x94or -OSiR23 substituents, a C8-C12-arylalkenyl group, a PR22, B(OR2)2 or SnR23 group, where R2 are identical or different and are each a C1-C4-alkyl or C6-aryl group, where the alkyl group may bear one or more identical or different fluorine, chlorine, OR2 or NR22 substituents and the aryl group may bear fluorine, chlorine, OR2 or NR22 substituents, and, in addition, two radicals R2 may be joined to one another to form a ring system, a C1-C14-heterocyclic group, where preferred heteroatoms are oxygen, nitrogen or sulfur which may in turn bear C1-C6-radicals or heteroatoms as substituents.
Very particular preference is given to indanones of the formula IV in which
R1xe2x80x3 is a linear, branched or cyclic C1-C8-alkyl group which may bear one or more identical or different fluorine, OR2 or NR22 substituents, a C6-aryl group which may bear fluorine, OR2 or NR22 substituents, a C7-C10-alkylaryl or arylalkyl group, which may each bear fluorine, chlorine, OR2 or NR22 substituents, a C2-C8-alkenyl group, a C2-C8-alkynyl group which may bear fluorine, OR2 or NR22 substituents, a C8-C10-arylalkenyl group which may bear fluorine, OR2 or NR22 substituents, an OR2, SiR23 or xe2x80x94OSiR23 group, where R2 are identical or different and are each a C1-C4-alkyl or phenyl group which may bear fluorine, chlorine, OR2a or NR2a2 substituents, a C2-C9-heterocyclic group, where preferred heteroatoms are oxygen, nitrogen and sulfur, which may in turn bear C1-C6-hydrocarbon radicals or heteroatoms as substituents, and
R3xe2x80x2 is an unsaturated C2-C14-group such as a C6-C14-aryl group which may bear fluorine, chlorine, R2, OR2a or NR2a2 substituents, a C7-C10-alkylaryl group or C7-C10-arylalkyl group, where the alkyl part may bear one or more identical or different fluorine, OR2a, NR2a2 or xe2x80x94OSiR2a3 substituents and the aryl part may bear one or: more identical or different fluorine, chlorine, OR2a or NR2a2 substituents, a C2-C8-alkenyl group which may bear one or more identical or different fluorine, OR2a, CO2R2a or NR2a2 substituents, a C2-C8-alkynyl group which may bear one or more identical or different fluorine, OR2a or NR2a2 substituents, a C8-C12-arylalkenyl group, a PR2a2, B(OR2a)2 or SnR2a3 group, where R2a are identical or different and are each a linear or branched C1-C4-alkyl group which may bear one or more fluorine substituents or a phenyl group which may bear one or more identical or different fluorine or OR2a substituents, and, in addition, two radicals R2a may be joined to one another to form a ring system, a C1-C14-heterocyclic group ,where preferred heteroatoms are oxygen, nitrogen or sulfur, which may in turn bear C1-C4-radicals or heteroatoms as substituents,
and Y10, Y11 and Y12 are each a hydrogen atom.
Illustrative examples of indanones of the formula IV, which do not, however, restrict the scope of the invention, are:
2-methyl-7-phenyl-1-indanone 2-methyl-7-(1-naphthyl)-1-indanone 2-methyl-7-(2-naphthyl)-1-indanone 2-methyl-7-(2-methyl-1-naphthyl)-1-indanone 2-methyl-7-(4-methyl-1-naphthyl)-1-indanone 2-methyl-7-(4-methoxy-1-naphthyl)-1-indanone 2-methyl-7-(6-methoxy-2-naphthyl)-1-indanone 2-methyl-7-(4-methylphenyl)-1-indanone 2-methyl-7-(3-methylphenyl)-1-indanone 2-methyl-7-(2-methylphenyl)-1-indanone 2-methyl-7-(3,5-dimethylphenyl)-1-indanone 2-methyl-7-(2,3-dimethylphenyl)-1-indanone 2-methyl-7-(2,4-dimethylphenyl)-1-indanone 2-methyl-7-(2,5-dimethylphenyl)-1-indanone 2-methyl-7-(3-butylphenyl)-1-indanone 2-methyl-7-(4-tert-butylphenyl)-1-indanone 2-methyl-7-mesityl-1-indanone 2-methyl-7-(4-biphenyl)-1-indanone 2-methyl-7-(3-biphenyl)-1-indanone 2-methyl-7-(2-biphenyl)-1-indanone 2-methyl-7-(3,5-diphenylphenyl)-1-indanone 2-methyl-7-(4-styryl)-1-indanone 2-methyl-7-(3-styryl)-1-indanone 2-methyl-7-(2-styryl)-1-indanone 2-methyl-7-(9-anthracenyl)-1-indanone 2-methyl-7-(9-phenanthrenyl)-1-indanone 2-methyl-7-(2-hydroxyphenyl)-1-indanone 2-methyl-7-(4-hydroxyphenyl)-1-indanone 2-methyl-7-(3-hydroxyphenyl)-1-indanone 2-methyl-7-(2,4-dihydroxyphenyl)-1-indanone 2-methyl-7-(3,5-dihydroxyphenyl)-1-indanone 2-methyl-7-(4-methoxyphenyl)-1-indanone 2-methyl-7-(3-methoxyphenyl)-1-indanone 2-methyl-7-(2-methoxyphenyl)-1-indanone 2-methyl-7-(2,4-dimethoxyphenyl)-1-indanone 2-methyl-7-(3,5-dimethoxyphenyl)-1-indanone 2-methyl-7-(3,4,5-trimethoxyphenyl)-1-indanone 2-methyl-7-(4-phenoxyphenyl)-1-indanone 2-methyl-7-(3,4-methylenedioxy)phenyl)-1-indanone 2-methyl-7-(4-thioanisyl)-1-indanone 2-methyl-7-(3-thioanisyl)-1-indanone 2-methyl-7-(4-nitrophenyl)-1-indanone 2-methyl-7-(3-nitrophenyl)-1-indanone 2-methyl-7-(2-nitrophenyl)-1-indanone 2-methyl-7-(4-methyl-3-nitrophenyl)-1-indanone 2-methyl-7-(4-methoxycarbonylphenyl)-1-indanone 2-methyl-7-(3-methoxycarbonylphenyl)-1-indanone 2-methyl-7-(2-methoxycarbonylphenyl)-1-indanone 2-methyl-7-(4-carboxylphenyl)-1-indanone 2-methyl-7-(2-carboxylphenyl)-1-indanone 2-methyl-7-(4-formylphenyl)-1-indanone 2-methyl-7-(4-acetylphenyl)-1-indanone 2-methyl-7-(4-pivaloylphenyl)-1-indanone 2-methyl-7-(4-aminophenyl)-1-indanone 2-methyl-7-(3-aminophenyl)-1-indanone 2-methyl-7-(2-aminophenyl)-1-indanone 2-methyl-7-(4-dimethylaminophenyl)-1-indanone 2-methyl-7-(3-dimethylaminophenyl)-1-indanone 2-methyl-7-(4-(1-pyrrolidino)phenyl)-1-indanone 2-methyl-7-(4-hydrazinophenyl)-1-indanone 2-methyl-7-(4-cyanophenyl)-1-indanone 2-methyl-7-(3-cyanophenyl)-1-indanone 2-methyl-7-(2-cyanophenyl)-1-indanone 2-methyl-7-(4-trifluoromethoxyphenyl)-1-indanone 2-methyl-7-(4-fluorophenyl)-1-indanone 2-methyl-7-(4-bromophenyl)-1-indanone 2-methyl-7-(2,4-difluorophenyl)-1-indanone 2-methyl-7-(4-chlorophenyl)-1-indanone 2-methyl-7-(3,5-dichlorophenyl)-1-indanone 2-methyl-7-(4-trifluoromethylphenyl)-1-indanone 2-methyl-7-(3-trifluoromethylphenyl)-1-indanone 2-methyl-7-(3,5-bis(trifluoromethyl)phenyl)-1-indanone 2-methyl-7-(2,4-bis(trifluoromethyl)phenyl)-1-indanone 2-methyl-7-(2-furyl)-1-indanone 2-methyl-7-(3-furyl)-1-indanone 2-methyl-7-(5-methyl-2-furyl)-1-indanone 2-methyl-7-(benzofuryl)-1-indanone 2-methyl-7-(2-thiophenyl)-1-indanone 2-methyl-7-(5-methyl-2-thiophenyl)-1-indanone 2-methyl-7-(3-thiophenyl)-1-indanone 2-methyl-7-(5-isobutyl-2-thiophenyl)-1-indanone 2-methyl-7-(benzothiophenyl)-1-indanone 2-methyl-7-(N-methyl-2-pyrrolyl)-1-indanone 2-methyl-7-(N-methyl-3-pyrrolyl)-1-indanone 2-methyl-7-(2-pyridyl)-1-indanone 2-methyl-7-(3-pyridyl)-1-indanone 2-methyl-7-(4-pyridyl)-1-indanone 2-methyl-7-(2-pyrimidyl)-1-indanone 2-methyl-7-(2-quinolyl)-1-indanone 2-methyl-7-(3-quinolyl)-1-indanone 2-methyl-7-(4-isoquinolyl)-1-indanone 2-methyl-7-(2-thiazolyl)-1-indanone 2-methyl-7-(2-benzothiazolyl)-1-indanone 2-methyl-7-(2-N-methylimidazolyl)-1-indanone 2-methyl-7-(2-N-methylbenzoimidazolyl)-1-indanone 2-methyl-7-(2-oxazolyl)-1-indanone 2-methyl-7-(N-methyltriazolyl)-1-indanone 2-methyl-7-benzyl-1-indanone 2-methyl-7-(hex-1-en-6-yl)-1-indanone 2-methyl-7-(hex-1-en-1-yl)-1-indanone 2-methyl-7-vinyl-1-indanone 2-methyl-7-(2-trimethylsilylethen-1-yl)-1-indanone 2-methyl-7-(2-phenylethyn-1-yl)-1-indanone 2-methyl-7-(2-tert-butylethyn-1-yl)-1-indanone 2-methyl-7-allyl-1-indanone 2-methyl-7-(2-trimethylsilylethyn-1-yl)-1-indanone 2-methyl-7-(2-phenylethen-1-yl)-1-indanone 2-methyl-7-trimethylstannyl-1-indanone 2-methyl-7-tributylstannyl-1-indanone 2-methyl-7-triphenylstannyl-1-indanone 2-methyl-7-(boronic acid pinacol ester)-1-indanone 2-methyl-7-(boronic acid trimethylene glycol ester)-1-indanone 2-methyl-7-(B-catecholborane)-1-indanone 2-methyl-7-diphenylphosphino-1-indanone 2-methyl-7-dibutylphosphino-1-indanone 2-methyl-7-(methoxyphenyl-methyl-phosphino)-1-indanone 2-ethyl-7-phenyl-1-indanone 2-ethyl-7-(4-tolyl)-1-indanone 2-ethyl-7-naphthyl-1-indanone 2-ethyl-7-(2-furyl)-1-indanone 2-isopropyl-7-(2-pyridyl)-1-indanone 2-isopropyl-7-phenyl-1-indanone 2-isopropyl-7-naphthyl-1-indanone 2-isobutyl-7-phenyl-1-indanone 2-isobutyl-7-naphthyl-1-indanone 2-cyclohexyl-7-phenyl-1-indanone 2-trifluoromethyl-7-phenyl-1-indanone 2-trifluoromethyl-7-(4-tolyl)-1-indanone 2-trifluoromethyl-7-naphthyl-1-indanone 2-trifluoromethyl-7-(4-methoxyphenyl)-1-indanone 2-trifluoromethyl-7-(3,5-bis(trifluoromethyl)phenyl)-1-indanone 2-methyl-4-methoxy-7-phenyl-1-indanone 2,6-dimethyl-7-phenyl-1-indanone 2,5-dimethyl-7-phenyl-1-indanone 2,5-dimethyl-7-p-tolyl-1-indanone 2,5-dimethyl-7-(2-thiophenyl)-1-indanone 2-methyl-5-phenyl-7-naphthyl-1-indanone 2-methyl-5,7-diphenyl-1-indanone 2-methyl-7-(4-fluorophenyl)-1-indanone 2-methyl-5-diphenylphosphino-7-(4-nitrophenyl)-1-indanone 2-methyl-5-chloro-7-phenyl-1-indanone 2,6-dimethyl-7-(4-methoxyphenyl)-1-indanone 2-ethyl-5-vinyl-7-(2-furyl)-1-indanone 2-isopropyl-5-trifluoromethyl-7-phenyl-1-indanone 2-cyclohexyl-5-methyl-7-(2-pyridyl)-1-indanone 2-trifluoromethyl-7-naphthyl-1-indanone 2-trimethylsilyl-5-isopropyl-7-(boronic acid pinacol ester)-1-indanone 2-dimethylamino-6-cyclohexyl-7-trimethylstannyl-1-indanone 2-ethyl-7-(9-phenanthrenyl)-1-indanone 2-ethyl-7-(2-pyridyl)-1-indanone 2-butyl-7-phenyl-1-indanone 2-butyl-7-(4-tolyl)-1-indanone 2-butyl-7-naphthyl-1-indanone 2-butyl-7-(2-furyl)-1-indanone 2-butyl-7-(p-phenanthrenyl)-1-indanone 2-butyl-7-(2-pyridyl)-1-indanone 2-ethyl-7-(4-tert-butylphenyl)-1-indanone 2-n-propyl-7-phenyl-1-indanone 2-n-propyl-7-naphthyl-1-indanone 2-n-propyl-7-(4-tert-butylphenyl)-1-indanone 2-n-propyl-7-(4-methylphenyl)-1-indanone 2-n-butyl-7-phenyl-1-indanone 2-n-butyl-7-naphthyl-1-indanone 2-n-butyl-7-(4-tert-butylphenyl)-1-indanone 2-n-butyl-7-(4-methylphenyl)-1-indanone
Both indanones of the formulae I and Ia and also indanones of the formulae II and IIa are suitable, inter alia, as intermediates in the preparation of metallocenes and active compounds in the fields of pharmacy and crop protection.
The indanones of the formulae II and IIa can easily be converted into the indenes of the formulae V and Va by literature methods (eg.: R. C. Larock, Comprehensive Organic Transformations, VCH, 1989, EP 0 629 632 A2).
In the formulae II, IIa, V and Va, the radicals R1, R3, Y4, Y5 and Y6 are as defined above for formulae II and Ia.
Metallocenes can be prepared from the indenes of the formulae V and Va by literature methods (eg. EP 576 970, EP 629 632). Preference is given to unbridged or bridged metallocenes of the formula (VI)
where R1, R3, Y4, Y5 and Y6 are as defined above for formula II, M is a transition element of group 4, 5 or 6 of the Periodic Table of the Elements, eg. titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, preferably titanium, zirconium, hafnium, particularly preferably zirconium,
R9 and R10 are identical or different and are each a hydrogen atom, hydroxy or a halogen atom or a C1-C40-group such as C1-C10-alkyl, C1-C10-alkoxy, C6-C10-aryl, C6-C10-aryloxy, C2-C10-alkenyl, C7-C40-arylalkyl, C7-C40-alkylaryl, C8-C40-arylalkenyl, preferably hydrogen, C1-C3-alkyl, in particular methyl, C1-C3-alkoxy, C6-aryl, C6-aryloxy, C2-C10-alkenyl, C7-C10-arylalkyl, C7-C10-alkylaryl, C8-C10-arylalkenyl or a halogen atom, in particular chlorine,
x is zero or 1,
R11 is a bridge such as
where M2 is carbon, silicon, germanium or tin, preferably silicon or carbon, in particular silicon,
p is 1, 2 or 3, preferably 1 or 2, in particular 1,
R12 and R13 are identical or different and are each a hydrogen atom, a halogen atom or a C1-C20-group such as C1-C20-alkyl, C6-C14-aryl, C1-C10-alkoxy, C2-C10-alkenyl, C7-C20-arylalkyl, C7-C20-alkylaryl, C6-C10-aryloxy, C1-C10-fluoroalkyl, C6-C10-haloaryl or C2-C10-alkynyl or
R12 and R13 together with the atom connecting them form a ring; preferably, R12 and R13 are hydrogen, C1-C6-alkyl, C6-C10-aryl, C1-C6-alkoxy, C2-C4-alkenyl, C7-C10-arylalkyl, C7-C10-alkylaryl, particularly preferably C1-C6-alkyl or C6-C10-aryl, or R12 and R13 together with the atom connecting them form a ring.
R3 are identical or different, preferably identical, and are preferably each a C6-C40-aryl group which may contain heteroatoms. Preference is given to C6-C40-aryl groups which may be halogenated, in particular fluorinated, or may bear halogenated, in particular fluorinated, C1-C20-hydrocarbon radicals. R3 are particularly preferably each a phenyl, naphthyl, phenanthryl or anthracenyl group which is fluorinated and/or bears fluorinated, in particular perfluorinated, C1-C10-hydrocarbon radicals such as CF3 or C2F5.
Particularly suitable metallocenes of the formula VI comprise the following molecular fragments:
MR9R10: ZrCL2, Zr(CH3)2, HfCl2, Hf(CH3)2
R1: linear C1-C10-alkyl
Y4, Y5, Y6: hydrogen
R3: 4-(C4-C8-alkyl)phenyl, where the 4-(C4-C8-alkyl) group is preferably a branched C4-C8-alkyl group, in particular a tert-butyl group,
R11: dimethylsilyl, diphenylsilyl, methylphenylsilyl.
Further preferred metallocene components of the metallocenes of the formula VI are combinations of the following molecular fragments:
MR9R10: ZrCl2, Zr(CH3)2,
R1: C1-C4-alkyl such as methyl, ethyl, isopropyl, n-butyl, sec-butyl,
Y6: hydrogen
Y4, Y5: hydrogen, C1-C4-alkyl, C6-C10-aryl,
R3: 4-fluorophenyl, 3,5-difluorophenyl, pentafluorophenyl, 4-trifluoromethylphenyl, 3-trifluoromethylphenyl, 2-trifluoromethylphenyl, 3,5-ditrifluoromethylphenyl, 2,6-ditrifluoromethylphenyl, pentatrifluoromethylphenyl, 4-pentafluoroethylphenyl, 3-pentafluoroethylphenyl, 2-pentafluoroethylphenyl, 3,5-dipentafluoroethylphenyl, 2,6-dipentafluoroethylphenyl, mono-, di-, tri- and tetrafluoronaphthyl, penta(pentafluoroethyl)-phenyl,
R11: dimethylsilanediyl, dimethylgermanediyl, CH2xe2x80x94CH2, CH(CH3)xe2x80x94CH2, CH(CH3)xe2x80x94CH(CH3), C(CH3)2xe2x80x94CH2, C(CH3)2xe2x80x94C(CH3)2.
Radicals having the same designation on the two indenyl ligands: can be identical to or different from one another. Thus, the two indenyl ligands can be identical or can be different from one another (eg. when one Y6=H, and the other Y6=CH3 or when one Y6=CH3 and the other Y6=C2H5).
Illustrative examples of metallocenes which can be prepared, which do not, however, restrict the scope of the invention, are:
dimethylsilanediylbis(2-methyl-4-(4-fluorophenyl)indenyl)ZrCl2 dimethylsilanediylbis(2-methyl-4-(3,5-difluorophenyl)indenyl)ZrCl2 dimethylsilanediylbis(2-methyl-4-(2,6-difluorophenyl)indenyl)ZrCl2 dimethylsilanediylbis(2-methyl-4-(pentafluorophenyl)indenyl)ZrCl2 dimethylsilanediylbis(2-methyl-4-(4-trifluoromethylphenyl)indenyl)ZrCl2 dimethylsilanediylbis(2-methyl-4-(3,5-ditrifluoromethylphenyl)indenyl)ZrCl2 dimethylsilanediylbis(2-methyl-4-(2,6-ditrifluoromethylphenyl)indenyl)ZrCl2 dimethylsilanediylbis(2-methyl-4-(pentatrifluoromethylphenyl)indenyl)ZrCl2 dimethylsilanediylbis(2-methyl-4-(4-pentafluoroethylphenyl)indenyl)ZrCl2 dimethylsilanediylbis(2-methyl-4-(3,5-dipentafluoroethylphenyl)indenyl)ZrCl2 dimethylsilanediylbis(2-methyl-4-(2,6-dipentafluoroethylphenyl)indenyl)ZrCl2 dimethylsilanediylbis(2-methyl-4-(penta(pentafluoroethyl)phenyl)indenyl)ZrCl2 dimethylsilanediylbis(2-methyl-4-(3,5-difluorophenyl)-6-phenylindenyl)ZrCl2 dimethylsilanediylbis(2-methyl-4-(3,5-difluoromethylphenyl)-6-phenylindenyl)ZrCl2 dimethylsilanediylbis(2-methyl-4-(4-pentafluoroethylphenyl)-6-phenylindenyl)ZrCl2 dimethylsilanediylbis(2-methyl-4-(3,5-dipentafluoroethylphenyl)-6-phenylindenyl)ZrCl2 dimethylsilanediylbis(2-methyl-4-(pentafluorophenyl)-6-phenylindenyl)ZrCL2 dimethylsilanediylbis(2-methyl-4-(3,5-ditrifluoromethylphenyl)-6-methylindenyl)ZrCl2 dimethylsilanediylbis(2-methyl-4-(3,5-ditrifluoromethylphenyl)-6-isopropylindenyl)ZrCl2 dimethylsilanediylbis[1-(2-n-propyl-4-(4-tert-butylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-n-butyl-4-(4-tert-butylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-n-pentyl-4-(4-tert-butylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis(2-n-butyl-4-(3,5-difluorophenyl)indenyl)ZrCl2 dimethylsilanediylbis(2-n-butyl-4-(4-trifluoromethylphenyl)indenyl)ZrCl2 dimethylsilanediylbis(2-n-butyl-4-(3,5-ditrifluoromethylphenyl)indenyl)ZrCl2 dimethylsilanediylbis(2-n-butyl-4-(4-pentafluoroethylphenyl)indenyl)ZrCl2 dimethylsilanediylbis(2-n-butyl-4-(3,5-dipentafluoroethylphenyl)indenyl)ZrCl2 dimethylsilanediylbis(2-n-butyl-4-(pentafluorophenyl)indenyl)ZrCl2 dimethylsilanediylbis(2-n-butyl-4-(3,5-difluorophenyl)indenyl)ZrCl2 dimethylsilanediylbis(2-n-butyl-4-(pentafluorophenyl)indenyl)ZrCl2 dimethylsilanediylbis(2-sec-butyl-4-(3,5-difluorophenyl)indenyl)ZrCl2 dimethylsilanediylbis(2-sec-butyl-4-(4-trifluoromethylphenyl)indenyl)ZrCl2 dimethylsilanediylbis(2-sec-butyl-4-(3,5-ditrifluoromethylphenyl)indenyl)ZrCl2 dimethylsilanediylbis(2-sec-butyl-4-(4-pentafluoroethylphenyl)indenyl)ZrCl2 dimethylsilanediylbis(2-sec-butyl-4-(3,5-dipentafluoroethylphenyl)indenyl)ZrCl2 dimethylsilanediylbis(2-sec-butyl-4-(pentafluorophenyl)indenyl)ZrCl2 dimethylsilanediylbis(2-sec-butyl-4-(3,5-difluorophenyl)indenyl)ZrCl2 dimethylsilanediylbis(2-sec-butyl-4-(pentafluorophenyl)indenyl)ZrCl2 dimethylsilanediylbis(2-isobutyl-4-(3,5-difluorophenyl)indenyl)ZrCl2 dimethylsilanediylbis(2-isobutyl-4-(4-trifluoromethylphenyl)indenyl)ZrCl2 dimethylsilanediylbis(2-isobutyl-4-(3,5-ditrifluoromethylphenyl)indenyl)ZrCl2 dimethylsilanediylbis(2-isobutyl-4-(4-pentafluoroethylphenyl)indenyl)ZrCl2 dimethylsilanediylbis(2-isobutyl-4-(3,5-dipentafluoroethylphenyl)indenyl)ZrCl2 dimethylsilanediylbis(2-isobutyl-4-(pentafluorophenyl)indenyl)ZrCl2 dimethylsilanediylbis(2-ethyl-4-(3,5-difluorophenyl)indenyl)ZrCl2 dimethylsilanediylbis(2-ethyl-4-(4-trifluoromethylphenyl)indenyl)ZrCl2 dimethylsilanediylbis(2-ethyl-4-(3,5-ditrifluoromethylphenyl)indenyl)ZrCl2 dimethylsilanediylbis(2-ethyl-4-(4-pentafluoroethylphenyl)indenyl)ZrCl2 dimethylsilanediylbis(2-ethyl-4-(3,5-dipentafluoroethylphenyl)indenyl)ZrCl2 dimethylsilanediylbis(2-ethyl-4-(pentafluorophenyl)indenyl)ZrCl2 1,2-ethanediylbis(2-methyl-4-phenylindenyl)zirconium dichloride 1,2-ethanediylbis(2-ethyl-4-phenylindenyl)zirconium dichloride 1,2-ethanediylbis(2-isobutyl-4-phenylindenyl)zirconium dichloride 1,2-ethanediylbis(2-n-butyl-4-phenylindenyl)zirconium dichloride 1,2-ethanediylbis(2-sec-butyl-4-phenylindenyl)zirconium dichloride 1,2-ethanediylbis(2-methyl-4-(1-naphthyl)indenyl)zirconium dichloride 1,2-ethanediylbis(2-ethyl-4-(1-naphthyl)indenyl)zirconium dichloride 1,2-ethanediylbis(2-isobutyl-4-(1-naphthyl)indenyl)zirconium dichloride 1,2-ethanediylbis(2-n-butyl-4-(1-naphthyl)indenyl)zirconium dichloride 1,2-ethanediylbis(2-sec-butyl-4-(1-naphthyl)indenyl)zirconium dichloride 1,2-ethanediylbis(2-methyl-4-(2-naphthyl)indenyl)zirconium dichloride 1,2-ethanediylbis(2-ethyl-4-(2-naphthyl)indenyl)zirconium dichloride 1,2-ethanediylbis(2-isobutyl-4-(2-naphthyl)indenyl)zirconium dichloride 1,2-ethanediylbis(2-n-butyl-4-(2-naphthyl)indenyl)zirconium dichloride 1,2-ethanediylbis(2-sec-butyl-4-(2-naphthyl)indenyl)zirconium dichloride 1,2-ethanediylbis(2-methyl-4-phenanthrylindenyl)zirconium dichloride 1,2-ethanediylbis(2-ethyl-4-phenanthrylindenyl)zirconium dichloride 1,2-ethanediylbis(2-isobutyl-4-phenanthrylindenyl)zirconium dichloride 1,2-ethanediylbis(2-n-butyl-4-phenanthrylindenyl)zirconium dichloride 1,2-ethanediylbis(2-sec-butyl-4-phenanthrylindenyl)zirconium dichloride 1,2-ethanediylbis(2-methyl-4-(3,5-dimethylphenyl)indenyl)zirconium dichloride 1,2-ethanediylbis(2-ethyl-4-(3,5-dimethylphenyl)indenyl)zirconium dichloride 1,2-ethanediylbis(2-n-butyl-4-(3,5-dimethylphenyl)indenyl)zirconium dichloride 1,2-ethanediylbis(2-sec-butyl-4-(3,5-dimethylphenyl)indenyl)zirconium dichloride 1,2-ethanediylbis(2-methyl-4-(4-methylphenyl)indenyl)zirconium dichloride 1, 2-ethanediylbis(2-ethyl-4-(4-methylphenyl)indenyl)zirconium dichloride 1,2-ethanediylbis(2-isobutyl-4-(4-methylphenyl)indenyl)zirconium dichloride 1,2-ethanediylbis(2-n-butyl-4-(4-methylphenyl)indenyl)zirconium dichloride 1,2-ethanediylbis(2-sec-butyl-4-(4-methylphenyl)indenyl)zirconium dichloride 1,2-ethanediylbis(2-methyl-4-anthracenylindenyl)zirconium dichlobride 1,2-ethanediylbis(2-ethyl-4-anthracenylindenyl)zirconium dichloride 1,2-ethanediylbis(2-isobutyl-4-anthracenylindenyl)zirconium dichloride 1,2-ethanediylbis(2-n-butyl-4-anthracenylindenyl)zirconium dichloride 1,2-ethanediylbis(2-sec-butyl-4-anthracenylindenyl)zirconium dichloride
Also preferred are the corresponding dimethylzirconium compounds and the corresponding compounds having a 1,2-(1-methylethane-diyl), 1,2-(1,1-dimethylethanediyl) or 1,2-(1,2-dimethylethane-diyl) bridge.
dimethylsilanediylbis[1-(2-methyl-4-phenylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(1-naphthyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(2-naphthyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(4-methylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(3-methylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(2-methylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(4-ethylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(3-ethylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(2-ethylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(4-butylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(4-isopropylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(3-isopropylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(2-isopropylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(4-tert-butylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(3-tert-butylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(4-cyclohexylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(3-cyclohexylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(4-triisopropylsilylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(4-biphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(3-biphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(2-biphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(4-biphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(4-styryl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(3-styryl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(2-styryl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(9-anthracenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(9-phenanthrenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(4-methyl-1-naphthyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(2-methyl-1-naphthyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(2,4-dimethylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(2,3-dimethylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(3,5-dimethylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(3,4-dimethylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(2,6-dimethylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(2,3,4-trimethylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(3,4,5-trimethylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(2,4,5-trimethylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(2,3,4-trimethylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-mesitylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(3,5-diphenylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(3,5-diisopropylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(4-methoxyphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(3-methoxyphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(2-methoxyphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(2,4-dimethoxyphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(3,5-dimethoxyphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(3,4-dimethoxyphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(3,4,5-trimethoxyphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(2,4,6-trimethoxyphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(4-phenoxyphenyl)indenyl)]zirconium dichloride dirmethylsilanediylbis[1-(2-methyl-4-(4-isopropoxyphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(4-fluorophenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(3-fluorophenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(2,4-difluorophenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(3,5-difluorophenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(2,3,5,6-tetrafluoro-4-methylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(4-N,N-dimethylaminophenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(3-N,N-dimethylaminophenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(2-N,N-dimethylaminophenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(4-(1-pyrrolidino)phenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(4-(1-piperidino)phenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4- (4-trifluoromethylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(3-trifluoromethylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(2-trifluoromethylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(3,5-bis(trifluoromethyl)phenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(2,4-bis(trifluoromethyl)phenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(3-trifluoromethoxyphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(2-methyl-4-trifluoromethoxyphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(4-pentafluoroethylphenylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(4-thioanisylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(3-thioanisylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(2-thioanisylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(2-pyridyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(3-pyridyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(4-pyridyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(2-pyrimidyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(2-furyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(3-furyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(5-methyl-2-furyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(2-benzofuryl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(2-thiophenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(3-thiophenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(5-methyl-2-thiophenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(5-isobutyl-2-thiophenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(2-benzothiophenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(2-thiazolyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(2-benzothiazolyl)indenyl)]zirconium dichloride dimeethylsilanediylbis[1-(2-methyl-4-(2-oxazolyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(N-methyl-2-pyrrolyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(N-methyl-3-pyrrolyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(2-quinolyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(3-quinolyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(isoquinolyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(N-methyltriazolyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(N-methyl-2-imidazolyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(N-methyl-2-benzoimidazolyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-butylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-cyclohexylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-isopropylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-benzylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-isobutylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(hex-1-en-6-yl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(hex-1-en-1-yl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-vinylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(2-trimethylsilylethen-1-yl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(2-phenylethyn-1-yl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(2-tert-butylethyn-1-yl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-allylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(2-trimethylsilylethyn-1-yl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(2-phenylethen-1-yl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(diphenylphosphino)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(dibutylphosphino)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-(dimethylphosphino)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-phenylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(1-naphthyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(2-naphthyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(4-methylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(3-methylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(2-methylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(4-ethylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(3-ethylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(2-ethylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(4-butylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(4-isopropylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(3-isopropylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(2-isopropylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(4-tert-butylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(3-tert-butylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(4-cyclohexylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(3-cyclohexylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(4-triisopropylsilylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(4-biphenyl)indenyl))]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(3-biphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(2-biphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(4-biphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(4-styryl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(3-styryl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(2-styryl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(9-anthracenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(9-phenanthrenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(4-methyl-1-naphthyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(2-methyl-1-naphthyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(2,4-dimethylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(2,3-dimethylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(3,5-dimethylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(3,4-dimethylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(2,6-dimethylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(2,3,4-trimethylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(3,4,5-trimethylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(2,4,5-trimethylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(2,3,4-trimethylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-mesitylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(3,5-diphenylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(3,5-diisopropylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(4-methoxyphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(3-methoxyphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(2-methoxyphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(2,4-dimethoxyphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(3,5-dimethoxyphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(3,4-dimethoxyphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(3,4,5-trimethoxyphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(2,4,6-trimethoxyphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(4-phenoxyphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-n-propyl-4-phenylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-n-propyl-4-naphthylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-n-propyl-4-(4-tert-butylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-n-propyl-4-p-tolylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(4-isopropoxyphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(4-fluorophenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(3-fluorophenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(2,4-difluorophenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(3,5-difluorophenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(2,3,5,6-tetrafluoro-4-methylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(4-N,N-dimethylaminophenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(3-N,N-dimethylaminophenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(2-N,N-dimethylaminophenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(4-(1-pyrrolidino)phenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(4-(1-piperidino)phenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(4-trifluoromethylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(3-trifluoromethylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(2-trifluoromethylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(3,5-bis(trifluoromethyl)phenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(2,4-bis(trifluoromethyl)phenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(3-trifluoromethoxyphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(2-ethyl-4-trifluoromethoxyphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(4-pentafluoroethylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(4-thioanisylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(3-thioanisylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(2-thioanisylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(2-pyridyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(3-pyridyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(4-pyridyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(2-pyrimidyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(2-furyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(3-furyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(5-methyl-2-furyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(2-benzofuryl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(2-thiophenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(3-thiophenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(5-methyl-2-thiophenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(5-isobutyl-2-thiophenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(2-benzothiophenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(2-thiazolyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(2-benzothiazolyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(2-oxazolyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(N-methyl-2-pyrrolyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(N-methyl-3-pyrrolyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(2-quinolyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(3-quinolyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(isoquinolyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(N-methyltriazole)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(N-methyl-2-imidazolyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(N-methyl-2-benzoimidazolyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-butylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-cyclohexylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-isopropylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-benzylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-isobutylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(hex-1-en-6-yl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(hex-1-en-1-yl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-vinylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(2-trimethylsilylethen-1-yl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(2-phenylethyn-1-yl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(2-tert-butylethyn-1-yl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-allylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(2-trimethylsilylethyn-1-yl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(2-phenylethen-1-yl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(diphenylphosphino)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(dibutylphosphino)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4-(dimethylphosphino)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-isopropyl-4-phenylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-isopropyl-4-(1-naphthyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-isopropyl-4-(2-naphthyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-isopropyl-4-(4-methylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-isopropyl-4-(3,5-dimethylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-isopropyl-4-(4-trifluoromethylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-isopropyl-4-(3,5-bis(trifluoromethyl)phenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-isopropyl-4-(4-methoxyphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-isopropyl-4-(2-furyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-isopropyl-4-(2-pyridyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-isopropyl-4-(2-thiophenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-isopropyl-4-(2-oxazolyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-isopropyl-4-allylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-isopropyl-4-cyclohexylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2,4-diisopropylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-isopropyl-4-butylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-isopropyl-4-benzylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-isopropyl-4-(hex-1-en-6-yl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-isopropyl-4-(hex-1-en-1-yl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-isopropyl-4-vinylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-isopropyl-4-(2-trimethylsilylethen-1-yl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-isopropyl-4-(2-phenylethyn-1-yl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-isopropyl-4-(2-tert-butylethyn-1-yl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-isobutyl-4-phenylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-isobutyl-4-(1-naphthyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-isobutyl-4-(2-naphthyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-isobutyl-4-(4-methylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-isobutyl-4-(3,5-dimethylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-isobutyl-4-(4-trifluoromethylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-isobutyl-4-(3,5-bis(trifluoromethyl)phenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-isobutyl-4-(4-methoxyphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-isobutyl-4-(2-furyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-isobutyl-4-(2-pyridyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-isobutyl-4-(2-thiophenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-isobutyl-4-(2-oxazolyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-isobutyl-4-allylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-isobutyl-4-cyclohexylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2,4-diisobutylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-isobutyl-4-butylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-isobutyl-4-benzylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-isobutyl-4-(hex-1-en-6-yl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-isobutyl-4-(hex-1-en-1-yl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-isobutyl-4-vinylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-isobutyl-4-(2-trimethylsilylethen-1-yl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-isobutyl-4-(2-phenylethyn-1-yl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-isobutyl-4-(2-tert-butylethyn-1-yl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-trifluoromethyl-4-phenylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-trifluoromethyl-4-(1-naphthyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-trifluoromethyl-4-(2-naphthyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-trifluoromethyl-4-(4-methylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-trifluoromethyl-4-(3,5-dimethylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-trifluoromethyl-4-(4-trifluoromethylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-trifluoromethyl-4-(3,5-bis(trifluoromethyl)phenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-trifluoromethyl-4-(4-methoxyphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-trifluoromethyl-4-(2-furyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-trifluoromethyl-4-(2-pyridyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-trifluoromethyl-4-(2-thiophenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-trifluoromethyl-4-(2-oxazolyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-trifluoromethyl-4-allylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-trifluoromethyl-4-cyclohexylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2,4-bis(trifluoromethylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-trifluoromethyl-4-butylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-trifluoromethyl-4-benzylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-trifluoromethyl-4-(hex-1-en-6-yl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-trifluoromethyl-4-(hex-1-en-1-yl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-trifluoromethyl-4-vinylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-trifluoromethyl-4-(2-trimethylsilylethen-1-yl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-trifluoromethyl-4-(2-phenylethyn-1-yl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-trifluoromethyl-4-(2-tert-butylethyn-1-yl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2,5-dimethyl-4-phenylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2,7-dimethyl-4-phenylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2,6-dimethyl-4-phenylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2,6-dimethyl-4-(1-naphthyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2,6-dimethyl-4-(2-naphthyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2,6-dimethyl-4-(4-methylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2,6-dimethyl-4-(4-methoxyphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2,6-dimethyl-4-(2-pyridyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2,7-dimethyl-4-(1-naphthyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2,7-dimethyl-4-(2-naphthyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2,7-dimethyl-4-(2-pyridyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-6-methoxy-4-phenylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4,6-diphenylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-4,6-diphenylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-cyclohexyl-6-methyl-4-phenylindenyl]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-6-vinyl-4-phenylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-6-benzyl-4-naphthylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-ethyl-5-methyl-4-(3,5-dimethylphenylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-phenyl-4-phenylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-phenyl-4-(1-naphthyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-phenyl-4-(2-naphthyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-phenyl-4-(4-methylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-phenyl-4-(3,5-dimethylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-phenyl-4-(4-trifluoromethylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-phenyl-4-(3,5-bis(trifluoromethyl)phenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-phenyl-4-(4-methoxyphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-phenyl-4-(2-furyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-phenyl-4-(2-pyridyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-phenyl-4-(2-thiophenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-phenyl-4-(2-oxazolyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-phenyl-4-allylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-phenyl-4-cyclohexylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2,4-diphenylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-phenyl-4-butylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-phenyl-4-benzylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-phenyl-4-(hex-1-en-6-yl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-phenyl-4-(hex-1-en-1-yl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-phenyl-4-vinylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-phenyl-4-(2-trimethylsilylethen-1-yl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-phenyl-4-(2-phenylethyn-1-yl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-phenyl-4-(2-tert-butylethyn-1-yl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-cyclohexyl-4-phenylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-cyclohexyl-4-(1-naphthyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-cyclohexyl-4-(2-naphthyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-cyclohexyl-4-(4-methylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-cyclohexyl-4-(3,5-dimethylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-cyclohexyl-4-(4-trifluoromethylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-cyclohexyl-4-(3,5-bis(trifluoromethyl)phenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-cyclohexyl-4-(4-methoxyphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-cyclohexyl-4-(2-furyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-cyclohexyl-4-(2-pyridyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-cyclohexyl-4-(2-thiophenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-cyclohexyl-4-(2-oxazolyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-cyclohexyl-4-allylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-cyclohexyl-4-cyclohexylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2,4-dicyclohexylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-cyclohexyl-4-butylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-cyclohexyl-4-benzylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-cyclohexyl-4-(hex-1-en-6-yl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-cyclohexyl-4-(hex-1-en-1-yl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-cyclohexyl-4-vinylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-cyclohexyl-4-(2-trimethylsilylethen-1-yl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-cyclohexyl-4-(2-phenylethyn-1-yl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-cyclohexyl-4-(2-tert-butylethyn-1-yl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-butyl-4-phenylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-butyl-4-(1-naphthyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-butyl-4-(2-naphthyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-butyl-4-(4-methylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-butyl-4-(3,5-dimethylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-butyl-4-(4-trifluoromethylphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-butyl-4-(3,5-bis(trifluoromethyl)phenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-butyl-4-(4-methoxyphenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-butyl-4-(2-furyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-butyl-4-(2-pyridyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-butyl-4-(2-thiophenyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-butyl-4-(2-oxazolyl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-butyl-4-allylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-butyl-4-cyclohexylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2,4-dibutylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-butyl-4-benzylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-butyl-4-(hex-1-en-6-yl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-butyl-4-(hex-1-en-1-yl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-butyl-4-vinylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-butyl-4-(2-trimethylsilylethen-1-yl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-butyl-4-(2-phenylethyn-1-yl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-butyl-4-(2-tert-butylethyn-1-yl)indenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4-phenylindenyl)]dimethylzirconium dimethylsilanediylbis[1-(2-methyl-4-phenylindenyl)]zirconium diethoxide dimethylsilanediylbis[1-(2-methyl-4-phenylindenyl)]zirconium diphenoxide dimethylsilanediylbis[1-(2-methyl-4-(1-naphthyl)indenyl)]-dimethylzirconium dimethylsilanediylbis[1-(2-methyl-4-(1-naphthyl)indenyl)]-dibenzylzirconium dimethylsilanediylbis[1-(2-methyl-4-(1-naphthyl)indenyl)]zirconium bis(dimethylamide) dimethylsilanediylbis[1-(2-methyl-4-(2-naphthyl)indenyl)]zirconium bis(diethylamide) dimethylsilanediylbis[1-(2-methyl-4-(pyridyl)indenyl)]dimethylzirconium dimethylsilanediylbis[1-(2-methyl-4-(3,5-bis(trifluoromethyl)phenyl)indenyl)]dimethylzirconium dimethylsilanediylbis[1-(2-methyl-4-(3,5-bis(trifluoromethyl)phenyl)indenyl)]zirconium dimethoxide dimethylsilanediylbis[1-(2-ethyl-4-(3,5-dimethylphenyl)indenyl)]-dimethylzirconium dimethylsilanediylbis[1-(2-dimethylamino-4-phenylindenyl)]-dimethylzirconium dimethylsilanediylbis[1-(2-N-piperino-4-naphthylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-trimethylsilyl-4-cyclohexylindenyl)]-dimethylzirconium dimethylsilanediylbis[1-(2-trimethylsilyloxy-4-phenylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2,6-dimethyl-4-phenylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-methyl-4,6-diphenylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2,5-dimethyl-4-naphthylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-cyclohexyl-6-methyl-4-phenylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2,5,6-trimethyl-4-phenylindenyl)]zirconium dichloride dimethylsilanediylbis[1-(2-isopropyl-5,6-difluoro-4-phenylindenyl)]zirconium dichloride 1,2-ethanediylbis[1-(2-methyl-4-phenylindenyl)]zirconium dichloride 1,2-ethanediylbis[1-(2-methyl-4-phenylindenyl)]dimethylzirconium 1,2-ethanediylbis[1-(2-methyl-4-(1-naphthyl)indenyl)]zirconium dichloride 1,2-ethanediylbis[1-(2-methyl-4-(2-naphthyl)indenyl)]zirconium dichloride 1,2-ethanediylbis[1-(2-ethyl-4-(3,5-bis(trifluoromethyl)phenyl)indenyl)]zirconium dichloride 1,2-ethanediylbis[1-(2-butyl-4-(2-pyridyl)indenyl)]zirconium dichloride 1,2-ethanediylbis[1-(2-methyl-4-(2-furyl)indenyl)]zirconium dichloride 1,2-ethanediylbis[1-(2-methyl-4-(2-thiophenyl)indenyl)]zirconium dichloride 1,2-ethanediylbis[1-(2-isopropyl-4-(4-methoxyphenyl)indenyl)]zirconium dichloride 1,2-ethanediylbis[1-(2-methyl-4-(4-methylphenyl)indenyl))]zirconium dichloride 1,2-ethanediylbis[1-(2-isobutyl-4-phenylindenyl)]zirconium dichloride 1,2-ethanediylbis[1-(2-methyl-4-(3-dimethylaminophenyl)indenyl)]zirconium dichloride 1,2-butanediylbis[1-(2-methyl-4-phenylindenyl)]zirconium dichloride 1,2-butanediylbis[1-(2-methyl-4-phenylindenyl)]dimethylzirconium 1,2-butanediylbis[1-(2-methyl-4-(1-naphthyl)indenyl)]zirconium dichloride 1,2-butanediylbis[1-(2-methyl-4-(2-naphthyl)indenyl)]zirconium dichloride 1,2-butanediylbis[1-(2-ethyl-4-(3,5-bis(trifluoromethyl)phenyl)indenyl)]zirconium dichloride 1,2-butanediylbis[1-(2-butyl-4-(2-pyridyl)indenyl)]zirconium dichloride 1,2-butanediylbis[1-(2-methyl-4-(2-furyl)indenyl)]zirconium dichloride 1,2-butanediylbis[1-(2-phenyl-4-(2-thiophenyl)indenyl)]zirconium dichloride 1,2-butanediylbis[1-(2-isopropyl-4-(4-methoxyphenyl)indenyl)]zirconium dichloride 1,2-butanediylbis[1-(2,5-dimethyl-4-(4-methylphenyl)indenyl)]zirconium dichloride 1,2-butanediylbis[1-(2-isobutyl-4-phenylindenyl)]zirconium dichloride 1,2-butanediylbis[1-(2-methyl-4-(3-dimethylaminophenyl)indenyl)]zirconium dichloride bis[2-methyl-4-phenylindenyl]zirconium dichloride bis[2-methyl-4-phenylindenyl]dimethylzirconium bis[2-methyl-4-(1-naphthyl)indenyl]zirconium dichloride bis[2-methyl-4-(2-naphthyl)indenyl]zirconium dichloride bis[2-ethyl-4-(3,5-bis(trifluoromethyl)phenyl)indenyl]zirconium dichloride bis[2-butyl-4-(2-pyridyl)indenyl]zirconium dichloride bis[2-methyl-4-(2-furyl)indenyl]zirconium dichloride bis[2-methyl-4-(2-thiophenyl)indenyl]zirconium dichloride bis[2-isopropyl-4-(4-methoxyphenyl)indenyl]zirconium dichloride bis[2-methyl-4-(4-methylphenyl)indenyl]zirconium dichloride bis[2-isobutyl-4-phenylindenyl]zirconium dichloride bis[(2-methyl-4-(3-dimethylaminophenyl)indenyl]zirconium dichloride bis[2-methyl-4-(3,5-dimethylphenyl)indenyl]zirconium dichloride bis[2-N-piperidino-4-(3,5-dimethylphenyl)indenyl]zirconium dichloride [2-butyl-4-(2-pyridyl)indenyl]cyclopentadienylzirconium dichloride [2-ethyl-4-(3,5-bis(trifluoromethyl)phenylindenyl)]-[1-methylboratabenzene]zirconium dichloride [2-methyl-4-(3,5-dimethylphenyl)indenyl]fluorenylzirconium dichloride [2-isobutyl-4-(4-methoxyphenyl)indenyl)]-[2-methylindenyl]zirconium dichloride [2-cyclohexyl-4-(3-fluorophenylindenyl]trimethylcyclopentadienylzirconium dichloride [2-phenyl-4-(3-dimethylaminophenylindenyl)]-[tert-butylmethylcyclopentadienyl]zirconium dichloride methylphenylsilanediylbis[1-(2-methyl-4-phenylindenyl)]zirconium dichloride methylphenylsilanediylbis[1-(2-methyl-4-phenylindenyl)]dimethylzirconium methylphenylsilanediylbis[1-(2-methyl-4-(1-naphthyl)indenyl))]zirconium dichloride methylphenylsilanediylbis[1-(2-methyl-4-(2-naphthyl)indenyl)]zirconium dichloride methylphenylsilanediylbis[1-(2-ethyl-4-(3,5-trifluoromethyl)phenyl)indenyl)]zirconium dichloride methylphenylsilanediylbis[1-(2-butyl-4-(2-pyridyl)indenyl)]zirconium dichloride methylphenylsilanediylbis[1-(2-methyl-4-(2-furyl)indenyl)]zirconium dichloride methylphenylsilanediylbis[1-(2-methyl-4-(2-thiophenyl)indenyl)]zirconium dichloride methylphenylsilanediylbis[1-(2-isopropyl-4-(4-methoxyphenyl)indenyl)]zirconium dichloride methylphenylsilanediylbis[1-(2-methyl-4-(4-methylphenyl)indenyl)]zirconium dichloride methylphenylsilanediylbis[1-(2-isobutyl-4-phenylindenyl)]zirconium dichloride methylphenylsilanediylbis[1-(2-methyl-4-(3-dimethylaminophenyl)indenyl)]zirconium dichloride isopropylidenebis[1-(2-methyl-4-phenylindenyl)]zirconium dichloride isopropylidenebis[1-(2-methyl-4-phenylindenyl)]dimethylzirconium isoprbpylidenebis[1-(2-methyl-4-(1-naphthyl)indenyl)]zirconium dichloride isopropylidenebis[1-(2-methyl-4-(2-naphthyl)indenyl)]zirconium dichloride isopropylidenebis[1-(2-ethyl-4-(3,5-bis(trifluoromethyl)phenyl)indenyl)]zirconium dichloride isopropylidenebis[1-(2-butyl-4-(2-pyridyl)indenyl)]zirconium dichloride isopropylidenebis[1-(2-methyl-4-(2-furyl)indenyl)]zirconium dichloride isopropylidenebis[1-(2-methyl-4-(2-thiophenyl)indenyl)]zirconium dichloride isopropylidenebis[1-(2-isopropyl-4-(4-methoxyphenyl)indenyl)]zirconium dichloride isopropylidenebis[1-(2-methyl-4-(4-methylphenyl)indenyl)]zirconium dichloride isopropylidenebis[1-(2-isobutyl-4-phenylindenyl)]zirconium dichloride isopropylidenebis[1-(2-methyl-4-(3-dimethylaminophenyl)indenyl)]zirconium dichloride dimethylsilanediyl[1-(2-methyl-4-phenylindenyl)]cyclopentadienylzirconium dichloride dimethylsilanediyl[1-(2-methyl-4-phenylindenyl)]-[(1-(2-methylindenyl)]zirconium dichloride dimethylsilanediyl[1-(2-methyl-4-phenylindenyl)]trimethylcyclopentadienylzirconium dichloride dimethylsilanediyl[1-(2-methyl-4-phenylindenyl)]-[tert-butylmethylcyclopentadienyl]zirconium dichloride dimethylsilanediyl[1-(2-methyl-4-phenylindenyl)]fluorenylzirconium dichloride dimethylsilanediyl[1-(2-ethyl-4-naphthylindenyl)]tetramethylcyclopentadienylzirconium dichloride dimethylsilanediyl[1-(2-methyl-4-(3,5-bistrifluoromethyl)indenyl)]cyclopentadienylzirconium dichloride dimethylsilanediyl[1-(2-methyl-4-(2-pyridyl)indenyl)]tetramethylcyclopentadienylzirconium dichloride dimethylsilanediyl[1-(2-methyl-4-(2,4-dimethoxyphenyl)indenyl)]-[1-methylboratabenzene]zirconium dichloride dimethylgermanediylbis[1-(2-methyl-4-phenylindenyl)]zirconium dichloride dimethylgermanediylbis[1-(2-methyl-4-phenylindenyl)]dimethylzirconium dimethylgermanediylbis[1-(2-methyl-4-(1-naphthyl)indenyl)]zirconium dichloride dimethylgermanediylbis[1-(2-methyl-4-(2-naphthyl)indenyl)]zirconium dichloride dimethylgermanediylbis[1-(2-ethyl-4-(3,5-bis(trifluoromethyl)phenyl)indenyl)]zirconium dichloride dimethylgermanediylbis[1-(2-butyl-4-(2-pyridyl)indenyl)]zirconium dichloride dimethylgermanediylbis[1-(2-methyl-4-(2-furyl)indenyl)]zirconium dichloride dimethylgermanediylbis[1-(2-methyl-4-(2-thiophenyl)indenyl)]zirconium dichloride dimethylgermanediylbis[1(2-isopropyl-4-(4-methoxyphenyl)indenyl)]zirconium dichloride dimethylgermanediylbis[1-(2-methyl-4-(4-methylphenyl)indenyl)]zirconium dichloride dimethylgermanediylbis[1-(2-isobutyl-4-phenylindenyl)]zirconium dichloride dimethylgermanediylbis[1-(2-methyl-4-(3-dimethylaminophenyl)indenyl)]zirconium dichloride
Further examples are the titanocenes and hafnocenes corresponding to the zirconocenes listed above.
The metallocenes which can be prepared from indanones via indenes are highly active catalyst components for olefin polymerization. Depending on the substitution pattern of the ligands, the metallocenes can be formed as a mixture of isomers. For the polymerization, the metallocenes are preferably used in isomerically pure form. The use of the racemate is sufficient in most cases.
However, it is also possible to use the pure enantiomer in the (+) or (xe2x88x92) form. An optically active polymer can be prepared using the pure enantiomers. However, the configurational isomers of the metallocenes should be separated off, since the polymerization-active center (the metal atom) in these compounds usually produces a polymer having different properties. For certain applications, for example flexible moldings, this can be quite desirable.
The present invention therefore also provides a process for preparing a polyolefin by polymerization of at least one olefin in the presence of a catalyst comprising at least one cocatalyst and at least one stereorigid metallocene compound of the formula I. For the purposes of the present invention, the term polymerization encompasses both homopolymerization and copolymerization.
In the process of the present invention, preference is given to polymerizing one or more olefins of the formula Rxcex1xe2x80x94CHxe2x95x90CHxe2x80x94Rxcex2, where Rxcex1 and Rxcex2 are identical or different and are each a hydrogen atom: or a hydrocarbon radical having from 1 to 20 carbon atoms, in particular from 1 to 10 carbon atoms, and Rxcex1 and Rxcex2 together with the atoms connecting them may form one or more rings. Examples of such olefins are 1-olefins having from 2 to 40 carbon atoms, preferably 2-10 carbon atoms, for example ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene or 1-octene, styrene, dienes such as 1,3-butadiene, isoprene, 1,4-hexadiene or cyclic olefins such as norbornene or ethylidenenorbornene. In the process of the present invention, preference is given to homopolymerizing ethylene or propylene or copolymerizing ethylene with one or more cyclic olefins such as norbornene and/or one or more acyclic 1-olefins having from 3 to 20 carbon atoms, eg. propylene, and/or one or more dienes having from 4 to 20 carbon atoms, eg. 1,3-butadiene or 1,4-hexadiene. Examples of such copolymers are ethylene-norbornene copolymers, ethylene-propylene copolymers and ethylene-propylene-1,4-hexadiene copolymers. The polymerization is preferably carried out at from xe2x88x9260 to 250xc2x0 C., particularly preferably from 50 to 200xc2x0 C. The pressure is preferably from 0.5 to 2000 bar, particularly preferably from 5 to 64 bar.
The polymerization can be carried out in solution, in bulk, in suspension or in the gas phase, continuously or batchwise, in one or more stages. Preferred embodiments are gas-phase and solution polymerization.
The catalyst used in the process of the present invention preferably comprises one metallocene compound. It is also possible to use mixtures of two or more metallocene compounds, eg. for preparing polyolefins having a broad or multimodal molar mass distribution.
In principle, suitable cocatalysts for the process of the present invention are all compounds which, owing to their Lewis acidity, can convert the neutral metallocene into a cation and stabilize the latter (xe2x80x9clabile coordinationxe2x80x9d). Furthermore, the catalyst or the anion formed therefrom should undergo no further reactions with the metallocene cation formed (EP 427 697). The cocatalyst used is preferably an aluminum compound and/or a boron compound.
The boron compound preferably has the formula RaxNH4xe2x88x92xBRb4, RaxPH4xe2x88x92BRb4, Ra3CBRb4 or BRb3, where x is from 1 to 4, preferably 3, the radicals Ra are identical or different, preferably identical, and are C1-C10-alkyl or C8-C18-aryl or two radicals Ra together with the atoms connecting them form a ring, and the radicals Rb are identical or different, preferably identical, and are C6-C18-aryl which may be substituted by alkyl, haloalkyl or fluorine. In particular, Ra is ethyl, propyl, butyl or phenyl and Rb is phenyl, pentafluorophenyl, 3,5-bistrifluoromethylphenyl, mesityl, xylyl or tolyl (EP 277 003, EP 277 004 and EP 426 638).
As cocatalyst, preference is given to using an aluminum compound such as aluminoxane and/or an aluminum alkyl.
The cocatalyst used is particularly preferably an aluminoxane, in particular of the formula C for the linear type and/or the formula D for the cyclic type,
where, in the formulae C and D, the radicals RC are identical or different and are each hydrogen or a C1-C20-hydrocarbon group such as a C1-C18-alkyl group, a C6-C18-aryl group or benzyl, and p is an integer from 2 to 50, preferably from 10 to 35.
Preferably, the radicals RC are identical and are hydrogen, methyl, isobutyl, phenyl or benzyl, particularly preferably methyl.
If the radicals RC are different, they are preferably methyl and hydrogen or alternatively methyl and isobutyl, with hydrogen or isobutyl preferably being present in a numerical proportion of from 0.01 to 40% (of the radicals RC).
The methods of preparing the aluminoxanes are known. The precise spatial structure of the aluminoxanes is not known (J. Am. Chem. Soc. (1993) 115, 4971). For example, it is conceivable that chains and rings are joined to form larger two-dimensional or three-dimensional structures.
Regardless of the method of preparation, all aluminoxane solutions have in common a variable content of unreacted aluminum starting compound which is present in free form or as adduct.
It is possible to preactivate the metallocene compound with a cocatalyst, in particular an aluminoxane, before use in the polymerization reaction. This significantly increases the polymerization activity. The preactivation of the metallocene compound is preferably carried out in solution. Here, the metallocene compound is preferably dissolved in a solution of the aluminoxane in an inert hydrocarbon. Suitable inert hydrocarbons are aliphatic or aromatic hydrocarbons. Preference is given to using toluene.
The concentration of the aluminoxane in the solution is in the range from about 1% by weight to the saturation limit, preferably from 5 to 30% by weight, in each case based on the total amount of solution. The metallocene can be used in the same concentration but it is preferably used in an amount of from 10xe2x88x924 to 1 mol per mol of aluminoxane. The preactivation time is from 5 minutes to 60 hours, preferably from 5 to 60 minutes. The preactivation is carried out at from xe2x88x9278 to 100xc2x0 C., preferably from 0 to 80xc2x0 C.
The metallocene compound is preferably employed in a concentration, based on the transition metal, of from 10xe2x88x923 to 10xe2x88x928 mol, preferably from 10xe2x88x924 to 10xe2x88x927 mol, of transition metal per dm3 of solvent or per dm3 of reactor volume. The aluminoxane is preferably used in a concentration of from 10xe2x88x926 to 10xe2x88x921 mol, preferably from 10xe2x88x925 to 10xe2x88x922 mol, per dm3 of solvent or per dm3 of reactor volume. The other cocatalysts mentioned are used in approximately equimolar amounts to the metallocene compound. However, higher concentrations are also possible in principle.
The aluminoxane can be prepared in various ways by known methods. One of the methods is, for example, reacting an aluminum-hydrocarbon compound and/or a hydridoaluminum-hydrocarbon compound with water (gaseous, solid, liquid or boundxe2x80x94for example as water of crystallization) in an inert solvent (for example toluene). To prepare an aluminoxane having different radicals RC, for example, two different aluminum trialkyls corresponding to the desired composition are reacted with water.
To remove catalyst poisons present in the olefin, a purification step using an aluminum compound, preferably an aluminum alkyl such as trimethylaluminum or triethylaluminum, is advantageous. This purification can be carried out either in the polymerization system itself or the olefin is brought into contact with the aluminum compound and subsequently separated off again before addition to the polymerization system.
As molar mass regulator and/or to increase the catalyst activity, hydrogen can be added in the process of the present invention. This makes it possible to obtain low molecular weight polyolefins such as waxes.
In the process of the present invention, the metallocene compound is preferably reacted with the cocatalyst outside the polymerization reactor in a separate step using a suitable solvent. In this step, the catalyst can be applied to a support.
In the process of the present invention, a prepolymerization can be carried out by means of the metallocene compound. The prepolymerization is preferably carried out using the (or one of the) olefin(s) used in the polymerization.
The catalyst used in the process of the present invention can be supported. The application to a support enables, for example, the particle morphology of the polyolefin prepared to be controlled.
Here, the metallocene compound can be reacted first with the support and subsequently with the cocatalyst. The cocatalyst can also be supported first and subsequently reacted with the metallocene compound. It is also possible to apply the reaction product of metallocene compound and cocatalyst to a support. Suitable support materials are, for example, silica gels, aluminum oxides, solid aluminoxane or other inorganic support materials such as magnesium chloride. Another suitable support material is a polyolefin powder in finely divided form. The supported cocatalyst can be prepared, for example, as described in EP 567 952.
Preferably, the cocatalyst, eg. aluminoxane, is applied to a support such as silica gels, aluminum oxides, solid aluminoxane, other inorganic support materials or else a polyolefin powder in finely divided form and then reacted with the metallocene.
As inorganic supports, it is possible to use oxides which have been produced flame-pyrolytically by combustion of element halides in a hydrogen/oxygen flame or can be prepared as silica gels having particular particle size distributions and particle shapes.
The preparation of the supported cocatalyst can be carried out, for example, as described in EP 578 838 in the following manner in a stainless steel reactor having an explosion-proof design with a pumped circulation system and a pressure rating of 60 bar, with inert gas supply, temperature control by means of jacket cooling and a second cooling circuit via a heat exchanger on the pumped circulation system. The pumped circulation system draws in the reactor contents via a connection in the bottom of the reactor by means of a pump and pushes it into a mixer and through a riser line via a heat exchanger back into the reactor. The mixer is configured such that in the inlet there is located a constricted tube cross section where the flow velocity is increased and into the turbulence zone of which there is introduced, axially and opposite to the flow direction, a thin feed line through which, pulsed, a defined amount of water under 40 bar of argon can be fed in. The reaction is monitored by means of a sampler on the pumped circulation system.
However, other reactors are also suitable in principle.
The above-described reactor having a volume of 16 dm3 is charged with 5 dm3 of decane under inert conditions. 0.5 dm3 (=5.2 mol) of trimethylaluminum are added at 25xc2x0 C. 250 g of silica gel SD 3216-30 (Grace AG), which have been dried beforehand at 120xc2x0 C. in an argon-fluidized bed, are then introduced into the reactor through a solids funnel and are homogeneously distributed by means of the stirrer and the pumped circulation system. A total amount of 76.5 g of water is added to the reactor in portions of 0.1 cm3 every 15 seconds over a period of 3.25 hours. The pressure, caused by the argon and the gases evolved, is kept constant at 10 bar by means of a pressure regulation valve. After all the water has been introduced, the pumped circulation system is switched off and stirring is continued for another 5 hours at: 25xc2x0 C.
The supported cocatalyst prepared in this way is used as a 10% strength suspension in n-decane. The aluminum content is 1.06 mmol of Al per cm3 of suspension. The isolated solid contains 31% by weight of aluminum and the suspension medium contains 0.1% by weight of aluminum.
Further possible ways of preparing a supported cocatalyst are described in EP 578 838.
The metallocene of the present invention is then applied to the; supported cocatalyst by stirring the dissolved metallocene with the supported cocatalyst. The solvent is removed and replaced by a hydrocarbon in which both cocatalyst and the metallocene are insoluble.
The reaction to form the supported catalyst system is carried out at from xe2x88x9220 to +120xc2x0 C., preferably from 0 to 100xc2x0 C., particularly preferably from 15 to 40xc2x0 C. The metallocene is reacted with the supported cocatalyst by combining the cocatalyst as a suspension having a concentration of from 1 to 40% by weight, preferably from 5 to 20% by weight, in an aliphatic, inert suspension medium such as n-decane, hexane, heptane or diesel oil with a solution of the metallocene in an inert solvent such as toluene, hexane, heptane or dichloromethane or with the finely milled solid metallocene. Conversely, a solution of the metallocene can also: be reacted with the solid cocatalyst.
The reaction is carried out by intensive mixing, for example by: stirring, at a molar Al/M1 ratio of from 100/1 to 10,000/1, preferably from 100/1 to 3000/1, and a reaction time of from 5 to 120 minutes, preferably from 10 to 60 minutes, particularly preferably from 10 to 30 minutes, under inert conditions. During the reaction time for preparing the supported catalyst system, particularly when using the metallocenes of the present invention having absorption maxima in the visible region, changes occur in the color of the reaction mixture and these enable the progress of the reaction to be followed.
After the reaction time has expired, the supernatant solution is separated off, for example by filtration or decantation. The remaining solid is washed from 1 to 5 times with an inert suspension medium such as toluene, n-decane, hexane, diesel oil or dichloromethane to remove soluble constituents in the catalyst formed, in particular to remove unreacted and therefore soluble metallocene.
The supported catalyst system prepared in this way can be resuspended as vacuum-dried powder or while still moist with solvent and metered into the polymerization system as a suspension in one of the abovementioned inert suspension media.
If the polymerization is carried out as a suspension or solution polymerization, an inert solvent customary for the Ziegler low-pressure process is used. For example, the polymerization is carried out in an aliphatic or cycloaliphatic hydrocarbon, for example propane, butane, hexane, heptane, isooctane, cyclohexane or methylcyclohexane. It is also possible to use a petroleum or hydrogenated diesel oil fraction. Toluene can also be used. Preference is given to carrying out the polymerization in the liquid monomer.
Before addition of the catalyst, in particular the supported catalyst system (comprising the metallocene of the present invention and a supported cocatalyst), it is possible to introduce, in addition, another aluminum alkyl compound such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum or isoprenylaluminum into the reactor to make the polymerization system inert (for example to remove catalyst poisons present in the olefin). This is added to the polymerization system in a concentration of from 100 to 0.01 mmol of Al per kg of reactor contents. Preference is given to triisobutylaluminum and triethylaluminum in a concentration of from 10 to 0.1 mmol of Al per kg of reactor contents. This makes it possible to select a small molar Al/M1 ratio in the synthesis of a supported catalyst system. If inert solvents are used, the monomers are metered in in gaseous or liquid form.
The following abbreviations are used in the present application:

Preparation of preparing substituted indanones

Abstract: comprises reacting an indanone of the formula I or Ia with a coupling component.