The invention relates to novel 2-(2-chlorophenyl)-3,4-dihydro-2H-pyrrole derivatives of the formula (I)

This application is a 371 of PCT/EP99/03063 filed May 5, 1999.
The invention relates to novel 2-(2-chlorophenyl)-3,4-dihydro-2H-pyrrole derivatives, to a plurality of processes for their preparation and to their use as pesticides.
Hitherto, only few substituted cyclic xcex1,xcex1xe2x80x2-diphenylimines are known: three 2,5-diphenyl-1-pyrrolines which are alkoxy-substituted in the 2-phenyl ring [5-(2,5-dimethoxyphenyl)-2-phenyl-3,4-dihydro-2H-pyrrole and 5-(4-methoxyphenyl)-2-phenyl-3,4-dihydro-2H-pyrrole from Chem. Ber. 96, 93 (1963) and the corresponding 4-propoxy compound from J. Prakt. Chem., Series 4, 1, 57 (1955)] and the 2,6-diphenyl-3,4,5,6-tetrahydropyridine, which is not substituted any further [cf., for example, Bull. Soc. Chim. Fr. 1974, 258 and Chem. Ber. 116, 3931 (1983)].
Nothing is known concerning their suitability for use as pesticides.
This invention, accordingly, provides novel 2-(2-chlorophenyl)-3,4-dihydro-2H-pyrrole derivatives of the formula (I)
in which
Ar represents the radical
in which
m represents 0, 1, 2, 3 or 4,
R1 represents halogen, cyano, trialkylsilyl, xe2x80x94COxe2x80x94NR4R5, tetrahydropyranyl or represents one of the following groupings
R2 represents hydrogen, halogen, cyano, nitro, alkyl, alkoxy, halogenoalkyl, halogenoalkoxy, alkoxyalkoxy or xe2x80x94S(O)oR3,
o represents 0, 1 or 2,
R3 represents alkyl or halogenoalkyl,
R4 and R5 independently of one another each represent hydrogen, alkyl, halogenoalkyl or represent phenyl or phenylalkyl, each of which is optionally mono- or polysubstituted by radicals from the list W1,
X represents a direct bond, oxygen, sulphur, carbonyl, carbonyloxy, oxycarbonyl, alkylene, alkenylene, alkinylene, alkyleneoxy, oxyalkylene, thioalkylene, alkylenedioxy or dialkylsilylene,
A represents phenyl, naphthyl or tetrahydronaphthyl, each of which is optionally mono- or poly-substituted by radicals from the list W1, or represents 5- to 10-membered heterocyclyl containing one or two aromatic rings and having one or more heteroatoms from the group consisting of nitrogen, oxygen and sulphur and being in each case optionally mono- or polysubstituted by radicals from the list W2,
B represents p-phenylene which is optionally mono- or disubstituted by radicals from the list W1,
Z represents oxygen or sulphur,
D represents hydrogen, alkyl, alkenyl, alkinyl, halogenoalkyl, halogenoalkenyl, in each case optionally halogen-, alkyl-, alkenyl-, halogenoalkenyl-, phenyl-, styryl-, halogenophenyl- or halogenostyryl-substituted cycloalkyl or cycloalkylalkyl, represents in each case optionally halogen- or alkyl-substituted cycloalkenyl or cycloalkenylalkyl, represents in each case optionally nitro-, halogen-, alkyl-, alkoxy-, halogenoalkyl- or halogenoalkoxy-substituted phenylalkyl, naphthylalkyl, tetrahydronaphthylalkyl or hetarylalkyl having 5 or 6 ring members and one or two heteroatoms from the group consisting of nitrogen, oxygen and sulphur, represents xe2x80x94COxe2x80x94R6, xe2x80x94COxe2x80x94NR7R8 or represents the grouping
xe2x80x94(CH2)pxe2x80x94(CR9R10)qxe2x80x94(CH2)rxe2x80x94G
or
Z and D together represent optionally nitro-, halogen-, alkyl-, alkoxy-, halogenoalkyl- or halogenoalkoxy-substituted phenoxyalkyl,
Y represents a direct bond, oxygen, sulphur, carbonyl, carbonyloxy, oxycarbonyl, alkylene, alkenylene, alkinylene, alkyleneoxy, oxyalkylene, thioalkylene, alkylenedioxy or represents p-phenylene which is optionally mono- or disubstituted by radicals from the list W1,
E represents hydrogen, alkyl, alkenyl, alkinyl, halogenoalkyl, halogenoalkenyl, in each case optionally halogen-, alkyl-, alkenyl-, halogenoalkenyl-, phenyl-, styryl-, halogenophenyl- or halogenostyryl-substituted cycloalkyl, represents in each case optionally halogen- or alkyl-substituted cycloalkenyl, represents phenyl which is optionally mono- to tetrasubstituted by radicals from the list W1 or represents 5- or 6-membered hetaryl having one or two heteroatoms from the group consisting of nitrogen, oxygen and sulphur and being in each case optionally mono- to tetrasubstituted by radicals from the list W2 or represents the grouping
xe2x80x94(CH2)pxe2x80x94(CR9R10)qxe2x80x94(CH2)rxe2x80x94G,
R6 represents alkyl, alkoxy, alkenyl, alkenyloxy, in each case optionally halogen-, alkyl-, alkenyl-, halogenoalkyl- or halogenoalkenyl-substituted cycloalkyl, cycloalkyloxy or cycloalkylalkyloxy or represents in each case optionally nitro-, halogen-, alkyl-, alkoxy-, halogenoalkyl- or halogenoalkoxy-substituted phenyl or naphthyl,
R7 represents hydrogen or alkyl,
R8 represents alkyl, halogenoalkyl, in each case optionally halogen-, alkyl-, alkenyl-, halogenoalkyl- or halogenoalkenyl-substituted cycloalkyl or cycloalkylalkyl or represents in each case optionally halogen-, alkyl-, alkoxy-, halogenoalkyl- or halogenoalkoxy-substituted phenyl or phenylalkyl,
p, q and r independently of one another each represent 0, 1, 2 or 3, their sum being smaller than 6,
R9 and R10 independently of one another each represent hydrogen or alkyl,
G represents cyano, represents an optionally halogen-, alkyl- or halogenoalkyl- and, at the point of linkage, optionally R11-substituted 5- or 6-membered heterocycle having 1 to 3 identical or different heteroatoms from the group consisting of nitrogen, oxygen and sulphur or one of the following groups
R11 represents hydrogen, alkyl, alkenyl, halogenoalkyl, halogenoalkenyl, optionally halogen-, alkyl- or halogenoalkyl-substituted cycloalkyl or represents phenyl which is optionally mono- to pentasubstituted by alkylcarbonylamino, alkylcarbonylalkylamino and/or radicals from the list W3,
R12 represents hydrogen, alkyl, alkenyl, halogenoalkyl, halogenoalkenyl, in each case optionally halogen-, alkyl- or halogenoalkyl-substituted cycloalkyl or cycloalkylalkyl or represents arylalkyl which is optionally mono- to penta-substituted by radicals from the list W3,
R13 and R14 independently of one another each represent hydrogen, alkyl, alkenyl, halogenoalkyl, halogenoalkenyl, alkoxy, in each case optionally halogen-, alkyl- or halogenoalkyl-substituted cycloalkyl or cycloalkylalkyl, represents aryl or arylalkyl, each of which is optionally mono- to pentasubstituted by radicals from the list W3, represent xe2x80x94OR12 or xe2x80x94NR11R12 or together represent an alkylene chain having 2 to 6 members in which optionally one methylene group is replaced by oxygen,
R15 represents xe2x80x94OR12, xe2x80x94NR11R12 or xe2x80x94N(R11)xe2x80x94COOR12,
R16, R17 and R18 independently of one another each represent alkyl,
W1 represents hydrogen, halogen, cyano, formyl, nitro, alkyl, trialkylsilyl, alkoxy, halogenoalkyl, halogenoalkoxy, halogenoalkenyloxy, alkylcarbonyl, alkoxycarbonyl, pentafluorothio or xe2x80x94S(O)oR3,
W2 represents halogen, cyano, formyl, nitro , alkyl, trialkylsilyl, alkoxy, halogenoalkyl, halogenoalkoxy, alkylcarbonyl, alkoxycarbonyl, pentafluorothio, xe2x80x94S(O)oR3 or xe2x80x94C(R11)xe2x95x90Nxe2x80x94R15,
W3 represents halogen, cyano, nitro, alkyl, alkoxy, halogenoalkyl, halogenoalkoxy, dialkylamino, xe2x80x94S(O)oR3, xe2x80x94COOR19 or xe2x80x94CONR20R21,
R19 represents hydrogen, alkyl, halogenoalkyl, optionally halogen-, alkyl- or halogenoalkyl-substituted cycloalkyl or represents phenyl which is optionally mono- to pentasubstituted by radicals from the list W4,
R20 and R21 independently of one another each represent hydrogen, alkyl, alkenyl, halogenoalkyl, halogenoalkenyl, alkoxy, in each case optionally halogen-, alkyl- or halogenoalkyl-substituted cycloalkyl or cycloalkylalkyl or represent aryl or arylalkyl, each of which is optionally mono- to pentasubstituted by radicals from the list W4, represent xe2x80x94OR16 or xe2x80x94NR17R18 or together represent an alkylene chain having 2 to 6 members in which optionally one methylene group is replaced by oxygen, and
W4 represents halogen, cyano, nitro, alkyl, alkoxy, halogenoalkyl, halogenoalkoxy, dialkylamino, alkoxycarbonyl, dialkylaminocarbonyl or xe2x80x94S(O)oR3.
Depending, inter alia, on the nature of the substituents, the compounds of the formula (I) may be present as geometric and/or optical isomers or isomer mixtures, of various compositions, which can be separated, if appropriate, in a customary manner. The present invention provides both the pure isomers and the isomer mixtures, their preparation and use and compositions comprising them. However, hereinbelow, for the sake of simplicity, compounds of the formula (I) are always referred to, although this may mean both the pure compounds and, if appropriate, also mixtures having varying proportions of isomeric compounds.
Furthermore, it has been found that the novel compounds of the formula (I) are obtained by one of the processes described below.
A) Cyclic imines of the formula (I)
in which
Ar is as defined above
can be prepared by
a) reacting aminoketone derivatives of the formula (VIII)
in which
Ar is as defined above
with an acid, followed by cyclocondensation, if appropriate in the presence of an acid binder, or
b) reducing the nitro group of nitroketones of the formula (XVIII)
in which
Ar is as defined above, where
an aminoketone intermediate of the formula (II) is formed which, however, is cyclocondensed in situ to (I), in particular in an acidic medium, or
c) hydrolysing imines of the formula (XXVII)
in which Ar is as defined above with aqueous acids
where
an aminoketone intermediate of the formula (II) is formed which, however, is cyclocondensed in situ to (I).
B) Cyclic imines of the formula (I) can also be prepared by reacting cyclic O-methylsulphonyl oximes of the formula (III)
in which
Ar is as defined above
with aryl Grignard compounds of the formula (IV)
in which
Hal represents bromine or iodine
in the presence of a diluent.
C) Cyclic imines of the formula (I-b)
in which
m is as defined above,
R1-1 represents A or one of the groupings below
where
A, B, D, E, W1 and Z are each as defined above and
R2-1 represents hydrogen, fluorine, cyano, nitro, alkyl, alkoxy, halogenoalkyl, halogenoalkoxy, alkoxyalkoxy or xe2x80x94SR3 where
R3 is as defined above
can be prepared by coupling compounds of the formula (V)
in which
R2-1 and m are each as defined above and
X1 represents bromine, iodine or xe2x80x94OSO2CF3
with boronic acids of the formula (VI)
R1-1B(OH)2xe2x80x83xe2x80x83(VI)
in which
R1-1 is as defined above
in the presence of a catalyst and in the presence of an acid binder and in the presence of a solvent.
D) Cyclic imines of the formula (I-c)
in which
R2 and m are each as defined above,
R1-2 represents one of the groupings below
xe2x80x83(m-b) xe2x80x94Bxe2x80x94Zxe2x80x94D1
(n-b) xe2x80x94Y1xe2x80x94E1
in which
B and Z are each as defined above,
Y1 represents oxygen or sulphur and
D1 and E1 represent the grouping
xe2x80x94(CH2)pxe2x80x94(CR9R10)qxe2x80x94(CH2)rxe2x80x94G
in which
R9, R10, G, p, q and r are each as defined above
can be prepared by condensing cyclic imines of the formula (I-d)
in which
R2 and m are each as defined above and
R1-3 represents one of the groupings below
in which
B, Y1 and Z are each as defined above
with compounds of the formula (VII)
Abxe2x80x94(CH2)pxe2x80x94(CR9R10)qxe2x80x94(CH2)rxe2x80x94Gxe2x80x83xe2x80x83(VII)
in which
R9, R10, G, p, q and r are each as defined above and
Ab represents a leaving group.
E) Cyclic imines of the formula (I-e)
in which
R2 and m are each as defined above and
R1-4 represents a grouping from the description of the compounds of the formula (I) according to the invention which contains the radical G, where
G represents one of the abovementioned groupings (e) to (k), can be prepared by generally customary and known derivatizations of the corresponding keto derivatives, carboxylic acid derivatives or nitrites, i.e. compounds of the formula (I) in which G represents cyano or one of the groupings (a) to (d).
F) Cyclic imines of the formula (I-f)
in which R1 is as defined above can also be prepared by reacting, in a first step,
xcex1) o-chloroacetopienone of the formula (F-I)
with dimethylmethyleneammonium chloride of the formula (F-II)
to give the compound of the formula (F-III)
and reacting this, in a second step,
xcex2) with benzyl cyanides of the formula (F-IV)
in which R1 is as defined above to give compounds of the formula (F-V)
which, in the next step,
xcex4) are derivatized with aqueous sodium hydroxide solution/H2O2 to give compounds of the formula (F-VI)
in which R1 is as defined above, and cyclizing these, in a final step,
xcex3) by reaction with PIFA (1,1-bis(trifluoroacetoxy)iodobenzene) of the formula (F-VII)
to cyclic imines of the formula (I-f).
G) Cyclic imines of the formula (I)
in which Ar is as defined above can also be prepared by reacting, in a first step,
xcex1) arylbutyrolactams of the formula (XI)
with o-chlorobenzoyl chloride
to give compounds of the formula G(I)
and reacting these, in a second step,
xcex2) with methyl o-chlorobenzoate
to give compounds of the formula G(II)
which, in a final step, are reacted
xcex4) with HBr/glacial acetic acid to give compounds of the formula (I)
Furthermore, it has been found that the novel compounds of the formula (I) exhibit very good activity as pesticides, in particular against arthropods in agriculture, but also against parasites in the keeping of useful animals and pets, combined with good compatibility with plants.
The formula (I) provides a general definition of the compounds according to the invention. Preferred substituents or ranges of the radicals listed in the formulae mentioned hereinabove and hereinbelow are illustrated below.
Ar preferably represents the radical
m preferably represents 0, 1, 2, 3.
R1 preferably represents a substituent in the meta or para position from the group consisting of hydrogen, halogen, cyano, tri-(C1-C6-alkyl)-silyl, xe2x80x94COxe2x80x94NR4R5, tetrahydropyranyl or one of the following groupings
R2 preferably represents hydrogen, halogen, cyano, nitro, C1-C16-alkyl, C1-C16-alkoxy, C1-C6-halogenoalkyl, C1-C6-halogenoalkoxy, C1-C8-alkoxy-C1-C8-alkoxy or xe2x80x94S(O)oR3.
o preferably represents 0, 1 or 2.
R3 preferably represents optionally fluorine- or chlorine-substituted C1-C6-alkyl.
R4 and R5 independently of one another each preferably represent hydrogen, C1-C6-alkyl, C1-C6-halogenoalkyl or represent phenyl or phenyl-C1-C4-alkyl, each of which is optionally mono- to trisubstituted by radicals from the list W1.
X preferably represents a direct bond, oxygen, sulphur, carbonyl, carbonyloxy, oxycarbonyl, C1-C4-alkylene, C2-C4-alkenylene, C2-C4-alkinylene, C1-C4-alkyleneoxy, C1-C4-oxyalkylene, C1-C4-thioalkylene, C1-C4-alkylenedioxy or di-C1-C4-alkylsilylene.
A preferably represents phenyl, naphthyl or tetrahydronaphthyl, each of which is optionally mono- to tetrasubstituted by radicals from the list W1, or represents 5- to 10-membered heterocyclyl containing 1 or 2 aromatic rings and having 1 to 4 heteroatoms, which contains 0 to 4 nitrogen atoms, 0 to 2 oxygen atoms and 0 to 2 sulphur atoms (in particular furyl, benzofuryl, thienyl, benzothienyl, oxazolyl, benzoxazolyl, thiazolyl, benzothiazolyl, pyrrolyl, pyridyl, pyrimidyl, 1,3,5-triazinyl, quinolinyl, isoquinolinyl, indolyl, purinyl, benzodioxolyl, indanyl, benzodioxanyl or chromanyl), and is in each case optionally mono- to tetrasubstituted by radicals from the list W2.
B preferably represents p-phenylene which is optionally mono- or disubstituted by radicals from the list W1.
Z preferably represents oxygen or sulphur.
D preferably represents hydrogen, C1-C16-alkyl, C2-C16-alkenyl, C2-C6-alkinyl, C1-C16-halogenoalkyl, C2-C16-halogenoalkenyl, in each case optionally halogen-, C1-C4-alkyl-, C2-C4-alkenyl-, C2-C4-halogenoalkenyl-, phenyl-, styryl-, halogenophenyl- or halogenostyryl-substituted C3-C8-cycloalkyl or C3-C8-cycloalkyl-C1-C6-alkyl, represents in each case optionally halogen- or C1-C4-alkyl-substituted C5-C8-cycloalkenyl or C5-C8-cycloalkenyl-C1-C4-alkyl, represents in each case optionally nitro-, halogen-, C1-C6-alkyl-, C1-C6-alkoxy-, C1-C6-halogenoalkyl- or C1-C6-halogenoalkoxy-substituted phenyl-C1-C6-alkyl, naphthyl-C1-C6-alkyl, tetrahydronaphthyl-C1-C6-alkyl or hetaryl-C1-C6-alkyl having 5 or 6 ring members and 1 or 2 heteroatoms from the group consisting of nitrogen, oxygen and sulphur (in particular furyl methyl, thienylmethyl, pyrrolylmethyl, oxazolylmethyl, isoxazolylmethyl, thiazolylmethyl or pyridylmethyl), represents xe2x80x94COxe2x80x94R6, xe2x80x94COxe2x80x94NR7R8 or represents the grouping
xe2x80x94(CH2)pxe2x80x94(CR9R10)qxe2x80x94(CH2)rxe2x80x94G.
Z and D together also preferably represent in each case optionally nitro-, halogen-, C1-C6-alkyl-, C1-C6-alkoxy-, C1-C6-halogenoalkyl- or C1-C6-halogenoalkoxy-substituted phenoxy-C1-C4-alkyl.
Y preferably represents a direct bond, oxygen, sulphur, carbonyl, carbonyloxy, oxycarbonyl, C1-C4-alkylene, C2-C4-alkenylene, C2-C4-alkinylene, C1-C4-alkyleneoxy, C1-C4-oxyalkylene, C1-C4-thioalkylene, C1-C4-alkylenedioxy or represents p-phenylene which is optionally mono- or disubstituted by radicals from the list W1.
E preferably represents hydrogen, C1-C16-alkyl, C2-C16-alkenyl, C2-C6-alkinyl, C1-C6-halogenoalkyl, C2-C16-halogenoalkenyl, optionally halogen-, C1-C4-alkyl-, C2-C4-alkenyl-, C2-C4-halogenoalkenyl-, phenyl-, styryl-, halogenophenyl- or halogenostyryl-substituted C3-C8-cycloalkyl, represents optionally halogen- or C1-C4-alkyl-substituted C5-C8-cycloalkenyl, represents phenyl which is optionally mono- to tetrasubstituted by radicals from the list W1 or represents 5- or 6-membered hetaryl having 1 or heteroatoms from the group consisting of nitrogen, oxygen and sulphur (in particular furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl or pyridyl) which is in each case optionally mono- to tetrasubstituted by radicals from the list W2 or represents the grouping
xe2x80x94(CH2)pxe2x80x94(CR9R10)qxe2x80x94(CH2)rxe2x80x94G.
R6 preferably represents C1-C12-alkyl, C1-C12-alkoxy, C2-C12-alkenyl, C2-C12-alkenyloxy, in each case optionally halogen-, C1-C4-alkyl-, C2-C4-alkenyl-, C1-C4-halogenoalkyl- or C2-C4-halogenoalkenyl-substituted C3-C8-cycloalkyl, C3-C8-cycloalkyloxy or C3-C8-cycloalkyl-C1-C6-alkyloxy or represents phenyl or naphthyl which is in each case optionally mono- to tetrasubstituted by nitro, halogen, C1-C12-alkyl, C1-C12-alkoxy, C1-C12-halogenoalkyl or C1-C12-halogenoalkoxy.
R7 preferably represents hydrogen or C1-C12-alkyl.
R8 preferably represents C1-C12-alkyl, C1-C12-halogenoalkyl, in each case optionally halogen-, C1-C4-alkyl-, C2-C4-alkenyl-, C1-C4-halogenoalkyl- or C2-C4-halogenoalkenyl-substituted C3-C8-cycloalkyl or C3-C8-cycloalkyl-C1-C6-alkyl or represents phenyl or phenyl-C1-C6-alkyl, each of which is optionally mono- to tetrasubstituted by halogen, C1-C12-alkyl, C1-C12-alkoxy, C1-C12-halogenoalkyl or C1-C12-halogenoalkoxy.
p, q and r independently of one another each preferably represent 0, 1, 2 or 3, their sum being smaller than 6.
R9 and R10 independently of one another each preferably represent hydrogen or C1-C4-alkyl.
G preferably represents cyano, represents a 5- or 6-membered heterocycle having 1 to 3 identical or different heteroatoms from the group consisting of nitrogen, oxygen and sulphur (in particular 5,6-dihydrodioxazin-2-yl, 3-pyridyl, 3-furyl, 3-thienyl, 2-thiazolyl, 5-thiazolyl, 2-dioxolanyl, 1,3-dioxan-2-yl, 2-dithiolanyl, 1,3-dithian-2-yl or 1,3-thioxan-2-yl) and being optionally mono- to trisubstituted by halogen, C1-C4-alkyl or C1-C4-halogenoalkyl and optionally, at the point of linkage, by the radical R11, or represents one of the following groupings:
R11 preferably represents hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C1-C4-halogenoalkyl, C2-C6-halogenoalkenyl, optionally halogen-, C1-C4-alkyl- or C1-C4-halogenoalkyl-substituted C3-C6-cycloalkyl or represents phenyl which is optionally mono- to pentasubstituted by C1-C4-alkylcarbonylamino, C1-C4-alkylcarbonyl-C1-C4-alkylamino and/or radicals from the list W3.
R12 preferably represents hydrogen, C1-C4-alkyl, C2-C6-alkenyl, C1-C4-halogenoalkyl, C2-C6-halogenoalkenyl, in each case optionally halogen-, C1-C4-alkyl- or C1-C4-halogenoalkyl-substituted C3-C6-cycloalkyl or C3-C6-cycloalkyl-C1-C4-alkyl or represents C6-C10-aryl-C1-C4-alkyl (in particular phenyl-C1-C4-alkyl or naphthyl-C1-C4-alkyl) which is optionally mono- to tetrasubstituted by radicals from the list W3.
R13 and R14 independently of one another each preferably represent hydrogen, C1-C4-alkyl, C3-C6-alkenyl, C1-C4-halogenoalkyl, C3-C6-halogenoalkenyl, C1-C4-alkoxy, in each case optionally halogen-, C1-C4-alkyl- or C1-C4-halogenoalkyl-substituted C3-C6-cycloalkyl or C3-C6-cycloalkyl-C1-C4-alkyl, represent phenyl or phenyl-C1-C4-alkyl, each of which is optionally mono- to pentasubstituted by radicals from the list W3, represent xe2x80x94OR12 or xe2x80x94NR11R12 or together represent an alkylene chain having 4 to 6 members in which optionally one methylene group is replaced by oxygen.
R15 preferably represents xe2x80x94OR12, xe2x80x94NR11R12 or xe2x80x94N(R11)xe2x80x94COOR12.
R16, R17 and R18 independently of one another each preferably represent C1-C6-alkyl.
W1 preferably represents hydrogen, halogen, cyano, formyl, nitro, C1-C6-alkyl, tri-C1-C4-alkylsilyl, C1-C16-alkoxy, C1-C6-halogenoalkyl, C1-C6-halogenoalkoxy, C2-C6-halogenoalkenyloxy, C1-C6-alkylcarbonyl, C1-C16-alkoxycarbonyl, pentafluorothio or xe2x80x94S(O)oR3.
W2 preferably represents halogen, cyano, formyl, nitro, C1-C6-alkyl, tri-C1-C4-alkylsilyl, C1-C16-alkoxy, C1-C6-halogenoalkyl, C1-C6-halogenoalkoxy, C1-C6-alkylcarbonyl, C1-C16-alkoxycarbonyl, pentafluorothio, xe2x80x94S(O)oR3 or xe2x80x94C(R11)xe2x95x90Nxe2x80x94R15.
W3 preferably represents halogen, cyano, nitro, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-halogenoalkyl, C1-C4-halogenoalkoxy, di-C1-C4-alkylamino, xe2x80x94S(O)oR3, xe2x80x94COOR19 or xe2x80x94CONR20R21.
R19 preferably represents hydrogen, C1-C4-alkyl, C1-C4-halogenoalkyl, optionally halogen-, C1-C4-alkyl- or C1-C4-halogenoalkyl-substituted C3-C7-cycloalkyl or represents phenyl which is optionally mono- to pentasubstituted by radicals from the list W4.
R20 and R21 independently of one another each preferably represent hydrogen, C1-C4-alkyl, C3-C6-alkenyl, C1-C4-halogenoalkyl, C3-C6-halogenoalkenyl, C1-C4-alkoxy, in each case optionally halogen-, C1-C4-alkyl- or C1-C4-halogenoalkyl-substituted C3-C6-cycloalkyl or C3-C6-cycloalkyl-C1-C4-alkyl or represent phenyl or phenyl-C1-C4-alkyl, each of which is optionally mono- to pentasubstituted by radicals from the list W4, represent xe2x80x94OR16 or xe2x80x94NR17R18 or together represent an alkylene chain having 4 to 6 members in which optionally one methylene group is replaced by oxygen.
W4 preferably represents halogen, cyano, nitro, C1-C6-alkyl, C1-C6-alkoxy, C1-C6-halogenoalkyl, C1-C6-halogenoalkoxy, di-C1-C4-alkylamino, C1-C6-alkoxycarbonyl, di-C1-C6-alkylaminocarbonyl or xe2x80x94S(O)oR3.
Ar particularly preferably represents the radical
m particularly preferably represents 0, 1 or 2.
R1 particularly preferably represents a substituent in the meta or para position from the group consisting of hydrogen, fluorine, chlorine, bromine, iodine, cyano, tri-(C1-C4-alkyl)-silyl, xe2x80x94COxe2x80x94NR4R5, tetrahydropyranyl or one of the following groupings
R2 particularly preferably represents hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, C1-C16-alkyl, C1-C16-alkoxy, in each case fluorine- or chlorine-substituted C1-C6-alkyl or C1-C6-alkoxy, represents C1-C8-alkoxy-C1-C8-alkoxy or xe2x80x94S(O)oR3.
o particularly preferably represents 0, 1 or 2.
R3 particularly preferably represents C1-C4-alkyl or in each case fluorine- or chlorine-substituted methyl or ethyl.
R4 and R5 independently of one another each particularly preferably represent hydrogen, C1-C6-alkyl, fluorine- or chlorine-substituted C1-C6-alkyl or represent phenyl or benzyl, each of which is optionally mono- or disubstituted by radicals from the list W1.
X particularly preferably represents a direct bond, oxygen, sulphur, carbonyl, carbonyloxy, oxycarbonyl, C1-C4-alkylene, C2-C4-alkenylene, C2-C4-alkinylene, C1-C4-alkylenoxy, C1-C4-oxyalkylene, C1-C4-thioalkylene, C1-C4-alkylenedioxy or di-C1-C4-alkylsilylene.
A particularly preferably represents phenyl, naphthyl or tetrahydronaphthyl, each of which is optionally mono- to trisubstituted by radicals from the list W1, or represents 5- to 10-membered heterocyclyl containing one or two aromatic rings and having 1 to 4 heteroatoms which contains 0 to 4 nitrogen atoms, 0 to 2 oxygen atoms and 0 to 2 sulphur atoms (in particular furyl, benzofuryl, thienyl, benzothienyl, oxazolyl, benzoxazolyl, thiazolyl, benzothiazolyl, pyrrolyl, pyridyl, pyrimidyl, 1,3,5-triazinyl, quinolinyl, isoquinolinyl, indolyl, purinyl, benzodioxolyl, indanyl, benzodioxanyl or chromanyl) and is in each case optionally mono- to trisubstituted by radicals from the list W2.
B particularly preferably represents p-phenylene which is optionally mono- or disubstituted by radicals from the list W1.
Z particularly preferably represents oxygen or sulphur.
D particularly preferably represents hydrogen, C1-C16-alkyl, C2-C16-alkenyl, C2-C6-alkinyl, in each case fluorine- or chlorine-substitited C1-C4-alkyl or C2-C4-alkenyl, represents C3-C6-cycloalkyl or C3-C6-cycloalkyl-C1-C4-alkyl, each of which is optionally substituted by fluorine, chlorine, bromine, C1-C4-alkyl, C2-C4-alkenyl, by fluorine- or chlorine-substituted C2-C4-alkenyl, by phenyl, styryl, in each case fluorine-, chlorine- or bromine-substituted phenyl or styryl, represents in each case optionally fluorine-, chlorine-, bromine- or C1-C4-alkyl-substituted C5-C6-cycloalkenyl or C5-C6-cycloalkenyl-C1-C4-alkyl, represents phenyl-C1-C4-alkyl, napthyl-C1-C4-alkyl, tetrahydronaphthyl-C1-C6-alkyl or hetaryl-C1-C4-alkyl having 5 or 6 ring members and one or two heteroatoms from the group consisting of nitrogen, oxygen and sulphur (in particular furylmethyl, thienylmethyl, pyrrolylmethyl, oxazolylmethyl, isoxazolylmethyl, thioazolylmethyl or pyridylmethyl), each of which is optionally substituted by nitro, fluorine, chlorine, bromine, C1-C6-alkyl, C1-C6-alkoxy, in each case fluorine- or chlorine-substituted C1-C4-alkyl or C1-C4-alkoxy, represents xe2x80x94COxe2x80x94R6, xe2x80x94COxe2x80x94NR7R8 or the grouping
xe2x80x94(CH2)pxe2x80x94(CR9R10)qxe2x80x94(CH2)rxe2x80x94G.
Z and D together also particularly preferably represent substituted phenoxy-C1-C3-alkyl which is optionally substituted by nitro, fluorine, chlorine, bromine, C1-C4-alkyl, C1-C4-alkoxy, in each case fluorine- or chlorine-substituted C1-C4-alkyl or C1-C4-alkoxy.
Y particularly preferably represents a direct bond, oxygen, sulphur, carbonyl, carbonyloxy, oxycarbonyl, C1-C4-alkylene, C2-C4-alkenylene, C2-C4-alkinylene, C1-C4-alkyleneoxy, C1-C4-oxyalkylene, C1-C4-thioalkylene, C1-C4-alkylenedioxy or represents p-phenylene which is optionally mono- or disubstituted by radicals from the list W1.
E particularly preferably represents hydrogen, C1-C16-alkyl, C2-C16-alkenyl, C2-C6-alkinyl, in each case fluorine- or chlorine-substituted C1-C4-alkyl or C2-C4-alkenyl, represents C3-C6-cycloalkyl which is optionally substituted by fluorine, chlorine, bromine, C1-C4-alkyl, C2-C4-alkenyl, by fluorine- or chlorine-substituted C2-C4-alkenyl, by phenyl, styryl or in each case fluorine-, chlorine- or bromine-substituted phenyl or styryl, represents optionally fluorine-, chlorine-, bromine- or C1-C4-alkyl-substituted C5-C6-cycloalkenyl, represents phenyl which is optionally mono- to trisubstituted by radicals from the list W1 or represents 5- or 6-membered hetaryl having 1 or 2 heteroatoms from the group consisting of nitrogen, oxygen and sulphur (in particular furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl or pyridyl), each of which is optionally mono- or disubstituted by radicals from the list W2, or represents the grouping
xe2x80x94(CH2)pxe2x80x94(CR9R10)qxe2x80x94(CH2)rxe2x80x94G.
R6 particularly preferably represents C1-C6-alkyl, C1-C6-alkoxy, C2-C6-alkenyl, C2-C6-alkenyloxy, represents C3-C6-cycloalkyl, C3-C6-cycloalkyloxy or C3-C6-cycloalkyl-C1-C2-alkyloxy, each of which is optionally substituted by fluorine, chlorine, C1-C3-alkyl or in each case fluorine- or chlorine-substituted C1-C2-alkyl or C2-C3-alkenyl, or represents phenyl which is optionally mono- or disubstituted by fluorine, chlorine, bromine, iodine, C1-C4-alkyl, C1-C4-alkoxy or by in each case fluorine- or chlorine-substituted C1-C3-alkyl or C1-C4-alkoxy.
R7 particularly preferably represents hydrogen or C1-C4-alkyl.
R8 particularly preferably represents C1-C4-alkyl or represents phenyl or benzyl, each of which is optionally mono- or disubstituted by fluorine, chlorine, bromine, C1-C4-alkyl or by in each case fluorine- or chlorine-substituted C1-C4-alkyl or C1-C4-alkoxy.
p, q and r independently of one another each particularly preferably represent 0, 1, 2 or 3, their sum being smaller than 6.
R9 and R10 independently of one another each particularly preferably represent hydrogen or C1-C4-alkyl.
G particularly preferably represents cyano, represents a 5- or 6-membered heterocycle having 1 to 3 identical or different heteroatoms from the group consisting of nitrogen, oxygen and sulphur (in particular 5,6-dihydrodioxazin-2-yl, 3-pyridyl, 3-furyl, 3-thienyl, 2-thiazolyl, 5-thiazolyl, 2-dioxolanyl, 1,3-dioxan-2-yl, 2-dithiolanyl, 1,3-dithian-2-yl or 1,3-thioxan-2-yl) and being optionally mono- to trisubstituted by fluorine, chlorine, bromine, C1-C4-alkyl or by fluorine- or chlorine-substituted C1-C4-alkyl and optionally, at the point of linkage, by the radical R11, or represents one of the following groupings:
R11 particularly preferably represents hydrogen, C1-C6-alkyl, C2-C6-alkenyl, in each case fluorine- or chlorine-substituted C1-C4-alkyl or C2-C6-alkenyl, represents C3-C6-cycloalkyl which is optionally substituted by fluorine, chlorine, C1-C4-alkyl or by fluorine- or chlorine-substituted C1-C4-alkyl, or represents phenyl which is optionally mono- to trisubstituted by C1-C4-alkylcarbonylamino, C1-C4-alkylcarbonyl-C1-C4-alkylamino and/or radicals from the list W3.
R12 particularly preferably represents hydrogen, C1-C4-alkyl, C3-C6-alkenyl, in each case fluorine- or chlorine-substituted C1-C4-alkyl or C3-C6-alkenyl, represents C3-C6-cycloalkyl or C3-C6-cycloalkyl-C1-C4-alkyl, each of which is optionally substituted by fluorine, chlorine, C1-C4-alkyl or by fluorine- or chlorine-substituted C1-C4-alkyl, or represents phenyl-C1-C4-alkyl or naphthyl-C1-C4-alkyl, each of which is optionally mono- to trisubstituted by radicals from the list W3.
R13 and R14 independently of one another each particularly preferably represent hydrogen, C1-C4-alkyl, C3-C6-alkenyl, in each case fluorine- or chlorine-substituted C1-C4-alkyl or C3-C6-alkenyl, represent C1-C4-alkoxy, represent C3-C6-cycloalkyl or C3-C6-cycloalkyl-C1-C4-alkyl, each of which is optionally substituted by fluorine, chlorine, C1-C4-alkyl or by fluorine- or chlorine-substituted C1-C4-alkyl, represent phenyl or phenyl-C1-C4-alkyl, each of which is optionally mono- to trisubstituted by radicals from the list W3, represent xe2x80x94OR12 or -NR11R12 or together represent xe2x80x94(CH2)5xe2x80x94, xe2x80x94(CH2)6xe2x80x94 or xe2x80x94(CH2)2xe2x80x94Oxe2x80x94(CH2)2xe2x80x94.
R15 particularly preferably represents xe2x80x94OR12, xe2x80x94NR11R12 or xe2x80x94N(R11)xe2x80x94COOR12.
R16, R17 and R18 independently of one another each particularly preferably represent C1-C4-alkyl.
W1 particularly preferably represents hydrogen, fluorine, chlorine, bromine, iodine, cyano, formyl, nitro, C1-C4-alkyl, C1-C4-alkoxy, in each case fluorine- or chlorine-substituted C1-C4-alkyl or C1-C4-alkoxy, represents C1-C4-alkylcarbonyl, C1-C4-alkoxycarbonyl or xe2x80x94S(O)oR3.
W2 particularly preferably represents fluorine, chlorine, bromine, cyano, formyl, nitro, C1-C4-alkyl, C1-C4-alkoxy, in each case fluorine- or chlorine-substituted C1-C4-alkyl or C1-C4-alkoxy, represents C1-C4-alkylcarbonyl, C1-C4-alkoxycarbonyl, xe2x80x94S(O)oR3 or xe2x80x94C(R11)xe2x95x90Nxe2x80x94R15.
W3 particularly preferably represents fluorine, chlorine, bromine, cyano, nitro, C1-C4-alkyl, C1-C4-alkoxy, in each case fluorine- or chlorine-substituted C1-C4-alkyl or C1-C4-alkoxy, represents di-C1-C4-alkylamino, xe2x80x94S(O)oR3, xe2x80x94COOR19 or xe2x80x94CONR20R21.
R19 particularly preferably represents hydrogen, C1-C4-alkyl, fluorine- or chlorine-substituted C1-C4-alkyl, represents C3-C6-cycloalkyl which is optionally substituted by fluorine, chlorine, C1-C4-alkyl or by fluorine- or chlorine-substituted C1-C4-alkyl, or represents phenyl, which is optionally mono- to trisubstituted by radicals from the list W4.
R20 and R21 independently of one another each particularly preferably represent hydrogen, C1-C4-alkyl, C3-C6-alkenyl, in each case fluorine- or chlorine-substituted C1-C4-alkyl or C3-C6-alkenyl, represent C1-C4-alkoxy, represent C3-C6-cycloalkyl or C3-C6-cycloalkyl-C1-C4-alkyl, each of which is optionally substituted by fluorine, chlorine, C1-C4-alkyl or by fluorine- or chlorine-substituted-C1-C4-alkyl, or represent phenyl or phenyl-C1-C4-alkyl, each of which is optionally mono- to trisubstituted by radicals from the list W4, represent xe2x80x94OR16 or xe2x80x94NR17R18 or together represent xe2x80x94(CH2)5xe2x80x94, xe2x80x94(CH2)6xe2x80x94 or xe2x80x94(CH2)2xe2x80x94Oxe2x80x94(CH2)2xe2x80x94.
W4 particularly preferably represents fluorine, chlorine, bromine, cyano, nitro, C1-C4-alkyl, C1-C4-alkoxy, in each case fluorine- or chlorine-substituted C1-C4-alkyl or C1-C4-alkoxy, di-C1-C4-alkylamino, C1-C4-alkoxycarbonyl, di-C1-C6-alkylaminocarbonyl or xe2x80x94S(O)oR3.
Ar very particularly preferably represents the radical
R1 very particularly preferably represents a substituent in the meta or para position from the group consisting of hydrogen, fluorine, chlorine, bromine, iodine, cyano, xe2x80x94COxe2x80x94NR4R5, tetrahydropyranyl or one of the groupings below
R2 very particularly preferably represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, methylthio, ethylthio, trifluoromethyl, difluoromethoxy, trifluoromethoxy or trifluormethylthio.
o very particularly preferably represents 0 or 2.
R3 very particularly preferably represents methyl, ethyl, n-propyl, isopropyl, difluoromethyl or trifluoromethyl.
R4 and R5 independently of one another each very particularly preferably represent hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl or represent phenyl or benzyl, each of which is optionally monosubstituted by a radical from the list W1.
X very particularly preferably represents a direct bond, oxygen, sulphur, carbonyl, xe2x80x94CH2xe2x80x94, xe2x80x94(CH2)2xe2x80x94, xe2x80x94CHxe2x95x90CHxe2x80x94 (E or Z), xe2x80x94Cxe2x89xa1Cxe2x80x94, xe2x80x94CH2Oxe2x80x94, xe2x80x94(CH2)2Oxe2x80x94, xe2x80x94CH(CH3)Oxe2x80x94, xe2x80x94OCH2xe2x80x94, xe2x80x94O(CH2)2xe2x80x94, xe2x80x94SCH2xe2x80x94, xe2x80x94S(CH2)2xe2x80x94, xe2x80x94SCH(CH3)xe2x80x94, C1-C4-alkylenedioxy, in particular xe2x80x94OCH2Oxe2x80x94, xe2x80x94O(CH2)2Oxe2x80x94 or xe2x80x94OCH(CH3)Oxe2x80x94.
A very particularly preferably represents phenyl which is optionally mono- or disubstituted by radicals from the list W1 or represents furyl, benzofuryl, thienyl, benzothienyl, oxazolyl, benzoxazolyl, thiazolyl, benzothiazolyl, pyrrolyl, pyridyl, pyrimidyl, 1,3,5-triazinyl, quinolinyl, isoquinolinyl, indolyl, purinyl, benzodioxolyl, indanyl, benzodioxanyl or chromanyl, each of which is optionally mono- or disubstituted by radicals from the list W2.
Z very particularly preferably represents oxygen or sulphur.
D very particularly preferably represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, the isomeric pentyls, the isomeric hexyls, n-heptyl, n-octyl, n-isooctyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, 2-propenyl, butenyl, pentenyl, hexenyl, propargyl, butinyl, pentinyl, xe2x80x94CF3, xe2x80x94CHF2, xe2x80x94CClF2, xe2x80x94CF2CHFCl, xe2x80x94CF2CH2F, xe2x80x94CF2CHF2, xe2x80x94CF2CCl3, xe2x80x94CH2CF3, xe2x80x94CF2CHFCF3, xe2x80x94CH2CF2CHF2, xe2x80x94CH2CF2CF3, represents cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, each of which is optionally mono- to trisubstituted by fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, ethenyl, 1-propenyl, 2,2-dimethylethenyl, xe2x80x94CHxe2x95x90CCl2, phenyl, styryl, in each case fluorine-, chlorine- or bromine-substituted phenyl or 4-chlorostyryl, represents cyclopentenyl, cyclohexenyl, cyclohexenylmethyl or cyclopentenylmethyl, each of which is optionally substituted by fluorine, chlorine, methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl or tert-butyl, represents benzyl, phenethyl, naphthylmethyl, tetrahydronaphthylmethyl, furylmethyl, thienylmethyl, pyrrolylmethyl, oxazolylmethyl, isoxazolylmethyl, thiazolylmethyl or pyridylmethyl, each of which is optionally mono- or disubstituted by nitro, fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, trifluoromethyl, trifluoromethoxy, difluoromethoxy or chlorodifluoromethoxy, represents xe2x80x94COxe2x80x94R6, xe2x80x94COxe2x80x94NR7R8 or the grouping
xe2x80x94(CH2)pxe2x80x94(CR9R10)qxe2x80x94(CH2)rxe2x80x94G.
Z and D together also very particularly preferably represent phenoxymethyl which is optionally mono- or disubstituted by nitro, fluorine, chlorine, bromine, methyl, ethyl, n-propyl, i-propyl, methoxy, ethoxy, n-propoxy, i-propoxy, trifluoromethyl, trifluoromethoxy, difluoromethoxy or chlorodifluoromethoxy.
Y very particularly preferably represents a direct bond, oxygen, sulphur, carbonyl, xe2x80x94CH2xe2x80x94, xe2x80x94(CH2)2xe2x80x94, xe2x80x94CHxe2x95x90CHxe2x80x94 (E or Z), xe2x80x94C/Cxe2x80x94, xe2x80x94CH2Oxe2x80x94, xe2x80x94(CH2)2Oxe2x80x94, xe2x80x94CH(CH3)Oxe2x80x94, xe2x80x94OCH2xe2x80x94, xe2x80x94O(CH2)2xe2x80x94, xe2x80x94SCH2xe2x80x94, xe2x80x94S(CH2)2xe2x80x94, xe2x80x94SCH(CH3)xe2x80x94, C1-C4-alkylenedioxy, in particular xe2x80x94OCH2Oxe2x80x94 or xe2x80x94O(CH2)2Oxe2x80x94 or represents p-phenylene which is optionally monosubstituted by a radical from the list W1.
E very particularly preferably represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, the isomeric pentyls, the isomeric hexyls, n-heptyl, n-octyl, n-isooctyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, 2-propenyl, butenyl, pentenyl, hexenyl, propargyl, butinyl, pentinyl, xe2x80x94CF3, xe2x80x94CHF2, xe2x80x94CClF2, xe2x80x94CF2CHFCl, xe2x80x94CF2CH2F, xe2x80x94CF2CHF2, xe2x80x94CF2CCl3, xe2x80x94CH2CF3, xe2x80x94CF2CHFCF3, xe2x80x94CH2CF2CHF2, xe2x80x94CH2CF2CF3, represents cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, each of which is optionally mono- to trisubstituted by fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, ethenyl, 1-propenyl, 2,2-dimethylethenyl, xe2x80x94CHxe2x95x90CCl2, phenyl, styryl, in each case fluorine-, chlorine- or bromine-substituted phenyl or by 4-chlorostyryl, represents cyclopentenyl or cyclohexenyl, each of which is optionally substituted by fluorine, chlorine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl, represents phenyl which is optionally mono- or disubstituted by radicals from the list W1, represents furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl or pyridyl, each of which is optionally mono- or disubstituted by radicals from the list W2, or represents the grouping
xe2x80x94(CH2)pxe2x80x94(CR9R10)qxe2x80x94(CH2)rxe2x80x94G.
R6 very particularly preferably represents methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, cyclopropyl, cyclohexyl, cyclohexyloxy, cyclohexylmethyloxy, phenyl, 2-chlorophenyl, 3-chlorophenyl, 2,6-difluorophenyl, 2,4-dichlorophenyl, 3,4-dichlorophenyl, 2-trifluoromethoxyphenyl or 4-trifluoromethoxyphenyl.
R7 very particularly preferably represents hydrogen.
R8 very particularly preferably represents methyl, ethyl or phenyl which is optionally monosubstituted by chlorine.
p, q and r independently of one another each very particularly preferably represent 0, 1, 2 or 3, their sum being smaller than 4.
R9 and R10 independently of one another each very particularly preferably represent hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl.
G very particularly preferably represents cyano, represents 5,6-dihydrodioxazin-2-yl, 3-pyridyl, 3-furyl, 3-thienyl, 2-thiazolyl, 5-thiazolyl, 2-dioxolanyl, 1,3-dioxan-2-yl, 2-dithiolanyl, 1,3-dithian-2-yl or 1,3-thioxan-2-yl, each of which is optionally mono- to trisubstituted by fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl or trifluoromethyl and optionally, at the point of linkage, by the radical R11, or represents one of the groupings below:
R11 very particularly preferably represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, the isomeric pentyls, the isomeric hexyls, xe2x80x94CF3, xe2x80x94CHF2, xe2x80x94CClF2, xe2x80x94CF2CHFCl, xe2x80x94CF2CH2F, xe2x80x94CF2CHF2, xe2x80x94CF2CCl3, xe2x80x94CH2CF3, C3-C6-alkenyl, C3-C6-alkenyl which is mono- to trisubstituted by fluorine or chlorine, represents cyclopropyl, cyclopentyl or cyclohexyl, each of which is optionally mono- or disubstituted by fluorine, chlorine, methyl, ethyl, n-propyl, isopropyl, xe2x80x94CF3, xe2x80x94CHF2, xe2x80x94CClF2, xe2x80x94CF2CHFCl, xe2x80x94CF2CH2F, xe2x80x94CF2CHF2, xe2x80x94CF2CCl3 or xe2x80x94CH2CF3, or represents phenyl which is optionally mono- or disubstituted by methylcarbonylamino, ethylcarbonylamino, methylcarbonyl-methylamino and/or radicals from the list W3.
R12 very particularly preferably represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, xe2x80x94CH2CF3, allyl, represents cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropylethyl, cyclopentylethyl or cyclohexylethyl, each of which is optionally mono- or disubstituted by fluorine, chlorine, methyl, ethyl, n-propyl, isopropyl, xe2x80x94CF3, xe2x80x94CHF2, xe2x80x94CClF2, xe2x80x94CF2CHFCl, xe2x80x94CF2CH2F, xe2x80x94CF2CHF2, xe2x80x94CF2CCl3 or xe2x80x94CH2CF3, or represents benzyl or phenethyl, each of which is optionally mono- or disubstituted by radicals from the list W3.
R13 and R14 independently of one another each very particularly preferably represent hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, xe2x80x94CH2CF3, methoxy, ethoxy, allyl, represent cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclopentylmethyl or cyclohexylmethyl, each of which is optionally mono- or disubstituted by fluorine, chlorine, methyl, ethyl, n-propyl, isopropyl or trifluoromethyl, represent phenyl, benzyl or phenethyl, each of which is optionally mono- or disubstituted by radicals from the list W3, represent xe2x80x94OR12 or xe2x80x94NR11R12.
R15 very particularly preferably represents xe2x80x94OR12, xe2x80x94NR11R12 or xe2x80x94N(R11)xe2x80x94COOR12.
R16, R17 and R18 independently of one another each very particularly preferably represent methyl, ethyl, n-propyl or isopropyl.
W1 very particularly preferably represents hydrogen, fluorine, chlorine, bromine, cyano, formyl, nitro, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, xe2x80x94CF3, xe2x80x94CHF2, xe2x80x94CClF2, xe2x80x94CF2CHFCl, xe2x80x94CF2CH2F, xe2x80x94CF2CHF2, xe2x80x94CF2CCl3, xe2x80x94CH2CF3, xe2x80x94CF2CHFCF3, xe2x80x94CH2CF2CHF2, xe2x80x94CH2CF2CF3, trifluoromethoxy, difluoromethoxy, chlorodifluoromethoxy, acetyl, propionyl, butyryl, isobutyryl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl or xe2x80x94S(O)oR3.
W2 very particularly preferably represents fluorine, chlorine, bromine, cyano, methyl, ethyl, n-propyl, isopropyl, trifluoromethyl, trifluoromethoxy, difluoromethoxy, chlorodifluoromethoxy, acetyl, trifluoromethylthio, xe2x80x94CHxe2x95x90Nxe2x80x94OCH3, xe2x80x94CHxe2x95x90Nxe2x80x94OC2H5, xe2x80x94CHxe2x95x90Nxe2x80x94OC3H7, xe2x80x94C(CH3)xe2x95x90Nxe2x80x94OCH3, xe2x80x94C(CH3)xe2x95x90Nxe2x80x94OC2H5, xe2x80x94C(CH3)xe2x95x90Nxe2x80x94OC3H7, xe2x80x94C(C2H5)xe2x95x90Nxe2x80x94OCH3, xe2x80x94C(C2H5)xe2x95x90Nxe2x80x94OC2H5 or xe2x80x94C(C2H5)xe2x95x90Nxe2x80x94OC3H7.
W3 very particularly preferably represents fluorine, chlorine, cyano, nitro, methyl, ethyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, dimethylamino, diethylamino, xe2x80x94COOR19 or xe2x80x94CONR20R21.
R19 very particularly preferably represents hydrogen, methyl, ethyl, n-propyl, isopropyl, tert-butyl, xe2x80x94CH2CF3, represents cyclopropyl, cyclopentyl or cyclohexyl, each of which is optionally mono- or disubstituted by fluorine, chlorine, methyl, ethyl, n-propyl, isopropyl or xe2x80x94CF3, or represents phenyl which is optionally mono- or disubstituted by radicals from the list W4.
R20 and R21 independently of one another each very particularly preferably represent hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, xe2x80x94CH2CF3, methoxy, ethoxy, allyl, represent cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclopentylmethyl or cyclohexylmethyl, each of which is optionally mono- or disubstituted by fluorine or chlorine, represent phenyl, benzyl or phenethyl, each of which is optionally mono- or disubstituted by the radicals from the list W4, represent xe2x80x94OR16 or xe2x80x94NR17R18.
W4 very particularly preferably represents fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, tert-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy or trifluoromethylthio.
Preference is furthermore given to compounds of the formula (I-a)
in which
R2 has the general, preferred, particularly preferred or very particularly preferred meanings mentioned above,
R1 represents hydrogen or phenyl which is mono- or disubstituted by radicals from the list W1 or represents one of the groupings below
B represents p-phenylene which is optionally monosubstituted by a radical from the list W1,
Y represents a direct bond or represents p-phenylene which is optionally mono- or disubstituted by radicals from the list W1 and
D and E each have the very particularly preferred meanings mentioned above, where
G represents cyano or one of the groupings below
xe2x80x83in which
R11 and R15 each have the general, preferred, particularly preferred or very particularly preferred meanings mentioned above and
W1 has the general, preferred, particularly preferred or very particularly preferred meaning mentioned above.
Preference is furthermore given to compounds of the formula (I-f)
in which
R1 represents hydrogen or
a) phenyl which is mono- or disubstituted by radicals from the list W2 or
b) hetaryl (in particular furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl,
xe2x80x83thiazolyl or pyridyl, specifically thienyl) which is mono- or disubstituted by radicals from the list W2.
Preference is furthermore given to compounds of the formula (I-g)
in which
Z represents hydrogen, fluorine, bromine, cyano, methyl, ethyl, n-propyl, isopropyl, trifluoromethyl, trifluoromethoxy, difluoromethoxy, chlorodifluoromethoxy, acetyl, trifluoromethylthio, xe2x80x94CHxe2x95x90Nxe2x80x94OCH3, xe2x80x94CHxe2x95x90Nxe2x80x94OC2H5, xe2x80x94CHxe2x95x90Nxe2x80x94OC3H7, xe2x80x94C(CH3)xe2x95x90Nxe2x80x94OCH3, xe2x80x94C(CH3)xe2x95x90Nxe2x80x94OC2H5, xe2x80x94C(CH3)xe2x95x90Nxe2x80x94OCt3H7, xe2x80x94C(C2H5)xe2x95x90Nxe2x80x94OC2H5 or xe2x80x94C(C2H5)xe2x95x90Nxe2x80x94OC3H7.
Preference is furthermore given to the compounds of the formula (I-f) listed in
The abovementioned general or preferred radical definitions or illustrations can be combined with one another at will, i.e. including combinations between the respective ranges and preferred ranges. They apply both to the end products and also, correspondingly, to the precursors and intermediates.
Preference according to the invention is given to the compounds of the formula (I) which contain a combination of the meanings listed above as being preferred (preferable).
Particular preference according to the invention is given to the compounds of the formula (I) which contain a combination of the meanings listed above as being particularly preferred.
Very particular preference according to the invention is given to the compounds of the formula (I) which contain a combination of the meanings listed above as being very particularly preferred.
Saturated or unsaturated hydrocarbon radicals such as alkyl or alkenyl can in each case be straight-chain or branched as far as this is possible, even in combination with heteroatoms, such as, for example, in alkoxy.
Optionally substituted radicals can be mono- or polysubstituted and, in the case of polysubstitution, the substituents can be identical or different. A plurality of radicals having the same indices, such as, for example, m radicals R2 for m greater than 1, can be identical or different.
Using, for example, tBOC-[1-(4-ethyl-2-methyl-phenyl)-3-(2-chlorophenyl-carboxyl)-1-propyl]-amine as starting material, the course of the reaction of the process (A) a) according to the invention can be represented by the following equation:
Using, for example, 1-(4-ethyl-2-methyl-phenyl)-1-nitro-3-(2-chlorophenylcarboxyl)-propane as starting material, the course of the reaction of the process (A) b) according to the invention can be represented by the following equation:
Using, for example, 1-(4-ethyl-2-methyl-phenyl)-1-(diphenylmethyleneimino)-3-(2-chlorophenylcarboxyl)-propane as starting material, the course of the reaction of the process (A) c) according to the invention can be represented by the following equation:
Using, for example, 2-(4-methoxyphenyl)-cyclobutane-O-methanesulfonyloxime and 2-chlorophenylmagnesium bromide as starting materials, the course of the reaction of the process (B) according to the invention can be represented by the following equation:
Using, for example, 2-(2-chlorophenyl)-5-(4-iodophenyl)-3 ,4-dihydro-2H-pyrrole and 4-cyanomethoxyphenyl boronic acid as starting materials, the course of the reaction of the process (C) according to the invention can be represented by the following equation:
Using, for example, 2-(2-chloro-phenyl)-5-(3xe2x80x2-chloro-4xe2x80x2-hydroxybiphenyl-4-yl)-3,4-dihydro-2H-pyrrole and methyl xcex1-bromovalerate as starting materials, the course of the reaction of the process (D) according to the invention can be represented by the following equation:
Using, for example, 5-(4xe2x80x2-cyclopropylcarbonylmethoxy-3-trifluoromethoxy-biphenyl-4-yl)-2-(2-chlorophenyl)-3,4-dihydro-2H-pyrrole and O-methylhydroxylamine as starting materials, the course of the reaction of the process (E) according to the invention can be represented by the following equation:
Using, for example, 4-bromobenzylcyanide, the course of the reaction of the process (F) according to the invention can be represented by the following equation:
Using, for example, 5-phenylpyrrolidin-2-one, the course of the process (G) according to the invention can be represented by the following equation:
The formula (VIII) provides a general definition of the aminoketone derivatives required for carrying out the process (A) a) according to the invention. In this formula, Ar preferably has those meanings which have already been mentioned in connection with the description of the cyclic imines of the formula (I) as being preferred. The aminoketone derivatives of the formula (VIII) are novel.
Aminoketone derivatives of the formula (VIII) can be prepared, for example, by reacting BOC-protected lactams of the formula (IX) with metal lated aromatics of the formula (X) at temperatures between 0xc2x0 C. and 80xc2x0 C., in accordance with the following equation:
In the formula (X), Met represents a monovalent metal radical such as Li, MgI, MgBr or MgCl.
Some metallated aromatics of the formula (X) are known, or they can be prepared by known methods, such as, for example, lithiation or Grignard reaction, from the corresponding aromatics or halogeno aromatics.
Protected lactams of the formula (IX) are obtained, for example, by BOC-protecting lactams of the formula (XI) using customary methods, such as, for example, metallation with butyl lithium and reaction with di-tert-butyl dicarbonate (cf., for example, T. W. Greene, P. G. M. Wuts, Protective Groups in Organic Synthesis, 2nd Ed., John Wiley and Sons, New York 1991).
Lactams of the formula (XI) can be prepared starting, for example, with xcfx89-alkoxylactams of the formula (XII), by two methods. The xcfx89-alkoxylactams can be reacted with aromatics of the formula (XIII) in the presence of an acidic catalyst, such as, for example, sulphuric acid, acetic acid or aluminium chloride and, if appropriate, in the presence of a diluent, such as, for example, dichloromethane or acetonitrile, in accordance with the following equation:
Alternatively, they can be reacted with aryl Grignard compounds of the formula (XIV) in the presence of a diluent, such as, for example, tetrahydrofuran, in accordance with the following equation [cf. Org. Prep. Proced. Int. 25, 255 (1993)]:
In formula (XII), R22 represents methyl or ethyl. In the formula (XIV), Hal represents chlorine, bromine or iodine.
The xcfx89-alkoxylactams of the formula (XII) are known, some of them are commercially available, and they can be prepared, for example, from the corresponding unsubstituted imides by cathodic or sodium borohydrite reduction, or from the unsubstituted lactams by anodic oxidation, in each case in the presence of methanol or ethanol (cf., for example, J. Org. Chem. 56, 1822 (1991); Synthesis 1980, 315).
The aromatics of the formula (XIII) are benzene derivatives which are generally known or which can be prepared using a wide choice of generally known methods of organic chemistry.
The aryl Grignard compounds of the formula (XIV) can be prepared in a customary manner from the corresponding aryl halides and magnesium. Aryl halides are generally known compounds of organic chemistry.
Lactams of the formula (XI) can also be prepared, for example, by cyclizing substituted xcfx89-benzoylcarboxylic acids of the formula (XV) with a reagent prepared from ammonium carbonate and formic acid at boiling point, in accordance with the following reaction scheme [cf. Recl. Trav. Chim. Pays-Bas 81, 788 (1962)]:
The xcfx89-benzoylcarboxylic acids of the formula (XV) required for this purpose can be prepared, for example, by reacting the dicarboxylic anhydrides of the formula (XVI) with aromatics of the formula (XIII) in the presence of a Lewis acid, such as, for example, aluminium chloride, and, if appropriate, in the presence of a diluent, such as, for example, benzene, in accordance with the following equation [cf. Recl. Trav. Chim. Pays-Bas 81, 788 (1962)]:
The anhydride (succinic anhydride) required for this purpose is commercially available.
Starting from the lactams of the formula (XI), all process steps up to the preparation of the cyclic imines of the formula (I), including the cyclocondensation according to process A a), can also be carried out as a xe2x80x9cone-pot reactionxe2x80x9d.
If Ar in the active compound of the formula (I) according to the invention as in the formula (I-b) shown above represents an optionally substituted biphenylyl, the corresponding biphenyl lactams of the formula (XI-a) can be prepared in an advantageous variant of the process described here by reacting, similarly to the process (C) described above and below, certain phenyl lactams of the formula (XVII) with boronic acids of the formula (VI) in accordance with the following equation:
The phenyl lactams of the formula (XVII) in which X1 represents bromine or iodine are a subset of the compounds of the formula (XI) whose preparation is mentioned above. The phenyl lactams of the formula (XVII) in which X1 represents trifluoromethanesulphonyl can be prepared analogously to the route described for process (C) from the corresponding compounds of the formula (XI) in which Ar is substituted by R1=hydroxyl.
The formula (XVIII) provides a general definition of the nitroketones required for carrying out the process A) b). In this formula, Ar preferably has those meanings which have already been mentioned in connection with the description of the cyclic imines of the formula (I) as being preferred. The nitroketones of the formula (XVIII) are novel.
Nitroketones of the formula (XVIII) can be prepared, for example, by condensing the xcfx89-chloroalkyl phenyl ketone of the formula (XXI) in the presence of a diluent, such as, for example, methanol, ethanol, another lower aliphatic alcohol or else tetrahydrofuran, and in the presence of an acid binder, such as, for example, sodium hydride or an alkali metal alkoxide, preferably of the corresponding alcohol which is used as diluent, in accordance with the following equation:
The xcfx89-chloroalkyl phenyl ketone of the formula (XXI) can be prepared in a known manner, such as, for example, by Friedel-Crafts acylation of chlorobenzene of the formula (XXII) (see below) with 3-chloropropionyl chloride.
The nitromethyl benzenes of the formula (XIX) are known or can be prepared in a known manner, such as, for example, by side-chain nitration of corresponding toluenes, or by reacting corresponding benzyl halides with silver nitrite [cf., for example, J. Am. Chem. Soc. 77, 6269 (1955); J. Am. Chem. Soc 86, 2681 (1964); Houben-Weyl, Methoden der Organischen Chemie, Georg Thieme Verlag Stuttgart, volume 10/1, 46-57 (halogen substitution), volume E16, 145-154 (both methods)]. The toluenes or benzyl halides required for this purpose are generally known compounds of organic chemistry.
The nitroketones of the formula (XVIII) can be prepared, for example, by Michael additions of nitromethylbenzenes of the formula (XIX) to phenyl vinyl ketone of the formula (XX) in the presence of a diluent, such as, for example, methanol, ethanol or another lower aliphatic alcohol, and in the presence of an acid binder, such as, for example, preferably an alkali metal alkoxide of the corresponding alcohol which is used as diluent, in accordance with the following equation (cf., for example, J. Prakt. Chem., Series 4, 1, 57 (1955); Houben-Weyl, Methoden der Organischen Chemie, Georg Thieme Verlag Stuttgart, volume 10/1, 199-206):
The phenyl vinyl ketone of the formula (XX) can be prepared, for example, by eliminating hydrogen chloride from xcex2-chloropropiophenone of the formula (XXI), which can be obtained, for example, by Friedel-Crafts acylation of chlorobenzene of the formula (XXII) with 3-chloropropionyl chloride, said elimination being carried out in the presence of an acid binder, such as, for example, potassium acetate, and in the presence of a diluent, such as, for example, methanol, in accordance with the following equation [cf., for example, J. Prakt. Chem., Series 4, 1, 57 (1955)]:
Chlorobenzenes of the formula (XXII) are commercially available.
The phenyl vinyl ketone of the formula (XX) can also be prepared by reacting O-methyl methyl-2-chloro-benzohydroxamate of the formula (XXIII) with vinyl magnesium bromide, in accordance with the following equation:
The O-methyl methyl-2-chloro-benzohydroxamate of the formula (XXIII) can be prepared by known methods, for example from the corresponding benzoic acid derivatives [cf., for example, Tetrahedron Lett. 22, 3815 (1981)].
Since the phenyl vinyl ketone of the formula (XX) is sensitive, it is, in a preferred variant for preparing the nitroketones of the formula (XVIII), directly reacted further with nitromethylbenzenes of the formula (XIX).
Nitroketones of the formula (XVIII) can also be prepared by adding, in accordance with the equation below, enamines of methyl phenyl ketones of the formula (XXVI) to xcex1-nitrostyrenes of the formula (XXVII) and subjecting the reaction product to an acidic hydrolysis:
In the formulae (XXIV), (XXV) and (XXVI), R23 and R24 together with the linking nitrogen atom represent a cyclic amino radical, such as, for example, 1-pyrrolidino, 1-piperidino or 4-morpholino.
In most cases, the addition proceeds in a [4+2]-cycloaddition to give isolatable 1,2-oxazine -N-oxide derivatives of the formula (XXV), and it is, if appropriate, carried out in the presence of a non-polar diluent, such as, for example, diethyl ether, at, for example, from xe2x88x9280xc2x0 to +20xc2x0 C. For the hydrolysis, use is made, for example, of aqueous mineral acids, such as hydrochloric acid, if appropriate in the presence of methanol or ethanol [cf. for example, Helv. Chim. Acta 68, 162 (1985); Tetrahedron 45, 2099 (1989)]. In many cases, it is advantageous to open the ring first to give compounds of the formula (XXIV), by simply dissolving the 1,2-oxazine-N-oxide derivative in methanol or ethanol, since otherwise the undesirable Nef reaction, which gives the corresponding diketo compound, occurs as a competing reaction [cf., for example, Tetrahedron 45, 2099 (1989)].
Some of the enamines of the formula (XXVI) are known, or they can be prepared, for example, from the correspondingly substituted acetophenones and the cyclic amines using standard methods (for example Org. Syntheses Vol. 58, 56, John Wiley and Sons, New York). Some of the acetophenones required for this purpose are commercially available or known, or they can be prepared by known methods of the chemistry of aromatics.
Some of the nitrostyrenes of the formula (XXVII) are known, or they can be prepared, for example, by formylation of the nitromethylbenzenes of the formula (XIX) given above (cf., for example, Houben-Weyl, Methoden der Organischen Chemie, Georg Thieme Verlag, Stuttgart, volume E16, 215).
The formula (XXVIII) provides a general definition of the imines required for carrying out the process A) c). In this formula, Ar preferably has those meanings which have already been mentioned in connection with the description of the cyclic imines of the formula (I) as being preferred.
The imines of the formula (XXVIII) can be prepared, for example, by carrying out Michael additions of N-diphenylmethylenebenzylamines of the formula (XXIX) to the phenyl vinyl ketone of the formula (XX), in accordance with the following equation:
The addition is carried out in the presence of an acid binder and in the presence of a diluent, such as, for example, acetonitrile or dichloromethane, and, if appropriate, in the presence of a reaction auxiliary, for example at room temperature. A preferred acid binder is aqueous alkali, such as 50% strength aqueous sodium hydroxide solution in the presence of a phase-transfer catalyst, such as, for example, triethylbenzylammonium chloride as reaction auxiliary [cf., for example, Synth. Commun.17, 211 (1987)].
The preparation of the phenyl vinyl ketone of the formula (XX) is described above. The N-diphenylmethylene benzylamines of the formula (XXIX) are obtained, for example, by reacting the corresponding benzylamines with benzophenone (cf. for example, Tetrahedron. Lett. 1978, 2641). The benzylamines required for this purpose are known, or they can be prepared by known methods, such as, for example, aminolysis of the corresponding benzyl halides (see above).
The formula (III) provides a general definition of the cyclic O-methanesulphonyl oximes required for carrying out the process (B) according to the invention. In this formula, Ar preferably has those meanings which have already been mentioned in connection with the description of the cyclic imines of the formula (1) as being preferred. The O-methanesulphonyl oximes of the formula (III) are novel.
The O-methylsulphonyl oximes of the formula (III) can be prepared by, for example according to the equation below, initially converting cyclic xcex1-aryl ketones of the formula (XXXI) by generally known methods into their oximes of the formula (XXX) and subsequently reacting these with methanesulphonyl chloride, similarly to the mesylation of alcohols:
Cyclic xcex1-aryl ketones of the formula (XXXI) can be prepared, for example, by epoxidizing 1-arylcycloalkenes of the formula (XXXIII) according to the equation below by customary methods, such as, for example, with m-chloroperbenzoic acid, to give oxirans of the formula (XXXII) and subsequently isomerizing these by acidic work-up [cf., for example, Tetrahedron 30, 2027 (1974)]:
It is, of course, also possible to isomerize oxirans of the formula (XXXII) obtained by other routes to give cyclic xcex1-aryl ketones of the formula (XXXI), for example by shaking a solution in chloroform with 20% strength sulphuric acid.
1-Arylcycloalkenes of the formula (XXXIII) can be prepared, for example, by reacting according to the equation below the aryl Grignard compounds of the formula (XIV) described above with cyclobutanone of the formula (XXXV) under customary Grignard conditions and dehydrating the cyclic benzyl alcohols of the formula (XXXIV) which have been obtained, for example, in this manner:
The dehydration can be carried out, for example, by dissolving the alcohol in a solvent of low polarity, such as hexane, and stirring with semi-concentrated sulphuric acid, for example at from 0xc2x0 C. to 20xc2x0 C. [cf., for example, Tetrahedron 30, 2027 (1974)].
Cyclobutanone of the formula (XXXV) is commercially available. The formula (IV) provides a definition of the aryl Grignard compounds furthermore required for carrying out the process (B) according to the invention.
Aryl Grignard compounds of the formula (IV) can be prepared from appropriate aryl halides and magnesium by the Grignard reaction. Aryl halides are generally known compounds of organic chemistry.
The cyclic imines of the formula (V) required for carrying out the process (C) according to the invention are, if X1 represents bromine or iodine, a subset of the compounds of the general formula (I) according to the invention, and they can be prepared, for example, by the processes (A) and (B). If X1 represents trifluoromethanesulphonyl, the compounds of the formula (V-a) can be prepared by reacting hydroxyl compounds of the formula (I-f), which can also be prepared by the processes (A) and (B), with trifluoromethanesulphonyl chloride or trifluoromethanesulphonic anhydride in the presence of an acid binder, such as, for example, pyridine, and, if appropriate, in the presence of a diluent, in accordance with the following equation:
The formula (VI) provides a general definition of the boronic acids likewise required for carrying out the process (C) according to the invention. In this formula, R1-1 preferably has those meanings which have already been mentioned in connection with the description of the cyclic imines of the formula (I-b) as being preferred.
Aromatic boronic acids of the formula (VI) are known or can be prepared by known methods [c.f. Chem. Rev. 45, 2457 (1995); Pure Appl. Chem. 66, 213 (1994)].
The cyclic imines of the formula (I-d) required for carrying out the process (D) according to the invention are a subset of the compounds of the general formula (I) according to the invention, and they can be prepared, for example, by processes (A) to (C).
The formula (VII) provides a definition of the compounds furthermore required for carrying out the process (D) according to the invention. In this formula, R9, R10, G, p, q and r each preferably have those meanings which have already been mentioned in connection with the description of the cyclic imines of the formula (I) as being preferred. Ab represents a customary leaving group, such as, for example, halogen, in particular chlorine or bromine; alkylsulphonyloxy, in particular methylsulphonyloxy; or optionally substituted arenesulphonyloxy, in particular phenylsulphonyloxy, p-chlorophenylsulphonyloxy or p-tolylsulphonyloxy.
The compounds of the formula (VII) are generally known compounds of organic chemistry.
The compounds of the formulae (F-I), (F-II), (F-IV) and (F-VII) furthermore required for carrying out the process (F) according to the invention are generally known compounds of organic chemistry.
The o-chlorobenzoyl chloride and methyl o-chlorobenzoate required for carrying out the process (G) according to the invention are commercially available.
Suitable acids for carrying out the process A) a) according to the invention are organic or inorganic Bronstedt acids, such as, for example, hydrogen fluoride, hydrogen chloride, sulphuric acid, phosphoric acid, formic acid, acetic acid, benzoic acid, citric acid, trifluoroacetic acid, methanesulphonic acid, trifluoromethanesulphonic acid or toluenesulphonic acid.
Particularly suitable is the acidolysis with trifluoroacetic acid, which is usually employed for cleaving off the tert-butoxycarbonyl amino protecting group (c.f., for example, T. W. Greene, P. G. M. Wuts, Protective Groups in Organic Synthesis, 2nd Ed., John Wiley and Sons, New York 1991).
The process (A) a) according to the invention is, if appropriate, carried out in the presence of a suitable acid acceptor. Suitable acid acceptors are all customary inorganic or organic bases. These preferably include alkaline earth metal or alkali metal hydroxides, amides, alkoxides, acetates, carbonates or bicarbonates, such as, for example, sodium hydroxide, potassium hydroxide or ammonium hydroxide, sodium amide, lithium diisopropylamide, sodium methoxide, sodium ethoxide, potassium tert-butoxide, sodium acetate, potassium acetate, calcium acetate or ammonium acetate, sodium carbonate, potassium carbonate or ammonium carbonate, sodium bicarbonate or potassium bicarbonate, and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N,N-dimethylbenzylamine, pyridine, N-methylpiperidine, N-methylmorpholine, N,N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU).
The process (A) a) according to the invention is, if appropriate, carried out in the presence of a diluent. Suitable diluents are water, organic solvents and mixtures of these. Examples include: aliphatic, alicyclic or aromatic hydrocarbons, such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as, for example, chlorobenzene, dichlorobenzene, methylene chloride, chloroform, carbon tetrachloride, dichloro-, trichloroethane or tetrachloroethylene; ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, diethylene glycol dimethyl ether or anisole, ketones, such as acetone, butanone, methyl isobutyl ketone or cyclohexanone; nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; amides, such as fornamide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; N-oxides, such as N-methylmorpholine N-oxide; esters, such as methyl acetate, ethyl acetate or butyl acetate; sulphoxides, such as dimethyl sulphoxide; sulphones, such as sulpholane, alcohols, such as methanol, ethanol, n- or i-propanol, N-, iso-, sec- or tert-butanol, ethanediol, propane-1,2-diol, ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether.
The reaction temperature for the process (A) a) according to the invention can be varied within a relatively wide range. In general, the reaction is carried out at temperatures between xe2x88x9250xc2x0 C. and +150xc2x0 C., preferably between xe2x88x9220xc2x0 C. and +100xc2x0 C.
When carrying out the process A) a), an excess of acid is generally employed.
The process A) b) according to the invention is carried out as a catalytic hydrogenation or using other generally known methods for reducing nitro groups (cf., for example, Houben-Weyl, Methoden der Organischen Chemie, Georg Thieme Verlag Stuttgart, volume 11/1, 394-409 and volume 4/1c, 490-506).
The process A) c) according to the invention is carried out as a hydrolysis according to generally known methods, for example using aqueous hydrochloric acid.
Suitable diluents for carrying out the processes A) b) and A) c) are the diluents mentioned above for the process A) a).
Suitable diluents for carrying out the process (B) according to the invention are inert organic solvents and mixtures of these. Examples include: aliphatic, alicyclic or aromatic hydrocarbons, such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as, for example, chlorobenzene, dichlorobenzene, methylene chloride, chloroform, carbon tetrachloride, dichloro-, trichloroethane or tetrachloroethylene; ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, diethylene glycol dimethyl ether or anisole.
Preference is given to using a solution of the Grignard compound of the formula (IV) in an ether and a solution of the O-methylsulphonyloxime of the formula (III) in a hydrocarbon.
The reaction temperature for the process (B) according to the invention can be varied within a relatively wide range. In general, the reaction is carried out at temperatures between xe2x88x92100xc2x0 C. and +50xc2x0 C., preferably between xe2x88x9280xc2x0 C. and +30xc2x0 C.
When carrying out the process (B) according to the invention, the Grignard compounds of the formula (IV) and the O-methylsulphonyl oxime of the formula (III) are employed in a molar ratio of from 1:1 to 3:1, preferably from 1:1 to 2:1.
Suitable catalysts for carrying out the process (C) according to the invention are palladium (0) complexes. Preference is given, for example, to tetrakis(triphenylphosphine)palladium.
Suitable acid acceptors for carrying out the process (C) according to the invention are inorganic or organic bases. These preferably include alkaline earth metal or alkali metal hydroxides, acetates, carbonates or bicarbonates, such as, for example, sodium hydroxide, potassium hydroxide, barium hydroxide or ammonium hydroxide, sodium acetate, potassium acetate, calcium acetate or ammonium acetate, sodium carbonate, potassium carbonate or ammonium carbonate, sodium bicarbonate or potassium bicarbonate, alkali metal fluorides, such as, for example, caesium fluoride, and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N,N-dimethylbenzylamine, pyridine, N-methylpiperidine, N-methylmorpholine, N,N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU).
Suitable diluents for carrying out the process (C) according to the invention are water, organic solvents and mixtures of these. Examples include: aliphatic, alicyclic or aromatic hydrocarbons, such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as, for example, chlorobenzene, dichlorobenzene, methylene chloride, chloroform, carbon tetrachloride, dichloro-, trichloroethane or tetrachloroethylene; ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, diethylene glycol dimethyl ether or anisole; alcohols, such as methanol, ethanol, n- or i-propanol, n-, iso-, sec- or tert-butanol, ethanediol, propane-1,2-diol, ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether.
The reaction temperature for the process (C) according to the invention can be varied within a relatively wide range. In general, the reaction is carried out at temperatures between 0xc2x0 C. and +140xc2x0 C., preferably between 50xc2x0 C. and +100xc2x0 C.
When carrying out the process (C) according to the invention, the boronic acids of the formula (VI) and the compounds of the formula (V) are employed in a molar ratio of from 1:1 to 3:1, preferably from 1:1 to 2:1. The catalyst is generally employed in amounts of from 0.005 to 0.5 mol, preferably 0.01 mol to 0.1 mol, per mole of the compound of the formula (V). In general, an excess of base is employed.
The process (D) according to the invention is preferably carried out in the presence of a suitable acid acceptor. Suitable acid acceptors are all customary inorganic or organic bases. These preferably include alkaline earth metal or alkali metal hydrides, hydroxides, amides, alkoxides, acetates, carbonates or bicarbonates, such as, for example, sodium hydride, sodium hydroxide, potassium hydroxide or ammonium hydroxide, sodium amide, lithium diisopropylamide, sodium methoxide, sodium ethoxide, potassium tert-butoxide, sodium acetate, potassium acetate, calcium acetate or ammonium acetate, sodium carbonate, potassium carbonate or ammonium carbonate, sodium bicarbonate or potassium bicarbonate and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N,N-dimethyl-benzylamine, pyridine, N-methylpiperidine, N-methylmorpholine, N,N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU).
The process (D) according to the invention can be carried out in the presence of a suitable phase-transfer catalyst. Examples of such catalysts include: tetrabutylammonium iodide, tetrabutylammonium bromide or tetrabutylammonium chloride, tributylmethylphosphonium bromide, trimethyl-C13/C15-alkylammonium chloride or trimethyl-C13/C15-alkyl ammonium bromide, dibenzyldimethylammonium methyl sulphate, dimethyl-C12/C14-alkylbenzylammonium chloride, 15-crown-5,18-crown-6 or tris-[2-(2-methoxyethoxy)-ethyl]-amine.
The process (D) according to the invention is preferably carried out in the presence of a diluent. Suitable diluents are, for example, all solvents listed for process (A).
The reaction temperature for the process (D) according to the invention can be varied within a relatively wide range. In general, the reaction is carried out at temperatures between xe2x88x9220xc2x0 C. and +100xc2x0 C., preferably between 0xc2x0 C. and 60xc2x0 C.
When carrying out the process (D) according to the invention, in general approximately equimolar amounts of the starting materials are employed. However, it is also possible to use an excess of the compound of the formula (VII).
The reactions in accordance with the process E) according to the invention are derivatization reactions known to the person skilled in the art, in particular of carboxylic esters and ketones (cf., for example, Houben-Weyl, Methoden der Organischen Chemie, Georg Thieme Verlag, Stuttgart, vol. VII/2b, in particular 1912 ff; vol. VIII about carboxylic esters and their derivatives; vol. E5, in particular p. 812 ff. and the literature quoted therein).
The steps of the process (F) according to the invention are, if appropriate, carried out in the presence of a diluent. Suitable diluents are water (not for F, xcex1), organic solvents and mixtures of these. Examples include: aliphatic, alicyclic or aromatic hydrocarbons, such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin, halogenated hydrocarbons, such as, for example, chlorobenzene, dichlorobenzene, methylene chloride, chloroform, carbon tetrachloride, dichloro-, trichloroethane or tetrachloroethylene; ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, diethylene glycol dimethyl ether or anisole; ketones, such as acetone, butanone, methyl isobutyl ketone or cyclohexanone; nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; amides, such as formamide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; N-oxides, such as N-methylmorpholine N-oxide; esters, such as methyl acetate, ethyl acetate or butyl acetate; sulphoxides, such as dimethyl sulphoxide; sulphones, such as sulpholane; alcohols, such as methanol, ethanol, n- or i-propanol, n-, iso-, sec- or tert-butanol, ethanediol, propane-1,2-diol, ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether; water.
The reaction temperature for the individual steps of the process (F) according to the invention can be varied within a relatively wide range. In general, the reactions are carried out at temperatures between xe2x88x9250xc2x0 C. and 250xc2x0 C., preferably between xe2x88x9220xc2x0 C. and +100xc2x0 C.
When carrying out the process (F), the chloroacetophenone (F-I) and the iminium salt (F-II) are employed in a molar ratio of from 1:1 to 2:1, preferably 1.1:1.
When carrying out the process (F), the compounds of the formula (F-III) and the benzyl cyanide of the formula (F-IV) are employed in a molar ratio of from 1:1 to 1:2, preferably 1:1.05.
When carrying out the process (F), the compounds of the formula (F-V) to NaOH and H2O2 are employed in a ratio of from 1:2.5:5 to 1:5:10, preferably 1:2.5:5, based on the equivalents.
When carrying out the process (F), PIFA (F-VII) and the compounds of the formula (F-VI) are employed in a molar ratio of from 1:1 to 3:1, preferably from 1:1 to 2:1.
The steps of the process (G) according to the invention are, if appropriate, carried out in the presence of a diluent. Suitable diluents are water (not for G. xcex1 and xcex2), organic solvents and mixtures of these. Examples include: aliphatic, alicyclic or aromatic hydrocarbons, such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decal in; halogenated hydrocarbons, such as, for example, chlorobenzene, dichlorobenzene, methylene chloride, chloroform, carbon tetrachloride, dichloro-, trichloroethane or tetrachloroethylene; ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, diethylene glycol dimethyl ether or anisole; ketones, such as acetone, butanone, methyl isobutyl ketone or cyclohexanone, nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; amides, such as formamide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; N-oxides, such as N-methylmorpholine N-oxide; esters, such as methyl acetate, ethyl acetate or butyl acetate; sulphoxides, such as dimethyl sulphoxide; sulphones, such as sulpholane; alcohols, such as methanol, ethanol, n- or i-propanol, n-, iso-, sec- or tert-butanol, ethanediol, propane-1,2-diol, ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether; water.
The reaction temperature for the individual steps of the process (F) according to the invention can be varied within a relatively wide range. In general, the reactions are carried out at temperatures between xe2x88x9250xc2x0 C. and 250xc2x0 C., preferably between xe2x88x9220xc2x0 C. and +100xc2x0 C.
The steps xcex1) and xcex2) of the process (F) according to the invention are preferably carried out in the presence of a suitable acid acceptor. Suitable acid acceptors are all customary inorganic or organic bases. These preferably include alkaline earth metal or alkali metal hydrides, hydroxides, amides, alkoxides, acetates, carbonates or bicarbonates, such as, for example, sodium acetate, potassium acetate, calcium acetate or ammonium acetate, sodium carbonate, potassium carbonate or ammonium carbonate, sodium bicarbonate or potassium bicarbonate, and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N,N-dimethylbenzylamine, pyridine, N-methylpiperidine, N-methylmorpholine, N,N-dimethylaminopyridine. diazabicyclooctane (DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU). o-Chlorobenzoyl chloride or methyl ester are employed in excess.
The reactions of the processes according to the invention can be carried out at atmospheric pressure or at elevated pressure; preference is given to working at atmospheric pressure. Work-up is carried out by customary methods of organic chemistry. The end products are preferably purified by crystallization, chromatographic purification or by removing the volatile components, if appropriate under reduced pressure.
The active compounds are suitable for controlling animal pests, in particular insects, arachnids and nematodes, encountered in agriculture, in forestry, in the protection of stored products and of materials, and in the hygiene field, and have good plant tolerance and low toxicity to warm-blooded animals. They are active against normally sensitive and resistant species and against all or some stages of development. The abovementioned pests include:
From the order of the Isopoda, for example, Oniscus asellus, Armadillidium vulgare and Porcellio scaber.
From the order of the Diplopoda, for example, Blaniulus guttulatus.
From the order of the Chilopoda, for example, Geophilus carpophagus and Scutigera spec.
From the order of the Symphyla, for example, Scutigerella immaculata.
From the order of the Thysanura, for example, Lepisma saccharina.
From the order of the Collembola, for example, Onychiurus armatus.
From the order of the Orthoptera, for example, Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella gernanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis and Schistocerca gregaria.
From the order of the Dermaptera, for example, Forficula auricularia.
From the order of the Isoptera, for example, Reticulitermes spp.
From the order of the Anoplura, for example, Pediculus humanus corporis, Haematopinus spp. and Linognathus spp.
From the order of the Mallophaga, for example, Trichodectes spp. and Damalinea spp.
From the order of the Thysanoptera, for example, Hercinothrips femoralis and Thrips tabaci.
From the order of the Heteroptera, for example, Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus and Triatoma spp.
From the order of the Homoptera, for example, Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus spp., Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. and Psylla spp.
From the order of the Lepidoptera, for example, Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima and Tortrix viridana.
From the order of the Coleoptera, for example, Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp.,
Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis and Costelytra zealandica.
From the order of the Hymenoptera, for example, Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa spp.
From the order of the Diptera, for example, Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae and Tipula paludosa.
From the order of the Siphonaptera, for example, Xenopsylla cheopis and Ceratophyllus spp.
From the order of the Arachnida, for example, Scorpio maurus and Latrodectus mactans.
From the order of the Acarina, for example, Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.
The phytoparasitic nematodes include Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Meloidogyne spp., Aplelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp.
The active compounds of the formula (I) according to the invention in particular have outstanding activity against mustard beetle larvae (Phaedon cochleariae), caterpillars of the owlet moth (Spodoptera frugiperda), larvae of the green rice leaf hopper (Nephotettix cincticeps), green peach aphids (Myzus persicae) and all stages of the common spider mite (Tetranychus urticae).
The active compounds can be converted to the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspension emulsion concentrates, natural and synthetic materials impregnated with active compound and very fine capsules in polymeric substances.
These formulations are produced in a known manner, for example preferably by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, if appropriate with the use of surface-active agents, that is emulsifying agents and/or dispersing agents and/or foam-forming agents.
If the extender used is water, it is also possible to employ, for example, organic solvents as auxiliary solvents. Suitable liquid solvents are essentially: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, mineral and vegetable oils, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, as well as water.
Suitable solid carriers are:
for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly disperse silica, alumina and silicates; suitable solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; suitable emulsifying and/or foam-forming agents are: for example non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates as well as protein hydrolysis products; suitable dispersing agents are: for example ligninsulphite waste liquors and methylcellulose.
Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Other additives can be mineral and vegetable oils.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.
The active compound according to the invention can be present in its commercially available formulations and in the use forms, prepared from these formulations, as a mixture with other active compounds, such as insecticides, attractants, sterilizing agents, bactericides, acaricides, nematicides, fungicides, growth-regulating substances or herbicides. The insecticides include, for example, phosphates, carbamates, carboxylates, chlorinated hydrocarbons, phenylureas and substances produced by microorganisms, inter alia.
Examples of particularly advantageous mixing components are the following:
Fungicides:
2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2xe2x80x2,6xe2x80x2-dibromo-2-methyl-4xe2x80x2-trifluoromethoxy-4xe2x80x2-trifluoro-methyl-1,3-thiazole-5-carboxanilide; 2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide; (E)-2-methoxyimino-N-methyl-2-(2-phenoxyphenyl)-acetamide; 8-hydroxyquinoline sulphate; methyl (E)-2-{2-[6-(2-cyanophenoxy)-pyrimidin-4-yloxy]-phenyl}-3-methoxyacrylate; methyl (E)-methoximino-[alpha-(o-tolyloxy)-o-tolyl]acetate; 2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole,
benalaxyl, benodanil, benomyl, binapacryl, biphenyl, bitertanol, blasticidin-S, bromuconazole, bupirimate, buthiobate,
calcium polysulphide, captafol, captan, carbendazim, carboxin, quinomethionate, chloroneb, chloropicrin, chlorothalonil, chlozolinate, cufraneb, cymoxanil, cyproconazole, cyprofuram,
dichlorophen, diclobutrazol, diclofluanid, diclomezine, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodine, drazoxolon,
edifenphos, epoxyconazole, ethirimol, etridiazole,
fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, fluoromide, fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminium, fthalide, fuberidazole, furalaxyl, furmecyclox, guazatine,
hexachlorobenzene, hexaconazole, hymexazol,
imazalil, imibenconazole, iminoctadine, iprobenfos (IBP), iprodione, isoprothiolane, kasugamycin, copper preparations such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulphate, copper oxide, oxine-copper and Bordeaux mixture,
mancopper, mancozeb, maneb, mepanipyrim, mepronil, metalaxyl, metconazole, methasulfocarb, methfuroxam, metiram, metsulfovax, myclobutanil, nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol,
ofurace, oxadixyl, oxamocarb, oxycarboxin,
pefurazoate, penconazole, pencycuron, phosdiphen, phthalide, pimaricin, piperalin, polycarbamate, polyoxin, probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon,
quintozene (PCNB),
sulphur and sulphur preparations,
tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole, thicyofen, thiophanate-methyl, thiram, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, trichlamide, tricyclazole, tridemorph, triflumizole, triforine, triticonazole,
validamycin A, vinclozolin,
zineb, ziram.
Bactericides:
bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furancarboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulphate and other copper preparations.
Insecticides/Acaricides/Nematicides:
abamectin, AC 303 630, acephate, acrinathrin, alanycarb, aldicarb, alphamethrin, amitraz, avermectin, AZ 60541, azadirachtin, azinphos A, azinphos M, azocyclotin, Bacillus thuringiensis, bendiocarb, benfuracarb, bensultap, beta-cyluthrin, bifenthrin, BPMC, brofenprox, bromophos A, bufencarb, buprofezin, butocarboxim, butylpyridaben,
cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap, CGA 157419, CGA 184699, chloethocarb, chlorethoxyfos, chlorfenvinphos, chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos M, cis-resmethrin, clocythrin, clofentezine, cyanophos, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypernethrin, cyromazine,
deltamethrin, demeton M, demeton S, demeton-S-methyl, diafenthiuron, diazinon, dichlofenthion, dichlorvos, dicliphos, dicrotophos, diethion, diflubenzuron, dimethoate, dimethylvinphos, dioxathion, disulfoton,
edifenphos, emamectin, esfenvalerate, ethiofencarb, ethion, ethofenprox, ethoprophos, etrimfos,
fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb, fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate, fenthion, fenvalerate, fipronil, fluazinam, flucycloxuron, flucythrinate, flufenoxuron, flufenprox, fluvalinate, fonofos, formothion, fosthiazate, fubfenprox, furathiocarb,
HCH, heptenophos, hexaflumuron, hexythiazox,
imidacloprid, iprobenfos, isazofos, isofenphos, isoprocarb, isoxathion, ivermectin, lambda-cyhalothrin, lufenuron,
malathion, mecarbam, mevinphos, mesulfenphos, metaldehyde, methacrifos, methamidophos, methidathion, methiocarb, methomyl, metolcarb, milbemectin, monocrotophos, moxidectin,
naled, NC 184, NI 25, nitenpyram,
omethoate, oxamyl, oxydemeton M, oxydeprofos,
parathion A, parathion M, permethrin, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos M, pirimiphos A, profenofos, promecarb, propaphos, propoxur, prothiofos, prothoate, pymetrozine, pyrachlofos, pyridaphenthion, pyresmethrin, pyrethrum, pyridaben, pyrimidifen, pyriproxyfen, quinalphos,
RH 5992,
salithion, sebufos, silafluofen, sulfotep, sulprofos,
tebufenozide, tebufenpyrad, tebupirimifos, teflubenzuron, tefluthrin, temephos, terbam, terbufos, tetrachlorvinphos, thiafenox, thiodicarb, thiofanox, thiomethon, thionazin, thuringiensin, tralomethrin, triarathene, triazophos, triazuron, trichlorfon, triflumuron, trimethacarb,
vamidothion, XMC, xylylcarb, YI 5301/5302, zetamethrin.
A mixture with other known active compounds, such as herbicides, or with fertilizers and growth-regulators is also possible.
The active compound according to the invention can furthermore be present in its commercially available formulations and in the use forms, prepared from these formulations, as a mixture with synergistic agents. Synergistic agents are compounds which increase the action of the active compounds, without it being necessary for the synergistic agent added to be active itself.
The active compound content of the use forms prepared from the commercially available formulations can vary within wide limits. The active compound concentration of the use forms can be from 0.0000001 to 95% by weight of active compound, preferably between 0.0001 and 1% by weight.
The compounds are employed in a customary manner appropriate for the use forms. When used against hygiene pests and pests of stored products, the active compound has an excellent residual action on wood and clay as well as a good stability to alkali on limed substrates.
The active compounds according to the invention are not only active against plant, hygiene and stored-product pests, but also, in the veterinary medicine sector, against animal parasites (ectoparasites), such as ixodid ticks, argasid ticks, scab mites, trombiculid mites, flies (stinging and sucking), parasitic fly larvae, lice, hair lice, bird lice and fleas. These parasites include:
From the order of the Anoplurida, for example, Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp. and Solenopotes spp.
From the order of the Mallophagida and the sub-orders Amblycerina and Ischnocerina, for example, Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp. and Felicola spp.
From the order of the Diptera and the sub-orders Nematocerina and Brachycerina, for example, Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp. and Melophagus spp.
From the order of the Siphonapterida, for example, Pulex spp., Ctenocephalides spp., Xenopyslla spp. and Ceratophyllus spp.
From the order of the Heteropterida, for example, Cimex spp., Triatoma spp., Rhodnius spp. and Panstrongylus spp.
From the order of the Blattarida, for example, Blatta orientalis, Periplaneta americana, Blattela germanica and Supella spp.
From the sub-class of the Acaria (Acarida) and the orders of the Meta- and Mesostigmata, for example, Argas spp., Ornithodorus spp., Otabius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Derrnacentor spp., Haemaphysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp., Sternostoma spp. and Varroa spp.
From the order of the Actinedida (Prostigmata) and Acaridida (Astigmata), for example, Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.
For example, they have an outstanding activity against all larval stages of the fly Lucilia cuprina and all development stages of the tick Amblyomma variegatum.
The active compounds of the formula (I) according to the invention are also suitable for controlling arthropods which attack agricultural livestock, such as, for example, cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese, honey bees, other domestic animals, such as, for example, dogs, cats, caged birds, aquarium fish, and so-called experimental animals, such as, for example, hamsters, guinea-pigs, rats and mice. By controlling these arthropods, it is intended to reduce deaths and decreased performances (in meat, milk, wool, hides, eggs, honey and the like), so that more economical and simpler animal keeping is made possible by using the active compounds according to the invention.
In the veterinary sector, the active compounds according to the invention are used in a known manner by enteral administration, for example in the form of tablets, capsules, drinks, drenches, granules, pastes, boluses, the feed-through method, suppositories, by parenteral administration, such as, for example, by means of injections (intramuscular, subcutaneous, intravenous, intraperitoneal and the like), implants, by nasal administration, by dermal administration, for example in the form of dipping or bathing, spraying, pouring-on and spotting-on, washing, dusting, and with the aid of shaped articles which comprise active compound, such as collars, ear tags, tail marks, limb bands, halters, marking devices and the like.
When administered to livestock, poultry, domestic animals and the like, the active compounds of the formula (I) can be used as formulations (for example powders, emulsions, flowables) which comprise the active compounds in an amount of 1 to 80% by weight, either directly or after dilution by a factor of 100 to 10,000, or they may be used in the form of a chemical bath.
Furthermore, it has been found that the compounds of the formula (I) according to the invention have a potent insecticidal action against insects which destroy industrial materials.
The following insects may be mentioned by way of preferred examples but without any limitation:
Beetles, such as
Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthes rugicollis, Xyleborus spec., Tryptodendron spec., Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. and Dinoderus minutus.
Dermapterans, such as
Sirex juvencus, Urocerus gigas, Urocerus gigas taignus and Urocerus augur.
Termites, such as
Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis and Coptotermes formosanus.
Bristletails, such as Lepisma saccharina.
Industrial materials are to be understood as meaning, in the present context, non-live materials, such as, preferably, synthetic materials, glues, sizes, paper and board, leather, wood and timber products, and paint.
The materials to be very particularly preferably protected against attack by insects are wood and timber products.
Wood and timber products which can be protected by the composition according to the invention or mixtures comprising such a composition are to be understood as meaning, for example, construction timber, wooden beams, railway sleepers, bridge components, jetties, wooden vehicles, boxes, pallets, containers, telephone poles, wood lagging, windows and doors made of wood, plywood, particle board, joiner""s articles, or wood products which, quite generally, are used in the construction of houses or in joinery.
The active compounds can be used as such, in the form of concentrates or generally customary formulations, such as powders, granules, solutions, suspensions, emulsions or pastes.
The formulations mentioned can be prepared in a manner known per se, for example by mixing the active compounds with at least one solvent or diluent, emulsifier, dispersant and/or binder or fixative, water repellent, if appropriate desiccants and UV stabilizers and, if appropriate, colorants and pigments and other processing auxiliaries.
The insecticidal compositions or concentrates used for the protection of wood and wooden materials comprise the active compound according to the invention at a concentration of 0.0001 to 95% by weight, in particular 0.001 to 60% by weight.
The amount of the compositions or concentrates employed depends on the species and the occurrence of the insects and on the medium. The optimum rate of application can be determined upon use in each case by test series. However, in general, it suffices to employ 0.0001 to 20% by weight, preferably 0.001 to 10% by weight, of the active compound, based on the material to be protected.
The solvent and/or diluent used is an organochemical solvent or solvent mixture and/or an oily or oil-type organochemical solvent or solvent mixture of low volatility and/or a polar organochemical solvent or solvent mixture and/or water and, if appropriate, an emulsifier and/or wetting agent.
Organochemical solvents which are preferably employed are oily or oil-like solvents having an evaporation number of above 35 and a flashpoint of above 30xc2x0 C., preferably above 45xc2x0 C. Substances which are used as such oily and oil-like solvents which have low volatility and are insoluble in water are suitable mineral oils or their aromatic fractions, or mineral-oil-containing solvent mixtures, preferably white spirit, petroleum and/or alkylbenzene.
Substances which are advantageously used are mineral oils with a boiling range of 170 to 220xc2x0 C., white spirit with a boiling range of 170 to 220xc2x0 C., spindle oil with a boiling range of 250 to 350xc2x0 C., petroleum or aromatics of boiling range 160 to 280xc2x0 C., essence of turpentine and the like.
In a preferred embodiment, liquid aliphatic hydrocarbons with a boiling range of 180 to 210xc2x0 C. or high-boiling mixtures of aromatic and aliphatic hydrocarbons with a boiling range of 180 to 220xc2x0 C. and/or spindle oil and/or monochloronaphthalene, preferably xcex1-monochloronaphthalene, are used.
The organic oily or oil-like solvents of low volatility and having an evaporation number of above 35 and a flashpoint of above 30xc2x0 C., preferably above 45xc2x0 C., can be partially replaced by organochemical solvents of high or medium volatility, with the proviso that the solvent mixture also has an evaporation number of above 35 and a flashpoint of above 30xc2x0 C., preferably above 45xc2x0 C., and that the insecticide is soluble or emulsifiable in this solvent mixture.
In a preferred embodiment, part of the organochemical solvent or solvent mixture is replaced by an aliphatic polar organochemical solvent or solvent mixture. Substances which are preferably used are aliphatic organochemical solvents having hydroxyl and/or ester and/or ether groups, such as, for example, glycol ether, esters and the like.
The organochemical binders used within the scope of the present invention are the synthetic resins and/or binding drying oils which are known per se and can be diluted with water and/or are soluble or dispersible or emulsifiable in the organochemical solvents employed, in particular binders composed of, or comprising, an acrylate resin, a vinyl resin, for example polyvinyl acetate, polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenol resin, hydrocarbon resin, such as indene/coumarone resin, silicone resin, drying vegetable and/or drying oils and/or physically drying binders based on a natural and/or synthetic resin.
The artificial resin used as the binder can be employed in the form of an emulsion, dispersion or solution. Up to 10% by weight of bitumen or bituminous substances can also be used as binder. In addition, colorants, pigments, water repellents, odour-masking substances and inhibitors or anticorrosives known per se and the like can also be employed.
The composition or the concentrate preferably comprises, in accordance with the invention, at least one alkyd resin or modified alkyd resin and/or a drying vegetable oil as the organochemical binder. Preferably used according to the invention are alkyd resins with an oil content of over 45% by weight, preferably 50 to 68% by weight.
All or some of the abovementioned binder can be replaced by a fixative (mixture) or a plasticizer (mixture). These additives are intended to prevent volatilization of the active compounds and crystallization or precipitation. They preferably replace 0.01 to 30% of the binder (based on 100% of binder employed).
The plasticizers are from the chemical classes of the phthalic esters, such as dibutyl phthalate, dioctyl phthalate or benzylbutyl phthalate, the phosphoric esters, such as tributyl phosphate, the adipic esters, such as di-(2-ethylhexyl) adipate, the stearates, such as butyl stearate or amyl stearate, the oleates, such as butyl oleate, the glycerol ethers or relatively high-molecular-weight glycol ethers, glycerol esters and p-toluenesulphonic esters.
Fixatives are chemically based on polyvinyl alkyl ethers, such as, for example, polyvinyl methyl ether, or ketones, such as benzophenone or ethylenebenzophenone.
Particularly suitable as a solvent or diluent is also water, if appropriate as a mixture with one or more of the abovementioned organochemical solvents or diluents, emulsifiers and dispersants.
Particularly effective protection of wood is achieved by large-scale industrial impregnation processes, for example vacuum, double-vacuum or pressure processes.
If appropriate, the ready-to-use compositions can additionally comprise other insecticides and, if appropriate, additionally one or more fungicides.
Suitable additional components which may be admixed are, preferably, the insecticides and fungicides mentioned in WO 94/29 268. The compounds mentioned in that document are expressly incorporated into the present application.
Very particularly preferred components which may be admixed are insecticides, such as chlorpyrifos, phoxim, silafluofin, alphamethrin, cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25, flufenoxuron, hexaflumuron and triflumuron, and fungicides, such as epoxyconazole, hexaconazole, azaconazole, propiconazole, tebuconazole, cyproconazole, metconazole, imazalil, dichlorfluanid, tolylfluanid, 3-iodo-2-propinyl-butyl carbamate, N-octyl-isothiazolin-3-one and 4,5-dichloro-N-octylisothiazolin-3-one.

Abstract: in which

Abstract: Ar represents substituted phenyl,