2-(N-phenylamino)pyrimidines of the formula I,

The present invention relates to the use of 2-(N-phenylamino)pyrimidines of the formula I,
where:
R1, R3 independently of one another are cyano, C1-C8-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, where the radicals alkyl, alkenyl and alkynyl may be substituted by cyano, halogen, C1-C4-alkoxy or C1-C4-alkoxycarbonyl, or are C3-C8-cycloalkyl or a group C(xe2x95x90NORx)Ry;
Rx is hydrogen, C1-C8-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, where the radicals alkyl, alkenyl and alkynyl may be substituted by cyano, halogen, C1-C4-alkoxy or phenyl;
Ry is hydrogen, C1-C8-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, where the radicals alkyl, alkenyl and alkynyl may be substituted by cyano, halogen or C1-C4-alkoxy;
R2 is halogen, C1-C8-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, where the radicals alkyl, alkenyl and alkynyl may be substituted by cyano, halogen, C1-C4-alkoxy or C1-C4-alkoxycarbonyl; or
R1 and R2 together with the two linking carbon atoms form a fused-on partially unsaturated 4- to 8-membered ring which may be up to trisubstituted by identical or different substituents selected from the group consisting of C1-C4-alkyl, halogen and C1-C4-alkoxycarbonyl, which may contain a carbonyl group and/or, in addition to the multiple bond of the pyrimidine ring, a double bond and/or which may be interrupted by O, S or Nxe2x80x94(C1-C4-alkyl);
R4 to R8 independently of one another are hydrogen, cyano, halogen, Ra, RaO, RaS(O)m, RaOxe2x80x94(Cxe2x95x90O), Ra(Cxe2x95x90O), RaRbNxe2x80x94(Cxe2x95x90O), RaHNxe2x80x94(Cxe2x95x90O), H2Nxe2x80x94(Cxe2x95x90O), Raxe2x80x94(Cxe2x95x90O)xe2x80x94NH, Raxe2x80x94(Cxe2x95x90O)xe2x80x94NRb or RaOxe2x80x94Nxe2x95x90C(Rb);
Ra, Rb are C1-C4-alkyl, C3-C6-alkenyl or C3-C6-alkynyl, each of which may be substituted by cyano, halogen, C1-C4-alkoxy, C1-C4-alkoxycarbonyl or phenyl, or are phenyl which may carry one to three substituents selected from the group consisting of halogen and C1-C4-alkyl;
m is 0, 1 or 2;
as fungicides.
Fungicidal 2-(N-phenylamino)pyrimidines carrying a hydrogen atom in the 5-position of the pyrimidine ring are known from EP-A 224 339, EP-A 270 111, EP-A 310 550, EP-A 457 726, DD 151404 and JP 03/271278.
2-(N-phenylamino)pyrimidines substituted in the 5-position have been described as intermediates for herbicidally active compounds (EP-A 337 944) and as pharmaceutics (WO-A 97/19065).
Finally, fungicidal 2-(N-phenylamino)pyrimidines which may be substituted in the 5-position and which carry a specific 2-nitrophenyl radical at the amino function are known from EP-A 172 786.
However, the compounds mentioned in EP-A 172 786 do not always fully meet the requirements which have to be met by active compounds in practice.
It is an object of the present invention to provide fungicidally active compounds having improved properties.
We have found that this object is achieved by the abovementioned compounds, some of which have already been mentioned in the publications EP-A 337 944 and WO-A 97/19065, which are outstandingly suitable for controlling harmful fungi. In addition, we have found novel 2-(N-phenylamino)pyrimidines having improved fungicidal activity.
It is a common feature of all aminopyrimidines according to the invention, both the novel aminopyrimidines and those known from EP-A 337 944 and WO-A 97/19065, that they carry hydrophobic substituents in each of positions 4, 5 and 6.
The novel 2-(N-phenylamino)pyrimidines can be prepared similarly to methods known from the literature. Particularly suitable are the process routes shown in Schemes 1 and 2.
The condensation reaction of the guanidines II with 1,3-dicarbonyl compounds of the formula III to give the 2-(N-phenylamino)pyrimidines I can be carried out as described in EP-A 337 944 and the literature cited therein.
With regard to the synthesis of the guanidines II, reference is made to Houben-Weyl, Methoden der Organischen Chemie, Stuttgart, Vol. VIII pp. 98, 180 to 189. The 1,3-diketones III can be prepared, for example, either by a) Claisen condensation or by b) alkylation or halogenation of a 1,3-diketone which is unsubstituted in the 2-position (Organikum, 1993 Barth Verlagsgesellschaft Leipzig, a) p.487 b) p. 536).
The preparation of the 2-(N-phenylamino)pyrimidines I starting from aniline derivatives of the formula IV and pyrimidine derivatives of the formula V where X is a nucleophilically replaceable group, such as halogen or C1-C4-alkylsulfonyl, is described in EP-A 337 944.
The compounds I according to the invention in which R3 is C(xe2x95x90NORx)Ry are preferably prepared from the aldehydes VI (see Scheme 3), and the aldehydes VI for their part can be synthesized similarly to EP-A 457 726.
Compounds Ia in which R3 is CH(xe2x95x90NORx) are obtained by reacting the aldehydes VI with the alkoxyamines VII under conditions known per se (Scheme 3).
Moreover, the aldehydes VI can be converted under conditions known per se with organometallic reagents, such as Grignard reagents VIII (Ryxe2x80x94Mgxe2x80x94X; Xxe2x95x90Cl, Br, I), into the secondary alcohols IX.
The oxidation of these alcohols IX, preferably according to Swern using oxalyl chloride/DMSO, gives the ketones X which for their part can be reacted with alkoxyamines VII to give the compounds Ib according to the invention.
The active compounds Ic in which R3 is cyano (Scheme 4) can preferably be prepared by reacting the aldehydes VI with hydroxylamine, followed by dehydration of the resulting oximes XI (similarly to EP-A 457 726).
In the definition of the compounds I given at the outset, collective terms which represent individual enumerations of each of the group members were used for the radicals R1 to R8, Rx and Ry and Ra and Rb. The radicals alkyl, alkoxy, alkoxycarbonyl, alkenyl and alkynyl can be straight-chain or branched.
Examples of meanings are:
halogen: fluorine, chlorine, bromine or iodine;
C1-C4-alkyl: methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl or 1,1-dimethylethyl;
C1-C8-alkyl: C1-C4-alkyl, as mentioned above, and also pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-3-methylpropyl, heptyl, octyl or 2-ethylhexyl;
C1-C2-haloalkyl: a C1-C2-alkyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, i.e. for example chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl or pentafluoroethyl;
C1-C4-alkoxy and the alkoxy moieties of C1-C4-alkoxycarbonyl: methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy or 1,1-dimethylethoxy;
C1-C2-haloalkoxy: a C1-C2-alkoxy radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, i.e. for example fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, bromodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromomethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy;
C2-C6-alkenyl: ethylene, prop-1-en-1-yl, prop-2-en-1-yl, 1-methylethenyl, buten-1-yl, buten-2-yl, buten-3-yl, 1-methylprop-1-en-1-yl, 2-methylprop-1-en-1-yl, 1-methylprop-2-en-1-yl and 2-methylprop-2-en-1-yl, penten-1-yl, penten-2-yl, penten-3-yl, penten-4-yl, 1-methylbut-1-en-1-yl, 2-methylbut-1-en-1-yl, 3-methylbut-1-en-1-yl, 1-methylbut-2-en-1-yl, 2-methylbut-2-en-1-yl, 3-methylbut-2-en-1-yl, 1-methylbut-3-en-1-yl, 2-methylbut-3-en-1-yl, 3-methylbut-3-en-1-yl, 1,1-dimethylprop-2-en-1-yl, 1,2-dimethylprop-1-en-1-yl, 1,2-dimethylprop-2-en-1-yl, 1-ethylprop-1-en-2-yl, 1-ethylprop-2-en-1-yl, hex-1-en-1-yl, hex-2-en-1-yl, hex-3-en-1-yl, hex-4-en-1-yl, hex-5-en-1-yl, 1-methylpent-1-en-1-yl, 2-methylpent-1-en-1-yl, 3-methylpent-1-en-1-yl, 4-methylpent-1-en-1-yl, 1-methylpent-2-en-1-yl, 2-methylpent-2-en-1-yl, 3-methylpent-2-en-1-yl, 4-methylpent-2-en-1-yl, 1-methylpent-3-en-1-yl, 2-methylpent-3-en-1-yl, 3-methylpent-3-en-1-yl, 4-methylpent-3-en-1-yl, 1-methylpent-4-en-1-yl, 2-methylpent-4-en-1-yl, 3-methylpent-4-en-1-yl, 4-methylpent-4-en-1-yl, 1,1-dimethylbut-2-en-1-yl, 1,1-dimethylbut-3-en-1-yl, 1,2-dimethylbut-1-en-1-yl, 1,2-dimethylbut-2-en-1-yl, 1,2-dimethylbut-3-en-1-yl, 1,3-dimethylbut-1-en-1-yl, 1,3-dimethylbut-2-en-1-yl, 1,3-dimethylbut-3-en-1-yl, 2,2-dimethylbut-3-en-1-yl, 2,3-dimethylbut-1-en-1-yl, 2,3-dimethylbut-2-en-1-yl, 2,3-dimethylbut-3-en-1-yl, 3,3-dimethylbut-1-en-1-yl, 3,3-dimethylbut-2-en-1-yl, 1-ethylbut-1-en-1-yl, 1-ethylbut-2-en-1-yl, 1-ethylbut-3-en-1-yl, 2-ethylbut-1-en-1-yl, 2-ethylbut-2-en-1-yl, 2-ethylbut-3-en-1-yl, 1,1,2-trimethylprop-2-en-1-yl, 1-ethyl-1-methylprop-2-en-1-yl, 1-ethyl-2-methylprop-1-en-1-yl or 1-ethyl-2-methylprop-2-en-1-yl;
C2-C6-alkynyl: ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1-pentynyl, 3-methyl-4-pentynyl, 4-methyl-1-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl or 1-ethyl-1-methyl-2-propynyl;
C3-C8-cycloalkyl: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
With a view to their use as fungicides, preference is given to 2-(N-phenylamino)pyrimidines I which have the following substituents, the preference existing in each case alone or in combination:
R1, R3 are cyano, C1-C8-alkyl, propynyl, C1-C2-haloalkyl, cyclopropyl or a group C(xe2x95x90NORx)Ry;
R2 is halogen or C1-C8-alkyl;
R4 to R8 independently of one another are hydrogen, cyano, halogen, C1-C2-haloalkyl, C1-C2-haloalkoxy, Ra or RaOxe2x80x94Nxe2x95x90C(Rb);
Ra, Rb are C1-C4-alkyl.
Particular preference is given to 2-(N-phenylamino)pyrimidines I having the following substituents, the preference existing in each case alone or in combination:
R1, R3 are cyano, methyl, ethyl, cyclopropyl, CH(xe2x95x90NOCH3), CH(xe2x95x90NOC2H5), C(xe2x95x90NOCH3)CH3 or C(xe2x95x90NOC2H5)CH3;
R2 is fluorine, chlorine, methyl or ethyl;
R4 to R8 independently of one another are hydrogen, cyano, halogen or C1-C4-alkyl.
Most preference is given to 2-(N-phenylamino)pyrimidines I having the following substituents, the preference existing in each case alone or in combination.
R1 is methyl or cyclopropyl;
R2 is methyl or fluorine;
R3 is CH(xe2x95x90NOCH3), CH(xe2x95x90NOC2H5), C(xe2x95x90NOCH3)CH3, C(xe2x95x90NOC2H5)CH3, cyano or methyl and
R4 to R8 are hydrogen.
The following groups of active compounds are preferred owing to their pronounced plant-fungicidal activity.
Group Ia: 2-(N-phenylamino)pyrimidines of the formula I in which
R1, R3 are cyano, C1-C8-alkyl, C2-C6-alkenyl, C2-C6-alkynyl or C3-C8-cycloalkyl;
R2 is halogen, C1-C8-alkyl, C2-C6-alkenyl, C2-C6-alkynyl or C1-C2-haloalkyl;
R4, R6, R8 independently of one another are hydrogen, cyano, halogen, Ra, RaO, RaS(O)m, RaOxe2x80x94(Cxe2x95x90O), Ra(Cxe2x95x90O), RaRbNxe2x80x94(Cxe2x95x90O), RaHNxe2x80x94(Cxe2x95x90O), H2Nxe2x80x94(Cxe2x95x90O), Raxe2x80x94(Cxe2x95x90O)xe2x80x94NH, Raxe2x80x94(Cxe2x95x90O)xe2x80x94NRb or RaOxe2x80x94Nxe2x95x90C(Rb);
R5, R7 independently of one another are hydrogen, cyano, Ra, RaO, RaS(O)m, RaOxe2x80x94(Cxe2x95x90O), Ra(Cxe2x95x90O), RaRbNxe2x80x94(Cxe2x95x90O), RaHNxe2x80x94(Cxe2x95x90O), H2Nxe2x80x94(Cxe2x95x90O), Raxe2x80x94(Cxe2x95x90O)xe2x80x94NH, Raxe2x80x94(Cxe2x95x90O)xe2x80x94NRb or RaOxe2x80x94Nxe2x95x90C(Rb);
Ra, Rb are C1-C4-alkyl, C3-C6-alkenyl or C3-C6-alkynyl, each of which may be substituted by cyano, halogen, C1-C4-alkoxy, C1-C4-alkoxycarbonyl or phenyl, or are phenyl which may carry one to three substituents selected from the group consisting of halogen and C1-C4-alkyl, and
m is 0, 1 or 2.
Preference is given to 2-(N-phenylamino)pyrimidines of the group Ia in which
R1 is cyano, methyl, ethyl, n-propyl, propynyl or cyclopropyl;
R2 is methyl, ethyl, fluorine or chlorine;
R3 is methyl;
R4, R6, R8 independently of one another are hydrogen, cyano, halogen, C1-C2-haloalkoxy, Ra or RaOxe2x80x94Nxe2x95x90C(Rb) and are preferably hydrogen, halogen or C1-C4-alkyl;
R5, R7 independently of one another are hydrogen, cyano, C1-C2-haloalkoxy, Ra or RaOxe2x80x94Nxe2x95x90C(Rb) and are preferably hydrogen, halogen or C1-C4-alkyl and
Ra, Rb are C1-C4-alkyl.
Group Ib: 2-(N-phenylamino)pyrimidines of the formula I in which
R1 is cyano or C2-C6-alkynyl and the radicals R2 to R8 are each as defined in claim 1.
Preference is given to 2-(N-phenylamino)pyrimidines of the group Ib in which
R1 is cyano or propynyl;
R2 is halogen or C1-C8-alkyl and is preferably fluorine, chlorine, methyl or ethyl;
R3 is cyano, C1-C8-alkyl, propynyl, C1-C2-haloalkyl or cyclopropyl and is preferably methyl, ethyl, n-propyl, propynyl or cyclopropyl;
R4 to R8 independently of one another are hydrogen, cyano, halogen, C1-C2-haloalkyl, C1-C2-haloalkoxy, Ra or RaOxe2x80x94Nxe2x95x90C(Rb) and are preferably hydrogen, halogen or C1-C4-alkyl and
Ra, Rb are C1-C4-alkyl.
Group Ic: 2-(N-phenylamino)pyrimidines of the formula I in which
R4 to R8 are hydrogen and the radicals R1 to R3 are each as defined in claim 1.
Preference is given to 2-(N-phenylamino)pyrimidines of the group Ic in which
R1, R3 are cyano, C1-CB-alkyl, propynyl, C1-C2-haloalkyl or cyclopropyl and are preferably methyl, ethyl, n-propyl, propynyl or cyclopropyl;
R2 is halogen or C1-C8-alkyl and is preferably fluorine, chlorine, methyl or ethyl and
R4 to R8 are hydrogen.
Group Id: 2-(N-phenylamino)pyrimidines of the formula I in which
R2 is halogen;
R4 , R8 independently of one another are hydrogen, cyano, halogen, C1-C2-haloalkoxy, Ra, RaO, RaS(O)m, RaOxe2x80x94(Cxe2x95x90O), Ra(Cxe2x95x90O), RaRbNxe2x80x94(Cxe2x95x90O), RaHNxe2x80x94(Cxe2x95x90O), H2Nxe2x80x94(Cxe2x95x90O), Raxe2x80x94(Cxe2x95x90O)xe2x80x94NH, Raxe2x80x94(Cxe2x95x90O)xe2x80x94NRb or RaOxe2x80x94Nxe2x95x90C(Rb);
R5 to R7 independently of one another are hydrogen, cyano, halogen, C1-C2-haloalkyl, C1-C2-haloalkoxy, Ra, RaO, RaS(O)m, RaOxe2x80x94(Cxe2x95x90O), Ra(Cxe2x95x90O), RaRbNxe2x80x94(Cxe2x95x90O), RaHNxe2x80x94(Cxe2x95x90O), H2Nxe2x80x94(Cxe2x95x90O), Raxe2x80x94(Cxe2x95x90O)xe2x80x94NH, Raxe2x80x94(Cxe2x95x90O)xe2x80x94NRb or RaOxe2x80x94Nxe2x95x90C(Rb);
Ra, Rb are C1-C4-alkyl, C3-C6-alkenyl or C3-C6-alkynyl, each of which may be substituted by cyano, C1-C4-alkoxy, C1-C4-alkoxycarbonyl or phenyl, or are phenyl, which may carry one to three substituents selected from the group consisting of halogen and C1-C4-alkyl, and
the radicals R1 and R3 are each as defined in claim 1.
Preference is given to 2-(N-phenylamino)pyrimidines of the group Id in which
R1, R3 are cyano, C1-C8-alkyl, propynyl, C1-C2-haloalkyl or cyclopropyl and are preferably methyl, ethyl, n-propyl, propynyl or cyclopropyl;
R2 is fluorine or chlorine;
R4, R8 independently of one another are hydrogen, cyano, halogen, C1-C2-haloalkoxy, Ra or RaOxe2x80x94Nxe2x95x90C(Rb) and are preferably hydrogen, halogen or C1-C4-alkyl;
R5 to R7 independently of one another are hydrogen, cyano, halogen, C1-C2-haloalkyl, C1-C2-haloalkoxy, Ra or RaOxe2x80x94Nxe2x95x90C(Rb) and are preferably hydrogen, halogen or C1-C4-alkyl and
Ra, Rb are C1-C4-alkyl.
Group Ie: 2-(N-phenylamino)pyrimidines of the formula I in which
R1, R3 are C1-C8-alkyl, C2-C6-alkenyl or C2-C6-alkynyl, where the radicals alkenyl and alkynyl may be substituted by cyano, halogen, C1-C4-alkoxy or C1-C4-alkoxycarbonyl;
R2 is C1-C8-alkyl, C2-C6-alkenyl or C2-C6-alkynyl;
R5, R7 independently of one another are hydrogen, cyano, Ra, RaO, RaS(O)m, RaOxe2x80x94(Cxe2x95x90O), Ra(Cxe2x95x90O), RaRbNxe2x80x94(Cxe2x95x90O), RaHNxe2x80x94(Cxe2x95x90O), H2Nxe2x80x94(Cxe2x95x90O), Raxe2x80x94(Cxe2x95x90O)xe2x80x94NH, Raxe2x80x94(Cxe2x95x90O)xe2x80x94NRb or RaOxe2x80x94Nxe2x95x90C(Rb);
the radicals R4, R6 and R8 are each as defined in claim 1.
Preference is given to 2-(N-phenylamino)pyrimidines of the group Ie in which
R1, R3 are methyl, ethyl, n-propyl or propynyl;
R2 is methyl, ethyl or n-propyl;
R4, R6, R8 independently of one another are hydrogen, cyano, halogen, C1-C2-haloalkyl, C1-C2-haloalkoxy, Ra or RaOxe2x80x94Nxe2x95x90C(Rb) and are preferably hydrogen, halogen or C1-C4-alkyl;
R5, R7 independently of one another are hydrogen, cyano, C1-C2-haloalkyl, C1-C2-haloalkoxy, Ra or RaOxe2x80x94Nxe2x95x90C(Rb) and are preferably hydrogen, cyano, C1-C4-alkyl or C1-C2-haloalkyl and
Ra, Rb are C1-C4-alkyl.
Group If: 2-(N-phenylamino)pyrimidines of the formula I in which
R4, R8 are hydrogen;
R5, R7 independently of one another are hydrogen, cyano, C1-C2-haloalkoxy, Ra, RaO, RaS(O)m, RaOxe2x80x94(Cxe2x95x90O), Ra(Cxe2x95x90O), RaRbNxe2x80x94(Cxe2x95x90O), RaHNxe2x80x94(Cxe2x95x90O), H2Nxe2x80x94(Cxe2x95x90O), Raxe2x80x94(Cxe2x95x90O)xe2x80x94NH, Raxe2x80x94(Cxe2x95x90O)xe2x80x94NRb or RaOxe2x80x94Nxe2x95x90C(Rb);
R6 is hydrogen, cyano, halogen, C1-C2-haloalkyl, C1-C2-haloalkoxy, Ra, RaO, RaS(O)m, RaOxe2x80x94(Cxe2x95x90O), Ra(Cxe2x95x90O), RaRbNxe2x80x94(Cxe2x95x90O), RaHNxe2x80x94(Cxe2x95x90O), H2Nxe2x80x94(Cxe2x95x90O), Raxe2x80x94(Cxe2x95x90O)xe2x80x94NH, Raxe2x80x94(Cxe2x95x90O)xe2x80x94NRb or RaOxe2x80x94Nxe2x95x90C(Rb);
Ra, Rb are C1-C4-alkyl, C3-C6-alkenyl or C3-C6-alkynyl, each of which may be substituted by cyano, C1-C4-alkoxy, C1-C4-alkoxycarbonyl or phenyl, or are phenyl which may carry one to three substituents selected from the group consisting of halogen and C1-C4-alkyl, and
the radicals R1 to R3 are each as defined in claim 1.
Preference is given to 2-(N-phenylamino)pyrimidines of the group If in which
R1, R3 are cyano, C1-C8-alkyl, propynyl, C1-C2-haloalkyl or cyclopropyl and are preferably methyl, ethyl, n-propyl, propynyl or cyclopropyl;
R2 is halogen or C1-C8-alkyl and is preferably fluorine, chlorine, methyl or ethyl;
R4, R8 are hydrogen;
R5, R7 independently of one another are hydrogen, cyano, C1-C2-haloalkoxy, Ra or RaOxe2x80x94Nxe2x95x90C(Rb) and are preferably hydrogen, cyano, Ra or RaOxe2x80x94Nxe2x95x90C(Rb);
R6 is hydrogen, cyano, halogen, C1-C2-haloalkyl, C1-C2-haloalkoxy, Ra or RaOxe2x80x94Nxe2x95x90C(Rb) and is preferably hydrogen, halogen or C1-C4-alkyl and
Ra, Rb are C1-C4-alkyl.
Group Ig: 2-(N-phenylamino)pyrimidines of the formula I in which
R1 is cyclopropyl;
R3 is cyano, C1-C8-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, where the radicals alkyl, alkenyl and alkynyl may be substituted by cyano, C1-C4-alkoxy or C1-C4-alkoxycarbonyl, or is C3-C8-cycloalkyl;
the radicals R2 and R4 to R8 are each as defined in claim 1.
Preference is given to 2-(N-phenylamino)pyrimidines of the group Ig in which
R1 is cyclopropyl;
R2 is halogen or C1-C8-alkyl and is preferably fluorine, chlorine, methyl or ethyl;
R3 is cyano, C1-C8-alkyl, propynyl or cyclopropyl and is preferably methyl, ethyl, n-propyl, propynyl or cyclopropyl;
R4 to R8 independently of one another are hydrogen, cyano, halogen, C1-C2-haloalkyl, C1-C2-haloalkoxy, Ra or RaOxe2x80x94Nxe2x95x90C(Rb) and are preferably hydrogen, halogen or C1-C4-alkyl and
Ra, Rb are C1-C4-alkyl.
Examples of particularly preferred 2-(N-phenylamino)pyrimidines are compiled in the Tables below.
2-(N-phenylamino)pyrimidines I.1-001 to I.1-379 of the formula I.1.
2-(N-phenylamino)pyrimidines I.2-001 to I.2-379 of the formula I.2, in which the meaning of (Rx)p is given by the rows of Table 1.
2-(N-phenylamino)pyrimidines I.3-001 to I.3-379 of the formula I.3, in which the meaning of (Rx)p is given by the rows of Table 1.
2-(N-phenylamino)pyrimidines I.4-001 to I.4-379 of the formula I.4, in which the meaning of (Rx)p is given by the rows of Table 1.
2-(N-phenylamino)pyrimidines I.5-001 to I.5-379 of the formula I.5, in which the meaning of (Rx)p is given by the rows of Table 1.
2-(N-phenylamino)pyrimidines I.6-001 to I.6-379 of the formula I.6, in which the meaning of (Rx)p is given by the rows of Table 1.
2-(N-phenylamino)pyrimidines I.7-001 to I.7-379 of the formula I.7, in which the meaning of (Rx)p is given by the rows of Table 1.
2-(N-phenylamino)pyrimidines I.8-001 to I.8-379 of the formula I.8, in which the meaning of (Rx)p is given by the rows of Table 1.
2-(N-phenylamino)pyrimidines I.9-001 to I.9-379 of the formula I.9, in which the meaning of (Rx)p is given by the rows of Table 1.
2-(N-phenylamino)pyrimidines I.10-001 to I.10-379 of the formula I.10, in which the meaning of (Rx)p is given by the rows of Table 1.
2-(N-phenylamino)pyrimidines I.11-001 to I.11-379 of the formula I.11, in which the meaning of (Rx)p is given by the rows of Table 1.
2-(N-phenylamino)pyrimidines I.12-001 to I.12-379 of the formula I.12, in which the meaning of (Rx)p is given by the rows of Table 1.
2-(N-phenylamino)pyrimidines I.13-001 to I.13-379 of the formula I.13, in which the meaning of (Rx)p is given by the rows of Table 1.
2-(N-phenylamino)pyrimidines I.14-001 to I.14-379 of the formula I.14, in which the meaning of (Rx)p is given by the rows of Table 1.
2-(N-phenylamino)pyrimidines I.15-001 to I.15-379 of the formula I.15, in which the meaning of (Rx)p is given by the rows of Table 1.
2-(N-phenylamino)pyrimidines I.16-001 to I.16-379 of the formula I.16, in which the meaning of (Rx)p is given by the rows of Table 1.
2-(N-phenylamino)pyrimidines I.17-001 to I.17-379 of the formula I.17, in which the meaning of (Rx)p is given by the rows of Table 1.
2-(N-phenylamino)pyrimidines I.18-001 to I.18-379 of the formula I.18, in which the meaning of (Rx)p is given by the rows of Table 1.
2-(N-phenylamino)pyrimidines I.19-001 to I.19-379 of the formula I.19, in which the meaning of (Rx)p is given by the rows of Table 1.
2-(N-phenylamino)pyrimidines I.20-001 to I.20-379 of the formula I.20, in which the meaning of (Rx)p is given by the rows of Table 1.
2-(N-phenylamino)pyrimidines I.21-001 to I.21-379 of the formula I.21, in which the meaning of (Rx)p is given by the rows of Table 1.
2-(N-phenylamino)pyrimidines I.22-001 to I.22-379 of the formula I.22, in which the meaning of (Rx)p is given by the rows of Table 1.
2-(N-phenylamino)pyrimidines I.23-001 to I.23-379 of the formula I.23, in which the meaning of (Rx)p is given by the rows of Table 1.
2-(N-phenylamino)pyrimidines I.24-001 to I.24-379 of the formula I.24, in which the meaning of (Rx)p is given by the rows of Table 1.
2-(N-phenylamino)pyrimidines I.25-001 to I.25-379 of the formula I.25, in which the meaning of (Rx)p is given by the rows of Table 1.
The compounds I are suitable for use as fungicides. They have outstanding activity against a broad spectrum of phytopathogenic fungi, in particular from the classes of the Ascomycetes, Deuteromycetes, Phycomycetes and Basidiomycetes. Some of them act systemically, and they can be employed in crop protection as foliar- and soil-acting fungicides.
They are especially important for controlling a large number of fungi on a variety of crop plants such as wheat, rye, barley, oats, rice, maize, grass, bananas, cotton, soya, coffee, sugar cane, grapevines, fruit species, ornamentals and vegetables such as cucumbers, beans, tomatoes, potatoes and cucurbits, and on the seeds of these plants.
Specifically, they are suitable for controlling the following plant diseases:
Alternaria species on vegetables and fruit,
Botrytis cinerea (gray mold) on strawberries, vegetables, ornamentals and grapevines,
Cercospora arachidicola on peanuts,
Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits,
Erysiphe graminis (powdery mildew) on cereals,
Fusarium and Verticillium species on various plants,
Helminthosporium species on cereals,
Mycosphaerella species on bananas and peanuts,
Phytophthora infestans on potatoes and tomatoes,
Plasmopara viticola on grapevines,
Podosphaera leucotricha on apples,
Pseudocercosporella herpotrichoides on wheat and barley,
Pseudoperonospora species on hops and cucumbers,
Puccinia species on cereals,
Pyricularia oryzae on rice,
Rhizoctonia species on cotton, rice and turf,
Septoria nodorum on wheat,
Uncinula necator on grapevines,
Ustilago species on cereals and sugar cane, and
Venturia species (scab) on apples and pears.
Moreover, the compounds I are suitable for controlling harmful fungi such as Paecilomyces variotii in the protection of materials (e.g. wood, paper, paint dispersions, fibers and fabrics) and in the protection of stored products.
The compounds I are applied by treating the fungi, or the plants, seeds, materials or the soil to be protected against fungal infection, with a fungicidally active amount of the active ingredients. Application can be effected both before and after infection of the materials, plants or seeds by the fungi.
In general, the fungicidal compositions comprise from 0.1 to 95, preferably 0.5 to 90, % by weight of active ingredient.
When used in crop protection, the rates of application are from 0.01 to 2.0 kg of active ingredient per ha, depending on the nature of the desired effect.
In the treatment of seed, amounts of active ingredient of from 0.001 to 0.1 g, preferably 0.01 to 0.05 g, are generally required per kilogram of seed.
When used in the protection of materials or stored products, the rate of application of active ingredient depends on the nature of the field of application and on the desired effect. Rates of application conventionally used in the protection of materials are, for example, from 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active ingredient per cubic meter of material treated.
The compounds I can be converted into the customary formulations, e.g. solutions, emulsions, suspensions, dusts, powders, pastes and granules. The use form depends on the particular purpose; it is intended to ensure in each case a fine and uniform distribution of the compound according to the invention.
The formulations are prepared in a known manner, e.g. by extending the active ingredient with solvents and/or carriers, if desired using emulsifiers and dispersants, it also being possible to use other organic solvents as auxiliary solvents if water is used as the diluent. Auxiliaries which are suitable are essentially: solvents such as aromatics (e.g. xylene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. mineral oil fractions), alcohols (e.g. methanol, butanol), ketones (e.g. cyclohexanone), amines (e.g. ethanolamine, dimethylformamide) and water; carriers such as ground natural minerals (e.g. kaolins, clays, talc, chalk) and ground synthetic minerals (e.g. highly disperse silica, silicates); emulsifiers such as nonionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants such as lignin-sulfite waste liquors and methylcellulose.
Suitable surfactants are alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates and fatty acids and their alkali metal and alkaline earth metal salts, salts of sulfated fatty alcohol glycol ether, condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or of napthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite waste liquors and methylcellulose.
Substances which are suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions are mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, strongly polar solvents, e.g. dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and water.
Powders, materials for spreading and dusts can be prepared by mixing or concomitantly grinding the active substances with a solid carrier.
Granules, e.g. coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Examples of solid carriers are mineral earths, such as silicas, silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.
In general, the formulations comprise from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, of the active ingredient. The active ingredients are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum).
The following are examples of formulations:
I. 5 parts by weight of a compound according to the invention are mixed intimately with 95 parts by weight of finely divided kaolin. This gives a dust which comprises 5% by weight of the active ingredient.
II. 30 parts by weight of a compound according to the invention are mixed intimately with a mixture of 92 parts by weight of pulverulent silica gel and 8 parts by weight of paraffin oil which had been sprayed onto the surface of this silica gel. This gives a formulation of the active ingredient with good adhesion properties (comprises 23% by weight of active ingredient).
III. 10 parts by weight of a compound according to the invention are dissolved in a mixture composed of 90 parts by weight of xylene, 6 parts by weight of the adduct of 8 to 10 mol of ethylene oxide and 1 mol of oleic acid N-monoethanolamide, 2 parts by weight of calcium dodecylbenzenesulfonate and 2 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil (comprises 9% by weight of active ingredient).
IV. 20 parts by weight of a compound according to the invention are dissolved in a mixture composed of 60 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 5 parts by weight of the adduct of 7 mol of ethylene oxide and 1 mol of isooctylphenol and 5 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil (comprises 16% by weight of active ingredient).
V. 80 parts by weight of a compound according to the invention are mixed thoroughly with 3 parts by weight of sodium diisobutylnaphthalene-alpha-sulfonate, 10 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 7 parts by weight of pulverulent silica gel, and the mixture is ground in a hammer mill (comprises 80% by weight of active ingredient).
VI. 90 parts by weight of a compound according to the invention are mixed with 10 parts by weight of N-methyl-xcex1-pyrrolidone, which gives a solution which is suitable for use in the form of microdrops (comprises 90% by weight of active ingredient).
VII. 20 parts by weight of a compound according to the invention are dissolved in a mixture composed of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 mol of ethylene oxide and 1 mol of isooctylphenol and 10 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which comprises 0.02% by weight of the active ingredient.
VIII. 20 parts by weight of a compound according to the invention are mixed thoroughly with 3 parts by weight of sodium diisobutylnaphthalene-xcex1-sulfonate, 17 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 60 parts by weight of pulverulent silica gel, and the mixture is ground in a hammer mill. Finely distributing the mixture in 20,000 parts by weight of water gives a spray mixture which comprises 0.1% by weight of the active ingredient.
The active ingredients can be used as such, in the form of their formulations or the use forms prepared therefrom, e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, materials for spreading, or granules, by means of spraying, atomizing, dusting, spreading or pouring. The use forms depend entirely on the intended purposes; it is intended to ensure in each case the finest possible distribution of the active ingredients according to the invention.
Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water. To prepare emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of wetter, tackifier, dispersant or emulsifier. Alternatively, it is possible to prepare concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such concentrates are suitable for dilution with water.
The active ingredient concentrations in the ready-to-use products can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.01 to 1%.
The active ingredients may also be used successfully in the ultra-low-volume process (ULV), it being possible to apply formulations comprising over 95% by weight of active ingredient, or even to apply the active ingredient without additives.
Various types of oils, herbicides, fungicides, other pesticides, or bactericides may be added to the active ingredients, if appropriate just immediately prior to use (tank mix). These agents can be admixed with the agents according to the invention in a weight ratio of 1:10 to 10:1.
In the use form as fungicides, the compositions according to the invention can also be present together with other active ingredients, e.g. with herbicides, insecticides, growth regulators, fungicides or else with fertilizers. Mixing the compounds I or the compositions comprising them in the use form as fungicides with other fungicides frequently results in a broader fungicidal spectrum of action.
The following list of fungicides together with which the compounds according to the invention can be used is intended to illustrate the possible combinations, but not to impose any limitation:
sulfur, dithiocarbamates and their derivatives, such as iron(III) dimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc ethylenebisdithiocarbamate, manganese ethylenebisdithiocarbamate, manganese zinc ethylenediaminebisdithiocarbamate, tetramethylthiuram disulfide, ammonia complex of zinc (N,N-ethylenebisdithiocarbamate), ammonia complex of zinc (N,Nxe2x80x2-propylenebisdithiocarbamate), zinc (N,Nxe2x80x2-propylenebisdithiocarbamate), N,Nxe2x80x2-polypropylenebis(thiocarbamoyl)disulfide;
nitro derivatives, such as dinitro(1-methylheptyl)phenyl crotonate, 2-sec-butyl-4,6-dinitrophenyl-3,3-dimethylacrylate, 2-sec-butyl-4,6-dinitrophenylisopropyl carbonate, diisopropyl 5-nitro-isophthalate;
heterocyclic substances, such as 2-heptadecyl-2-imidazoline 45 acetate, 2,4-dichloro-6-(o-chloroanilino)-s-triazine, O,O-diethyl phthalimidophosphonothioate, 5-amino-1-[bis(dimethylamino)phosphinyl]-3-phenyl-1,2,4-triazole, 2,3-dicyano-1,4-dithioanthraquinone, 2-thio-1,3-dithiolo[4,5-b]-quinoxaline, methyl 1-(butylcarbamoyl)-2-benzimidazolecarbamate, 2-methoxycarbonylaminobenzimidazole, 2-(2-furyl)benzimidazole, 2-(4-thiazolyl)benzimidazole, N-(1,1,2,2-tetrachloroethylthio)tetrahydrophthalimide, N-trichloromethylthiotetrahydrophthalimide, N-trichloromethylthiophthalimide;
N-dichlorofluoromethylthio-Nxe2x80x2,Nxe2x80x2-dimethyl-N-phenylsulfodiamide, 5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole, 2-thiocyanatomethylthiobenzothiazole, 1,4-dichloro-2,5-dimethoxybenzene, 4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone, pyridine-2-thiol 1-oxide, 8-hydroxyquinoline or its copper salt, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine 4,4-dioxide, 2-methyl-5,6-dihydro-4H-pyran-3-carboxanilide, 2-methylfuran-3-carboxanilide, 2,5-dimethylfuran-3-carboxanilide, 2,4,5-trimethylfuran-3-carboxanilide, cyclohexyl 2,5-dimethylfuran-3-carboxamide, N-cyclohexyl-N-methoxy-2,5-dimethylfuran-3-carboxamide, 2-methylbenzanilide, 2-iodobenzanilide, N-formyl-N-morpholine-2,2,2-trichloroethyl acetal, piperazine-1,4-diylbis-1-(2,2,2-trichloroethyl)formamide, 1-(3,4-dichloroanilino)-1-formylamino-2,2,2-trichloroethane, 2,6-dimethyl-N-tridecylmorpholine or its salts, 2,6-dimethyl-N-cyclododecylmorpholine or its salts, N-[3-(p-tert-butylphenyl)-2-methylpropyl]-cis-2,6-dimethylmorpholine, N-[3-(p-tert-butylphenyl)-2-methylpropyl]piperidine, 1-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-ylethyl]-1H-1,2,4-triazole, 1-[2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolan-2-ylethyl]-1H-1,2,4-triazole, N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-Nxe2x80x2-imidazolylurea, 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanone, 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanol, (2RS, 3RS)-1-[3-(2-chlorophenyl)-2-(4-fluorophenyl)oxiran-2-ylmethyl]-1H-1,2,4-triazole, xcex1-(2-chlorophenyl)-xcex1-(4-chlorophenyl)-5-pyrimidinemethanol, 5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine, bis(p-chlorophenyl)-3-pyridinemethanol, 1,2-bis(3-ethoxycarbonyl-2-thioureido)benzene, 1,2-bis(3-methoxycarbonyl-2-thioureido)benzene;
strobilurins such as methyl E-methoxyimino-[xcex1-(o-tolyloxy)-o-tolyl]acetate, methyl E-2-{2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]-phenyl}-3-methoxyacrylate, methyl-E-methoxyimino-[xcex1-(2-phenoxyphenyl)]acetamide, methyl-E-methoxyimino-[xcex1-(2,5-dimethylphenoxy)-o-tolyl]acetamide;
anilinopyrimidines such as N-(4,6-dimethylpyrimidin-2-yl)aniline, N-[4-methyl-6-(1-propynyl)pyrimidin-2-yl]aniline, N-[4-methyl-6-cyclopropylpyrimidin-2-yl]aniline;
phenylpyrroles such as 4-(2,2-difluoro-1,3-benzodioxol-4-yl)pyrrole-3-carbonitrile;
cinnamamides such as 3-(4-chlorophenyl)-3-(3,4-dimethoxyphenyl)acryloylmorpholine;
and a variety of fungicides such as dodecylguanidine acetate, 3-[3-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl]glutarimide, hexachlorobenzene, methyl N-(2,6-dimethylphenyl)-N-(2-furoyl)-DL-alaninate, DL-N-(2,6-dimethylphenyl)-N-(2xe2x80x2-methoxyacetyl)alanine methyl ester, N-(2,6-dimethylphenyl)-N-chloroacetyl-D,L-2-amino-butyrolactone, DL-N-(2,6-dimethylphenyl)-N-(phenylacetyl)alanine methyl ester, 5-methyl-5-vinyl-3-(3,5-dichlorophenyl)-2,4-dioxo-1,3-oxazolidine, 3-(3,5-dichlorophenyl-5-methyl-5-methoxymethyl-1,3-oxazolidine-2,4-dione, 3-(3,5-dichlorophenyl)-1-isopropylcarbamoylhydantoin, N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide, 2-cyano-[N-(ethylaminocarbonyl)-2-methoximino]acetamide, 1-[2-(2,4-dichlorophenyl)pentyl]-1H-1,2,4-triazole, 2,4-difluoro-xcex1-(1H-1,2,4-triazolyl-1-methyl)benzhydryl alcohol, N-(3-chloro-2,6-dinitro-4-trifluoromethylphenyl)-5-trifluoro-methyl-3-chloro-2-aminopyridine, 1-((bis(4-fluorophenyl)methylsilyl)methyl)-1H-1,2,4-triazole.

Use of 2-(n-phenylamino)pyrimidines as fungicides, and novel 2-(n-phenylamino) pyrimidines

Abstract: where:

Abstract: R2 is halogen, C1-C8-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, where the radicals alkyl, alkenyl and alkynyl may be substituted by cyano, halogen, C1-C4-alkoxy or C1-C4-alkoxycarbonyl, or

Abstract: R1 and R2 together with the two linking carbon atoms form a fused-on partially unsaturated 4- to 8-membered ring which may be up to trisubstituted by identical or different substituents selected from the group consisting of C1-C4-alkyl, halogen and C1-C4-alkoxy-carbonyl, which may contain a carbonyl group and/or, in addition to the multiple bond of the pyrimidine ring, a double bond and/or which may be interrupted by O, S or Nxe2x80x94(C1-C4-alkyl);

Abstract: the substituents R4 to R8, Rx, Ry, Ra and Rb are as defined in the description;

Abstract: are used as fungicides.


The present invention relates inter alia to compositions comprising conjugated polymers and a small molecule, devices comprising the composition and the application of the devices.

Commercial applications of white light emitting devices are manifold. White light emitting devices are not only used for lighting, but also in displays and as backlit. The requirements for modern white light emitting devices demand the development of new technologies. Displays in smartphones, tablet computers, TVs, and modern thin lighting devices, for instance, require thin and potentially flexible light sources with excellent performance characteristics. Thin electroluminescent organic light emitting devices, thus, represent an attractive target in order to accomplish specific requirements of new technologies. Particularly, organic light emitting diodes (OLEDs) and organic light emitting electrochemical cells (OLEC, LEC or LEEC) are considered as being promising electroluminescent devices.
Organic light emitting diodes (OLEDs), in which organic semiconductors are used as functional materials are disclosed, for example, in U.S. Pat. Nos. 4,539,507, 5,151,629, EP 0676461 and WO 98/27136. The organic light emitting materials being employed for this purpose are increasingly often organometallic complexes which exhibit phosphorescence instead of fluorescence (M. A. Baldo et al., Appl. Phys. Lett. 1999, 75, 4-6). For quantum-mechanical reasons, an up to four-fold increase in energy and power efficiency is possible using organometallic compounds as phosphorescent emitters. In accordance with the prior art, the triplet emitters in phosphorescent OLEDs are, in particular, iridium and platinum complexes, which are typically cyclometallated. The emitters currently available emit light in the range from blue to red.
The scientific and industrial interest in OLEDs is particularly high due to their potential commercial applications for lighting and display technologies. OLEDs exhibit several advantages over existing and established technologies such as low energy consumption, low thickness and high flexibility of the devices. Furthermore, OLEDs represent a uniform irradiation source as compared to the spotlight of other light sources such as inorganic LEDs.
The possibilities to achieve white light emission in OLEDs (WOLEDs) are manifold. Single-color white OLEDs comprise one emitter with a broad emission spectrum, but achieving the desired color coordinates might be difficult with this basic approach. Therefore, multi-color approaches have been developed. The multi-color approach can be realized in different ways. Firstly, the emissive layer (EML) of an OLED can be multiple doped. Secondly, different emissive layers in a single OLED can be used (sublayer-approach). Thirdly, red, green and blue light emitting subpixel can be used to white emission. Moreover, different OLEDs can be stacked in order to get WOLDs (tandem OLED). K. Meerholz et al. provide an overview on white OLEDs in Adv. Mater. 2011, 23, 233-248.
However, OLEDs also have some disadvantages. The preparation of OLEDs is often quite complex and costly, as OLEDs exhibit a multi-layered structure comprising a number of different functional layers such as substrate, anode, hole injection layer (HIL), hole transport layer (HTL), emissive layer (EML), electron transport layer (ETL), electron injection layer (EIL), cathode and potentially further layers.
Depending on the specific technical application a suitable alternative to an OLED is an organic light emitting electrochemical cell (OLEC, LEEC or LEC). The preparation of OLECs—particularly if curves or three-dimensional surfaces occur—is less complex as compared to the preparation of OLEDs. This is due to the fact that the requirements relating to homogeneity of the layer is less stringent. Thus, the production costs in particular for mass production are much lower as compared to the ones of OLEDs.
Furthermore, OLECs do not rely on air-sensitive charge-injection layers or metals such as Ba or Cs for electron injection, which further simplifies their preparation and makes them more cost efficient, as compared to OLEDs. This is due to the less stringent requirements for encapsulation of OLECs.
The underlying technology of OLECs differs from the one of OLEDs or LEDs. Both OLEDs and LEDs are diodes with forward bias and reverse bias. In contrast to OLECs the I-V (current-voltage) curves of both OLEDs and LEDs are asymmetric. They represent semiconductor technologies whereas an OLEC is basically an electrochemical or more precisely an electrolytic cell. Charge transport in OLEDs occurs via the movement of holes and electrons from molecule to molecule (hopping) until holes and electrons form so called excitons, i.e. electron-hole-pairs. Light is emitted when electrons and holes recombine. In OLECs, upon applying a voltage, the electroactive compound, being a conjugated polymer or a small molecule, is oxidized (p-type doped) at the anode and reduced (n-type doped) at the cathode.
The p- and n-type doping regions grow in size until they meet to form a so called p-n junction. Further, an exciton is formed on the organic emissive compounds in the p-n junction. The radiative decay of the exciton leads to the emission of light. The original work and the principle of OLECs have been published by Qibing Pei et al. in Science, 1995, 269, 1086-1088. OLECs show symmetric I-V curves, have low driving voltages, and there is no need for reactive metals as cathode.
But the time needed for forming p-n junction is long. Therefore, the turn-on is not instantaneous. In addition, lifetime of OLECs is often very short as compared to highly efficient OLEDs. Thus, up to date OLECs aren't suitable for, e.g., display applications, but many other applications are possible such as light emitting label for, e.g. packaging.
One way to achieve white light emission with OLEDs is to use a conjugated polymer as emissive material in polymer light emitting diodes (PLEDs) as disclosed in EP 1670844 B1. The white copolymer as disclosed in EP 1670844 B1 comprises blue, red and preferably also green emitters. In order to get a broad emission in OLEDs, one has to tailor the composition of the light emitting components of the polymer so that energy transfer from the blue light emitting component to the green one and further to the red one is only partially. As energy transfer in conjugated polymers is believed to occur via Förster energy transfer, the composition of green emitter and especially that of red emitter has to be very low, usually less than 0.05 mol % related to the total polymer, or even less. This results in several problems such as 1) the color is very sensitive to the concentration of red emitter. Small variations regarding the concentration can cause significant changes of the color and 2) a trace of the red emitter may also cause difficulties regarding reliability of the preparation of the polymer and 3) traces of red emitters might cause color shifts depending on the applied voltage. It is well accepted on the prior art, that high efficient light emission in organic electroluminescent devices can be attained by the use of phosphorescent emitters. For this reason the polymers as disclosed in EP 1670844 B1 comprise also phosphorescent metal complexes as repeating units. However, due to so called "long-range resonantly enhanced triplet formation" one skilled person will expect that a mixture or blend of a phosphorescent metal complex and a conjugated polymer will effectively quench the emission of the polymer. White emission of such systems is either not possible or of insufficient quality.


A method for blending poly(ether imide)s with polyesters comprising: (a) adding polyester monomers and poly(ether imide) in a polymerization reactor at any point during a polyester polymerization process; and (b) polymerizing the polyester monomers in the presence of the poly(ether imide) under standard conditions to produce a blend.

This invention relates to a general method for preparing homogeneous blends of poly(ethylene naphthalate) and other polyesters with poly(ether imide)s.
A novel blend of poly(ethylene naphthalate) (PEN) with poly(ether imide) (PEI) was disclosed in U.S. Pat. No. 5,599,658 as a resin formulation with a number of useful properties which makes it especially advantageous for use in photographic film. In particular, a film manufactured from this blend at a certain composition range generally retains the desirable properties of PEN film, while having a lower propensity to take up core-set curl. This property permits its use in small diameter cartridgesxe2x80x94for example, diameters in the range of -12.5 mmxe2x80x94without suffering the consequence of an increased curl in the wound film. It is also possible to use less extreme annealing conditions (lower annealing temperature and/or shorter annealing time) with a film comprising the said blend formulation to achieve equivalent core-set propensity to that of PEN film.
However, preparation of the blend formulation in accordance with U.S. Pat. No. 5,599,658, the contents of which are incorporated herein in their entirety, requires thorough drying of all components and an additional compounding step using, typically, a twin-screw extruder or equivalent melt compounding equipment. These additional steps raise the cost of the blend and make it less attractive economically compared to the unblended PEN resin. In addition, the need to heat the resin components to high temperature during compounding can lead to thermal and hydrolytic degradation as well as contamination of the blended resin with debris from the compounding equipment.
What is needed in the art is a method of preparing a blend of poly(ether imide) (PEI) with poly(ethylene naphthalate) (PEN), poly(ethylene terephthalate) (PET) and other polyesters that overcomes the problems noted above.
The present invention discloses an in-situ process of blending PEI and polyesters that provides better control of the blended polymer viscosity and avoids problems heretofore encountered in the blending process.
The conventional, high temperature compounding step can be eliminated by adding the PEI resin directly into the reactor used for preparing the PEN polymer. The invention discloses that, contrary to expectation, the presence of PEI pellets in the polyester polymerization reaction vessel has no adverse effect on the kinetics and extent of the polymerization reaction and allows easy blending and homogenizing of the added PEI resin with the polymerizing PEN species. The final resin obtained by this xe2x80x9cin-situxe2x80x9d blending process is a homogeneously dispersed PEN/PEI blend with a sufficiently high inherent viscosity (IV) and a single glass transition temperature (Tg).
Poly(ethylene naphthalene), sometimes abbreviated as PEN, previously has been used as a support for magnetic recording and playback tapes and had been proposed for use as a support for photographic film, for example in U.S. Pat. No. 4,141,735, U.S. Pat. No. 5,294,473 and U.S. Pat. No. 5,368,997. The ""473 and ""997 patents broadly describe copolyesters with PEN and blends of PEN with other polymers, but not with a poly(ether imide). The PEN used in the polymer blend of this invention can be the same polymer as described in this prior art, such as U.S. Pat. No. 5,368,997, the disclosure of which is incorporated herein by reference. Preferably it is PEN, particularly poly(ethylene-2,6-naphthalate).
The PEN used in the polymer blends of this invention preferably has molecular weights represented by inherent viscosities in the range of 0.5 to 0.9 dl/g. (Inherent viscosity is measured in a Ubbelhode capillary viscometer (Shott Gerate 536-13) at 25xc2x0 C. and at a polymer concentration of 0.25 g/dL in a 50/50 mixture by weight of pentafluorophenol and 1,2,4-trichlorobenzene.) The PEN used in the polymer blends of this invention preferably has a glass transition temperature (Tg), above about 118xc2x0 C.
Poly(ether imide), sometimes abbreviated as PEI, is the condensation product of a bis(etherdianhydride) and an organic diamine. Its synthesis, structure and use are described in U.S. Pat. Nos. 3,803,085, 3,847,867, 3,905,942, 4,011,198 and 4,293,684. The particular PEI used in the polymer blends of this invention can be as described in this prior art, such as U.S. Pat. No. 3,847,867, the disclosure of which is incorporated herein by reference. A preferred PEI is one in which the bis(etherdianhydride) is 2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride (also known as Bisphenol A dianhydride) and the organic diamine is m-phenylene diamine.
Preferably, the PEI has a molecular weight represented by a melt viscosity in the range of 103 to 105 poise. Melt viscosity is measured according to the following procedure: A sample of the PEI in pellet form is dried under vacuum at 150xc2x0 C. for 10 hrs. The dried sample is loaded into a parallel disk (25 mm diameter) fixture of a Rheometrics System IV(copyright) rheometer (manufactured by Rheometrics, Inc., Possumtown Rd., Piscataway, N.J. 08854) and its temperature is raised to 305xc2x0 C. The viscosity of the melt is determined by shearing the resin at a constant oscillating frequency of 1 rad/s.
The PEI used in this invention preferably has a glass transition temperature (Tg) which is above 150xc2x0 C. In addition, the PEI should be miscible with the PEN. By miscible is meant that the blend of the two polymers has a single glass transition temperature (Tg) and that a photographic film base made from the blend is clear. The PEI is available commercially from the General Electric Company, One Plastics Ave., Pittsfield, Mass. 01201, under the Ultem(copyright) trade name. Representative grades are Ultem 1000(copyright) and Ultem 1010(copyright).
Blending of PEI with polyesters, such as PET and PEN is broadly described in U.S. Pat. No. 4,141,927 and Research Disclosure, November 1987, Item 28338, pages 677-8. (Research Disclosure is published by Kenneth Mason Publications, Ltd., Dudley Annex, 12a North Street, Emsworth, Hampshire P010 7DQ, ENGLAND.) These patents and publication do not describe the blends of this invention or suggest that they would be suitable for use as a photographic film base. Nor does any of this art suggest that blending PEI with PEN would have any influence on the core-set and post-process curl characteristics of a film based prepared from the blend, let alone suggest that such a blend would provide a film base in which these characteristics were improved.
The blends of this invention preferably have the following physical characteristics: a Tg of greater than 125xc2x0 C.; a tensile modulus greater than 350 Kg/mm2; light transmission greater than 80%; and haze less than 3%. The way in which these characteristics are determined is described in the Examples in U.S. Pat. No. 5,599,658.
While the relative proportions of PEN and PEI may vary somewhat with variations in the particular PEI employed, as well as with the presence of other components in the blend, preferred proportions of PEN and PEI in the blends of this invention are from 70 to 95 weight percent PEN and from 5 to 30 weight percent of PEI. When the proportion of PEI is increased, we have found that the tensile modulus is decreased, the crystallinity of the blend is lowered and a sheet formed from the blend becomes difficult to stretch. When the proportion of PEI is decreased below the said range, we have found that the improvement in physical performance of the blend becomes insignificant. Preferably the proportion of PEI is between 10 and 20 percent by weight. Most preferably the proportion of PEI is between 12 and 17 percent by weight. These are the preferred proportions for PEI prepared from bisphenol A dianhydride and m-phenylene diamine.
Film base is prepared from the polymer blend by techniques known to those skilled in the art. These techniques are described in detail in Schrader U.S. Pat. No. 4,141,735, the disclosure of which is incorporated herein by reference. A film base is understood to be a planar sheet having a thickness in the range of 50 to 200 xcexcm, preferably a thickness of 70 to 110 xcexcm.
In a typical operation, the film base is formed by extruding the polymer blend at a temperature of 290 to 320xc2x0 C. through a sheeting die and casting the molten sheet on a chill roll at a temperature of 60 to 120xc2x0 C. The cast sheet is then stretched biaxially to from 2 to 5 times its initial lateral dimensions. tretching can be at a temperature in the range of from 130 to 170xc2x0 C. Biaxial stretching can be sequential or simultaneous. After stretching the film base is heatset at a temperature in the range of 200 to 250xc2x0 C. for time in the range of 0.1 to 10 sec. If the film base is to be annealed, it can be annealed at a temperature in the range of from 50xc2x0 C. up to the Tg of the polymer blend for a time in the range of 0.1 to 1000 hours. Film base with core-set characteristics useful for small diameter film cartridges can be obtained with preferred blends of this invention by annealing at temperatures of between about 90 and 125 xc2x0 C. for times of 6 to 72 hrs.
Film base prepared from polymer blends of this invention can contain other components commonly found in film supports for photographic elements. These include dyes, lubricants and particles of organic and inorganic materials such as glass beads. These are described in more detail in Research Disclosure, February 1995, Item 37038, pages 79-114.
Film base prepared from polymer blends of this invention can bear layers commonly found on film supports used for photographic elements. These include magnetic recording layers, subbing layers between other layers and the support, photosensitive layers, interlayers and overcoat layers, as are commonly found in photographic elements. These layers can be applied by techniques known in the art and described in the references cited in Research Disclosure Item 37038 cited above.
Magnetic recording layers that can be used in photographic elements of this invention are described in U.S. Pat. Nos. 3,782,947; 4,279,945; 5,147,768; 5,252,441; 5,254,449; 5,395,743; 5,397,826; 5,413,902; 5,427,900, 5,432,050, 5,434,037, 5,436,120, in Research Disclosure November 1992, Item 34390, pages 869 et seq.
Photographic elements of this invention can have the structures and components shown on Research Disclosure 37038 cited above and can be imagewise exposed and processed using known techniques and compositions, including those described in the Research Disclosure Item 37038 cited above.
Blending of PEI with polyesters, such as PET and PEN, is broadly described in U.S. Pat. No. 4,141,927 and Research Disclosure, November 1987, Item 28338, pages 677-8 (Research Disclosure is published by Kenneth Mason Publications, Ltd., Dudley Annex, 12a North Street, Emsworth, Hampshire P010 7DQ, UK). Both of these publications cite examples of a melt or a solution blending process for the PEI and polyester components. However, they do not describe nor do they suggest the possibility of an xe2x80x9cin-situxe2x80x9d blending process such as is claimed in the present invention. In-situ blending has been applied in previous inventions to the preparation of blends of mostly addition-type polymers, e.g., various polyolefins (U.S. Pat. Nos. 5,225,457; 5,126,398; 5,149,738; 5,047,468; 5,677,375 and 4,522,962) and styrenics (E.P. No. 135,168). The polymers of the present invention, polyesters, are produced by a condensation-type polymerization process, which is fundamentally different from the addition process used for preparing polyolefins and styrenics or from the condensation process of other polymers. The general procedure of the polyester polymerization process is well known to those skilled in the art. Suitable polyesters for this invention are any that are manufactured by a polycondensation process at temperatures greater than the glass transition temperature of the poly(ether imide). Some examples of such polyesters and copolyesters include polycondensation products of diacid (or diester analogs) and glycols such as terephthalic acid, naphthoic acid, 5-sodiosulfoisophthalic acid, isophthalic acid, ethlylene glycol, diethylene glycol, poly(ethylene glycol), poly(propylene glycol), cyclohexane dimethanol, butanediol, neopentyl glycol, trimethylol propane and pentaerythritol. The weight ratio of polyester:poly(ether imide) in the blend is 95:5 to 70:30, preferably 80:20 to 90:10. The poly(ether imide) may be added to a continuous polymerization reactor or a batch polymerization reactor. In one embodiment of the invention the polyester is poly(ethylene-2,6-naphthalate). In another embodiment the poly(ether imide) is a condensation polymer of 2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl] propane dianhydride and m-phenylene diamine. The weight ratio of poly(ethylene-2,6-naphthalate):the condensation polymer of 2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl] propane dianhydride and m-phenylene diamine in the blend is 80:20 to 90:10.
In yet another embodiment, the polyester is poly(ethylene terephthalate). The weight ratio of poly(ethylene terephthalate):poly(ether imide) in the blend is 95:5 to 70:30. A preferred poly(ether imide) is the condensation polymer of 2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl] propane dianhydride and m-phenylene diamine. The weight ratio of poly(ethylene terephthalate):the condensation polymer of 2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl] propane dianhydride and m-phenylene diamine in the blend is 95:5 to 70:30, preferably 80:20 to 90:10.
The method of the invention is useful to prepare a blend for film supports in photographic elements. An exemplary photographic element may comprise a film support bearing at least one photographic layer, the film support comprising a homogenous blend of from 70 to 95 weight percent poly(ethylene naphthalate) and from 30 to 5 weight percent of a poly(ether imide), preferably 80 to 90 weight percent poly(ethylene naphthalate) and from 20 to 10 weight percent of a poly(ether imide).

In-situ blending of polyesters with poly(ether imide)


A lighting device convertible between reading light and pen light configurations uses only a single off/on light actuating switch in either configuration. The lighting device includes a main body, pivoting arm, hinge, light generating element, batteries and switch member and button. The main body has opposite front and rear ends and defines a recess at the front end. The pivoting arm has opposite front and rear ends. The hinge pivotally mounts the rear end of the pivoting arm to the rear end of the main body to allow pivotal movement of the pivoting arm between an erect position angularly spaced from the main body, the reading light configuration, and a lowered position adjacent to the main body, the pen light configuration. The light generating element is mounted to the pivoting arm adjacent to the front end thereof for providing light therebelow when the pivoting arm is in the erect position and is insertable within the recess of the main body and exposed only at the front end of the main body to provide light directly forwardly of the main body when the pivoting arm is in the lowered position. The batteries are mounted within the main body and electrically interconnected to the light generating element and switch member. The switch member and button are mounted to the main body for switching the light generating element between off and on states.

1. Field of the Invention
The present invention generally relates to portable lighting devices and, more particularly, is concerned with a lighting device convertible between reading light and pen light configurations and having a single off/on light actuating switch.
2. Description of the Prior Art
Lighting devices variously configured as miniature flashlights and as book or reading lights are well known in the prior art. Examples of lighting devices which are configured as book or reading lights are disclosed in U.S. Pat. No. 4,432,042 to Zeller, U.S. Pat. No. 4,598,340 to Dwosh et al, U.S. Pat. No. 4,680,681 to Fisherman et al, U.S. Pat. No. 5,203,622 to Sottile, U.S. Pat. No. 5,280,416 to Hartley et al and U.S. Pat. No. 5,442,528 to Vandenbelt. A drawback of these and other prior art lighting devices is that their designs restrict them to a single type of use or purpose, either as a flashlight or as a reading light. They are configured to function as one or the other, not both. This requires consumers to purchase more than one lighting device for different functions or uses which results in higher cost to them and more devices which must be carried with them.
Consequently, a need exists for a lighting device having dual functionality or use, both as a flashlight and as a book or reading light, which will overcome the drawbacks of the prior art without introducing any new problems in place thereof.

Lighting device convertible between reading light and pen light configurations and having single light actuating switch


A system for testing an embedded processor, such as an embedded processor for a spacecraft. The system comprises an Emulated Spacecraft Control Processor (ESCP) which contains the embedded processor, a simulation engine, and a host computer. The emulated spacecraft control processor includes a dual-port memory for emulating the memory for the embedded processor and data transfer logic which monitors cycles of the embedded processor to arbitrate access to the dual-port memory, the data transfer logic is operative to allow an access to the dual-port memory when the embedded processor performs an I/O cycle, wherein the access is performed before a subsequent machine cycle of the embedded processor.

The present invention relates generally to spacecraft simulation, and more particularly to systems for non-intrusive memory transfers for embedded processor-based systems.
The increasing size and complexity of various spacecraft and control subsystems therefore have created a need for detailed validation and verification before deployment. Examples of spacecraft subsystems requiring validation and verification include: (i) multiprocessor-based systems which can have complex software architectures; (ii) fault detection and response systems providing extended autonomous operations; (iii) multiple-articulated payloads and multibody control; (iv) precision payload pointing systems with multiple interacting elements; and (v) sophisticated ground software for automated spacecraft operations.
However, system-level ground testing to verify full system performance of a spacecraft can be costly and/or inadequate. Present implementations of hardware-in-the-loop systems to provide ground testing require special purpose interface hardware and harnessing to create a test environment whereby system hardware or emulations thereof can be integrated with high-fidelity, non-linear, real-time simulations and then instrumented to facilitate verification and validation testing.
Embedded processors and software that constitute various spacecraft subsystems implement asynchronous, real-time processes that require non-intrusive instrumentation to facilitate adequate testing. It is imperative that the real-time behavior of the systems under test not be compromised by instrumentation. Otherwise, the system under test is not truly the system to be used operationally.
Known implementations of such systems required a substantial amount of harnessing and interfacing devices to accommodate non-intrusive instrumentation; typically embedded processor memory monitoring and control. The amount of harnessing and interfacing devices reduces the overall reliability of the system and increases the cost. Known systems employ bus monitoring schemes to facilitate memory monitoring. More capable mechanisms may allow for memory modification. However, these do not operate on a real time basis. That is, the previous implementations have resident arbitration schemes that control access to the data buses. These arbitration schemes initiate wait states that are not found in actual running. Thus, known systems employ complex mechanisms to monitor the contents of embedded processor memories and implement intrusive mechanisms to modify memory.
U.S. Pat. No. 5,808,921 is commonly assigned and was co-invented by the inventor of the present invention. In the ""921 patent, a system for selected and limited, non-intrusive (input/output) I/O access was provided when the CPU was in a memory cycle. The dual port memory mimicked the I/O buffer. Thus, when the ""921 system was in a memory cycle, it was not using the I/O and thus data was transferred via the I/O. Thus, the dual port memory emulated the I/O space. The U.S. Pat. No. 5,808,921 has limited functionality because only the I/O space is emulated and only a portion thereof. U.S. Pat. No. 5,808,921 is hereby incorporated by reference.
It would therefore be desirable to increase the functionality of a simulator and to provide a method and apparatus for providing non-intrusive memory access without extraneous wait states so that crucial instrumentation, in the form of memory status and control, on the embedded, real-time application, can be performed in support of overall system verification and validation.
It is an object of the present invention to provide a low-cost, reliable system for verifying an embedded processor-based system which emulates the entire memory and which requires less facility resources (e.g. test equipment) in comparison to previously-implemented hardware-in-the-loop systems.
A further object of the present invention is to provide a system for testing an embedded processor-based system which does not require special purpose interface hardware and harnessing to integrate the embedded processor-based system with instrumentation to monitor the contents of embedded memories.
In carrying out the above objects, the present invention provides a system for testing an embedded processor, such as an embedded processor for a spacecraft. The system comprises an Emulated Spacecraft Control Processor (ESCP) which contains the embedded processor, a simulation engine, and a host computer. The emulated spacecraft control processor includes a dual-port memory for emulating the input/output interface for the embedded processor and data transfer logic which monitors cycles of the embedded processor to arbitrate access to the dual-port memory, the data transfer logic is operative to allow an access to the dual-port memory when the embedded processor performs a I/O cycle, wherein the access is performed before a subsequent memory cycle of the embedded processor.
In a preferred embodiment, the simulation engine executes program steps asynchronously with respect to the embedded processor. Here, the Emulated Spacecraft Control Processor includes an overlayed dual-port memory for emulating the memory for the embedded processor and data transfer logic which monitors cycles of the embedded processor to arbitrate access to the dual-port memory. The data transfer logic is operative to allow simulation engine access to the dual-port memory when the embedded processor performs an I/O cycle, wherein the access is performed before a subsequent machine cycle of the embedded processor. The data transfer logic is operative to inhibit access by the simulation engine to the dual-port memory when a memory cycle is performed by the embedded processor.
Also in a preferred embodiment, the simulated sensor data, the command data, the actuator command data, and the telemetry data are communicated via an industry standard bus. Here, the system further comprises an interactive bus manager which communicates the command data and the telemetry data between the bus and the host computer. Additionally, the simulated sensor data and actuator command data are communicated between the simulation engine and the Emulated Spacecraft Control Processor using the industry standard bus.
Further in carrying out the above objects, the present invention provides a method of testing an embedded processor based upon the above-described steps.
Embodiments of the present invention are advantageous in that the simulation engine and the Emulated Spacecraft Control Processor share memory space without any compromise of the real-time performance of the embedded processor.
These and other features, aspects, and embodiments of the present invention will become better understood with regard to the following description, appended claims, and accompanying drawings.

Non-intrusive memory access for embedded processors


An interlock mechanism for a tractor transmission having a creeper gear arrangement is disclosed wherein the operation of the tractor engine is halted whenever the creeper arrangement is left in a condition conducive to incurring unwanted creep. The interlock mechanism is in the form of an electrical circuit operably connected to the fuel shutoff valve to halt the flow of fuel to the tractor engine whenever the creeper arrangement is left in a neutral state with the clutch engaged. The interlock mechanism provides electrical power to the fuel shutoff valve under normal operating conditions. Switches associated with the operative components of the transmission control the flow of electrical current through the interlock circuit.

This invention relates generally to off-road motor vehicles, such as tractors, and more particularly, to an interlock mechanism cooperable with a creeper gear to control engagement thereof under specified conditions.
Contemporary tractor transmissions have become mechanically complicated, incorporating sixteen or more forward speeds and usually half as many speeds in reverse, along with hydraulic, electric or electronically controlled shifting mechanisms to change the selected speed of operation of the tractor. The various operations for which tractors are employed require such a wide range of options and speeds of operation. Some specialized harvesting operations, among others, require very slow speeds of operation, which are typically provided through a "creeper gear" or range of gears.
Creeper options for tractors introduce design challenges. When in "creeper gear", the tractor is usually capable of a very slow speed of movement over the ground with the ability to pull with several thousands of pounds of force. In some tractor transmissions, internal drag between the gears and the oil bath for the gears can transmit this pulling force from the engine to the output shaft of the transmission even though the transmission gears are not engaged, i.e. the transmission is in neutral, resulting in unwanted creep of the tractor.
It is desirable to provide a tractor transmission having a crooper gear arrangement in which the unwanted creep, occurring when the transmission is in a neutral state through drag within the transmission, is prevented by an interlock mechanism associated with the tractor engine.


A method of making imaged elements such as lithographic printing plates is achieved by imagewise exposing an infrared radiation-sensitive positive-working imageable element to provide exposed and non-exposed regions. The imaged element is developed using a single processing solution having a pH of from about 9 to about 11.5 and containing carbonate ion and at least 1 weight % of one or more anionic surfactants, to remove predominantly only the exposed regions to provide an image and to provide a protective coating on the imaged surface. The imageable element comprises a substrate and a radiation absorbing compound, and has an imageable layer on the substrate that comprises a developability-enhancing compound and a poly(vinyl acetal) in which at least 25 mol % of its recurring units comprise pendant nitro-substituted phenolic groups.

In lithographic printing, ink receptive regions, known as image areas, are generated on a hydrophilic surface. When the surface is moistened with water and ink is applied, the hydrophilic regions retain the water and repel the ink, the ink receptive regions accept the ink and repel the water. The ink is then transferred to the surface of suitable materials upon which the image is to be reproduced. In some instances, the ink can be first transferred to an intermediate blanket that in turn is used to transfer the ink to the surface of the materials upon which the image is to be reproduced.
Imageable elements useful to prepare lithographic (or offset) printing plates typically comprise one or more imageable layers applied over a hydrophilic surface of a substrate (or intermediate layers). The imageable layer(s) can comprise one or more radiation-sensitive components dispersed within a suitable binder. Following imaging, either the exposed regions or the non-exposed regions of the imageable layer(s) are removed by a suitable developer, revealing the underlying hydrophilic surface of the substrate. If the exposed regions are removed, the element is considered as positive-working. Conversely, if the non-exposed regions are removed, the element is considered as negative-working. In each instance, the regions of the imageable layer(s) that remain are ink-receptive, and the regions of the hydrophilic surface revealed by the developing process accept water or aqueous solutions (typically a fountain solution), and repel ink.
Similarly, positive-working compositions can be used to form resist patterns in printed circuit board (PCB) production, thick-and-thin film circuits, resistors, capacitors, and inductors, multichip devices, integrated circuits, and active semiconductive devices.
"Laser direct imaging" methods (LDI) have been known that directly form an offset printing plate or printing circuit board using digital data from a computer, and provide numerous advantages over the previous processes using masking photographic films. There has been considerable development in this field from more efficient lasers, improved imageable compositions and components thereof.
Thermally sensitive imageable elements can be classified as those that undergo chemical transformation(s) in response to, exposure to, or adsorption of, suitable amounts of thermal energy. The nature of thermally induced chemical transformation may be to ablate the imageable composition in the element, or to change its solubility in a particular developer, or to change the tackiness or hydrophilicity or hydrophobicity of the surface layer of the thermally sensitive layer. As such, thermal imaging can be used to expose predetermined regions of an imageable layer that can serve as a lithographic printing surface or resist pattern in PCB production.
Positive-working imageable compositions containing novolak or other phenolic polymeric binders and diazoquinone imaging components have been prevalent in the lithographic printing plate and photoresist industries for many years. Imageable compositions based on various phenolic resins and infrared radiation absorbing compounds are also well known.
WO 2004/081662 (Memetea et al.) describes the use of various developability-enhancing compounds of acidic nature with phenolic polymers or poly(vinyl acetals) to enhance the sensitivity of positive-working compositions and elements so that required imaging energy is reduced. Some of the particularly useful poly(vinyl acetals) for such compositions and elements are described in U.S. Pat. No. 6,255,033 (Levanon et al.) and U.S. Pat. No. 6,541,181 (Levanon et al.).
Thermally imageable elements containing certain developability-enhancing materials and poly(vinyl acetal)s are described in copending and commonly assigned U.S. Ser. No. 11/677,599 (filed Feb. 22, 2007 by Levanon, Postel, Rubin, and Kurtser), U.S. Ser. No. 11/769,766 (filed Jun. 28, 2007 by Levanon, Lurie, and Kampel), and U.S. Ser. No. 11/959,492 (filed Dec. 18, 2007 by Nakash and Levanon).
Imageable elements containing phenolic resins are described in U.S. Pat. No. 6,410,203 (Nakamura). After imaging, the elements are developed with any of a variety of developers including silicate-containing, carbonate, phosphate, and borate developers.
Copending and commonly assigned U.S. Ser. No. 12/025,089 (filed Feb. 4, 2008 by Levanon, Nakash, and Kurtser) describes the use of carbonate developers for processing positive-working imageable elements containing poly(vinyl acetal)s. However, the usual water rinsing and gumming steps must be used after development with these developers.

Method of imaging and developing positive-working imageable elements


Disclosed are apparatus and methods used for handling semiconductor wafers or similar articles. In particular, the apparatus disclosed is capable of flexibly gripping items of various shapes and sizes in a manner that substantially reduces or eliminates the likelihood of damage thereto. The apparatus is particularly suited to being used as a robotic end effector for handling wafers using edge-gripping techniques.

The present invention relates generally to apparatus and methods for handling semiconductor wafers or similar articles. More particularly, the present invention relates to a robotic end effector for handling semiconductor wafers using edge-gripping techniques.
Semiconductor manufacturing requires an ultra-clean environment for the silicon wafers during the manufacturing process; therefore it is highly desirable to have few moving parts in the wafer processing environment due to the risk of wear particles and the like migrating to the wafer surface, thereby contaminating the wafer and resulting in reduced production yields. Currently, the handling of semiconductor wafers and similar articles is accomplished using complex mechanical systems that require many moving parts.
Various examples of devices for handling wafers can be found in U.S. Pat. Nos. 4,449,885, 4,553,069, 4,681,213, 4,752,180, 4,773,687, 5,011,594, 5,046,909, 5,054,834, 5,547,515, 5,555,634, 5,692,873, 5,647,626, 5,765,890, 6,077,026, 6,086,976, 6,112,735, 6,116,848, 6,120,360, and 6,283,701, the disclosures of which are hereby incorporated herein by reference in their entirety. These devices hold wafers by various methods including mechanical clamping, vacuum pressure, electrostatic attraction, adhesives, chucks, and carrying trays.
Several drawbacks with current wafer holding techniques exist. For example, multiple moving parts have inherent reliability problems and are prone to failure. Additionally, vacuum pressure, clamping, and electrostatic devices typically require complex operating systems. Also, vacuum pressure, clamping and adhesives can damage wafer surfaces.
Certain devices exist for flexibly gripping items of various shapes; however, most are not suitable for handling semiconductor wafers. Examples of such devices can be found in U.S. Pat. Nos. 4,540,034, 4,839,947, and 5,121,908, the disclosures of which are hereby incorporated herein by reference in their entirety.
The invention relates to an apparatus for handling semiconductor wafers wherein the apparatus has a minimal number of moving parts. The invention is particularly useful in the handling of semiconductor wafers of varying diameters. Further, the apparatus handles wafers in a manner that substantially reduces or eliminates the likelihood of wafer damage. In addition, the apparatus can handle wafers by gripping the edges of the wafers, thereby eliminating the need for a carrier.
In one aspect, the invention includes a robotic end effector that includes at least one arm, a flexure joint, and a force element. In various embodiments, the force element can be an electric solenoid device, a pneumatic actuator, a piezoelectric actuator, or similar devices as known to those skilled in the art. In other embodiments, the end effector includes a second arm. One or both arms can be arcuate. The arms can be approximately the same length and the arms can include fingers for contacting the edges of a wafer. Furthermore, the apparatus need not be mounted on a robotic arm.
In another aspect, the invention relates to methods of handling wafers. One method includes the steps of moving an end effector into contact with a wafer, applying a force to the end effector, and removing the force on the end effector. Applying a force to the end effector causes at least one arm of the end effector to open by rotating away from the wafer. Once the end effector has fully grasped the wafer, the opening force is effectively removed. In one embodiment, the method includes the step of actuating a force element to open the flexure joint and release the wafer.
These and other objects, along with advantages and features of the present invention herein disclosed, will become apparent through reference to the following description, the accompanying drawings, and the claims. For example, the invention is scaleable and practical for use in handling materials other than semiconductor wafers. Furthermore, it is to be understood that the features of the various embodiments described herein are not mutually exclusive and can exist in various combinations and permutations.

Apparatus and methods for handling semiconductor wafers


The preferred embodiments described herein provide a memory device and method for sensing while programming a non-volatile memory cell. In one preferred embodiment, a memory device is provided with a memory cell and a detection circuit. While the memory cell is being programmed, the detection circuit determines whether the memory cell is in a programmed state. If the memory cell is in a programmed state, the programming of the memory cell is terminated. As compared with prior programming approaches, this preferred embodiment reduces programming time and power while increasing programming bandwidth (the number of memory cells that can be programmed per unit time). In another preferred embodiment, a plurality of memory cells along a wordline are programmed simultaneously. Other preferred embodiments are provided, and each of the preferred embodiments can be used alone or in combination with one another.

Several methods are known for programming non-volatile memory cells. One method applies a programming pulse of a sufficiently long duration to guarantee that the memory cell will be programmed. In order to guarantee that every memory cell will be programmed using this method, programming time and power are set for worst-case conditions. Accordingly, this xe2x80x9cover-provisioningxe2x80x9d approach can result in excessive average programming time, power, and energy. In another method, a series of short, high-voltage programming pulses is applied to the memory cell. After each programming pulse, a nominal-voltage reading pulse is applied to determine whether the memory cell is in a programmed state. If the memory cell is in a programmed state, no further programming pulses are applied. Otherwise, an additional programming pulse is applied, and the sequence of reading and programming continues until the memory cell is in a programmed state. One disadvantage of this approach is the time and power overhead associated with switching between program and read voltages. Additionally, because the time-dependent dielectric breakdown (TDDB) for programmable read-only (PROM) type memory cells increases with multiple, short programming pulses (as compared to a long, continuous programming pulse), this approach can result in excessive programming energy. The time delays associated with these approaches can be especially noticeable to a user when the memory cell is part of a field-programmable memory device used with portable consumer products, such as digital cameras.
There is a need, therefore, for a memory device and method that will overcome the disadvantages described above.
The present invention is defined by the following claims, and nothing in this section should be taken as a limitation on those claims.
By way of introduction, the preferred embodiments described below provide a memory device and method for sensing while programming a non-volatile memory cell. In one preferred embodiment, a memory device is provided with a memory cell and a detection circuit. While the memory cell is being programmed, the detection circuit determines whether the memory cell is in a programmed state. If the memory cell is in a programmed state, the programming of the memory cell is terminated. As compared with prior programming approaches, this preferred embodiment reduces programming time and power while increasing programming bandwidth (the number of memory cells that can be programmed per unit time). In another preferred embodiment, a plurality of memory cells along a wordline are programmed simultaneously. Other preferred embodiments are provided, and each of the preferred embodiments can be used alone or in combination with one another.
The preferred embodiments will now be described with reference to the attached drawings.

Memory device and method for sensing while programming a non-volatile memory cell


A portable rowing machine is disclosed that includes a tubular frame consisting of two parallel tubes positioned and supported by floor brackets, a seat that is removably situated on top of the tubular frame and slidable along the tubular frame on rollers mounted to the underside of the seat, swivel arms attached to brackets and extending perpendicularly outward from the tubular frame, and oar arms attached to the ends of the swivel arms. The tubular frame includes a telescoping portion enabling adjustment of the length of the frame from a compact storage size to a size desired for a users leg length. The swivel arm brackets are pivotally positionable in a storage position and a working position. The oar arms are adjustable in length to suit the users body size. A clutch bearing and band brake assembly provides oar arm motion resistance comparable to rowing a boat.

Many variations on exercise machines are well known in the prior art. One particular type of exercise machine that remains very popular is the rowing machine. Generally, rowing machines include a frame upon which a seat is slidably engaged, foot rests at one end of the frame and rowing arms attached to the frame extending out to the side and providing resistance to movement in one direction to simulate the rowing motion developed when one rows a small boat.
Rowing machines provide a rigorous workout since the arm, back and leg muscles must be used to overcome the resistance presented by a rowing machine. In addition, abdominal muscles receive a good workout when rowing takes place.
Some of the drawbacks of rowing machines known in the prior art include excessive weight, bulkiness and designs that are not readily folded up or collapsed to reduce the size of the machine (height, width and length) for easy storage thereof.
Thus, what is needed is a rowing machine that provides all of the exercise features of rowing a boat that is a rugged and sturdy design yet readily collapsible and folded up for convenient storing of the rowing machine when not in use.


Corneal implants and methods for producing such implants are disclosed. The present corneal implants comprise a lens body which is optically clear and is structured to be surgically attached in or on the cornea of a mammalian eye, the lens body including a hydrogel composition containing water, a collagen component and a polymeric material covalently bonded to the collagen component. The hydrogel composition has enhanced biostability relative to an identical hydrogel composition without the polymeric material.

The present invention relates to corneal implants and methods for producing such implants. In particular, the invention relates to corneal implants structured to be surgically attached in or on the cornea of a mammalian eye which include a hydrogel composition and which have enhanced biostability.
The cornea comprises five layers, including an outer layer of epithelial cells, Bowman's membrane immediately posterior of the cells, the stroma immediately posterior of Bowman's membrane, Descemet's membrane immediately posterior of the stroma and the endothelium immediately posterior of Descemet's membrane. A number of surgical operations involve implanting a corrective lens structure into or onto one or more of these corneal components. For example, in one form of eye surgery, the layer of epithelial cells is removed and a corrective lens structure is placed and secured at the location where the cells were removed. In another form of eye surgery, the layer of epithelial cells is removed and then a wedge-shaped annulus from Bowman's membrane and the underlying stroma is removed. An incision is then made from the posterior end of the resulting groove radially outwardly in an annual zone to define a flap. A corrective lens structure is attached by inserting the wing of the lens structure beneath the corneal flap and fixing, e.g., suturing, it in place. In addition, a corrective lens structure can be placed entirely within the stroma. This surgical procedure involves making an incision in the cornea to gain access to the stroma and also involves disrupting the stroma by placing a lens structure therein.
In each of these surgical procedures, it is highly desirable, even necessary, for the long term viability of such lens onlays or implants that the cornea, e.g., the epithelial cells and/or stromal keratocytes, grow onto the lens structure and/or adhere to the lens structure. Achieving such growth and adhesion has been one substantial problem inhibiting the use of such corneal onlay and implant procedures.
Hydrogel compositions have been suggested for use as materials of construction for corneal implants. As used herein, the term "hydrogel composition" refers to a composition including a material, for example, a polymeric material, and sufficient amount of water to cause the composition to swell relative to the anhydrous material. Such hydrogel compositions often include at least about 38% by weight of water, and may include as much as about 60% or about 80% or about 90% or more by weight of water. One concern of using hydrogel compositions as corneal implants is the relative inability of such compositions to support the growth and/or adhesion of epithelial cells on and/or to the implants.
One hydrogel composition that has been suggested for use in corneal implants is a hydrogel of water and collagen. Such a hydrogel composition has a sufficient nutrient, for example, glucose, diffusivity, and cytophilicity, that is the ability to support at least one of epithelial cell growth and epithelial cell adhesion, to be useful in corneal implants. One problem which has become apparent with such collagen hydrogels is a substantial susceptibility to being degraded by enzymes present in the eye. This is a significant concern since the corneal implant is surgically attached to the eye and is intended for long term, even permanent, placement in the eye.
Therefore, it would be advantageous to provide hydrogel compositions for use in corneal implants which have many, if not all, of the beneficial properties of hydrogels of collagen and water and, in addition, have enhanced biostability relative to such collagen/water hydrogels.


The draft control consists of a three-point hitch mechanism which automatically raises or lowers the hitched implement so that a predetermined draft load can be maintained. An increase or decrease draft load on the implement is sensed by an upper hitch arm. A linkage mechanism transfers this force through a number of links of proper length, such that, the implement is raised with excessive draft load and lowered the implement as the draft load decreases from the excessive level. The draft load that is to be maintained is determined by the location of the middle link in one of a plurality of holes in the attaching linkage. Structure is provided to lock out the draft control.

This invention relates to draft controls, and more particularly, to mechanically load-responsive three-point hitch draft controls.
It is customary for large vehicles, such as large farm tractors to utilize a three-point hitch for the attachment of implements. The vehicle is subjected to draft loads which are a result of ground resistance to the ground-engaging implement. A conventional means of controlling the draft load on the vehicle produced by the ground-engaging implement is to utilize servodraft control systems.
As the lawn and garden tractor has grown in size, it has become increasingly popular to utilize three-point hitch assemblies for the attachment of ground-engaging implements thereto. The utilization of three-point hitches on lawn and garden tractors enables the operator greater control over the implement and also the ability to use larger implements. The use of servo control systems in lawn and garden size tractors equipped with three-point hitches is economically disadvantageous.
The present invention presents a load-responsive mechanical draft control system particularly suited for deployment in lawn and garden size tractors having three-point hitches.