Organic compounds -- part of the class 532-570 series – Organic compounds – Oxygen containing
Reexamination Certificate
2002-10-21
2004-08-03
Keys, Rosalynd (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Oxygen containing
C568S655000, C568S656000, C570S128000, C570S129000
Reexamination Certificate
active
06770788
ABSTRACT:
The present invention provides a two-step process for the preparation of pesticidal fluoroolefin compounds of formula I
wherein
R is hydrogen or C
1
-C
4
-alkyl, and
R
1
is C
1
-C
4
-alkyl or cyclopropyl, or
R and R
1
are taken together with the carbon atom to which they are attached to form a cyclopropyl group;
Ar is phenyl which is unsubstituted or substituted with any combination of from one to three halogen, C
1
-C
4
-alkyl, C
1
-C
4
-haloalkyl, C
1
-C
4
-alkoxy or C
1
-C
4
-haloalkoxy groups, or
1- or 2-naphthyl which is unsubstituted or substituted with any combination of from one to three halogen, C
1
-C
4
-alkyl, C
1
-C
4
-haloalkyl, C
1
-C
4
-alkoxy or C
1
-C
4
-haloalkoxy groups;
Ar
1
is phenoxyphenyl which is unsubstituted or substituted with any combination of from one to five halogen, C
1
-C
4
-alkyl, C
1
-C
4
-haloalkyl, C
1
-C
4
-alkoxy or C
1
-C
4
-haloalkoxy groups,
biphenyl which is unsubstituted or substituted with any combination of from one to five halogen, C
1
-C
4
-alkyl, C
1
-C
4
-haloalkyl, C
1
-C
4
-alkoxy or C
1
-C
4
-haloalkoxy groups,
phenyl which is unsubstituted or substituted with any combination of from one to five halogen, C
1
-C
4
-alkyl, C
1
-C
4
-haloalkyl, C
1
-C
4
-alkoxy or C
1
-C
4
-haloalkoxy groups,
benzylphenyl which is unsubstituted or substituted with any combination of from one to five halogen, C
1
-C
4
-alkyl, C
1
-C
4
-haloalkyl, C
1
-C
4
-alkoxy or C
1
-C
4
-haloalkoxy groups, or
benzoylphenyl which is unoubstituted or substituted with any combination of from one to five halogen, C
1
-C
4
-alkyl, C
1
-C
4
-haloalkyl, C
1
-C
4
-alkoxy or C
1
-C
4
-haloalkoxy groups,
which comprises reacting fluorobromoolefin compounds of formula II
wherein Ar, R and R
1
are as described above, with organozinc compounds of formula III or IV
BrZnCH
2
Ar
1
III
Zn[CH
2
Ar
1
]
2
IV
wherein Ar
1
is as described above, in the presence of a palladium catalyst and a solvent,
which compounds of formula II are obtained by reacting aldehyde compounds of formula V
wherein Ar, R and R
1
are as defined above, with
(a) fluorotribromomethane,
(b) a tri(substituted)phosphine or a hexaalkylphosphoramide or a mixture thereof, and
(c) zinc,
in the presence of a solvent.
In compounds of formula I, the configuration of the groups ArCRR
1
— and —CH
2
Ar
1
about the double bond is preferably predominately mutually trans. “Predominately trans” means that the trans-compound is present at a percentage of at least 80%, preferably above 95%.
The present invention also relates to the fluorobromoolefin compounds of formula II.
Pesticidal fluoroolefin compounds and processes for their preparation are described in WO 94/06741 and GB-A 2 288 803.
However, those processes are not entirely statisfactory because the fluoroolefin compounds are produced in relatively low yields from multi-step processes.
It was therefore an object of the present invention to provide an improved process for the preparation of fluoroolefin compounds.
Accordingly, a two-step overall process for the preparation of fluoroolefin compounds of formula I starting form aldehyde compounds of formula V, via intermediate compounds of formula II, has been found.
Furthermore, compounds of formula II have been found.
Advantageously, the inventive process affords compounds of formula I which are predominately in the trans-configuration.
WO 94/06741 and GB-A 2 288 903 disclose that fluoroolefin compounds are obtained in four steps starting from aldehyde compounds of formula V.
Exemplary of halogen hereinabove are fluorine, chlorine, bromine and iodine;
The term “alkyl” is defined as a saturated, straight or branched chain hydrocarbon with 1 to 4 carbon atoms, such as methyl, ethyl, propyl, 1-methyl-ethyl, butyl, 1-methyl-propyl, 2-methyl-propyl and 1,1-dimethyl-propyl.
The term “alkoxy” is defined as a saturated, straight or branched chain hydrocarbon with 1 to 4 carbon atoms (as described above) which is bond to the backbone via an oxygen (—O—) atom;
The term “haloalkyl” is defined as an alkyl group, as defined above, wherein the hydrogen atoms may be partially or totally substituted with halogen atoms as defined above, wherein the halogen atoms may be the same or different, for example C
1
-C
2
-halo-alkyl such as chloro-methyl, bromomethyl, dichloro-methyl, trichloro-methyl, fluoro-methyl, difluoro-methyl, trifluoro-methyl, chloro-fluoro-methyl, dichlorofluoro-methyl, chloro-difluoro-methyl, 1-chloro-ethyl, 1-bromo-ethyl, 1-fluoro-ethyl, 2-fluoro-ethyl, 2,2-difluoro-ethyl, 2,2,2-trifluoro-ethyl, 2-chloro-2-fluoro-ethyl, 2-chloro-2,2-difluoro-ethyl, 2,2-dichloro-2-fluoro-ethyl, 2,2,2-trichloro-ethyl and pentafluoro-ethyl, wherein the halogen atoms may be the same or different.
The term “haloalkoxy” is defined as an alkoxy group as defined above, wherein the hydrogen atoms may be partially or totally substituted with one or more halogen atoms as defined above, wherein the halogen atoms may be the same or different.
Wavy lines in structural formulae depict the carbon-carbon double bond in both the E- or the Z- isomeric configuration.
Groups containing two or more rings, such as phenoxyphenyl, biphenyl, benzylphenyl and benzoylphenyl, which may be substituted, may be substituted on either ring unless otherwise specified herein.
In a preferred embodiment of the present invention, a fluorobromoolefin of formula II is reacted with at least one molar equivalent, such as 1 to 2 molar equivalents, of an organozinc compound of formula III or IV, and 0,001 to 0,2, preferably 0,01 to 0,1 molar equivalent of a palladium catalyst in the presence of a solvent, preferably in a temperature range of −70° C. to 70° C.
The product compounds of formula I may be isolated by diluting the reaction mixture with water and extracting the product with a suitable extraction solvent. In the isolation procedure, conventional extraction solvents such as ether, ethyl acetate, toluene, and dichloromethane may be utilized.
Preferred palladium catalysts for use in the present invention include, but are not limited to, bis(dibenzylideneacetone)palladium(0), tetrakis(triphenylphosphine)palladium(0), bis(acetonitrile)palladium(II)chloride, bis(triphenylphosphine)palladium(II)chloride, [1,4-bis(diphenylphosphine)butane]palladium(II)dichloride, [1,1′-bis(diphenylphosphino)ferrocene]palladium(II)diacetate, palladium(II)acetate, palladium(II)chloride and mixtures thereof.
Preferred solvents for use in the preparation of compounds of formula I include, but are not limited to, aromatic hydrocarbons such as toluene, benzene, xylenes and mesitylene, halogenated aromatic hydrocarbons such as chlorobenzene and fluorobenzene, carboxylic acid amides, such as N,N-dimethylformamide, ethers such as tetrahydrofuran and dioxane, and halogenated hydrocarbons such as chloroform and carbon tetrachloride, and mixtures thereof.
Preferred solvents for use in the preparation of compounds of formula I include carboxylic acid amides and ethers and mixtures thereof, preferably N,N-dimethylformamide and tetrahydrofuran and mixtures thereof.
In a preferred embodiment of the present invention for the preparation of fluorobromoolefin compounds of formula II, aldehyde compounds of formula v are reacted with at least one molar equivalent, such as 2 to 6 molar equivalents, of fluorotribromomethane, and at least one molar equivalent, such as 2 to 7 molar equivalents, of a tri(substituted)phosphine, and at least one molar equivalent, such as 1 to 4 molar equivalents, of zinc, preferably zinc dust, in the presence of a solvent, preferably in a temperature range of −20° C. to 70° C.
Preferred tri(substituted)phosphines for use in this invention include, but are not limited to, triaryl-phosphines such as tri-phenylphosphine or tri-p-tolyl-phosphine, and tri(branched C
3
-C
6
-alkyl)-phosphines such as triisopropylphosphine or tritertiarybutylphosphine, and mixtures thereof.
Preferred tri(substituted)phosphines which produce compounds of formula II with a preferred ratio of (E):(Z)-isomer include triisopropylphos
BASF - Aktiengesellschaft
Keil & Weinkauf
Keys Rosalynd
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