Process and intermediate compounds for the preparation of...

Details Process and intermediate compounds for the preparation of... Process and intermediate compounds for the preparation of...

1999-07-02

2001-03-27

Shaver, Paul F. (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Silicon containing

C556S478000, C556S488000, C546S014000, C548S110000, C549S214000, C570S128000, C570S129000

Reexamination Certificate

active

06207846

ABSTRACT:

BACKGROUND OF THE INVENTION
Difluorovinylsilane compounds which are useful as insecticidal and acaricidal agents, and a process for their preparation, are described in U.S. Pat. No. 5,710,102. However, the process described in U.S. Pat. No. 5,710,102 is not entirely satisfactory because the difluorovinylsilane compounds are produced in relatively low yields. Accordingly, a need exists in the art for an improved process for the preparation of these compounds.
It is, therefore, an object of the present invention to provide an improved process for the preparation of difluorovinylsilane compounds.
It is also an object of the present invention to provide intermediate compounds useful in the preparation of difluorovinylsilane compounds.
Other objects and advantages of the present invention will be apparent to those skilled in the art from the description below and the appended claims.
SUMMARY OF THE INVENTION
The present invention provides an improved process for the preparation of a difluorovinylsilane compound of the formula I
wherein
Ar is phenyl, optionally 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, C
1
-C
4
haloalkoxy, C(O)R
2
or S(O)
n
R
3
groups,
1- or 2-naphthyl, optionally 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, C
1
-C
4
haloalkoxy, C(O)R
2
or S(O)
n
R
3
groups, or
a 5- or 6-membered heteroaromatic ring, optionally 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, C
1
-C
4
haloalkoxy, C(O)R
2
or S(O)
n
R3 groups;
R and R
1
are each independently C
1
-C
4
alkyl or
C
3
-C
5
cycloalkyl;
Ar
1
is phenoxyphenyl, optionally 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, C
1
-C
4
haloalkoxy or C(O)R
4
groups,
phenyl, optionally 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, C
1
-
4
haloalkoxy or C(O)R
4
groups,
biphenyl, optionally 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, C
1
-C
4
haloalkoxy or C(O)R
4
groups,
phenoxypyridyl, optionally 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 C
1
-C
4
haloalkoxy or C(O)R
4
groups,
benzylpyridyl, optionally 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, C
1
-C
4
haloalkoxy or C(O)R
4
groups,
benzylphenyl, optionally substituted with any combination of from one to five halogen, C
1
-C
4
alikyl, C
1
-C
4
haloalkyl, C
1
-C
4
alkoxy, C
1
-C
4
haloalkoxy or C(O)R
4
groups,
1- or 2-naphthyl, optionally 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, C
1
-C
4
haloalkoxy or C(O)R
4
groups, or
a 5- or 6-membered heteroaromatic ring, optionally 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, C
1
-C
4
haloalkoxy or C(O)R
4
groups;
n is an integer of 0, 1 or 2;
R
2
and R
4
are each independently C
1
-C
4
alkyl, benzyl or phenyl; and
R
3
is C
1
-C
4
alkyl or C
1
-C
4
haloalkyl; and the fluorine atoms attached to the double bond are trans with respect to each other, which process comprises:
(a) reacting a 3-aryl-1,1,2-trifluoro-1-propene compound of the formula II
F
2
C=CFCH
2
Ar
1
  (II)
wherein Ar
1
is as described above with a reducing agent to form a 3-aryl-1,2-difluoro-1-propene compound a the formula III
wherein the fluorine atoms attached to the double bond are predominately trans with respect to each other;
(b) reacting the 3-aryl-1,2-difluoro-1-propene compound with a lithium base to form a 3-aryl-1,2-di-fluoro-1-propenyllithium compound of the formula IV
wherein the fluorine atoms attached to the double bond are predominately trans with respect to each other; and
(c) reacting the 3-aryl-1,2-difluoro-1-propenyl-lithium compound with an arylchlorosilane compound of the formula V
wherein Ar, R and R
1
are as described above.
The present invention also relates to the intermediate 3-aryl-1,1,2-trifluoro-1-propene; 3-aryl-1,2-difluoro-1-propene; and 3-aryl-1,2-difluoro-1-propenyllithium compounds.
DETAILED DESCRIPTION OF THE INVENTION
A preferred embodiment of the present invention comprises reacting a 3-aryl-1,1,2-trifluoro-1-propene compound of formula II with a reducing agent, preferably at a temperature ranging from about −50° C. to 50° C., more preferably from about −10° C. to 25° C., in the presence of a first solvent, to form a 3-aryl-1,2-difluoro-1-propene compound of formula III, reacting the formula III compound with a lithium base, preferably at a temperature ranging from about −100° C. to 0° C., more preferably from about −70° C. to −50° C., in the presence of a second solvent to form a 3-aryl-1,2-difluoro-1-propenyllithium compound of formula IV, and reacting the formula IV compound in situ with an arylchlorosilane compound of formula V, preferably at a temperature ranging about −100° C. to 50° C., more preferably about −70° C. to 30° C.
The present invention also relates to the 3-aryl-1,1,2-trifluoro-1-propene, 3-aryl-1,2-difluoro-1-propene, and 3-aryl-1,2-difluoro-1-propenyllithium compounds which are utilized in the process of this invention. Those compounds may be represented by the structural formula VI
wherein
W is H, F or Li;
Ar
1
is phenoxyphenyl, optionally 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, C
1
-C
4
haloalkoxy or C(O)R
4
groups,
phenyl, optionally 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, C
1
-C
4
haloalkoxy or C(O)R
4
groups,
biphenyl, optionally 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, C
1
-C
4
haloalkoxy or C(O)R
4
groups,
phenoxypyridyl, optionally 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, C
1
-C
4
haloalkoxy or C(O)R
4
groups,
benzylpyridyl, optionally 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, C
1
-C
4
haloalkoxy or C(O)R
4
groups,
benzylphenyl, optionally 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, C
1
-C
4
haloalkoxy or C(O)R
4
groups,
1- or 2-naphthyl, optionally 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, C
1
-C
4
haloalkoxy or C(O)R
4
groups, or
a 5- or 6-membered heteroaromatic ring, optionally 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, C
1
-C
4
haloalkoxy or C(O)R
4
groups; and
R
4
is C
1
-C
4
alkyl, benzyl or phenyl; and when W is H or Li, the fluorine atoms attached to the double bond are predominately trans with respect to each other.
Preferred formula VI compounds are those wherein W is H, F or Li; and
Ar
1
is 3-phenoxyphenyl, optionally substituted with any combination of from one to five halogen, C
1
-C
4
alkyl, C
l
-C
4
haloalkyl, C
1
-C
4
alkoxy or C
1
-C
4
haloalkoxy groups,
phenyl, optionally 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
biphenyl, optionally 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.
Especially preferred intermediate compounds of formula VI are those wherein
W is H, F or Li; and
Ar
1
is 3-phenoxyphenyl, optionally 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

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