Processes for the preparation of 2-arylvinyl alkyl ether and...

Details Processes for the preparation of 2-arylvinyl alkyl ether and... Processes for the preparation of 2-arylvinyl alkyl ether and...

1999-08-12

2001-09-18

Keys, Rosalynd (Department: 1621)

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

Organic compounds

Oxygen containing

C568S426000, C568S437000, C568S559000, C568S660000, C568S661000, C568S662000, C568S663000

Reexamination Certificate

active

06291721

ABSTRACT:

BACKGROUND OF THE INVENTION
2-Arylvinyl alkyl ether compounds, a method for their preparation, and their use as intermediates in the preparation of 1,4-diaryl-2-fluoro-2-butene insecticidal and acaricidal agents are described in EP 811593-A1. The method described in EP 811593-A1 for the preparation of 2-arylvinyl alkyl ether compounds requires the use of phosphonium halide compounds. However, this method is not entirely satisfactory because the required phosphonium halide compounds are relatively expensive and produce undesirable by-products which are difficult to remove from the 2-arylvinyl alkyl ether compounds. Accordingly, a need exists in the art for an improved process for the preparation of 2-arylvinyl alkyl ether compounds which avoids the use of phosphonium halide compounds.
It is, therefore, an object of the present invention to provide an improved process for the preparation of 2-arylvinyl alkyl ether compounds which avoids the use of phosphonium halide compounds.
It is also an object of the present invention to provide an improved process for the preparation of 1,4-diaryl-2-fluoro-2-butene 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 a new process for the preparation of 2-arylvinyl alkyl ether compounds of the structural formula I
wherein
R is hydrogen, C
1
-C
4
alkyl, C
1
-C
4
haloalkyl, C
3
-C
6
cycloalkyl or C
3
-C
6
halocycloalkyl;
R
1
is C
1
-C
6
alkyl; and
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 or C
1
-C
4
haloalkoxy 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 or C
1
-C
4
haloalkoxy 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 or C
1
-C
4
haloalkoxy groups,
which process comprises:
(a) (1) reacting an aldehyde compound of the structural formula II
wherein R and Ar are as described above with an alkanol compound of the structural formula III
R
1
OH  (III)
wherein R
1
is as described above and a first acid to form an acetal compound of the structural formula IV
(2) reacting the formula IV compound with a second acid in the presence of an aprotic solvent at an elevated temperature, or
(b) reacting an aldehyde compound of the structural formula II
wherein R and Ar are as described above with an alkanol compound of the structural formula III
R
1
OH  (III)
wherein R
1
is as described above and a first acid in the presence of an aprotic solvent at an elevated temperature, or
(c) reacting an acetal compound of the structural formula IV
wherein R, R
1
and Ar are as described above with a first acid in the presence of an aprotic solvent at an elevated temperature.
The present invention further provides a new process for the preparation of 1,4-diaryl-2-fluoro-2-butene compounds of the structural formula V
wherein
R is hydrogen, C
1
-C
4
alkyl, C
1
-C
4
haloalkyl, C
3
-C
6
cycloalkyl or C
3
-C
6
halocycloalkyl;
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 or C
1
-C
4
haloalkoxy 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 or C
1
-C
4
haloalkoxy 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 or C
1
-C
4
haloalkoxy groups; and
Ar
1
is phenoxyphenyl optionally substituted with any combination of from one to six halogen, C
1
-C
4
alkyl, C
1
-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 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 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,
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 or C
1
-C
4
haloalkoxy 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 or C
1
-C
4
haloalkoxy 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 or C
1
-C
4
haloalkoxy groups,
benzoylphenyl 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,
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 or C
1
-C
4
haloalkoxy 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 or C
1
-C
4
haloalkoxy groups,
which process comprises the steps of:
(a) preparing a 2-arylvinyl alkyl ether compound of the structural formula I
wherein R and Ar are as described above and R
1
is C
1
-C
6
alkyl by:
(1) reacting an aldehyde compound of the structural formula II
wherein R and Ar are as described above with an alkanol compound of the structural formula III
R
1
OH  (III)
wherein R
1
is as described above and a first acid to form an acetal compound of the structural formula IV
and reacting the formula IV compound with a second acid in the presence of an aprotic solvent at an elevated temperature, or
(2) reacting an aldehyde compound of the structural formula II
wherein R and Ar are as described above with an alkanol compound of the structural formula III
R
1
OH  (III)
wherein R
1
is as described above and a first acid in the presence of an aprotic solvent at an elevated temperature, or
(3) reacting an acetal compound of the structural formula IV
wherein R, R
1
and Ar are as described above with a first acid in the presence of an aprotic solvent at an elevated temperature;
(b) preparing a 3-aryl-2-fluoropropenal compound of the structural formula VI
wherein R and Ar are as described above by reacting the 2-arylvinyl alkyl ether compound with dichlorofluoromethane and a first base in the presence of water and optionally a phase transfer catalyst to form an intermediate compound, and reacting the intermediate compound in situ with water at an elevated temperature;
(c) preparing a 1,4-diaryl-2-fluoro-1,3-butadiene compound of the structural formula VII
wherein R, Ar and Ar
1
are as described above by:
(1) reacting the 3-aryl-2-fluoropropenal compound with an arylmethanesulfonyl fluoride or arylmethanephosphonate compound of the structural formula VIII
Ar
1
CH
2
Y  (VIII)
wherein Y is SO
2
F or P(O)(OR
2
)
2
, R
2
is C
1
-C
4
alkyl, and Ar
1
is as described above in the presence of a second base, or
(2) reacting the 3-aryl-2-fluoropropenal compound with an arylmethanelithium compound of the structural formula IX
Ar
1
CH
2
Li  (IX)
wherein Ar
1
is as described above to form a 1,4-diaryl-2-fluoro-1-buten-3-ol compound of the structural formula X
and reacting the formula X compound with a sulfonyl chloride or sulfonic acid anhydride compound and a third base, or
(3) reacting the 3-aryl-2-fluoropropenal compound with an aryltriphenylphosphonium halide of the structural formula XI
 (C
6
H
5
)
3
+
PCH
2
Ar
1
X
−
  (XI)
wherein X is Cl or Br and Ar
1
is as described above in the presence of a fourth base; and
(d) reacting the 1,4-diaryl-2-fluoro-1,3-butadiene compound with: (1) an alkaline earth metal in the presenc

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