Drug – bio-affecting and body treating compositions – Designated organic active ingredient containing – Having -c- – wherein x is chalcogen – bonded directly to...
Reissue Patent
1991-06-20
2001-03-06
Killos, Paul J. (Department: 1204)
Drug, bio-affecting and body treating compositions
Designated organic active ingredient containing
Having -c-, wherein x is chalcogen, bonded directly to...
C514S337000, C514S338000, C514S346000, C514S347000, C514S348000, C514S349000, C514S350000, C514S351000, C514S352000, C514S353000, C514S354000, C514S355000, C514S357000, C514S379000, C514S443000, C514S450000, C514S452000, C514S469000, C514S470000, C514S506000, C514S510000, C514S520000, C514S524000, C514S525000, C514S646000, C514S648000, C514S654000, C514S655000, C514S657000, C514S658000, C514S676000, C514S677000, C514S679000, C514S680000, C514S681000, C514S682000, C514S685000, C514S686000, C514S712000, C514S
Reissue Patent
active
RE037087
ABSTRACT:
The invention relates to new alkane and alkoxyalkane derivatives, processes for their preparation and insecticidal and acaricidal compositions containing these compounds.
It is already known that certain alkane and alkoxyalkane derivatives possess insecticidal and acaricidal properties (DE-OS No. 31 17 510 and DE-OS No. 33 17 908).
The object of the present invention is the preparation of new compounds that combat insects and spider mites better than compounds known for this purpose.
The alkane and alkoxyalkane derivatives of the invention are of the general formula I
in which
R
1
is aromatic or aromatic substituted by C
1-4
alkyl, halo-C
1-4
alkyl, phenyl-C
1-4
alkyl, C
2-4
alkenyl, halo-C
2-4
alkenyl, phenyl-C
2-4
alkenyl, C
2-4
alkynyl, halo-C
2-4
alkynyl, phenyl-C
2-4
alkynyl, C
1-4
alkoxy, halo-C
1-4
alkoxy, phenyl-C
1-4
alkoxy, C
2-4
alkenyloxy, halo-C
2-4
alkenyloxy, phenyl-C
2-4
alkenyloxy, C
2-4
alkynyloxy, halo-C
2-4
alkynyloxy, phenyl-C
2-4
alkynyloxy, alkylsulphonyloxy, haloalkylsulphonyloxy, arylsulphonyloxy, halo, cyano, nitro, aryloxy, haloaryloxy, C
1-4
alkyl-aryloxy, or nitroaryloxy,
R
2
is hydrogen or C
1-4
alkyl,
R
3
is hydrogen, cyano or ethynyl,
R
4
is phenyl or pyridyl or these groups substituted by one or more of C
1-6
alkyl, halo-C
1-6
alkyl, phenyl-C
1-6
alkyl, C
2-6
alkyl interrupted by an O-, N- or S-atom, C
2-4
alkenyl, halo-C
2-4
alkenyl, phenyl-C
2-4
alkenyl, C
1-4
alkoxy, halo-C
1-4
alkoxy, phenyl-C
1-4
alkoxy, C
2-4
alkenyloxy, halo-C
2-4
alkenyloxy, phenyl-C
2-4
alkenyloxy, C
2-4
alkynyloxy, halo-C
2-4
alkynyloxy, phenyl-C
2-4
alkynyloxy, aryloxy, haloaryloxy, C
1-4
alkylaryloxy, arylamino, haloarylamino, C
1-4
alkylarylamino, aryl-N-C
1-4
alkylamino, aryl-N-C
1-4
acylamino, aroyl, haloaroyl, C
1-4
alkylaroyl, aryl, haloaryl, C
1-4
alkylaryl or halo, and
A is C
2
or O.
It has been found that these compounds have a better insecticidal and acaricidal activity than structurally similar compounds.
The compounds of the invention are surprisingly highly active against a number of important plant pests, such as for example Plutella xylostella, Epilachna verivestis and Spodoptera littoralis. For this activity, highly active insecticides are known that can be used for combating these plant pests. The compounds of the invention also have activity against a number of economically important animal ectoparasites and public health pests.
The aromatic group designated as R
1
in general formula I includes aryl and heteroaryl such as phenyl, 1-naphthyl, 2-naphthyl, benzofuran-5-yl, benzothiophen-5-yl, benzofuran-6-yl, benzothiophen-6-yl, benzoxazol-5-yl, benzoxazol-6-yl, indan-5-yl, indan-6-yl, 1,4-benzodioxan-6-yl, 1,3-benzodioxan-6-yl, 1,3-benzodioxan-7-yl, 1,3-benzodioxol-5-yl and 5,6,7,8-tetrahydronaphthyl.
Compounds of the invention showing particularly good insecticidal and acaricidal activity are those in which in general formula I
R
1
is chlorophenyl, bromophenyl, fluorophenyl, methylphenyl, methoxyphenyl, ethoxyphenyl, difluoromethoxyphenyl, fluorethoxyphenyl, or trifluoroethoxyphenyl,
R
2
is hydrogen or methyl,
R
3
is hydrogen,
R
4
is phenoxyphenyl, fluorophenoxyphenyl or phenoxypyridyl and
A is CH
2
or O.
The compounds of the invention exist as optional isomers. The invention includes all isomers as well as mixtures of them.
The compounds of the invention, where A=CH
2
, can be prepared for example
(a) reacting a compound of general formula II
or of general formula III
first with a base and then with a compound of general formula IV
to give a compound of general formula V
and then reducing this to the desired product, or
(b) reacting a compound of general formula VI
first with a base and then with a compound of general formula VII
to give a compound of general formula VIII
and then reducing this to the desired product, or
(c) condensing a compound of general formula IX
with an aldehyde of general formula X
R
4
CHO (X)
to given an &agr;,&bgr;-unsaturated compound of general formula XI
and then reducing this to the desired product or
(d) condensing a compound of general formula XII
with an aldehyde of general formula IV
to give an &agr;,&bgr;-unsaturated compound of general formula XIII
and then reducing this to the desired product, in which R
1
, R
2
, R
3
and R
4
have the meanings given above and R
5
is alkyl or phenyl, R
6
is is alkyl and X is halogen.
The compounds of the invention, where A=O, can be prepared for example
(a) reacting a compound of general formula XIV
with a compound of general formula XV
in the presence of a base and using a solvent, or
(b) reacting a compound of general formula XVI
with a compound of general formula XVII
in the presence of a base and using a solvent, in which R
1
, R
2
, R
3
and R
4
have the meanings given above and Z is halogen, methanesulphonate or toluenesulphonate.
The reaction with the phosphonium salts or the phosphonates of general formula II, III and VI can be carried out, for example in the presence of an inert solvent, such as that generally used in Wittig reactions. Suitable solvents include alaphatic or aromatic hydrocarbons, such as for example hexane, benzene or toluene, and ethers such as for example diethyl ether and tetrahydrofuran. Other suitable solvents are amides, such as dimethylformamide or hexamethylphosphoric acid triamide. In some cases, alcohols or dimethyl sulphoxide can be used.
Suitable bases for the Wittig reaction include metal alcoholates, such as for example sodium ethanolate, metal hydrides, such as for example sodium hydride, metal amides, such as for example sodium amide and organometalic compounds, such as for example phenyllithium or butyllithium.
The compounds of general formula I in which the group R
1
is an alkoxyphenyl or haloalkoxyphenyl group etc., and A=CH
2
, can also be obtained by treatment of a hydroxyphenyl derivative that can be prepared by hydrolysis of another alkoxyphenyl derivative, for example with the corresponding alkyl halide.
The etherification is generally carried out in solution. Suitable bases include metal alcoholates, such as for example potassium tert.-butylate, metal hydrides, such as for example sodium hydride, metal amides, such as for example lithium diisopropylamide and metal alkyl compounds, such as for example ethyl mangnesium bromide or butyllithium.
Suitable solvents, as opposed to the reactants, especially the bases, include inert substances such as aliphatic and aromatic hydrocarbons such as for example hexane, benzene or toluene and ethers such as for example diethyl ether, tetrahydrofuran or dimethoxyethane. Suitable further amides include dimethylformamide, N-methylpyrrolidone or hexamethylphosphoric acid triamide.
The etherification can further be carried out in a two phase system by using a catalyst and optionally a solvent. Bases that can be used include alkali metal hydroxides or alkali metal carbonates, either as solids or an aqueous solution. Suitable solvents are the reactants themselves as long as they are liquid. Otherwise they can be used in substances which are inert to the bases and which are immiscible with water, such as aliphatic or aromatic hydrocarbons, such as for example hexane, benzene of toluene. Suitable catalysts include crown ethers and quaternary ammonium salts, such are described in Dehmlow and Dehmlow, Phase Transfer Catalysts, Weinheim 1980.
The reaction can be carried out at temperatures between −78° and 140° C., preferably at 20°-80° C., generally at room temperature.
The carbonyl compounds starting materials of general formula IV in which R
2
=H, and those of general formula VII are known either as such or as their analogues (R
1
=phenyl) and can be prepared according to methods described in the literature (F. E. Herkes, D. J. Burton, J. Org. Chem. 32, 1316 (1967); R. Stewart, K. C. Teo, Can. J. Chem. 58, 2491 (1980); C. Aaron, D. Dull, J. L. Schmiegel, D. Jaeger, Y. Ohashi, H. S. Mosher J. Org. Chem. 32, 2797 (1967).
The aldehyde compounds of formula IV, used as starting mat
Baumert Dietrich
Franke Heinrich
Franke Helga
Giles David
Joppien Hartmut
Killos Paul J.
Ostrolenk Faber Gerb & Soffen, LLP
Schering Aktiengesellschaft
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