Production of insecticidally active vinyl-cyclopropane carboxylic acid esters

Insecticidally active vinyl-cyclopropane carboxylic acid esters of the formula ##STR1## are prepared by reacting ##STR2## in which R.sup.12 is a radical selected from the group consisting of ##STR3## with an alcoholate of the formula EQU M--O--R.sup.8. Various processes for making the intermediates are also described. Many of the intermediates and end products are new.

The present invention relates to an unobvious process for the preparation 
of certain vinyl-substituted cyclopropanecarboxylic acid esters, some of 
which are known, which can be used as intermediates for the preparation of 
insecticidally active compounds or which can be used themselves as 
insecticides. 
The present invention also relates to certain new vinyl-substituted 
cyclopropanecarboxylic acid esters as well as to intermediates for their 
preparation. 
Various chrysanthemumic acid esters, for example the pyrethrins, jasmolins 
or cinerins, are naturally occurring cyclopropanecarboxylic acid esters 
having an insecticidal action. They possess valuable properties which, 
however, are impaired by, for example, easy oxidative degradation. 
Synthetic products have also been found, for example m-phenoxybenzyl or 
5-benzyl-3-furylmethyl esters of 
2,2-dimethyl-3-(.beta.,.beta.-dihalogenovinyl)-cyclopropanecarboxylic 
acids, the insecticidal activity of which is said to be higher than that 
of the corresponding chrysanthemumic acid esters. In addition, the 
synthetic products are said to have a higher stability towards oxidative 
degradation (Nature 244, 456 (1973); J. Agr. Food. Chem. 21, 767 (1973)). 
Various processes for the synthesis of these synthetic products are known. 
The reaction of diazoacetic acid esters with 
1,1-dichloro-4-methyl-1,3-pentadiene leads, after hydrolysis, to 
2,2-dimethyl-3-(.beta.,.beta.-dichlorovinyl)-cyclopropanecarboxylic acid 
which is suitable for use as an intermediate for the synthesis of 
pyrethroids (Coll. Czech. Chem. Commun. 24, 2230 (1959)). 
The ozonization of naturally occurring chrysanthemumic acid esters gives 
2,2-dimethyl-3-formyl-cyclopropanecarboxylic acid esters as intermediates 
for the Wittig reaction with triphenyldichloromethylenephosphorane (South 
African Patent No. 733,528). 
However, these processes can be carried out on a relatively large scale 
only with difficulty. 
Further processes which lead to 
2,2-dimethyl-3-(.beta.,.beta.-dihalogenovinyl)-cyclopropanecarboxylic 
acids and esters have been disclosed. Thus, certain allyl alcohols are 
reacted with ortho-esters and subjected to a rearrangement reaction at 
160.degree. C. An addition reaction with CCl.sub.4, which may take place 
by a free radical mechanism, and subsequent cyclization give the 
carboxylic acid derivatives, from which the acids mentioned above can be 
obtained. In this process, various by-products are formed in the 
individual reaction stages and some of these products can make it 
difficult to isolate intermediate stages and their presence is evidenced 
by reduced yield (German Offenlegungsschriften (German Published 
Specifications) Nos. 2,539,895 and 2,544,150). 
The known processes for introducing, in particular, a halogenovinyl group 
in the 3-position of the cyclopropanecarboxylic acid have, according to 
circumstances, various disadvantages, of which the following can be 
particularly serious: 
(1) formation of undesired by-products, 
(2) relatively high reaction temperatures in some cases, 
(3) several reaction stages and 
(4) relatively low total yields over all reaction steps. 
The processes mentioned above are thus ill-suited to the industrial 
preparation of many cyclopropane-carboxylic acid esters containing 
different substituents. 
Furthermore, it has been found that vinyl-substituted 
cyclopropanecarboxylic acids can be obtained by allowing monochloroketene, 
produced in situ, to act on ethylenically unsaturated compounds (German 
Offenlegungsschrift (German Published Specification) No. 2,539,048). 
However, this process is not universally applicable and can be carried out 
only with ethylenically unsaturated compounds wherein the double bond is 
activated by suitable substituents. 
(1) The present invention provides a process for the preparation of a 
vinyl-substituted cyclopropanecarboxylic acid ester of the general formula 
##STR4## 
in which R.sup.1, R.sup.2 and R.sup.3, which need not be identical, each 
represent hydrogen, halogen, CN, optionally substituted alkyl or alkenyl, 
aralkyl, aryl, alkoxycarbonyl, dialkylaminocarbonyl, acyloxy, 
alkylsulphonyl or arylsulphonyl, 
R.sup.4, R.sup.5, R.sup.6 and R.sup.7, which need not be identical, each 
represent hydrogen, optionally substituted alkyl or alkenyl, halogen, CN, 
aralkyl or aryl, it being possible for any of the pairs R.sup.1 and 
R.sup.2, R.sup.2 and R.sup.3, R.sup.1 and R.sup.4, R.sup.4 and R.sup.5, 
R.sup.4 and R.sup.7 and R.sup.5 and R.sup.6, conjointly with the adjacent 
carbon atom(s), to form a multi-membered carbocyclic ring with up to 8 
ring carbon atoms, and 
R.sup.8 represents an alcoholic radical, 
in which process (1.1) an .alpha.-halogenocyclobutanone, of the general 
formula 
##STR5## 
in which R.sup.1 to R.sup.7 have the meanings stated above and 
Hal represents halogen, 
is reacted with an alcoholate of the general formula 
EQU M--O--R.sup.8 (III), 
in which 
R.sup.8 has the meaning stated above and 
M represents an equivalent of an alkali metal cation or alkaline earth 
metal cation, 
if appropriate in the presence of a diluent, or 
(1.2) a cyclobutanone of the general formula 
##STR6## 
in which R.sup.1 to R.sup.7 have the meanings stated above, 
is halogenated, if appropriate in the presence of a diluent, and the 
halogenation product is subsequently reacted with an alcoholate of the 
general formula (III) above, or 
(1.3) an .alpha.-halogenocyclobutanone of the general formula 
##STR7## 
in which R.sup.12 represents a group 
##STR8## 
R.sup.1 to R.sup.7 have the meanings stated above, and Hal represents 
halogen, 
is reacted with an alcoholate of the general formula (III) above, if 
appropriate in the presence of a diluent, or 
(1.4) a cyclobutanone of the general formula 
##STR9## 
in which R.sup.12 has the meaning stated above, 
R.sup.1 to R.sup.7 have the meanings stated above, and 
Hal represents halogen, 
is halogenated, if appropriate in the presence of a diluent, and the 
halogenation product is subsequently reacted with an alcoholate of the 
general formula (III), or in which (2), provided that a new 
vinyl-substituted cyclopropanecarboxylic acid ester of the general formula 
(I) is to be prepared 
in which 
R.sup.1 and R.sup.2, which may be identical or different, each have the 
meaning stated above, 
R.sup.3 represents halogen, CN, C.sub.2-6 -alkyl or substituted C.sub.1-6 
-alkyl and 
R.sup.4 to R.sup.8 have the meanings stated above, 
(2.1) a cyclopropanecarboxylic acid of the general formula 
##STR10## 
in which R.sup.1 to R.sup.7 have the meanings stated under 2, is reacted 
with an alcohol of the general formula 
EQU R.sup.8 --OH (VIII) 
in which 
R.sup.8 has the meaning stated above, 
if appropriate in the presence of a basic or acid catalyst and of diluent 
and if necessary at an elevated temperature, or 
(2.2) a cyclopropanecarboxylic acid of the formula (VII) is reacted with an 
inorganic or organic acid halide and the cyclopropanecarboxylic acid 
halide formed is subsequently reacted with an alcohol of the formula 
(VIII), if appropriate in the presence of a base, or 
(2.3) the alkali metal, alkaline earth metal or ammonium salt of a 
cyclopropanecarboxylic acid of the formula (VII) is reacted with a 
compound of the general formula 
EQU R.sup.8 -R.sup.9 (XI), 
in which 
R.sup.8 has the meaning stated above and 
R.sup.9 represents halogen, methanesulphonoxy, benzenesulphonoxy, 
p-toluenesulphonoxy or a radical --O--SO.sub.2 --O--R.sup.8, 
or 
(2.4) a C.sub.1 -C.sub.4 alkyl ester of a cyclopropanecarboxylic acid of 
the formula (VII) is reacted with an alcohol of the formula (VIII), if 
appropriate in a diluent and in the presence of a basic catalyst. 
The process variants 1.1 to 1.4 for the preparation of the 
vinyl-substituted cyclopropanecarboxylic acid esters, some of which are 
known, are distinguished, in comparison with known processes for the 
preparation of such compounds, by the fact that, by choosing suitable 
starting compounds, it has been possible to make these vinyl-substituted 
cyclopropanecarboxylic acid esters easily, even on a large scale. In 
addition, the processes according to the invention are widely applicable 
and not limited to certain small groups of compounds. A further advantage 
of the process variants 1.1 to 1.4 is that it is possible to obtain the 
desired cyclopropanecarboxylic acid esters directly, without having to 
isolate the cyclopropanecarboxylic acids on which they are based. Process 
variant 1.2, in which cyclobutanones are used directly as the starting 
materials, without it being necessary to isolate the 
.alpha.-halogenocyclobutanones or cyclopropanecarboxylic acids which are 
possible as intermediate stages, is particularly advantageous. 
(3) .alpha.-Halogenocyclobutanones of the formula (II) which can be used in 
process variant 1.1 are known (German Offenlegungsschrift (German 
Published Specification) No. 2,539,048) and can all be prepared in a 
simple manner: 
(3.1) by halogenating a cyclobutanone of the general formula 
##STR11## 
in which the radicals R.sup.1 to R.sup.7 have the meanings stated under 1, 
if appropriate in the presence of a diluent, or 
(3.2) by halogenating a cyclobutanone of the general formula 
##STR12## 
in which the radicals R.sup.1 and R.sup.4 to R.sup.7 have the meanings 
stated under 1, 
if appropriate in the presence of a diluent, or 
(3.3) by halogenating a cyclobutanone of the general formula 
##STR13## 
in which R.sup.12 has the meaning stated under 1.3 and 
R.sup.1 to R.sup.7 have the meanings stated under 1, 
if appropriate in the presence of a diluent. 
(4) The new .alpha.-halogenocyclobutanones, which can be used in process 
variant 1.1, of the formula (II) in which 
R.sup.1 to R.sup.7 have the meanings indicated under 1, provided that at 
least one of R.sup.1, R.sup.2 and R.sup.3 has a meaning other than 
hydrogen, methyl or alkoxycarbonyl, 
can be obtained, in addition to the processes indicated under 3.1 to 3.3, 
by reacting 
(4.1) a 1,3-diene of the general formula 
##STR14## 
in which R.sup.1 to R.sup.4 and R.sup.7 have the meanings indicated under 
2, 
with chloroketene of the formula 
##STR15## 
which is optionally produced in situ, if appropriate in the presence of a 
diluent. 
If a vinyl-substituted .alpha.-bromocyclobutanone is reacted with sodium 
ethylate in process variant 1.1, the course of the reaction can be 
represented by the following equation: 
##STR16## 
The .alpha.-halogenocyclobutanones of the formula (II) in which the 
radicals R.sup.1 to R.sup.7 have the meanings stated under 2, are 
preferably used in process variant 1.1. 
Furthermore, particularly preferred .alpha.-halogenocyclobutanones of the 
formula (II) for use in process variant 1.1 are those in which 
R.sup.1, R.sup.2 and R.sup.3, which need not be identical, each represent 
hydrogen, halogen (especially fluorine, chlorine or bromine), CN, 
straight-chain, branched or cyclic C.sub.1-6 -alkyl or alkenyl [either of 
which may be optionally substituted by halogen (especially fluorine or 
chlorine), C.sub.1-4 -alkoxy, CN or C.sub.1-4 -halogenoalkoxy], benzyl, 
phenylethyl, phenyl or naphthyl [any of which may be optionally 
substituted by halogen (especially chlorine), C.sub.1-4 -alkyl, C.sub.1-4 
-halogenoalkyl, NO.sub.2 or CN], C.sub.1-4 -alkoxycarbonyl, 
dialkylaminocarbonyl with 1-4 carbon atoms per alkyl moiety, C.sub.1-4 
-alkylsulphonyl (especially methylsulphonyl), phenylsulphonyl [optionally 
substituted by halogen, C.sub.1-4 -alkyl, C.sub.1-4 -halogenoalkyl, 
NO.sub.2 or CN] or C.sub.1-4 -acyloxy (especially acetoxy or 
trifluoroacetoxy), and 
R.sup.4 to R.sup.7, which need not be identical, each represent hydrogen, 
straight-chain, branched or cyclic C.sub.1-6 -alkyl or alkenyl [either of 
which may be optionally substituted by halogen, (especially fluorine or 
chlorine), C.sub.1-4 -alkoxy or CN], halogen (especially chlorine or 
bromine), CN or benzyl, phenylethyl, phenyl or naphthyl [any of which may 
be optionally substituted by halogen (especially chlorine), C.sub.1-4 
-alkyl, C.sub.1-4 -halogenoalkyl, NO.sub.2 or CN], it being possible for 
any of the pairs R.sup.1 and R.sup.2, R.sup.2 and R.sup.3, R.sup.1 and 
R.sup.4, R.sup.4 and R.sup.5, R.sup.4 and R.sup.7 and R.sup.5 and R.sup.6, 
together with the adjacent carbon atom(s), to form a 5 to 7 membered 
carbocyclic ring. 
Especially preferred .alpha.-halogenocyclobutanones of the formula (II) are 
those in which R.sup.1, R.sup.2 and R.sup.3, which need not be identical, 
each represent hydrogen, halogen (especially fluorine, chlorine or 
bromine), CN, acetoxy, benzenesulphonyl, methoxycarbonyl, phenyl, 
dimethylaminocarbonyl, chlorovinyl, methyl or ethyl, and 
R.sup.4 to R.sup.7, which need not be identical, each represent hydrogen, 
methyl, ethyl, cyclohexyl, chlorine or CN, it being possible for the pair 
R.sup.5 and R.sup.6 or the pair R.sup.4 and R.sup.7, together with the 
adjacent carbon atom(s), to form a 6-membered carbocyclic ring. 
Particularly suitable .alpha.-halogenocyclobutanones of the formula (II) 
are: 
2,2-dimethyl-3-(.alpha.-methyl-.beta.,.beta.-dichlorovinyl)-cyclobutanone, 
2,2-diethyl-3-(.alpha.,.beta.-dichlorovinyl)-cyclobutanone, 
2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trifluorovinyl)-cyclobutanone, 
2,2-diethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclobutanone, 
2,2-dimethyl-3-(.alpha.,.beta.-dichlorovinyl)-cyclobutanone, 
2,2-dimethyl-3-(.beta.,.beta.-dibromovinyl)-cyclobutanone, 
2,2-dimethyl-3-(.alpha.-fluoro-.beta.,.beta.-dichlorovinyl)-cyclobutanone, 
2,2-dimethyl-3-(.beta.-chlorovinyl)-cyclobutanone, 
2,2,3-trimethyl-3-(.alpha.,.beta.,.beta.-trifluorovinyl)-cyclobutanone, 
2,2-dimethyl-3-(.beta.,.beta.-difluorovinyl)-cyclobutanone, 
2-ethyl-2-methyl-3-(.beta.,.beta.-dichlorovinyl)-cyclobutanone, 
2-ethyl-2-methyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclobutanone, 
2-ethyl-2,3-dimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclobutanon 
e, 2,2-diethyl-3-(.beta.,.beta.-dibromovinyl)-cyclobutanone, 
2-ethyl-2-methyl-3-(.beta.,.beta.-dibromovinyl)-cyclobutanone, 
2-ethyl-2-methyl-3-(.alpha.-fluoro-.beta.,.beta.-dichlorovinyl)-cyclobutan 
one, 
2,2-dimethyl-3-(.alpha.-ethyl-.beta.,.beta.-dichlorovinyl)-cyclobutanone, 
2-ethyl-2,3-dimethyl-3-(.beta.,.beta.-dichlorovinyl)-cyclobutanone, 
2,2-dimethyl-3-(.alpha.,.beta.-dibromovinyl)-cyclobutanone, 
2,2-dimethyl-3-(.beta.-bromo-.beta.-chlorovinyl)-cyclobutanone, 
2,2-dimethyl-4-ethyl-3-(.beta.,.beta.-dichlorovinyl)-cyclobutanone, 
2,2,4-trimethyl-3-(.alpha.,.beta.-dibromovinyl)-cyclobutanone, 
2,2-dimethyl-4-n-butyl-3-(.beta.,.beta.-dichlorovinyl)-cyclobutanone, 
2-methyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclobutanone, 
2,2-dimethyl-3-(.beta.,.beta.-dichlorovinyl)-cyclobutanone, 
2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclobutanone, 
2,2,3-trimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclobutanone, 
2,2-di-n-propyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclobutanone, 
2,2-dimethyl-3-(.alpha.-cyano-.beta.,.beta.-dichlorovinyl)-cyclobutanone, 
2,2-dimethyl-3-n-butyl-3-(.beta.,.beta.-dichlorovinyl)-cyclobutanone, 
2,2-dimethyl-3-(.beta.-chloro-.beta.-methoxycarbonylvinyl)-cyclobutanone, 
2,2-dimethyl-3-(.beta.,.beta.-dicyanovinyl)-cyclobutanone, 
2,3-dimethyl-3-(.beta.,.beta.-dibromovinyl)-cyclobutanone, 
2,2-dimethyl-3-(.beta.,.beta.-dibromovinyl)-4-n-butyl-cyclobutanone, 
2,2-dimethyl-3-(.alpha.-chloro-.beta.-acetoxyvinyl)-cyclobutanone, 
2,2-di-n-butyl-3-methyl-3-(.alpha.-chloro-.beta.-cyanovinyl)-cyclobutanone 
, 2,2-dimethyl-3-(.alpha.-methylsulphonylvinyl)-cyclobutanone, 
2,2-diethyl-3-(.beta.,.beta.-dichlorovinyl)-4-cyclohexyl-cyclobutanone, 
2,3-dimethyl-2-chloro-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclobutano 
ne, 2-methyl-2-phenyl-3-(.beta.,.beta.-dichlorovinyl)-cyclobutanone, 
2,2-dimethyl-3-(.beta.-chloro-.beta.-phenylvinyl)-cyclobutanone, 
2,2-dimethyl-3-(.beta.,.beta.-bis(trifluoromethyl)-vinyl)-cyclobutanone 
and 2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-4-benzyl-cyclobu 
tanone which are substituted in the 4-position by chlorine or bromine. 
Spiro-cyclic cyclobutanones which are halogenated in the 3-position are: 
3-(.beta.,.beta.-dichlorovinyl)-spiro[3,5]nonan-1-one, 
3-(.alpha.,.beta.,.beta.-trichlorovinyl)-spiro[3,5]nonan-1-one, 
3-(.beta.,.beta.-dibromovinyl)-spiro[3,5]nonan-1-one, 
3-(.beta.,.beta.-dichlorovinyl)-spiro[3,4]octan-1-one, 
3-(.beta.,.beta.-dichlorovinyl)-2-methyl-spiro[3,5]nonan-1-one, 
3-(.alpha.,.beta.-dichlorovinyl)-spiro[3,5]nonan-1-one and 
3-(.alpha.,.beta.,.beta.-trifluorovinyl)-spiro[3,5]nonan-1-one. 
Alcoholates of the formula (III) which are preferably employed in process 
variant 1.1 are: alkali metal and alkaline earth metal alcoholates, such 
as, for example, sodium methylate, sodium ethylate, lithium n-propylate 
and potassium tert.-butylate. However, alkali metal alcoholates of higher 
alcohols, such as benzyl alcohols substituted in the m-position by benzyl, 
furfuryl-3, furfuryl-2, m-fluorophenoxy, trichlorovinyloxy, phenoxy, 
.beta.,.beta.-dichlorovinyloxy, buta-1,3-dienyloxy or 
perchlorobuta-1,3-dienyloxy, or 4-phenyl-3,4-dichlorobut-2-enol, 
4-phenyl-4-methyl-but-2-enol, 4-phenyl-3-chloro-4-methyl-but-2-enol, 
vitamin A alcohol, 5,5-dichloropenta-2,4-dienol, pyrethrenolone and 
.alpha.-ethynyl-m-phenoxybenzyl alcohol, also find use. 
Alcoholates of the formula (III) in which R.sup.8 represents a radical of 
the general formula 
##STR17## 
in which R.sup.a represents hydrogen, cyano or ethynyl, 
R.sup.b represents hydrogen, a C.sub.1-4 alkyl radical, a phenoxy, benzyl 
or phenylthio group, or a vinyl or buta-1,3-dienyl radical which is 
optionally substituted by halogen, 
R.sup.c represents hydrogen, halogen or a C.sub.1-4 alkyl radical and 
R.sup.d represents oxygen, sulphur or a vinylene group, 
are particularly suitable. 
The process variant 1.1 according to the invention is preferably carried 
out in an inert organic solvent, such as methanol, if sodium methylate is 
used, or ethanol, if sodium ethylate is used, or an ether, such as diethyl 
ether, tetrahydrofuran or 1,2-dimethoxyethane, tetramethylenesulphone, 
dimethylformamide or a hydrocarbon, such as benzene or toluene. The 
reaction can be carried out at a temperature of about -30.degree. to 
+150.degree. C., preferably of about 20.degree. to 60.degree. C. Sometimes 
the components already react with one another sufficiently rapidly at 
0.degree. C. The reaction time depends on the reactants, the reaction 
temperature and the .alpha.-halogenoketone used, and can vary from about 1 
to 10 hours. 
Theoretically, one equivalent of an alcoholate is necessary for the ring 
contraction. However, the reaction can also be carried out with an excess 
of up to one equivalent of alcoholate or with an amount of alcoholate 
which is slightly less than the equivalent amount, namely about 0.1 
equivalent less. 
For working up, any excess of the alcoholate which may be present is 
neutralized with, for example, alcoholic hydrochloric acid, while cooling; 
the reaction mixture is then filtered and the cyclopropanecarboxylic acid 
ester is separated off by distillation or crystallization of the filtrate. 
However, an alternative procedure is to introduce the reaction mixture 
into hydrochloric acid, diluted with ice, and to extract the desired ester 
using an organic solvent. 
(5) Cyclobutanones of the formula (IV) which can be used in process variant 
1.2 are known (J.Org. Chem. 32, 2704 (1967); Houben-Weyl, Volume IV part 
4, page 174 et seq.). They can be prepared in a simple manner by (5.1) 
reacting an .alpha.-chloroenamine of the general formula 
##STR18## 
in which R.sup.5 and R.sup.6 have the meaning stated under 1 and 
R.sup.10 and R.sup.11, which may be identical or different, each represent 
C.sub.1-4 -alkyl or, with the adjacent N atom, form a heterocyclic ring 
which optionally also contains one or more further hetero-atoms, 
with an olefin of the general formula 
##STR19## 
in which R.sup.1 to R.sup.4 and R.sup.7 have the meanings stated under 1, 
if appropriate in a diluent in the presence of a Lewis acid or a silver 
salt and subsequently hydrolyzing the product, if appropriate in the 
presence of an aqueous base or acid, or by (5.2) hydrolyzing an imonium 
salt of the general formula 
##STR20## 
in which R.sup.1 to R.sup.7 have the meanings stated under 1, 
R.sup.10 and R.sup.11 have the meanings stated under 5.1 and 
Z represents an equivalent of an anion, 
if appropriate in a diluent and if appropriate in the presence of an 
aqueous base or acid, or by 
(5.3) reacting a ketene of the general formula 
##STR21## 
in which R.sup.5 and R.sup.6 have the meanings stated under 1, with an 
olefin of the general formula (XII) 
in which 
R.sup.1 to R.sup.4 and R.sup.7 have the meaning indicated under 1, 
if appropriate in the presence of a diluent and if appropriate in the 
presence of a catalyst, or by 
(5.4) reacting a ketene of the general formula 
##STR22## 
in which R.sup.7 has the meaning stated under 1, 
with an olefin of the general formula 
##STR23## 
in which R.sup.1 to R.sup.6 have the meanings stated under 1, 
if appropriate in the presence of a diluent and if appropriate in the 
presence of a catalyst, or by 
(5.5) reacting a ketene acylal of the general formula 
##STR24## 
in which R.sup.5 and R.sup.6 have the meanings stated under 1, 
with an olefin of the general formula (XII) in which 
R.sup.1 to R.sup.4 and R.sup.7 have the meanings stated under 1, 
if appropriate in a diluent and in the presence of a catalyst, or by 
(5.6) halogenating the vinyl group of a cyclobutanone of the general 
formula (IV) in which 
R.sup.1 to R.sup.7 have the meaning stated under 1, provided that one of 
R.sup.1 to R.sup.3 is hydrogen, 
if appropriate in a diluent, and subsequently dehydrohalogenating the 
reaction product, or by 
(5.7) dehydrohalogenating a cyclobutanone of the general formula 
##STR25## 
in which R.sup.1 to R.sup.7 have the meanings stated under 1, but at least 
one of the radicals R.sup.1 to R.sup.3 represents hydrogen, 
if appropriate in a diluent, or by 
(5.8) hydrolyzing an imonium salt of the general formula 
##STR26## 
in which R.sup.1 to R.sup.7 have the meanings stated under 1, 
R.sup.10, R.sup.11 and Z have the meanings stated under 5.2 and 
R.sup.12 has the meaning stated under 1.3, 
if appropriate in the presence of an aqueous base or acid and subsequently 
dehydrohalogenating the product, or by 
(5.9) reacting an .alpha.-chloroenamine of the general formula (XIII) in 
which 
R.sup.5, R.sup.6, R.sup.10 and R.sup.11 have the meanings stated under 5.1, 
with an olefin of the general formula 
##STR27## 
in which R.sup.12, R.sup.4 and R.sup.7 have the meanings stated under 1 
and 1.3, 
if appropriate in a diluent and in the presence of a Lewis acid or a silver 
salt, and subsequently hydrolyzing the product in the presence of an 
aqueous acid or base. 
(6) Those cyclobutanones of the formula (IV) (which can be used in process 
variant 1.2) are new wherein R.sup.1 to R.sup.7 have the meanings stated 
under 1 and at least one of the radicals R.sup.1, R.sup.2 and R.sup.3 to 
have a meaning other than hydrogen or methyl and R.sup.5 has a meaning 
other than phenyl. 
Preferred cyclobutanones of the formula (IV) for use in process variant 1.2 
are those in which 
R.sup.1, R.sup.2 and R.sup.3, which may be identical or different, each 
represent hydrogen, halogen (especially chlorine or bromine), CN, 
straight-chain, branched or cyclic C.sub.1-6 -alkyl or alkenyl [either of 
which may be optionally substituted by halogen (especially fluorine or 
chlorine), C.sub.1-4 -alkoxy, CN or C.sub.1-4 -halogenoalkoxy], benzyl, 
phenylethyl, phenyl or naphthyl [any of which may be optionally 
substituted by halogen (especially chlorine), C.sub.1-4 -alkyl, C.sub.1-4 
-halogenoalkyl, NO.sub.2 or CN], C.sub.1-4 -alkoxycarbonyl, 
dialkylaminocarbonyl with 1-4 carbon atoms per alkyl moiety C.sub.1-4 
-alkylsulphonyl (especially methylsulphonyl), phenylsulphonyl [optionally 
substituted by halogen, C.sub.1-4 -alkyl, C.sub.1-4 -halogenoalkyl, 
NO.sub.2 or CN] or C.sub.1-4 -acyloxy, (especially acetoxy, or 
trifluoroacetoxy), and 
R.sup.4 to R.sup.7, which may be identical or different, each represent 
hydrogen, straight-chain, branched or cyclic C.sub.1-6 -alkyl or alkenyl 
[either of which is optionally substituted by halogen (especially fluorine 
or chlorine), C.sub.1-4 -alkoxy or CN], halogen (especially chlorine or 
bromine), CN or benzyl, phenylethyl, phenyl or naphthyl [any of which may 
be optionally substituted by halogen (especially chlorine), C.sub.1-4 
-alkyl, C.sub.1-4 -halogenoalkyl, NO.sub.2 or CN], it being possible for 
any of the pairs R.sup.1 and R.sup.2, R.sup.2 and R.sup.3, R.sup.1 and 
R.sup.4, R.sup.4 and R.sup.5, R.sup.4 and R.sup.7 and R.sup.5 and R.sup.6, 
conjointly with the adjacent carbon atom(s), to form a 5 to 7-membered 
carbocyclic ring. 
Cyclobutanones in which the radicals R.sup.1 to R.sup.7 have the meaning 
mentioned in process variant 1.1 as being especially preferred are 
particularly preferably employed in process variant 1.2. 
Individual cyclobutanones which are advantageously employed are those from 
which the .alpha.-halogenocyclobutanones mentioned in process variant 1.1 
are derived. 
Halogenating agents which can be used in process variant 1.2 are: bromine, 
chlorine, mixtures of bromine and chlorine, sulphuryl chloride, 
N-halogenoimides, such as, for example, N-bromosuccinimide, and 
2,4,4,5-tetrabromocyclohexa-2,5-dienone. 
The following are preferably used: bromine, chlorine and mixtures of 
bromine and chlorine. 
In the halogenation, the cyclobutanones and the halogenating agent are 
generally employed in equivalent amounts or with a slight excess of 
halogenating agent of about 0.1 to 0.2 equivalent. 
The procedure is to bring together the cyclobutanone, diluent and 
halogenating agent and to allow the mixture to react. If appropriate, a 
catalyst, for example an acid, preferably HBr or acetic acid, is added to 
the mixture in order to catalyze the reaction. An alternative procedure is 
to add the halogenating agent to the initially introduced cyclobutanone 
and diluent at the rate at which it is consumed. If appropriate, the 
halogenation can also be carried out without the presence of a diluent. 
Diluents which can be used in process variant 1.2 are inert organic 
solvents, such as hydrocarbons, for example hexane, benzene or toluene, 
chlorinated hydrocarbons, such as methylene chloride or carbon 
tetrachloride, ethers, such as diethyl ether, or esters, such as ethyl 
acetate. 
The halogenation in process variant 1.2 is carried out, in general, at 
about 0.degree. to 40.degree. C., preferably at room temperature. The 
halogenation is carried out, in general, under normal pressure. The 
hydrogen halide which may be formed during the reaction can be removed, if 
appropriate, by bubbling nitrogen through the reaction solution. 
After the halogenation has ended, an alcoholate of the formula (III) is 
added to the reaction solution without intermediate isolation of the 
reaction products. Alcoholates which can be used are preferably alkali 
metal or alkaline earth metal alcoholates, especially sodium or potassium 
alcoholates, of alcohols which have been indicated as being preferred in 
process variant 1.1. 
The resulting reaction solution is added to a solution or suspension of the 
alcoholate in the corresponding alcohol or in an inert organic solvent, as 
has been described above. However, it is also possible to add a solution 
or suspension of the alcoholate to the resulting reaction solution. The 
procedure is generally carried out at a temperature of about -30.degree. 
to 150.degree. C., preferably about 20.degree. to 60.degree. C. The 
reaction time can vary from about 1 to 10 hours. The alcoholates are 
generally added to the reaction solution in an at least equimolar ratio, 
but appropriately in about a 1.5 to 1.7 molar ratio. 
For working up, the alcoholate, which is optionally present in excess, is 
neutralized with, for example, alcoholic hydrochloric acid, while cooling; 
the reaction mixture is filtered and the resulting cyclopropanecarboxylic 
acid ester is separated off by distillation or crystallization of the 
filtrate. However, an alternative procedure can be to introduce the 
reaction mixture into hydrochloric acid, diluted with ice, and to extract 
the desired ester with an organic solvent. 
The .alpha.-halogenocyclobutanones of the formula (V) which can be used in 
process variant 1.3 are new. 
They are obtained by the process 3.3 described hereinbelow. However, they 
can also be obtained by halogenation or HCl addition to the corresponding 
vinyl-substituted .alpha.-halogenocyclobutanones by methods which are in 
themselves known. 
.alpha.-Halogenocyclobutanones of the formula (V) in which R.sup.1 to 
R.sup.7 have the meanings mentioned above as being preferred or especially 
preferred in process variant 1.1 are preferably used in process variant 
1.3. 
Preferred alcoholates of the formula (III) which are used in process 
variant 1.3 are those which are indicated above as being preferred in 
process variant 1.1. 
The procedure for the ring contraction of the halogenated cyclobutanone in 
process variant 1.3 is identical to that described in process variant 1.1. 
The alcoholates used are preferably those of C.sub.1 -C.sub.4 alcohols 
since one equivalent of the alcoholate is consumed for the 
dehydrohalogenation and does not lead to the formation of the ester. This 
would be uneconomical in the case of expensive alcohols. 
In addition to the ring contraction described, a dehydrohalogenation takes 
place in the side chain, and this requires a further equivalent of 
alcoholate. 
The cyclobutanones of the formula (VI) which can be used in process variant 
1.4 are new. 
They can be prepared by processes 5.8 and 5.9 described herein below or are 
obtained by halogenating or adding HCl onto the corresponding 
vinyl-substituted cyclobutanones by processes which are in themselves 
known. 
The cyclobutanones of the formula (VI), in which R.sup.1 to R.sup.7 have 
the preferred or especially preferred meanings indicated in process 
variant 1.1, are preferably used in process variant 1.4. 
Alcoholates of the formula (III) which are preferably used are the same as 
those indicated in process variant 1.3. 
The procedure in process variant 1.4 is identical to that described in 
process variant 1.2. As in process variant 1.3, a dehydrohalogenation of 
the side chain takes place simultaneously with the ring contraction in 
process variant 1.4 also. 
The new vinyl-substituted cyclopropanecarboxylic acid esters of the formula 
(I) in which R.sup.1 to R.sup.8 have the meaning indicated under 2 can 
also be prepared by the process variants 2.1 to 2.4, which are also 
according to the invention. 
The following may be mentioned as preferred new cyclopropanecarboxylic acid 
esters: the m-phenoxybenzyl ester of 
2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclopropanecarboxyl 
ic acid, 
2-ethyl-2-methyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclopropanecarb 
oxylic acid, 
2,2-diethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclopropanecarboxyli 
c acid, 
2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trifluorovinyl)-cyclopropanecarboxyl 
ic acid, 
2,2,3-trimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclopropanecarbo 
xylic acid, 
2,2-dimethyl-3-(.alpha.-fluoro-.beta.,.beta.-dichlorovinyl)-cyclopropaneca 
rboxylic acid, 
2,2-dimethyl-3-(.alpha.-cyano-.beta.,.beta.-dichlorovinyl)-cyclopropanecar 
boxylic acid, 
2,2-dimethyl-3-(.alpha.,.delta.,.delta.-trichlorobuta-1,3-dienyl)-cyclopro 
panecarboxylic acid, 
1,2,2-trimethyl-3-(.alpha.-cyano-.beta.,.beta.-dichlorovinyl)-cyclopropane 
carboxylic acid, 
1,2,3-trimethyl-3-(.alpha.,.beta.,.beta.-trifluorovinyl)-cyclopropanecarbo 
xylic acid, 
2,2-dimethyl-3-(.alpha.-chloro-.beta.-methylsulphonyl-vinyl)-cyclopropanec 
arboxylic acid, 
2,2-diethyl-3-methyl-3-(.alpha.-cyano-.beta.,.beta.-dibromovinyl)- and 
2-(.alpha.-fluoro-.beta.,.beta.-dichlorovinyl)-spiro[2,5]octane-1-carboxyl 
ic acid, the methyl esters of 
2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclopropanecarboxyl 
ic acid, 
2,2-diethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclopropanecarboxyli 
c acid, 
2,2,3-trimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclopropanecarbo 
xylic acid, 
2-methyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)cyclopropanecarboxylic 
acid, 
2-methyl-2-n-propyl-3-(.alpha.-fluoro-.beta.,.beta.-dibromovinyl)-cyclopro 
panecarboxylic acid, 
1,2,2-trimethyl-3-(.alpha.-cyano-.beta.,.beta.-dichlorovinyl)-cyclopropane 
carboxylic acid, 
1,2,3-trimethyl-3-(.alpha.,.beta.,.beta.-trifluorovinyl)cyclopropanecarbox 
ylic acid and 
2-ethyl-2-propyl-3-(.beta.-bromo-.alpha.,.beta.-dichlorovinyl)-cyclopropan 
ecarboxylic acid, the ethyl esters of 
2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)cyclopropanecarboxyli 
c acid, 2,2-diethyl-3-(.alpha.,.beta.-dichlorovinyl)-cyclopropanecarboxylic 
acid, 
2,2-diethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclopropanecarboxyli 
c acid, 
2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trifluorovinyl)-cyclopropanecarboxyl 
ic acid, 
2,2,3-trimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclopropanecarbo 
xylic acid, 
2,2-dimethyl-3-(.alpha.-chloro-.beta.-acetoxyvinyl)-cyclopropanecarboxylic 
acid, 
2,2-dimethyl-3-(.alpha.-fluoro-.beta.,.beta.-dichlorovinyl)-cyclopropaneca 
rboxylic acid, 
2,2-dimethyl-3-(.alpha.-cyano-.beta.,.beta.-dichlorovinyl)-cyclopropanecar 
boxylic acid, 
1,2,2,3-tetramethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclopropanec 
arboxylic acid, 
2,2-dimethyl-3-(.beta.,.delta.,.delta.-trichlorobuta-1,3-dienyl)-cycloprop 
anecarboxylic acid, 
2-(.alpha.,.beta.,.beta.'-trichlorovinyl)-spiro[2,5]octane-1-carboxylic 
acid, 
2,2-dimethyl-3-(.alpha.-chloro-.beta.-methylsulphonyl-vinyl)-cyclopropanec 
arboxylic acid and 
2,2-dimethyl-3-[.alpha.-chloro-.beta.,.beta.-bis-(trifluoromethyl)-vinyl]- 
cyclopropanecarboxylic acid, the n-propyl esters of 
2,2-diethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclopropanecarboxyli 
c acid, 
2,2,3-trimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclopropanecarbo 
xylic acid, 
2-methyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)cyclopropanecarboxylic 
acid, 
1,2,3-trimethyl-3-(.alpha.,.beta.,.beta.-trifluorovinyl)-cyclopropanecarbo 
xylic acid and 
2-(.alpha.,.beta.,.beta.-trichlorovinyl)-spirohexane-1-carboxylic acid, 
the .alpha.-cyano-m-phenoxybenzyl esters of 
2,2-diethyl-3-(.alpha.,.beta.-dichlorovinyl)-cyclopropanecarboxylic acid, 
2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trifluorovinyl)-cyclopropanecarboxyl 
ic acid, 
2,2-dimethyl-3-(.alpha.-fluoro-.beta.,.beta.-dichlorovinyl)-cyclopropaneca 
rboxylic acid, 
2-methyl-2-n-propyl-3-(.alpha.-fluoro-.beta.,.beta.-dibromovinyl)-cyclopro 
panecarboxylic acid, 
1,2,2,3-tetramethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclopropanec 
arboxylic acid, 
2-(.alpha.,.beta.,.beta.-trichlorovinyl)-spiro[2,5]octane-1-carboxylic 
acid, 
1,2,3-trimethyl-3-(.alpha.,.beta.,.beta.-trifluorovinyl)-cyclopropanecarbo 
xylic acid and 2,2 
-dimethyl-3-(.alpha.-chloro-.beta.,.beta.-bis-(trifluoromethyl)vinyl)-cycl 
opropanecarboxylic acid, the 5-benzyl-3-furylmethyl esters of 
2,2-diethyl-3-(.alpha.,.beta.-dichlorovinyl)-cyclopropanecarboxylic acid, 
2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trifluorovinyl)-cyclopropanecarboxyl 
ic acid, 
2,2-dimethyl-3-(.alpha.-fluoro-.beta.,.beta.-dichlorovinyl)-cyclopropaneca 
rboxylic acid, 
1,2,2,3-tetramethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclopropanec 
arboxylic acid and 
2-(.alpha.,.beta.,.beta.-trichlorovinyl)-spiro[2,5]octane-1-carboxylic 
acid and the 3,4,5,6-tetrahydrophthalimidomethyl esters of 
2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclopropanecarboxyl 
ic acid, 
2,2-dimethyl-3-(.alpha.-fluoro-.beta.,.beta.-dichlorovinyl)-cyclopropaneca 
rboxylic acid and 
2-(.alpha.,.beta.,.beta.-trichlorovinyl)-spiro[2,5]octane-1-carboxylic 
acid. 
Cyclopropanecarboxylic acids of the formula (VII), or their salts, or their 
esters with C.sub.1-3 -alcohols of the formula (VIII), in which 
R.sup.1, R.sup.2 and R.sup.4 to R.sup.7 have the preferred or especially 
preferred meanings indicated in process variant 1.2 and R.sup.3 represents 
chlorine, bromine, CN, straight-chain, branched or cyclic alkyl with 2-6 
carbon atoms or straight-chain or cyclic alkyl which has up to 4 carbon 
atoms and is substituted by halogen, especially fluorine or chlorine, CN 
or C.sub.1-4 -alkoxy, 
are preferably employed in this process. 
Individual cyclopropanecarboxylic acids, or their salts or their C.sub.1-3 
-alkyl esters, which are advantageously employed are 
2,2-dimethyl-3-(.alpha.-fluoro-.beta.,.beta.-dichlorovinyl)cyclopropanecar 
boxylic acid, 
2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclopropanecarboxyl 
ic acid ethyl ester, 
2,2-dimethyl-3-(.alpha.,.beta.-dichlorovinyl)-cyclopropanecarboxylic acid, 
2-trifluorovinyl-spiro[2,5]octane-1-carboxylic acid, sodium 
2,2-diethyl-3-(.alpha.,.beta.,.beta.-trifluorovinyl)-cyclopropane 
carboxylate, 
1,2,2-trimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)cyclopropanecarbox 
ylic acid methyl ester, lithium 
2,2-dimethyl-3-(.alpha.-cyano-.beta.,.beta.-dichlorovinyl)-cyclopropane 
carboxylate, 
2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trifluorovinyl)-cyclopropanecarboxyl 
ic acid, sodium 2,2-dimethyl-3-(.alpha.-methylsulphonylvinyl)-cyclopropane 
carboxylate and 
2-methyl-2,3-diethyl-3-(.alpha.-fluoro-.beta.,.beta.-dibromovinyl)-cyclopr 
opanecarboxylic acid ethyl ester. 
Process variant 2.1 can be carried out by employing a 
cyclopropanecarboxylic acid of the formula (VII) and an alcohol of the 
formula (VIII) in an at least equimolar ratio. In general, however, the 
reaction is carried out with an excess of alcohol. 
Diluents which can be used are inert organic solvents. 
Catalysts which can be used are acids, such as p-toluenesulphonic acid, 
benzenesulphonic acid, hydrochloric acid and sulphuric acid. 
The reaction is in general, carried out at about 60.degree. to 150.degree. 
C. 
Process variant 2.2 is carried out in general by reacting a 
cyclopropanecarboxylic acid of the formula (VII) with an equimolar amount 
of an acid halide to give the carboxylic acid halide and reacting this, 
without isolating it, with an alcohol of the formula (VIII) in the 
presence of a tertiary base. 
If appropriate, the formation of the acid chloride is carried out in the 
presence of a diluent, such as benzene, toluene or methylene chloride, at 
a temperature of about 0.degree. to 100.degree. C. 
Acid halides which may be used are thionyl chloride, phosphorus 
trichloride, phosphorus tribromide or benzoyl chloride. 
According to process variant 2.3, the new cyclopropanecarboxylic acid 
esters of the general formula (I) are also obtainable by reacting a salt 
of the new cyclopropanecarboxylic acids with an alkylating agent, such as, 
for example, a halide or sulphonate, in an inert diluent. 
Suitable salts are, for example, the alkali metal or ammonium salts; 
alkylating agents are, for example, benzyl chloride, benzyl bromide, 
m-phenoxybenzyl bromide or vitamin A bromide. 
Suitable diluents are dimethylformamide, acetonitrile, pentan-3-one or 
acetone. 
In general, the reaction is carried out at a reaction temperature of about 
20.degree. to 100.degree. C., preferably about 25.degree. to 80.degree. C. 
The working up can be carried out by distillation after the salts which 
have precipitated during the reaction have been separated off; frequently 
water is added to the reaction mixture, the product is taken up in a 
solvent which is substantially water immiscible and the solvent is 
evaporated off. The esters thus obtained can be purified by distillation. 
If high-boiling esters, which can undergo decomposition during 
distillation, are obtained, they are freed from residues of solvent or 
alkylating agent in vacuo at temperatures of up to about 150.degree. C. 
According to process variant 2.3, the new cyclopropanecarboxylic acid 
esters of the general formula (I) in which R.sup.1 to R.sup.8 have the 
meanings indicated under 2 are also obtainable by reacting a salt of the 
new cyclopropanecarboxylic acids with an alkylating agent, such as, for 
example, a halide or sulphonate, in an inert diluent. 
Suitable salts are, for example, the alakli metal or ammonium salts; 
alkylating agents are, for example, benzyl chloride, benzyl bromide or 
m-phenoxybenzyl bromide. 
Suitable diluents are dimethylformamide, acetonitrile, pentan-3-one, or 
acetone. 
In general, the reaction is carried out at a reaction temperature of about 
20.degree. to 100.degree. C., preferably about 25.degree. to 80.degree. C. 
The working up can be carried out by distillation after the salts which 
have precipitated during the reaction have been separated off; frequently 
water is added to the reaction mixture, the product is taken up in a 
solvent which is substantially water immiscible and the solvent is 
evaporated off. The esters thus obtained can be purified by distillation. 
If high-boiling esters, which can undergo decomposition during 
distillation, are obtained, they are freed from residues of solvent or 
alkylating agent in vacuo at temperatures of up to 150.degree. C. 
According to process variant 2.4, the C.sub.1-4 -alkyl esters of the new 
cyclopropanecarboxylic acids according to formula (VII) can be 
transesterified in a manner which is in itself known. Thus, for example, 
it can be advantageous initially to prepare a C.sub.1 -C.sub.4 alkyl 
ester, preferably the ethyl ester, of a new cyclopropanecarboxylic acid of 
the general formula (VII) by reacting an .alpha.-halogenocyclobutanone of 
the general formula (II) with a sodium alcoholate, for example sodium 
ethylate, and then to transesterify this lower alkyl ester with an alcohol 
which is of interest biologically, using a basic catalyst. Bases for this 
process are, for example, sodium alcoholates. Such transesterifications 
proceed between equimolar amounts of alcohol and ester, but, in general, 
the alcohol is used in excess and the lower alcohol formed during the 
reaction, such as, for example, ethanol, is removed by distillation. 
Solvents for the trans-esterfication are, for example, toluene or xylene. 
(7) Vinyl-substituted cyclopropanecarboxylic acids, which can be used in 
process variants 2.1 and 2.2, of the formula (VI) in which the radicals 
R.sup.1 to R.sup.7 have the meanings stated under 1 are known (German 
Offenlegungsschrift (German Published Specification) No. 2,539,048, DOS 
(German Published Specification) No. 2,544,150 and Nature 244, 456, 
(1973)). 
They can be prepared by (7.1) reacting .alpha.-halogenocyclobutanones of 
the formula (II) in which R.sup.1 to R.sup.7 and Hal have the meanings 
stated under 1, with an aqueous base, if appropriate in a diluent, or by 
(7.2) halogenating cyclobutanones of the formula (IV) in which R.sup.1 to 
R.sup.7 have the meanings stated under 1, if appropriate in a diluent, and 
subsequently reacting the product with an aqueous base. 
(8) The new cyclopropanecarboxylic acids of the formula (VII) in which 
R.sup.1 to R.sup.7 have the meanings stated under 2 are preferably 
obtained by this procedure. 
Particularly preferably, the following new cyclopropanecarboxylic acids may 
be mentioned: 
2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclopropanecarboxyl 
ic acid, 
2,2-diethyl-3-(.alpha.,.beta.-dichlorovinyl)-cyclopropanecarboxylic acid, 
2-ethyl-2-methyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclopropanecarb 
oxylic acid, 
2,2-diethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)cyclopropanecarboxylic 
acid, 
2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trifluorovinyl)-cyclopropanecarboxyl 
ic acid, 
2,2,3-trimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclopropanecarbo 
xylic acid, 
2,2-dimethyl-3-(.alpha.-chloro-.beta.-acetoxyvinyl)-cyclopropanecarboxylic 
acid, 
2-methyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclopropanecarboxylic 
acid, 
2,2-dimethyl-3-(.alpha.-fluoro-.beta.,.beta.-dichlorovinyl)-cyclopropaneca 
rboxylic acid, 
2-methyl-2-n-propyl-3-(.alpha.-fluoro-.beta.,.beta.-dibromovinyl)-cyclopro 
panecarboxylic acid, 
2,2-dimethyl-3-(.alpha.-cyano-.beta.,.beta.-dichlorovinyl)-cyclopropanecar 
boxylic acid, 
1-ethyl-2,2-dimethyl-3-(.alpha.,.beta.-dichlorovinyl)-cyclopropanecarboxyl 
ic acid, 
1,2,2,3-tetramethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclopropanec 
arboxylic acid, 
2,2-dimethyl-3-(.beta.,.delta.,.delta.-trichlorobuta-1,3-dienyl)-cycloprop 
anecarboxylic acid, 
2-(.alpha.,.beta.,.beta.-trichlorovinyl)-spiro[2,5]octane-1-carboxylic 
acid, 
2-(.alpha.,.beta.,.beta.-trifluorovinyl)-1-methyl-spiro[2,5]octane-1-carbo 
xylic acid, 
1,2,2-trimethyl-3-(.alpha.-cyano-.beta.,.beta.-dichlorovinyl)-cyclopropane 
carboxylic acid, 
2,2,3-trimethyl-3-(.alpha.-chloro-.beta.,.beta.-dicyanovinyl)-cyclopropane 
carboxylic acid, 
1,2,3-trimethyl-3-(.alpha.,.beta.,.beta.-trifluorovinyl)cyclopropanecarbox 
ylic acid, 
2,2-dimethyl-3-(.alpha.-chloro-.beta.-methoxycarbonyl)-cyclopropanecarboxy 
lic acid, 
2,2-dimethyl-3-(.alpha.-chloro-.beta.-methylsulphonyl-vinyl)-cyclopropanec 
arboxylic acid, 
2,2-diethyl-3-methyl-3-(.alpha.-cyano-.beta.,.beta.-dibromovinyl)-cyclopro 
panecarboxylic acid, 
2-ethyl-2-propyl-3-(.beta.-bromo-.alpha.,.beta.-dichlorovinyl)-cyclopropan 
ecarboxylic acid, 
2,2-dimethyl-3-[.alpha.-chloro-.beta.,.beta.-bis-(trifluoromethyl)-vinyl]c 
yclopropanecarboxylic acid, 
2-(.alpha.-fluoro-.beta.,.beta.-dichlorovinyl)-spiro[2,5]octane-1-carboxyl 
ic acid, 2-(.alpha.,.beta.,.beta.-trichlorovinyl)-spirohexane-1-carboxylic 
acid, 2,2-dimethyl-3 
-(.alpha.-chloro-.beta.-dimethylaminocarbonyl-vinyl)-cyclopropanecarboxyli 
c acid and 
2-phenyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)cyclopropane-carboxylic 
acid. 
The new and known .alpha.-halogenocyclobutanones which are used as starting 
materials in process variants 1.1, 1.3 and in process 7.1 are obtainable 
by processes 3.1 to 3.3 and 4.1. 
Cyclobutanones of the formula (IV) in which R.sup.1 to R.sup.7 have the 
preferred and especially preferred meanings indicated under 1.1 are 
preferred and especially preferred in process 3.1. 
Individual cyclobutanones which may be mentioned and which can be employed 
in process 3.1 are preferably those cyclobutanones from which the 
.alpha.-halogenocyclobutanones indicated under 1.1 are derived. 
Suitable halogenating agents for process 3.1 are those mentioned in process 
variant 1.2. However, bromine or chlorine is preferably used. 
If appropriate, process 3.1 is carried out in a diluent. Suitable diluents 
are inert organic aprotic solvents, such as, for example, hydrocarbons and 
chlorinated hydrocarbons, such as methylene chloride, carbon 
tetrachloride, chloroform, 1,2-dichloroethane, n-hexane or ligroin; 
ethers, such as diethyl ether; and esters, such as ethyl acetate. In 
addition to the aprotic solvents, protic solvents can also be used, such 
as, for example, formic acid, acetic acid, propionic acid or butyric acid. 
Moreover, these can catalyze the formation of the 
.alpha.-halogenocyclobutanone derivatives. Further suitable catalysts are, 
for example, hydrogen halide acids, such as hydrogen chloride, hydrogen 
bromide or hydrogen iodide; mineral acids, such as, for example, sulphuric 
acid, perchloric acid or phosphoric acid; and also Lewis acids, such as 
aluminum trichloride, ferric chloride, zinc chloride or titanium 
tetrachloride. If appropriate, the halogenation can also be catalyzed by 
UV light. 
The reaction temperature for the halogenation can be chosen within a wide 
range. The reaction can take place, both at -70.degree. C. and at 
+80.degree. C., depending on the structure of the cyclobutanone derivative 
to be halogenated. A temperature range of about -10.degree. to +40.degree. 
C., preferably about 15.degree. to 25.degree. C., proves useful for the 
preparation. Specifically, the halogenation can be carried out by 
introducing the halogen into the reaction solution incrementally, the rate 
of the addition depending on the conversion of the halogen, that is to say 
the addition of a further amount of halogen is made only when halogen 
which has previously been introduced has reacted. Another method used at 
times is to add together the reactants (cyclobutanone derivative and 
halogen and, if appropriate, solvent and catalyst) and to allow them to 
react at 15.degree. to 25.degree. C. A further variant is to drive out 
part of the hydrogen halide, formed during the reaction, from the reaction 
solution with nitrogen or to remove it by reaction with a basic compound, 
such as, for example, calcium carbonate or sodium carbonate. 
The working up of the reaction solution can be so carried out that the 
hydrogen halide is driven out with nitrogen or air and the reaction 
solution is employed direct, if necessary after removing excess halogen 
with sodium thiosulphate, in process variant 1.1 or process 7.1, 
especially if, by reaction with an aqueous alkali metal base, the 
corresponding cyclopropanecarboxylic acid is to be obtained or if, by 
reaction with an alkali metal salt of a C.sub.1 -C.sub.4 alcohol, such as 
ethanol, a cyclopropanecarboxylic acid ester of this C.sub.1 -C.sub.4 
alcohol is to be obtained. The crude .alpha.-halogenoketone can be 
obtained free from hydrogen halide by washing with water, if appropriate 
with the addition of a solvent which is immiscible with water, and can be 
isolated in the pure form by crystallization or distillation. 
The cyclobutanones of the general formula (X) which can be used in process 
3.2 are new. 
They can be obtained by reacting known cyclobutenones (Houben-Weyl, Volume 
IV part 4, page 174 et seq.) with organo-metallic compounds, such as 
ethynylmagnesium bromide or propargyllithium, with the addition of 
catalysts, such as copper salts, which promote a 1,4-addition. 
The resulting 3-ethynylcyclobutanones are halogenated both in the 
.alpha.-position relative to the keto group and on the triple bond. It is 
also possible to add hydrogen halide into the triple bond before the 
halogenation and thus to obtain 1-halogenovinyl- or 
2-halogenovinyl-substituted cyclobutanones instead of 
1,2-dihalogenovinyl-substituted cyclobutanones. 
The procedure of process 3.2 corresponds to that described in process 3.1, 
with the proviso that, where appropriate, 2 equivalents of halogenating 
agent are necessary for the halogenation. 
The cyclobutanones of the general formula (VI) which can be used in process 
3.3 are new; they can be obtained by the process described under 5.9. 
The procedure of process 3.3 also corresponds to that described in process 
3.1. 
Some of the new .alpha.-halogenocyclobutanones of the formula (II) in which 
R.sup.1 to R.sup.7 have the meaning indicated under 4 can also be 
obtained, according to the invention, by process 4.1. 
The 1,3-dienes employed in process 4.1 are known or can be obtained by 
known methods. 1,3-Dienes of the formula (XII) in which R.sup.1 to R.sup.7 
have the preferred meanings indicated under 1.1 are preferably employed. 
1,3-Dienes of the formula (XII) in which R.sup.1 to R.sup.7 have the 
especially preferred meaning indicated under 1.1 are particularly 
preferred. 
Particularly suitable 1,3-dienes of the formula (XII) are those indicated 
in process 5.1. 
Chloroketene, which can be used in process 4.1, is known; if appropriate, 
it can be prepared in situ. With regard to the process conditions for this 
reaction, the conditions described in German Offenlegungsschrift (German 
Published Specification) No. 2,539,048 may be referred to. 
As already mentioned, some of the cyclobutanones which can be used in 
process variant 1.2 and processes 3.1 to 3.3 and 7.2 are new. Their 
preparation is carried out by processes 5.1 to 5.9. Starting materials of 
the formulae (IV), (XII), (XIII), (XV), (XVI), (XVII), (XVIII), (XIX), 
(XX), (XXI), and (XXII) in which R.sup.1 -R.sup.7 have the preferred and 
particularly preferred meaning indicated under 1.1 are preferably and 
particularly preferably employed in these processes. R.sup.10 and R.sup.11 
preferably represent methyl or ethyl or, conjointly with the adjacent N 
atom, form a piperidine or morpholine ring. 
The addition of a ketene or masked ketene (acylal or 
.alpha.-chloro-enamine) onto a double bond is common to processes 5.1 to 
5.5 and 5.9. Cycloaddition reactions with ketenes to give 4-membered 
cyclic ketones proceed strictly stereospecifically, but frequently 
regio-unspecifically. The more rich in electrons the double bond of the 
olefin, the more readily they occur. Thus, for example, dimethylketene 
adds onto 1-dialkylaminoalkenes or 1-alkoxyalkenes considerably better 
than onto the corresponding unsubstituted alkene. The cycloaddition of 
.alpha.-chloro-enamines on to 1,3-dienes having electron-attracting 
substituents, which proceeds unexpectedly smoothly, proves particularly 
valuable for the preparation. The cyclobutanones of the general formula 
(IV) are obtained in high yields under mild reaction conditions after the 
hydrolysis of the imonium salts which are formed as intermediates. A 
particular characteristic of this reaction is the observed 
regio-specificity of the addition. Indications of the formation of the 
regio-isomeric cyclobutanones are not obtained. 
Specific examples of the .alpha.-chloro-enamines of the general formula 
(XIII) which are employed in process 5.1 are: 
1-chloro-1-dimethylamino-2-methyl-1-propene, 
1-chloro-1-piperidino-2-methyl-1-propene, 
1-chloro-1-diethylamino-2-methyl-1-propene, 
1-chloro-1-dimethylamino-1-propene, 
1-chloro-1-morpholino-2-methyl-1-propene, 
1-chloro-1-methylethylamino-2-methyl-1-propene, 
1-chloro-1-dimethylamino-2-ethyl-1-butene, 
1-chloro-1-dimethylamino-2-methyl-1-butene, 
(1-chloro-1-dimethylamino-methylene)-cyclohexane, 
1,2-dichloro-1-dimethylamino-2-methyl-1-propene and 
1-chloro-1-dimethylamino-2-methyl-2-phenyl-1-propene. 
These .alpha.-chloro-enamines are known or can be prepared by known 
processes. 
A large number of olefins of the general formula (XII) can be used as 
reactants in the cycloaddition reaction according to process 5.1, for 
example: 1-chlorobuta-1,3-diene, 2-chlorobuta-1,3-diene, 
1,1-difluorobuta-1,3-diene, 1,1,2-trifluorobuta-1,3-diene, 
1,1,2-trichlorobuta-1,3-diene, 1,1-dichlorobuta-1,3-diene, 
1,1-dichloro-2-fluorobuta-1,3-diene, 1,1-dichloro-2-methylbuta-1,3-diene, 
1,1-dichloro-2-ethylbuta-1,3-diene, 1,1-dichloro-3-methylbuta-1,3-diene, 
1,1,2-trifluoro-3-methylbuta-1,3-diene, 
1,1,2-trichloro-3-methylbuta-1,3-diene, 1,1-dicyanobuta-1,3-diene, 
1,1-dicyano-2-methylbuta-1,3-diene, 1,1-difluoro-2-chlorobuta-1,3-diene, 
1,1,2-trichloro-3-cyanobuta-1,3-diene, 1,1-dichloro-2-bromobuta-1,3-diene, 
2-chloro-3-methylbuta-1,3-diene, 1,2-dichlorobuta-1,3-diene, 
1,2-dibromobuta-1,3-diene, 1,1-dibromobuta-1,3-diene, 
1,1-dibromo-2-fluorobuta-1,3-diene, 1,1-dibromo-2-chlorobuta-1,3-diene, 
1,1-dichloropenta-1,3-diene, 1,1-dichloro-hexa-1,3-diene, 
1,1,2-trichloro-penta-1,3-diene, 1,1-dichloro-3-methylpenta-1,3-diene, 
1,1,2-trichloro-3-methylpenta-1,3-diene, 1,1-dichloro-hepta-1,3-diene, 
1,1,2-trichloro-hepta-1,3-diene, 1,1 -dichloro-octa-1,3-diene, 
1,1-dichloro-nona-1,3-diene, 1,1-dibromo-penta-1,3-diene, 
1-acetoxy-2-chloro-buta-1,3-diene, 1,1-bis-trifluoromethyl-buta-1,3-diene, 
2-methanesulphonyl-buta-1,3-diene, 1,1-dibromo-2-fluoro-penta-1,3-diene, 
1,1-dichloro-2-fluoro-penta-1,3-diene, 
1,3-dibromo-2-methyl-penta-1,3-diene, 
1-(.beta.,.beta.-dichlorovinyl)-1-cyclohexene, 
1-vinyl-2-chloro-1-cyclohexene and 
1-(.beta.,.beta.-dichlorovinyl)-1-cyclopentene. 
For process 5.1, it is necessary to convert the .alpha.-chloroenamine into 
a reactive form. This can be carried out by reacting the 
.alpha.-chloro-enamine with, for example, silver tetrafluoroborate. Other 
salts, such as, for example, silver hexafluorophosphate, silver 
perchlorate or silver hexafluoroarsenate can be used. With regard to 
isolating the cyclobutanones of the general formula (IV), it is cheaper to 
use zinc chloride for carrying out the cycloaddition reaction with 
.alpha.-chloro-enamines according to process 5.1. Thus, in the case of 
addition on to halogenovinyl-substituted olefins under the mild reaction 
conditions used (see below), no reaction of the zinc chloride with the 
diene takes place. However, a large number of other compounds, such as, 
for example, Lewis acid (iron(III) chloride, titanium tetrachloride, 
aluminum chloride, boron trifluoride or tin chloride) can be used in 
process 5.1. 
The reaction of an .alpha.-chloro-enamine of the general formula (XIII) 
with an olefin of the general formula (XII) can be carried out by 
initially introducing the olefin, if appropriate in a solvent, together 
with a Lewis acid and adding the .alpha.-chloro-enamine dropwise, if 
appropriate in a solvent, while stirring. An exothermic effect can occur 
in this procedure. However, an alternative procedure can be initially to 
introduce the .alpha.-chloro-enamine, if appropriate in a solvent, to 
produce the reactive ketene-imonium cation by adding a Lewis acid and to 
add the olefin dropwise, if appropriate in a solvent. An exothermic effect 
can also occur in this procedure. A further variant is to add together the 
reactants (.alpha.-chloro-enamine, Lewis acid and olefin), if appropriate 
in a solvent, and to stir the mixture. An exothermic effect can again 
occur here. Solvents which can be employed are halogenated hydrocarbons, 
such as, for example, methylene chloride, chloroform, carbon 
tetrachloride, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane or 
1,2-dichloroethylene, or acetonitrile, ethers or acetic acid esters, and 
also, for example, hydrocarbons, such as cyclohexane or petroleum ether, 
and also tetramethylene-sulphone or dimethylformamide. 
The cycloaddition of an .alpha.-chloro-enamine onto an olefin in the 
presence of a Lewis acid is a reaction which proceeds stoichiometrically. 
However, it is advisable to employ a small excess of 
.alpha.-chloro-enamine and Lewis acid (maximum about 20%). 
The reaction temperature can be chosen within a wide range. Thus, the 
reaction according to the invention can be carried out both at about 
-10.degree. C. and +80.degree. C. In many cases it has been shown that the 
cycloaddition reaction already occurs in the temperature range of 
20.degree. to 40.degree. C., which is easy to control industrially, that 
is to say at room temperature or slightly above. A reaction time of about 
1/2 to 24 hours is sufficient for a complete conversion. 
For working up, the reaction mixture of process 5.1 is hydrolyzed by adding 
water, an aqueous base or an acid. In this procedure, the 
cyclobutanone-imonium salt, which is formed as an intermediate, is 
converted into the cyclobutanone derivative of the general formula (IV), 
if appropriate by warming the solution to a temperature of about 
20.degree. to 100.degree. C., preferably about 40.degree. to 60.degree. 
C., and this cyclobutanone derivative is separated off by extraction with 
an organic solvent, such as, for example, toluene or dibutyl ether. By 
means of fractional distillation, if appropriate under reduced pressure, 
and/or crystallization it can be obtained in an analytically pure form for 
characterization. In many cases the purification is superfluous and the 
crude cyclobutanone can be employed directly in process variant 1.2 or 
processes 7.2 or 3.1. A prerequisite for this is that the solvent used for 
the extraction or cycloaddition reaction does not react with the 
halogenating agent. 
The imonium salts which can be used in processes 5.2 or 5.8 are new; they 
are prepared by process 9.1 or 9.2 (see below). 
Ketenes which can be used in processes 5.3 and 5.4 are known or can be 
prepared in a manner which is in itself known by (a) dehalogenating an 
.alpha.-halogenocarboxylic acid halide, for example 
.alpha.-bromoisobutyric acid bromide, in an inert solvent, such as, for 
example, ether or ethyl acetate, with zinc, if appropriate activated zinc, 
in an inert gas atmosphere (nitrogen) and distilling off the ketene 
formed, together with the inert solvent, the solvent and ketene being 
employed directly for the cycloaddition reaction (Houben-Weyl, Volume IV, 
part 4, page 174 et seq.); or (b) dehydrohalogenating acid chlorides, for 
example isobutyric acid bromide, with a tertiary amine, such as, for 
example, triethylamine or dicyclohexyl-ethylamine; or (c) reacting an 
.alpha.-diazoketone with mercury oxide; or (d) dissociating a ketene 
dimer, for example 2,2,4,4-tetramethylcyclobutane-1,3-dione, by the action 
of heat. 
Ketene acetals which can be used in process 5.5 are known from German 
Auslegeschrift (German Published Specification) No. 1,199,259 and can be 
prepared by the processes described there. 
The cyclobutanones which can be used in process 5.6 are new; they can be 
prepared by processes 5.1 to 5.5 and 5.8. 
The cyclobutanones which can be used in process 5.7 are new; they can be 
prepared by adding halogen onto the vinyl group of cyclobutanones which 
can be prepared according to processes 5.1 to 5.5 and 5.8. 
Process 5.9 can be carried out under the same conditions as indicated for 
process 5.1. The cyclobutanone-imonium salts formed as intermediates in 
these processes are hydrolyzed, without isolating them, to the 
corresponding cyclobutanones (see above). 
The conversion, to be carried out in processes 5.2 and 5.8, of an isolated 
cyclobutanone-imonium salt of the general formulae (XV) and (XXI) into the 
corresponding cyclobutanone is carried out analogously to the procedure 
described in process 5.1. The conversion can also be carried out by 
subjecting the reaction solution, which has optionally been acidified or 
rendered alkaline, to steam distillation and separating off the 
cyclobutanone derivative from the steam distillate by extraction with an 
organic solvent and then, as given above, purifying. The zinc salts which 
remain in the aqueous phase, for example if dry zinc chloride is used as 
the Lewis acid, can be recovered by working up. 
Processes 5.3 to 5.5 are carried out in an autoclave or bomb tube under 
pressure, for example analogously to the reaction conditions indicated in 
German Offenlegungsschrift (German Published Specification) No. 1,199,259. 
(9) The imonium salts of the general formulae (XV) and (XXI) which can be 
used in processes 5.2 and 5.8 are new. They are obtained when (9.1) an 
.alpha.-chloroenamine of the general formula (XIII) in which R.sup.5, 
R.sup.6, R.sup.10 and R.sup.11 have the meanings stated under 5.1, is 
reacted with an olefin of the formula (XIV) in which R.sup.1 to R.sup.4 
and R.sup.7 have the meanings stated under 5.1, if appropriate in a 
diluent and in the presence of a silver salt, or when (9.2) an 
.alpha.-chloroenamine of the general formula (XIII), in which R.sup.5, 
R.sup.6, R.sup.10 and R.sup.11 have the meanings stated under 5.1, is 
reacted with an olefin of the formula (XXII) in which R.sup.1 to R.sup.4 
and R.sup.7 have the meanings stated under 5.9, if appropriate in a 
diluent and in the presence of a silver salt. 
The reaction in processes 9.1 and 9.2 is carried out as described for 
process 5.1. It is generally carried out in the presence of a 
stoichiometric amount of a silver salt, such as silver perchlorate, silver 
hexafluorophosphate, silver hexafluoroarsemate or, preferably, silver 
tetrafluoroborate. After the addition reaction of the 
.alpha.-chloroenamine and the olefin has been carried out, which is 
effected by a procedure analogous to that described in 5.1, the silver 
chloride formed is filtered off, the solvent is distilled off from the 
filtrate and the residue is crystallized. 
The vinyl-substituted cyclopropanecarboxylic acids, or their salts, which 
can be used for process variants 2.1 to 2.3 can be obtained by processes 
7.1 or 7.2. 
In process 7.1, the .alpha.-halogenoketone is reacted with water in the 
presence of a base; the salt, which is formed, of the 
cyclopropanecarboxylic acid is separated off and the acid is liberated by 
acidifying the alkaline solution with a mineral acid. This conversion can 
be carried out, if appropriate, with the addition of a solvent, such as, 
for example, toluene, methylene chloride, lower alcohols, such as ethanol 
or isopropanol, or dibutyl ether. 
The reaction temperature can be chosen relatively freely; it can be about 
0.degree. to 100.degree. C., preferably about 20.degree. to 40.degree. C. 
Alkali metal or alkaline earth metal hydroxides, such as sodium hydroxide, 
potassium hydroxide, lithium hydroxide or barium hydroxide; or tertiary 
amines, such as triethylamine or triethanolamine, can be used as bases; 
sodium hydroxide or potassium hydroxide is preferably employed. 
At least two equivalents of a monoacidic base are necessary for complete 
conversion of the .alpha.-halogenocyclobutanone into the salt of the 
cyclopropane carboxylic acid. Consequently, the .alpha.-halogenoketone of 
the general formula (II) is also reacted with about 2 to 8 equivalents, 
preferably about 2 to 4 equivalents, of a monoacidic base. 
The liberation of the acid from its salt can be effected by adding aqueous 
mineral acid, such as, for example, hydrochloric acid, sulphuric acid or 
phosphoric acid. The resulting cyclopropanecarboxylic acid can be purified 
by distillation or crystallization. In many cases, the acids are obtained 
in such a pure form that they can be further processed directly. 
In the procedure of process 7.2, a cyclobutanone of the general formula 
(IV) is initially halogenated. In this procedure, the reaction is carried 
out as indicated in process 3.1. 
As already mentioned, the cyclopropanecarboxylic acid esters obtainable by 
the processes according to the invention are suitable for combating animal 
pests and as intermediates for the preparation of active compounds for 
combating animal pests. 
The active compounds are well tolerated by plants, have a favorable level 
of toxicity to warm-blooded animals, and can be used for combating 
arthropod pests, especially insects and acarids, which are encountered in 
agriculture, in forestry, in the protection of stored products and of 
materials, and in the hygiene field. They are active against normally 
sensitive and resistant species and against all or some stages of 
development. The abovementioned pests include: 
from the class of the Isopoda, for example Oniscus asellus, Armadillidium 
vulgare and Porcellio scaber; 
from the class of the Diplopoda, for example Blaniulus guttulatus; 
from the class of the Chilopoda, for example Geophilus carpophagus and 
Scutigera spec.; 
from the class of the Symphyla, for example Scutigerella immaculata; 
from the order of the Thysanura, for example Lepisma saccharina; 
from the order of the Collembola, for example Onychiurus armatus; 
from the order of the Orthoptera, for example Blatta orientalis, 
Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta 
domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, 
Melanoplus differentialis and Schistocerca gregaria; 
from the order of the Dermaptera, for example Forficula auricularia; 
from the order of the Isoptera, for example Reticulitermes spp.; 
from the order of the Anoplura, for example Phylloxera vastatrix, Pemphigus 
spp., Pediculus humanus corporis, Haematopinus spp. and Linognathus spp.; 
from the order of the Mallophaga, for example Trichodectes spp. and 
Damalinea spp.; 
from the order of the Thysanoptera, for example Hercinothrips femoralis and 
Thrips tabaci; 
from the order of the Heteroptera, for example Eurygaster spp., Dysdercus 
intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus and 
Triatoma spp.; 
from the order of the Homoptera, for example Aleurodes brassicae, Bemisia 
tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, 
Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, 
Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humuli, 
Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix 
cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, 
Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus 
spp. and Psylla spp.; 
from the order of the Lepidoptera, for example Pectinophora gossypiella, 
Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, 
Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis 
chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistis 
citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, 
Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, 
Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, 
Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria 
mellonella, Cacoecia podana, Capua recticulana, Choristoneura fumiferana, 
Clysia ambiguella, Homona magnanima and Tortrix viridana; 
from the order of the Coleoptera, for example Anobium punctatum, 
Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, 
Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon 
cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna 
varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., 
Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, 
Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma 
spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, 
Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., 
Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, 
Amphimallon solstitialis and Costelytra zealandica; 
from the order of the Hymenoptera, for example Diprion spp., Hoplocampa 
spp., Lasius spp., Monomorium pharaonis and Vespa spp.; 
from the order of the Diptera, for example Aedes spp., Anopheles spp., 
Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora 
erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., 
Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma 
spp., Tabanus spp., Tannia spp., hortulanus Oscinella frit, Phorbia spp., 
Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae and Tipula paludosa; 
from the order of the Siphonaptera, for example Xenopsylla cheopis and 
Ceratophyllus spp.; 
from the class of the Arachnida, for example Scorpio maurus and Latrodectus 
mactans; 
from the order of the Acarina, for example Acarus siro, Argas spp., 
Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta 
oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma 
spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., 
Tarsonemus spp., Bryobia praetiosa, Panonychus spp. and Tetranychus spp.. 
When used against hygiene pests and pests of stored products, the active 
compounds are distinguished by an excellent residual activity on wood and 
clay as well as a good stability to alkali on limed substrates. 
The active compounds according to the instant invention can be utilized, if 
desired, in the form of the usual formulations or compositions with 
conventional inert (i.e. plant compatible or herbicidally inert) pesticide 
diluents or extenders, i.e. diluents, carriers or extenders of the type 
usable in conventional pesticide formulations or compositions, e.g. 
conventional pesticide dispersible carrier vehicles such as gases, 
solutions, emulsions, wettable powders, suspensions, powders, dusting 
agents, foams, pastes, soluble powders, granules, aerosols, 
suspension-emulsion concentrates, seed-treatment powders, natural and 
synthetic materials impregnated with active compound, very fine capsules 
in polymeric substances and in coating compositions, for use on seed, and 
formulations used with burning equipment, such as fumigating cartridges, 
fumigating cans, fumigating coils and the like, as well as ULV cold mist 
and warm mist formulations. 
These are prepared in known manner, for instance by extending the active 
compounds with conventional pesticide dispersible liquid diluent carriers 
and/or dispersible solid carriers optionally with the use of carrier 
vehicle assistants, e.g. conventional pesticide surface-active agents, 
including emulsifying agents and/or dispersing agents, whereby, for 
example, in the case where water is used as diluent, organic solvents may 
be added as auxiliary solvents. The following may be chiefly considered 
for use as conventional carrier vehicles for this purpose: aerosol 
propellants which are gaseous at normal temperatures and pressures, such 
as halogenated hydrocarbons, e.g. dichlorodifluoromethane and 
trichloromethane, as well as butane, propane, nitrogen and carbon dioxide; 
inert dispersible liquid diluent carriers, including inert organic 
solvents, such as aromatic hydrocarbons (e.g. benzene, toluene, xylene, 
alkyl naphthalenes, etc.), halogenated, especially chlorinated, aromatic 
hydrocarbons (e.g. chlorobenzenes, etc.), cycloalkanes, (e.g. cyclohexane, 
etc.), paraffins (e.g. petroleum or mineral oil fractions), chlorinated 
aliphatic hydrocarbons (e.g. methylene chloride, chloroethylenes, etc.), 
alcohols (e.g. methanol, ethanol, propanol, butanol, glycol, etc.) as well 
as ethers and esters thereof (e.g. glycol monomethyl ether, etc.), amines 
(e.g. ethanolamine, etc.), amides (e.g. dimethyl formamide, etc.), 
sulfoxides (e.g. dimethyl sulfoxide, etc.), acetonitrile, ketones (e.g. 
acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 
etc.), and/or water; as solid carriers, ground natural minerals, such as 
keolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or 
diatomaceous earth, and ground synthetic minerals, such as 
highly-dispersed silicic acid, alumina and silicates; as solid carriers 
for granules; crushed and fractionated natural rocks such as calcite, 
marble, pumice, sepiolite and dolomite, as well as synthetic granules of 
inorganic and organic meals, and granules of organic material such as 
sawdust, coconut shells, maize cobs and tobacco stalks; whereas the 
following may be chiefly considered for use as conventional carrier 
vehicle assistants, e.g. surface-active agents, for this purpose: 
emulsifying agents, such as non-ionic and/or anionic emulsifying agents 
(e.g. polyethylene oxide esters of fatty acids, polyethylene oxide ethers 
of fatty alcohols, alkyl sulfates, alkyl sulfonates, aryl sulfonates, 
albumin hydrolyzates, etc., and especially alkyl arylpolyglycol ethers, 
magnesium stearate, sodium oleate, etc.); and/or dispersing agents, such 
as lignin, sulfite waste liquors, methyl cellulose, etc. 
Adhesives such as carboxymethylcellulose and natural and synthetic polymers 
in the form of powders, granules or latices, such as gum arabic, polyvinyl 
alcohol and polyvinyl acetate, can be used in the formulations. 
It is possible to use colorants such as inorganic pigments, for example 
iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such 
as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, 
and trace nutrients such as salts of iron, manganese, boron, copper, 
cobalt, molybdenum and zinc. 
Such active compounds may be employed alone or in the form of mixtures with 
one another and/or with such solid and/or liquid dispersible carrier 
vehicles and/or with protection agents, such as other insecticides, or 
acaricides, nematicides, bactericides, rodenticides, herbicides, 
fertilizers, growth-regulating agents, etc., if desired, or in the form of 
particular dosage preparations for specific application made therefrom, 
such as solutions, emulsions, suspensions, powders, pastes, and granules 
which are thus ready for use. 
As concerns commercially marketed preparations, these generally contemplate 
carrier composition mixtures in which the active compound is present in an 
amount substantially between about 0.1-95% by weight, and preferably 
0.5-90% by weight, of the mixture, whereas carrier composition mixtures 
suitable for direct application or field application generally contemplate 
those in which the active compound is present in an amount substantially 
between about 0.0000001-100, preferably 0.01-10%, by weight of the 
mixture. Thus, the present invention contemplates overall compositions 
which comprise mixtures of a conventional dispersible carrier such as (1) 
a dispersible inert finely divided carrier solid, and/or (2) a dispersible 
carrier liquid such as an inert organic solvent and/or water, preferably 
including a surface-active effective amount of a carrier vehicle 
assistant, e.g. a surface-active agent, such as an emulsifying agent 
and/or a dispersing agent, and an amount of the active compound which is 
effective for the purpose in question and which is generally between about 
0.0001-95%, and preferably 0.01-95%, by weight of the mixture. 
The active compounds can also be used in accordance with the well known 
ultra-low-volume process with good success, i.e. by applying such compound 
if normally a liquid, or by applying a liquid composition containing the 
same, via very effective atomizing equipment, in finely divided form, e.g. 
average particle diameter of from 50-100 microns, or even less, i.e. mist 
form, for example by airplane crop spraying techniques. Only up to at most 
about a few liters/hectare are needed, and often amounts only up to about 
15 to 1000 g/hectare, preferably 40 to 600 g/hectare, are sufficient. In 
this process it is possible to use highly concentrated liquid compositions 
with said liquid carrier vehicles containing from about 20 to about 95% by 
weight of the active compound or even the 100% active substance alone, 
e.g. about 20-100% by weight of the active compound. 
Furthermore, the present invention contemplates methods of selectively 
killing, combating or controlling pests, e.g. insects, which comprises 
applying to at least one of correspondingly (a) such insects, and (b) the 
corresponding habitat thereof, i.e. the locus to be protected, e.g. to a 
growing crop, to an area where a crop is to be grown or to a domestic 
animal, a correspondingly combative or toxic amount, i.e. an 
insecticidally effective amount, of the particular active compound of the 
invention alone or together with a carrier vehicle as noted above. The 
instant formulations or compositions are applied in the usual manner, for 
instance by spraying, atomizing, vaporizing, scattering, dusting, 
watering, squirting, pouring, fumigating, and the like. 
It will be realized, of course, that the concentration of the particular 
active compound utilized in the admixture with the carrier vehicle will 
depend upon the intended application. Therefore, in special cases it is 
possible to go above or below the aforementioned concentration ranges. 
The following preparative examples illustrate the processes according to 
the invention. Where spectroscopic data are indicated, they relate, in the 
case of IR spectra, to characteristic absorption maxima; in the case of 
NMR spectra they also relate to tetramethylsilane as an internal standard. 
The symbols used denote: s=singlet, d=doublet, t=triplet, q=quartet, 
m=multiplet, br=broad and do=double.

EXAMPLE 1 
Preparation of 
2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclobutanone 
A solution of 10.0 g of 
2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclobutanone-dimeth 
ylimonium tetrafluoroborate in 200 ml of water was warmed to 
40.degree.-60.degree. C. for 30 minutes. An oil separated out which was 
extracted with methylene chloride. Drying the methylene chloride phase 
with sodium sulphate and concentration gave 6.1 g (90%) of 
2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclobutanone. 
EXAMPLE 2 
Preparation of 2,2-dimethyl-3-(.beta.,.beta.-dichlorovinyl)-cyclobutanone 
74.0 g (0.54 mol) of anhydrous zinc chloride were added to 56.0 g (0.45 
mol) of 1,1-dichlorobuta-1,3-diene in 400 ml of methylene chloride, while 
stirring, and 60.0 g (0.45 mol) of 
1-chloro-1-dimethylamino-2-methyl-1-propene in 300 ml of methylene 
chloride were then added dropwise, while stirring. During this procedure, 
the temperature of the reaction solution rose from 18.degree. C. initially 
to 35.degree.-40.degree. C. After stirring for 2 hours under reflux, the 
mixture was cooled to 20.degree. C. and, after standing overnight (15 
hours) at 15.degree. to 20.degree. C. and, after standing overnight (15 
hours) at 15.degree. to 20.degree. C., 1,200 ml of 1 N NaOH were added 
dropwise, while stirring. 300 ml of methylene chloride were added, the 
mixture was acidified with 10% strength aqueous hydrochloric acid and the 
phases were separated. The organic phase was washed with water until it 
gave a neutral reaction, clarified over anhydrous sodium sulphate and 
evaporated. This gave 85.1 g of a yellow-brown oil, which was subjected to 
fractional distillation. 
Yield: 73.5 g (84.5%) of a colorless oil of boiling point 
100.degree.-104.degree. C./12 mm Hg; n.sub.D.sup.20 =1.4912. 
IR (CCl.sub.4) 1,790 cm.sup.-1 (CO). 
NMR (CDCl.sub.3) .delta.1.13 s (3H), 1.29 s (3H), 2.80-3.30 m (3H) and 
5.90-6.10 ppmm (1H). 
C.sub.8 H.sub.10 Cl.sub.2 O--calculated: C, 49.76; H, 5.22; Cl, 36.73. 
(193.1)--found: C, 49.8; H, 5.33; cl, 36.1. 
EXAMPLE 3 
Preparation of 
4-bromo-2,2-dimethyl-3-(.beta.,.beta.-dichlorovinyl)-cyclobutanone 
A solution of 1.6 g (0.01 mol) of bromine in 4.5 ml of glacial acetic acid 
was added dropwise at 20.degree. C. to a solution of 1.95 g (0.01 mol) of 
2,2-dimethyl-3-(.beta.,.beta.-dichlorovinyl)-cyclobutanone in 2 ml of 
glacial acetic acid at such a rate that the reaction solution was 
decolorized before each addition of bromine. After subsequently stirring 
for 3 hours at 20.degree. C., the reaction mixture was added to ice. The 
oil which had separated out was taken up in methylene chloride, the 
methylene chloride solution was washed with water until it gave a neutral 
reaction and clarified over anhydrous sodium sulphate and the organic 
phase was concentrated. This gave 2.72 g of a yellow-colored oil which, 
according to the NMR spectrum, no longer contained the starting ketone. 
Instead of this, signals occurred which indicated the presence of the two 
stereoisomeric 
4-bromo-2,2-dimethyl-3-(.beta.,.beta.-dichlorovinyl)-cyclobutanones. 
EXAMPLE 4 
Preparation of 
2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclobutanone-dimeth 
ylimonium tetrafluoroborate 
7.0 g (0.052 mol) of 1-chloro-1-dimethylamino-2-methyl-1-propene in 15 ml 
of methylene chloride were added dropwise to a suspension of 10.2 g (0.052 
mol) of silver tetrafluoroboratein 70 ml of methylene chloride and 11.0 g 
(0.07 mol) of 1,1,2-trichlorobutadiene in the course of one hour at 
-60.degree. C., while stirring. The reaction mixture was allowed to warm 
to 20.degree.-25.degree. C. and after being left to stand (15 hours) 
silver chloride was filtered off. Evaporation of the filtrate in vacuo 
left 21.07 g of a cycloadduct which, when recrystallized twice from 
chloroform/ether, gave 10.3 g of colorless crystals of melting point 
129.degree.-131.degree. C. 
C.sub.10 H.sub.15 BCl.sub.3 F.sub.4 N--(342,4)--Calculated: C, 35.08; H, 
4.42; N, 4.09. Found: C, 35.1; H, 4.31; N, 4.14. 
NMR (CD.sub.3 CN): .delta.1.40 s (3H), 1.63 s (3H), 3.45 m (6H) and 3.5-4.0 
ppm m (3H). 
EXAMPLE 5 
Preparation of 
2,2-dimethyl-3-(.beta.,.beta.-dichlorovinyl)-cyclopropanecarboxylic acid 
A mixture of the isomeric 
4-bromo-2,2-dimethyl-3-(.beta.,.beta.-dichlorovinyl)-cyclobutanones, 
obtained from 0.01 mol of 
2,2-dimethyl-3-(.beta.,.beta.-dichlorovinyl)-cyclobutanone according to 
Example 3, was stirred with 15 ml of 2 N NaOH overnight (15 hours) at 
20.degree. C. The neutral products were extracted with ether, the alkaline 
aqueous phase was acidified with 10% strength aqueous hydrochloric acid 
and the acids were extracted with ether. Washing the ether extract with 
saturated sodium chloride solution and subsequent clarification over 
sodium sulphate (anhydrous) gave, after evaporating the organic phase, 
1.35 g (65%) (relative to 
2,2-dimethyl-3-(.beta.,.beta.-dichlorovinyl)-cyclobutanone employed) of 
crystalline 
2,2-dimethyl-3-(.beta.,.beta.-dichlorovinyl)-cyclopropanecarboxylic acid 
which, according to the NMR spectrum, was a 22:78 mixture of the cis-trans 
isomers. Fractional crystallization from n-hexane gave sterically 
homogeneous 
2,2-dimethyl-3-trans-(.beta.,.beta.-dichlorovinyl)-cyclopropanecarboxylic 
acid of melting point 87.degree. to 89.degree. C. 
IR (CCl.sub.4) 1,705 cm.sup.-1 (CO). NMR (CDCl.sub.3) .delta.1.20 s (3H), 
1.32 s (3H), 1.55 d (1H, J=5.5 Hz) 2.25 dod (1H, J=8 Hz and 5.5 Hz), and 
5.63 ppm d (1H, J=8 Hz). 
After separating off the dominant trans-acid from a relatively large amount 
of crude acid, the sterically homogeneous 
2,2-dimethyl-3-cis-(.beta.,.beta.-dichlorovinyl)-cyclopropanecarboxylic 
acid was obtained by fractional crystallization from pentane. 
Melting point 92.degree. to 94.degree. C. 
EXAMPLE 6 
Preparation of 
2,2-dimethyl-3-(.beta.,.beta.-dichlorovinyl)-cyclopropanecarboxylic acid 
ethyl ester 
A solution of 1.6 g (0.01 mol) of bromine in 5 ml of carbon tetrachloride 
was added dropwise, to the point of decolorization, to 1.95 g (0.01 mol) 
of 2,2-dimethyl-3-(.beta.,.beta.-dichlorovinyl)-cyclobutanone in 5 ml of 
carbon tetrachloride, which contained 5% of hydrogen bromide at 25.degree. 
C. The mixture was subsequently stirred for 2 hours, the hydrogen bromide 
formed was removed by passing a dry stream of nitrogen through and the 
reaction solution was concentrated. The residue was taken up in 15 ml of 
absolute ether and the ether solution was added dropwise to a suspension 
of 0.9 g of sodium ethylate in 10 ml of absolute ether, while cooling with 
ice. The mixture was subsequently stirred for 2 hours and the temperature 
of the reaction mixture was allowed to rise to 20.degree. to 25.degree. C. 
The solution, which had an alkaline reaction, was neutralized with 
ethanolic hydrochloric acid and then added to ice. Extraction with ether, 
clarification of the ether phase over anhydrous sodium sulphate and 
concentration gave, after fractional distillation, 1.4 g (61%) of 
colorless ethyl ester of boiling point 75.degree. to 80.degree. C./0.2-0.3 
mm Hg which, according to the NMR spectrum (CDCl.sub.3) was identical to a 
specimen prepared from 
2,2-dimethyl-3-(.beta.,.beta.-dichlorovinyl)-cyclopropanecarboxylic acid 
via the acid chloride. 
EXAMPLE 7a 
Preparation of 
2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclobutanone 
A solution of 150 ml of dry methylene chloride and 45.0 g (0.336 mol) of 
1-chloro-1-dimethylamino-2-methyl-1-propene was added dropwise to a 
mixture of 53.0 g (0.336 mol) of 1,1,2-trichlorobuta-1,3-diene, 55.0 g 
(0.405 mol) of anhydrous zinc chloride and 250 ml of dry methylene 
chloride; the temperature of the solution rose from 20.degree. C. 
initially to 35.degree. C. The solution was stirred for 5 hours under 
reflux and allowed to cool to 20.degree. C.; 850 ml of 1 N NaOH were added 
dropwise at 20.degree. C., while stirring. After adding 800 ml of carbon 
tetrachloride, the phases were separated and the organic phase was washed 
with water until it gave a neutral reaction and clarified over anhydrous 
sodium sulphate. Evaporation of the solvent gave 68.1 g (89%) of 
2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclobutanone as a 
yellowish oil. 
Boiling point 118.degree.-121.degree. C./12 mm Hg; n.sub.D.sup.20 =1.512. 
IR (CCl.sub.4) 1,790 cm.sup.-1 (CO). NMR (CDCl.sub.3) .delta.1.17 s (3H), 
1.39 s (3H) and 3.30-3.80 ppm m (3H). C.sub.8 H.sub.9 Cl.sub.3 
O--calculated: C, 42.23; H, 3.99; Cl, 46.75. (227.5)--found: C, 42.5; H, 
3.92; Cl, 46.2. 
EXAMPLE 7b 
Preparation of 
2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclobutanone 
(variation using a Lewis acid) 
In each case, 0.3 mol of the Lewis acid indicated below was suspended in 
160 ml of methylene chloride and a solution of 36.8 g (0.275 mol) of 
1-chloro-1-dimethylamino-2-methyl-1-propene in 40 ml of methylene chloride 
was added in the course of 30 minutes, while cooling (15.degree. C.) and 
stirring. The mixture was heated to reflux for 5 hours, 300 ml of water 
were added, whilst cooling with ice, and the mixture was stirred for 15 
hours at 20.degree. C. Separation of the phases and washing of the organic 
phase with water until neutral, drying over sodium sulphate and 
concentrating in vacuo gave the crude ketone which, in each case, was 
subjected to fractional distillation. 
The yields indicated below were obtained: 
______________________________________ 
Lewis acid Yield of ketone 
______________________________________ 
Zinc chloride 91.5% 
Aluminum chloride 66% 
Tin(II) chloride 61% 
Titanium(IV) chloride 
71% 
Tin(IV) chloride 73% 
______________________________________ 
EXAMPLE 8 
Preparation of 
2,2,3-trimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclobutanone 
58.0 g (0.336 mol) of 1,1,2-trichloro-3-methyl-buta-1,3-diene and 55.0 g 
(0.405 mol) of anhydrous zinc chloride in 250 ml of dry methylene chloride 
were heated under reflux with 45.0 g (0.336 mol) of 
1-chloro-1-dimethylamino-2-methyl-1-propene in 150 ml of dry methylene 
chloride for 4 hours and the mixture was then worked up according to 
Example 2. Fractional distillation gave 47.0 g (58%) of crystalline 
2,2,3-trimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclobutanone of 
melting point 42.degree. to 44.degree. C. (from n-hexane). 
IR (CCl.sub.4) 1,790 cm.sup.-1 (CO). NMR (CDCl.sub.3) .delta.1.21 s (3H), 
1.39 s (3H), 1.45 s (3H), 2.70 d (1H, J=17 Hz) and 3.97 ppm d (1H, J=17 
Hz). C.sub.9 H.sub.11 Cl.sub.3 O--calculated: C, 44.76; H, 4.59; Cl, 
44.03. found: C, 44.6; H, 4.58; Cl, 43.7. 
The following cyclobutanones were prepared by the process described: 
______________________________________ 
Physical 
Example character- 
No. Compound istics 
______________________________________ 
9 2,2-diethyl-3-(.beta.,.beta.-dichloro- 
vinyl)-cyclobutanone 
n.sub.D.sup.20 1.4963 
10 2-Ethyl-2-methyl-3-(.beta.,.beta.- 
dichlorovinyl)-cyclo- 
butanone n.sub.D.sup.20 1.4922 
11 2,2-Diethyl-3-(.alpha.,.beta., .beta.- 
trichlorovinyl)- 
cyclobutanone n.sub.D.sup.20 1.5153 
12 2-Ethyl-2-methyl-3-(.alpha.,.beta.,.beta.- 
trichloroviyl)-cyclo- 
butanone n.sub.D.sup.20 1.5141 
13 3-(.alpha.,.beta.,.beta.-trichloroviyl)- 
spiro[3,5]-nonan-1-one 
n.sub.D.sup.20 1.5379 
14 3-(.beta.,.beta.-dichloroviyl)- 
spiro[3,5]-nonan-1-one 
melting point 
59.degree.-60.degree. C. 
15 2,2,3-Trimethyl-3-(.beta.,.beta.- 
dichlorovinyl)-cyclo- 
butanone boiling point 
118.degree.-121.degree. C. 
15 mm Hg 
16 2,2-Dimethyl-3-(.beta.-chloro- 
vinyl)-cyclobutanone 
n.sub.D.sup.20 1.4747 
17 2,2,4-Trimethyl-3-(.beta.- 
ethoxycarboylvinyl)- 
cyclobutanone boiling point 
86.degree.-98.degree. C./0.075 
mm Hg 
______________________________________ 
In addition, the following cyclobutanones could be prepared: 
2,2-dimethyl-3-(.alpha.-methyl-.beta.,.beta.-dichlorovinyl)-cyclobutanone, 
2,2-diethyl-3-(.alpha.,.beta.-dichlorovinyl)-cyclobutanone, 
2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trifluorovinyl)-cyclobutanone, 
2,2-dimethyl-3-(.alpha.,.beta.-dichlorovinyl)-cyclobutanone, 
2,2-dimethyl-3-(.beta.,.beta.-dibromovinyl)-cyclobutanone, 
2,2-dimethyl-3-(.alpha.-fluoro-.beta.,.beta.-dichlorovinyl)-cyclobutanone, 
2,2-dimethyl-3-(.beta.-chlorovinyl)-cyclobutanone, 
2,2,3-trimethyl-3-(.alpha.,.beta.,.beta.-trifluorovinyl)-cyclobutanone, 
2,2-dimethyl-3-(.beta.,.beta.-difluorovinyl)-cyclobutanone, 
2-ethyl-2,3-dimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclobutanon 
e, 2,2-diethyl-3-(.beta.,.beta.-dibromovinyl)-cyclobutanone, 
2-ethyl-2-methyl-3-(.beta.,.beta.-dibromovinyl)-cyclobutanone, 
2-ethyl-2-methyl-3-(.alpha.-fluoro-.beta.,.beta.-dichlorovinyl)-cyclobutan 
one, 
2,2-dimethyl-3-(.alpha.-ethyl-.beta.,.beta.-dichlorovinyl)-cyclobutanone, 
2-ethyl-2,3-dimethyl-3-(.beta.,.beta.-dichlorovinyl)-cyclobutanone, 
3-(.beta.,.beta.-dichlorovinyl)-spiro[3,5]-nonan-1-one, 
2,2-dimethyl-3-(.alpha.,.beta.-dibromovinyl)-cyclobutanone, 
3-(.beta.,.beta.-dibromovinyl)-spiro[3,5]-nonan-1-one, 
2,2-dimethyl-3-(.beta.-bromo-.beta.-chlorovinyl)-cyclobutanone, 
2,2-dimethyl-4-ethyl-3-(.beta.,.beta.-dichlorovinyl)-cyclobutanone, 
2,2,4-trimethyl-3-(.alpha.,.beta.-dibromovinyl)-cyclobutanone, 
2,2-dimethyl-4-n-butyl-3-(.beta.,.beta.-dichlorovinyl)-cyclobutanone and 
2-methyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclobutanone. 
EXAMPLE 18 
Preparation of 
4-bromo-2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclobutanon 
A solution of 42.5 g (0.186 mol) of 
2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclobutanone, 31.1 
g (0.194 mol) of bromine and 150 ml of 1% strength hydrobromic acid in 
carbon tetrachloride was allowed to stand at 20.degree. to 25.degree. C. 
for 15 hours. The hydrogen bromide formed was then driven out with 
nitrogen and the solution was wahsed with water until it gave a neutral 
reaction, clarified over anhydrous sodium sulphate and concentrated. This 
gave 56.7 g (quantitative) of crystalline 
4-bromo-2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclobutanon 
e which, according to the NMR spectrum, contained only one of the two 
isomeric bromoketones. 
Melting point 76.degree. to 77.degree. C. (from n-hexane). IR (CCl.sub.4) 
1,800 cm.sup.-1 (CO). NMR (CDCl.sub.3) .delta.1.25 s (3H), 1.50 s (3H), 
3.74 d (1H, J=8.5 Hz) and 5.46 ppm d (1H, J=8.5 Hz). C.sub.8 H.sub.8 
BrCl.sub.3 O--calculated: C, 31.36; H, 2.63; Br, 26.1; Cl, 34.7. (306.4) 
found: C, 31.3; H, 2.70; Br, 25.7; Cl, 34.3. 
EXAMPLE 19 
Preparation of 
4-bromo-2,2,4-trimethyl-3-(.beta.,.beta.-dichlorovinyl)-cyclobutanone 
208 g (0.01 mol) of 
2,2,4-trimethyl-3-(.beta.,.beta.-dichlorovinyl)-cyclobutanone (mixture of 
isomers) in 8 ml of glacial acetic acid were reacted with 1.6 g (0.01 mol) 
of bromine according to Example 3. This gave, after working up, 2.65 g of 
a yellowish oil, the NMR spectrum (CDCl.sub.3) of which showed the 
following signals: .delta.1.20 s (3H), 1.34 s (3H), 1.39 s (3H), 1.52 s 
(3H), 1.78 s (3H), 1.92 s (3H), 3.08 d (1H, J=8.5 Hz), 3.68 d (1H, J=9 
Hz), 6.00 d (1H, J=9 Hz) and 6.26 ppm d (1H, J=8.5 Hz). 
From the comparison of the intensities of the signals at .delta.1.92/1.78, 
3.08/3.68 and 6.26/6.00 ppm, an isomer ratio of the 
4-bromo-2,2,4-trimethyl-3-(.beta.,.beta.-dichlorovinyl)-cyclobutanones of 
about 3:2 was calculated. 
EXAMPLE 20 
Preparation of 
4-bromo-2,2,3-trimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclobuta 
none 
23.0 g (0.144 mol) of bromine were added to a solution of 33.6 g (0.14 mol) 
of 2,2,3-trimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclobutanone 
in 120 ml of carbon tetrachloride, which contained 1% of hydrobromic acid, 
at 20.degree. C. After standing for 20 hours at 20.degree. C., the 
solution was decolorized. It was worked up as described for Example 18 and 
40.2 g (89%) of almost homogeneous crystalline 
4-bromo-2,2,3-trimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclobuta 
none were isolated. 
Melting point 81.degree. to 82.degree. C. (from n-hexane). According to the 
evidence of the NMR spectrum of the crude product, only one of the 
isomeric bromoketones was present. 
IR (CCl.sub.4) 1,800 cm.sup.-1 (CO). NMR (CDCl.sub.3) .delta.1.31 s (3H), 
1.47 s (6H) and 5.82 ppm s (1H). C.sub.9 H.sub.10 BrCl.sub.3 
O--calculated: C, 33.73; H, 3.15; Br, 24.9; Cl, 33.2. (320.5)--found: C, 
34.0; H, 3.22; Br, 24.4; Cl, 32.9. 
The following .alpha.-bromocyclobutones were prepared by the process 
described: 
______________________________________ 
Physical 
Example character- 
No. Compound istics 
______________________________________ 
21 4-Bromo-2,2-diethyl-3- 
(.alpha.,.beta.,.beta.-trichlorovinyl)- 
cyclobutanone IR(CCl.sub.4) 1790 cm.sup.-1 
22 4-Bromo-2-ethyl-2-methyl- 
3-(.alpha.,.beta.,.beta.-trichlorovinyl)- 
cyclobutanone IR(CCl.sub.4) 1790 cm.sup.-1 
23 2-Bromo-3-(.alpha.,.beta.,.beta.-tri- 
chlorovinyl)-spiro[3,5] 
nonan-1-one melting point 
76.degree.-77.degree. C. 
______________________________________ 
In addition, the following cyclobutanones could be brominated in the 
4-position: 
2,2-dimethyl-3-(.alpha.-methyl-.beta.,.beta.-dichloro-vinyl)-cyclobutanone 
, 2,2-diethyl-3-(.alpha.,.beta.-dichlorovinyl)-cyclobutanone, 
2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trifluorovinyl)-cyclobutanone, 
2,2-dimethyl-3-(.alpha.,.beta.-dichlorovinyl)-cyclobutanone, 
2,2-dimethyl-3-(.beta.,.beta.-dibromovinyl)-cyclobutanone, 
2,2-dimethyl-3-(.alpha.-fluoro-.beta.,.beta.-dichlorovinyl)-cyclobutanone, 
2,2-dimethyl-3-(.beta.-chlorovinyl)-cyclobutanone, 
2,2,3-trimethyl-3-(.alpha.,.beta.,.beta.-trifluorovinyl)-cyclobutanone, 
2,2-dimethyl-3-(.beta.,.beta.-difluorovinyl)-cyclobutanone, 
2-ethyl-2-methyl-3-(.beta.,.beta.-dichlorovinyl)-cyclobutanone, 
2-ethyl-2,3-dimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclobutanon 
e, 2,2-diethyl-3-(.beta.,.beta.-dibromovinyl)-cyclobutanone, 
2-ethyl-2-methyl-3-(.beta.,.beta.-dibromovinyl)-cyclobutanone, 
2-ethyl-2-methyl-3-(.alpha.-fluoro-.beta.,.beta.-dichlorovinyl)-cyclobutan 
one, 
2,2-dimethyl-3-(.alpha.-ethyl-.beta.,.beta.-dichlorovinyl)-cyclobutanone, 
2-ethyl-2,3-dimethyl-3-(.beta.,.beta.-dichlorovinyl)-cyclobutanone, 
2,2-dimethyl-3-(.alpha.,.beta.-dibromovinyl)-cyclobutanone, 
2,2-dimethyl-3-(.beta.-bromo-.beta.-chlorovinyl)-cyclobutanone, 
2,2-dimethyl-4-ethyl-3-(.beta.,.beta.-dichlorovinyl)-cyclobutanone, 
2,2,4-trimethyl-3-(.alpha.,.beta.-dibromovinyl)-cyclobutanone, 
2,2-dimethyl-4-n-butyl-3-(.beta.,.beta.-dichlorovinyl)-cyclobutanone, 
2-methyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclobutanone, 
2,2-di-n-propyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclobutanone, 
2-hexyl-3-(.beta.,.beta.-dichlorovinyl)-cyclobutanone, 
2-methyl-2-butyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclobutanone, 
2,2-dimethyl-3-(.alpha.-cyano-.beta.,.beta.-dichlorovinyl)-cyclobutanone, 
2,2-dimethyl-3-n-butyl-3-(.beta.,.beta.-dichlorovinyl)-cyclobutanone, 
2,2-dimethyl-3-(.beta.-chloro-.beta.-methoxycarbonylvinyl)-cyclobutanone, 
2,2-dimethyl-3-(.beta.,.beta.-dicyanovinyl)-cyclobutanone, 
2,3-dimethyl-3-(.beta.,.beta.-dibromovinyl)-cyclobutanone, 
2,2-dimethyl-3-(.beta.,.beta.-dibromovinyl)-4-n-butyl-cyclobutanone, 
2,2-di-n-butyl-3-methyl-3-(.alpha.-chloro-.beta.-cyanovinyl)-cyclobutanone 
, 2,2-dimethyl-3-(.alpha.-methylsulphonylvinyl)-cyclobutanone, 
2,2-diethyl-3-(.beta.,.beta.-dichlorovinyl)-4-cyclohexyl-cyclobutanone, 
2-methyl-2-phenyl-3-(.beta.,.beta.-dichlorovinyl)-cyclobutanone, 
2,2-dimethyl-3-(.beta.-chloro-.beta.-phenylvinyl)-cyclobutanone, 
2,2-dimethyl-3-(.beta.,.beta.-bis-(trifluoromethyl)-vinyl)-cyclobutanone, 
2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-4-benzylcyclobutanon 
e and 2-cyclohexyl-3-(.beta.,.beta.-dichlorovinyl)-cyclobutanone; and the 
following spiro-cyclic cyclobutanones could be brominated in the 
2-position: 3 -(.beta.,.beta.-dichlorovinyl)-spiro [3,5]nonan-1-one, 
3-(.beta.,.beta.-dibromovinyl)-spiro[5,3]nonan-1-one, 
3-(.beta.,.beta.-dichlorovinyl)-spiro[4,3]octan-1-one, 
3-(.beta.,.beta.-dichlorovinyl)-2-methyl-spiro[5,3]nonan-1-one, 
3-(.alpha.,.beta.-dichlorovinyl)-spiro[5,3]nonan-1-one and 
3-(.alpha.,.beta.,.beta.-trifluorovinyl)-spiro[3,5]nonan-1-one. 
EXAMPLE 24 
Preparation of 
4-chloro-2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclobutano 
ne 
A total of 17 ml of previously condensed chlorine (about 0.3 mol) were 
passed into a solution of 55.9 g (0.246 mol) of 
2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclobutanone in 200 
ml of carbon tetrachloride at 20.degree. C., while stirring. After 
allowing to stand (15 hours), hydrogen chloride and unreacted chlorine 
were removed by passing nitrogen into the reaction solution and the 
mixture was then extracted with water, 5% strength sodium thiosulphate 
solution and again with water. Drying the organic phase over sodium 
sulphate and concentration gave 63.95 g of a crystalline product which was 
crystallized from 100 ml of n-hexane. Melting point 77.degree.-78.degree. 
C. 
C.sub.8 H.sub.8 Cl.sub.4 O--(262.0)--Calculated: C, 36.68; H, 3.08; Cl, 
54.14. Found: C, 36.5; H, 2.87; Cl, 53.8. IR(CCl.sub.4): 1810 cm.sup.-1. 
NMR (CDCl.sub.3): .delta.=1.25 s (3H), 1.48 s (3H), 3.65 and 5.36 ppm AB 
quartet (J=8.5 Hz, 2H). 
EXAMPLE 25 
Preparation of 
2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclopropanecarboxyl 
ic acid 
58.6 g (0.26 mol) of crude 
2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclobutanone in 330 
ml of carbon tetrachloride, which contained 1% of hydrogen bromide, were 
allowed to stand at 20.degree. C. with 41.5 g (0.26 mol) of bromine for 15 
hours. The hydrogen bromide formed was substantially driven out from the 
decolorized solution and 570 ml of 1.3 N NaOH were added to the solution 
at 20.degree. C. in the course of 2 hours, while stirring. After 6 hours, 
the organic phase was separated off. Acidification of the aqueous alkaline 
phase with concentrated hydrochloric acid, while cooling, gave, after 
extraction by shaking with ether, washing until neutral and clarification 
of the ether phase over anhydrous sodium sulphate, 56.6 g (89.3%) of 
crystalline 
2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclopropanecarboxyl 
ic acid which, according to the NMR spectrum and within the accuracy of 
measurement, contained only one of the two isomers. Melting point 
90.degree. to 93.degree. C. (from petroleum ether). 
EXAMPLE 26 
Preparation of 
1,2,2-trimethyl-3-(.beta.,.beta.-dichlorovinyl)-cyclopropanecarboxylic 
acid 
The crude 
4-bromo-2,2,4-trimethyl-3-(.beta.,.beta.-dichlorovinyl)-cyclobutanone 
(2.55 g) obtained according to Example 19 was suspended in 25 ml of 2 N 
NaOH and the suspension was stirred at 20.degree. C. for 6 hours. The 
mixture was worked up as described for Example 5 to give 1.93 g (86%) 
(relative to 0.01 mol of 
2,2,4-trimethyl-3-(.beta.,.beta.-dichlorovinyl)cyclobutanone) of 
crystalline 
1,2,2-trimethyl-3-(.beta.,.beta.-dichlorovinyl)-cyclopropanecarboxylic 
acid as a mixture of isomers of melting point 87.degree. to 95.degree. C. 
Fractional crystallization gave the homongenous isomers. 
ISOMER A 
NMR (CDCl.sub.3) .delta. 1.11 s (3H), 1.23 s (3H), 1.30 s (3H), 2.39 d (1H, 
J=7.5 Hz), 5.63 d (1H, J=7.5 Hz) and 9.80 ppm s (1H). 
ISOMER B 
NMR (CDCl.sub.3) .delta. 1.30 s (6H), 1.45 s (3H), 1.68 d (1H, J=8.5 Hz), 
6.26 s (1H, J=8.4 Hz) and 9.60 ppm s (1H). 
EXAMPLE 27 
Preparation of 
2,2,3-trimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclopropanecarbo 
xylic acid 
A suspension of 21.16 g (0.066 mol) of 
4-bromo-2,2,3-trimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclobuta 
none in 150 ml of 1 N NaOH was stirred for 10 hours at 20.degree. C. The 
mixture was worked up as indicated for Example 5 to give 1.58 g of neutral 
products (unreacted bromoketone) and 13.73 g (87%) of crystalline 
2,2,3-trimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)cyclopropanecarbox 
ylic acid of melting point 152.degree. to 153.degree. C. (from 
benzene/n-hexane). 
IR (CCl.sub.4) 1700 cm.sup.-1. NMR (CDCl.sub.3) .delta. 1.30 s (6H), 1.50 s 
(3H), 1.79 s and 1.95 s (1H) and 9.8 ppm s (1H). C.sub.9 H.sub.11 Cl.sub.3 
O.sub.2 --Calculated: C, 41.97; H, 4.31; Cl, 41.30. (257.6)--Found: C, 
42.2; H, 4.33; Cl, 41.1. 
EXAMPLE 28 
Preparation of 
2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclopropanecarboxyl 
ic acid 
A suspension of 30.6 g (0.1 mol) of 
4-bromo-2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclobutanon 
e in 150 ml of 2 N NaOH was stirred at 20.degree. to 25.degree. C. for 10 
hours. The homogeneous solution was extracted with dibutyl ether in order 
to remove neutral products, acidified with 10% strength aqueous sodium 
chloride, while cooling, and 
2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclopropanecarboxyl 
ic acid, which was obtained in crystalline form, was filtered off and 
washed until neutral. 
Yield 23.8 g (about 100%). IR (CCl.sub.4) 1,705 cm.sup.-1 (CO). NMR 
(C.sub.6 D.sub.6) .delta. 0.86 s (1H), 1.16 s (1H), 1.99 d (1H, J=5.5 Hz) 
2.34 d (1H, J=5.5 Hz) and 12.1 ppm s (1H). C.sub.8 H.sub.9 Cl.sub.3 
O.sub.2 --calculated: C, 39.46; H, 3.73; Cl, 43.68. found: C, 39.3; H, 
3.81; Cl, 43.4. 
The following cyclopropane-carboxylic acids were prepared by the process 
described: 
______________________________________ 
Physical 
Example character- 
No. Compound istics 
______________________________________ 
29 2,2-Diethyl-3-(.alpha.,.beta.,.beta.-tri- 
chlorovinyl)-cyclopropane- 
carboxylic acid melting point 
117.degree.-118.degree. C. 
30 2-Ethyl-2-methyl-3-(.alpha.,.beta.,.beta.- 
trichlorovinyl)-cyclo- 
propanecarboxylic acid 
melting point 
50.degree.-77.degree. C. 
31 2-(.alpha.,.beta.,.beta.-trichlorovinyl)- 
spiro[2,5]octane-1-carboxy- 
lic acid melting point 
129.degree.-131.degree. C. 
______________________________________ 
In addition, the following cyclopropanecarboxylic acids could be prepared: 
2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trifluorovinyl)cyclopropanecarboxyli 
c acid, 2,2-diethyl-3-(.beta.,.beta.-dichlorovinyl)-cyclopropanecarboxylic 
acid, 
2,2,3-trimethyl-3-(.beta.,.beta.-dichlorovinyl)-cyclopropanecarboxylic 
acid, 2,2-dimethyl-3-(.beta.,.beta.-dibromovinyl)-cyclopropanecarboxylic 
acid, 2,2-dimethyl-3-(.alpha.,.beta.-dibromovinyl)-cyclopropanecarboxylic 
acid, 
2,2-dimethyl-3-(.alpha.-cyano-.beta.,.beta.-dichlorovinyl)-cyclopropanecar 
boxylic acid, 
1-ethyl-2,2-dimethyl-3-(.beta.,.beta.-dichlorovinyl)cyclopropanecarboxylic 
acid, 2-(.beta.,.beta.-dichlorovinyl)-spiro[2,5]octane-1-carboxylic acid, 
2,2-dimethyl-3-(.beta.,.beta.-dibromovinyl)cyclopropanecarboxylic acid, 
2,2-dimethyl-3-(.alpha.-chloro-.beta.,.beta.-difluorovinyl)-cyclopropaneca 
rboxylic acid, 
2-(.beta.,.beta.-dichlorovinyl)-spiro[2,4]-heptane-1-carboxylic acid and 
2-methyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclopropanecarboxylic 
acid. 
EXAMPLE 32 
Preparation of 
2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclopropanecarboxyl 
ic acid 
A suspension of 40.63 g (0.154 mol) of 
4-chloro-2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclobutano 
ne in 500 ml of 1 N NaOH (0.5 mol) was stirred for 15 hours at 
20.degree.-25.degree. C. Neutral products were separated off by extraction 
with ether and the alkaline solution was acidified with hydrochloric acid, 
while cooling. Extraction with ether, washing with water until neutral, 
drying over sodium sulphate and evaporation in vacuo gave 23.1 g (62%) of 
colorless crystals of 
2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclopropanecarboxyl 
ic acid of melting point 89.degree.-91.degree. C. 
EXAMPLE 33 
Preparation of 2,2-dimethyl-3-(bromovinyl)-cyclopropanecarboxylic acid 
ethyl ester 
32.0 g (0.2 mol) of bromine in 40 ml of carbon tetrachloride were added 
dropwise to a solution of 12.4 g (0.1 mol) of 
2,2-dimethyl-3-vinylcyclobutanone in 100 ml of carbon tetrachloride at 
10.degree. C. in the course of 2 hours. The mixture was subsequently 
stirred for 1 hour, hydrogen bromide formed was dispelled with nitrogen 
and the solution was washed successively with water, 1% strength aqueous 
sodium thiosulphate solution and water, clarified over anhydrous sodium 
sulphate and concentrated in vacuo. 
Yield: 31.83 g. 
IR (CCl.sub.4): 1805 cm.sup.-1. C.sub.8 H.sub.11 Br.sub.3 O--Calculated: Br 
66.2%. (363)--Found: 65.3%. 
A solution of 31.0 g of 
2,2-dimethyl-3-(.alpha.,.beta.-dibromoethyl)-4-bromo-cyclobutanone in 40 
ml of absolute ethanol was added dropwise to a solution of 4.6 g (0.2 mol) 
of sodium in 70 ml of absolute ethanol at 0.degree.-5.degree. and the 
mixture was subsequently stirred for 1 hour at 40.degree.-50.degree.. 
Ethanolic hydrochloric acid was added to the cooled solution in order to 
neutralize the excess base, the sodium bromide which had separated out was 
filtered off and the filtrate was concentrated. Fractional distillation 
gave two main fractions: 
(A) 7.55 g of a colorless oil of boiling point 53.degree.-58.degree. 
C./0.2-0.3 mm Hg 
IR (CCl.sub.4): 1725 cm.sup.-1 (ester-carbonyl). NMR (CDCl.sub.3): signals 
at, inter alia .delta. 5,55 (2 vinyl protons), 4.15 (2 methylene protons 
of the ethyl group), 1.30 (3 methyl protons), 1.20 (3 methyl protons) and 
1.26 ppm (3 methyl protons of the ethyl group). C.sub.10 H.sub.15 
BrO.sub.2 --Calculated: C, 48.59; H, 6.12; Br, 32.34. (247.1)--Found: C, 
48.6; H, 5.83; Br, 32.2. (Calculated for 
2,2-dimethyl-3-(bromovinyl)-cyclopropanecarboxylic acid ethyl ester). 
(B) 5.2 g of a colorless oil of boiling point 63.degree.-70.degree. 
C./0.1-0.3 mm Hg. 
According to the analytical data (IR, NMR and elementary analysis), this 
was a mixture of isomeric 
2,2-dimethyl-3-(bromovinyl)-cyclopropanecarboxylic acid ethyl esters. 
EXAMPLE 34 
Preparation of 
2-(.alpha.,.beta.,.beta.-trichlorovinyl)-spiro[2,5]octane-1-carboxylic 
acid ethyl ester 
16.1 g (0.0463 mol) of 
2-bromo-3-(.alpha.,.beta.,.beta.-trichlorovinyl)spiro[3,5]nonan-1-one in 
80 ml of ether were added dropwise to a solution of 1.07 g (0.0463 mol) of 
sodium in 20 ml of ethanol in the course of 30 minutes at 
15.degree.-20.degree. C., while stirring and cooling. After heating under 
reflux for one hour, the reaction mixture was poured onto ice and 
extracted with ether. Washing the organic phase with saturated sodium 
bicarbonate solution and water, drying over sodium sulphate and subsequent 
concentration gave 13.3 g of oil which was subjected to fractional 
distillation. This gave 11.3 g (78%) of ethyl ester of boiling point 
116.degree. C./0.15 mm Hg, n.sub.D.sup.20 1.5125. 
C.sub.13 H.sub.17 Cl.sub.3 O.sub.2 -- (311.7)-- Calculated: C, 50.1; H, 
5.5; Cl, 34.1. Found: C, 50.1; H, 5.3; Cl, 33.9. IR (CCl.sub.4): 1735 
cm.sup.-1 (ester-carbonyl). NMR (CDCl.sub.3): .delta.=1.28 t (3H J=7.5 
Hz), 1.3-2.0 m (10H), 2.05 and 2.48, AB-quartet (J=5.5 Hz, 2H) and 4.18 
ppm q (2 H J=7.5 Hz). 
EXAMPLE 35 
Preparation of 
2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclopropanecarboxyl 
ic acid ethyl ester 
7.66 g (0.025 mol) of 
4-bromo-2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclobutanon 
e in 40 ml of dry ether were added dropwise to a suspension of 1.7 g (0.025 
mol) of sodium ethylate in 9 ml of anhydrous ethanol at 15.degree. C. The 
mixture was subsequently stirred for 1 hour at 15.degree. C. and poured 
onto ice/1 N HCl. The phases were separated, the aqueous phase was washed 
twice with ether and the combined ether extracts were then washed with 
aqueous sodium bicarbonate solution and water until they gave a neutral 
reaction. Drying over anhydrous sodium sulphate gave 5.94 g (87%) of 
2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclopropanecarboxyl 
ic acid ethyl ester. 
Boiling point 73.degree. to 74.degree. C./0.2 mm Hg; n.sub.D.sup.20 
=1.4920. IR (CCl.sub.4) 1,726 cm.sup.-1 (CO). NMR (CDCl.sub.3) .delta. 
1.20 s (3H), 1.30 t (3H, J=7.5 Hz), 1.33 s (3H), 2.04 d (1H, J=6 Hz), 2.45 
d (1H, J=6 Hz) and 4.19 ppm q (2H, J=7,5 Hz). 
0.9 g of 
2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclopropanecarboxyl 
ic acid were obtained from the bicarbonate extract by acidification with 
10% strength hydrochloric acid and extraction with ether. 
C.sub.10 H.sub.13 Cl.sub.3 O.sub.2 --calculated: C, 44.23; H, 4.83; Cl, 
39.17. (271.6)--found: C, 43.9; H, 5.09; Cl, 38.6. 
The following esters could be prepared by the above process: 
2,2-dimethyl-3-(.beta.,.beta.-dibromovinyl)-cyclopropanecarboxylic acid 
ethyl ester, 
2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trifluorovinyl)-cyclopropanecarboxyl 
ic acid methyl ester, 
2,2-diethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclopropanecarboxyli 
c acid ethyl ester, 
2,2-diethyl-3-(.beta.,.beta.-dichlorovinyl)-cyclopropanecarboxylic acid 
ethyl ester, 
2,2,3-trimethyl-3-(.beta.,.beta.-dichlorovinyl)-cyclopropanecarboxylic 
acid ethyl ester, 
1,2,2-trimethyl-3-(.beta.,.beta.-dichlorovinyl)-cyclopropanecarboxylic 
acid ethyl ester, 
2,2-dimethyl-3-(.beta.,.beta.-dichlorovinyl)-cyclopropanecarboxylic acid 
methyl ester, 
2-(.beta.,.beta.-dichlorovinyl)-spiro[2,5]octane-1-carboxylic acid ethyl 
ester and 
2-methyl-2-ethyl-3-(.beta.,.beta.-dichlorovinyl)-cyclopropanecarboxylic 
acid n-propyl ester. 
EXAMPLE 36 
Preparation of 
2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclopropanecarboxyl 
ic acid m-phenoxybenzyl ester 
A solution of 12.2 g (0.05 mol) of 
2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclopropanecarboxyl 
ic acid and 6.85 g (0.0575 mol) of thionyl chloride in 50 ml of dry benzene 
was heated under reflux for 1.5 hours. Excess thionyl chloride and gaseous 
reaction products were removed under a waterpump vacuum. 20 ml of dry 
benzene, 15 ml of dry pyridine and 8.0 g (0.04 mol) of m-phenoxy-benzyl 
alcohol were added successively to the resulting residue. After standing 
for 15 hours at 20.degree. C., the reaction mixture was poured onto ice, 
with the addition of 100 ml of benzene, and the benzene phase was 
separated off and washed successively with dilute hydrochloric acid, 
water, 2 N Na.sub.2 CO.sub.3 and water. Drying over sodium sulphate and 
evaporation gave 16.5 g of a colorless oil which, in order to separate off 
unreacted m-phenoxybenzyl alcohol, was dissolved in 100 ml of n-hexane and 
filtered through 50 g of silica gel. Distillation in a bulb tube gave 14.7 
g of 
2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclopropanecarboxyl 
ic acid m-phenoxybenzyl ester as a colorless oil of boiling point 
190.degree. to 195.degree. C./0.01 mm Hg. The ester proved to be 
homogeneous in analysis by thin-layer chromatography. 
IR (CCl.sub.4) 1,735 cm.sup.-1 (CO). NMR (CDCl.sub.3) .delta. 1.18 s (3H), 
1.27 s (3H), 2.07 d (1H, J=6 Hz), 2.44 d (1H, J=6 Hz), 5.12 s (2H) and 
6.90-7.50 ppm m (9H). C.sub.21 H.sub.19 Cl.sub.3 O.sub.3 --calculated: C, 
59.1; H, 4.46; Cl, 25.0. (425.5)--found: C, 59.2; H, 4.70; Cl, 25.1. 
The aqueous phase which resulted during the working up was acidified with 
dilute hydrochloric acid and 1.45 g of 
2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclopropanecarboxyl 
ic acid were recovered by extraction with ether. 
EXAMPLE 37 
Preparation of 
2,2-dimethyl-3-(.alpha.-bromo-.beta.,.beta.-dichlorovinyl)-cyclopropanecar 
boxylic acid ethyl ester 
A solution of 3.2 g (0.02 mol) of bromine in 5 ml of carbon tetrachloride 
was added dropwise to 1.95 g (0.01 mol) of 
2,2-dimethyl-3-(.beta.,.beta.-dichlorovinyl)-cyclobutanone in 5 ml of 
carbon tetrachloride, which contained 5% of hydrogen bromide, at 
25.degree. C. The mixture was subsequently stirred for 6 hours, hydrogen 
bromide which had formed was removed by passing a dry stream of nitrogen 
through and the reaction solution was concentrated. The residue, the NMR 
spectrum (CDCl.sub.3) of which, in agreement with the bromination of the 
dichlorovinyl group by the second mol equivalent of bromine, showed no 
signal for a vinyl proton, was dissolved in 30 ml of ether and the 
solution was added dropwise to a solution of 0.7 g (about 0.03 mol) of 
sodium in 30 ml of absolute ethanol at 20.degree. to 25.degree. C. The 
mixture was allowed to react further for 1 hour at 60.degree. C. and was 
worked up as described for Example 6. This gave 2.19 g (69%) of 
2,2-dimethyl-3-(.alpha.-bromo-.beta.,.beta.-dichlorovinyl)-cyclopropanecar 
boxylic acid ethyl ester of boiling point 85.degree. to 90.degree. C./0.3 
mm Hg. 
Calculated: Br, 25.3. Found: Br, 25.0. 
EXAMPLE 38 
Preparation of 
2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclopropanecarboxyl 
ic acid m-phenoxybenzyl ester 
5.0 g (0.025 mol) of m-phenoxybenzyl alcohol were added to a solution of 
0.520 g (0.0226 mol) of sodium in 10 ml of absolute ethanol, under 
nitrogen, and the ethanol was distilled off in vacuo. Two 50 ml portions 
of absolute toluene were added to the residue and the mixture was 
evaporated to dryness in vacuo. 5.75 g (0.019 mol) of 
4-bromo-2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclobutanon 
e in 20 ml of absolute toluene were added dropwise to a suspension of the 
resulting solid residue in 30 ml of absolute toluene at 15.degree. C. and 
the mixture was subsequently stirred for 6 hours at 20.degree. C. 
According to analysis by thin layer chromatography, complete conversion 
had taken place. The reaction mixture was added to ice/dilute hydrochloric 
acid and the organic phase was separated off, washed until it gave a 
neutral reaction and filtered over 100 g of silica gel. 
Yield: 5.12 g (60%) of 
2,2-dimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclopropanecarboxyl 
ic acid m-phenoxybenzyl ester. 
According to analysis by thin layer chromatography and the NMR spectrum, 
the product was identical to the product obtained in Example 36. 
EXAMPLE 39 
Preparation of 
2,2,3-trimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)cyclopropanecarbox 
ylic acid m-phenoxybenzyl ester 
10.3 g of 
2,2,3-trimethyl-3-(.beta.,.beta.,.beta.-trichlorovinyl)cyclopropanecarboxy 
lic acid (0.04 mol) were reacted, according to Example 36, with 5.8 g 
(0.048 mol) of thionyl chloride in 50 ml of dry benzene to give the acid 
chloride. 25 ml of benzene, 15 ml of pyridine and 8.0 g (0.04 mol) of 
m-phenoxybenzyl alcohol were added successively to the crude acid 
chloride. After standing for 10 hours at 20.degree. C., the mixture was 
worked up according to Example 36 to give 16.2 g of crude ester. 
Chromatography to silica gel and fractional distillation gave 13.1 g (74%) 
of 
2,2,3-trimethyl-3-(.alpha.,.beta.,.beta.-trichlorovinyl)-cyclopropanecarbo 
xylic acid m-phenoxybenzyl ester as a colorless oil of boiling point 
200.degree. to 210.degree. C./0.1-0.15 mm Hg. 
IR (CCl.sub.4) 1,730 cm.sup.-1 (CO). NMR (CDCl.sub.3) .delta. 1.24 s (3H), 
1.29 s (3H), 1.45 s (3H), 1.87 s and 1.99 s (1H), 5.10 s (2H) and 
6.80-7.50 ppmm (9H). C.sub.22 H.sub.21 Cl.sub.3 O.sub.3 --Calculated: C, 
60.08; H, 4.81; Cl, 24.19. Found: C, 60.4; H, 4.65; Cl, 24.0. 
It will be appreciated that the instant specification and examples are set 
forth by way of illustration and not limitation, and that various 
modifications and changes may be made without departing from the spirit 
and scope of the present invention.