Halovinylbenzyl esters and their use for controlling pests

Halovinylbenzyl esters of the formula I ##STR1## where R.sup.1 is ##STR2## R.sup.2 is H, CN, lower alkyl, lower alkenyl, lower alkynyl, lower haloalkyl or lower haloalkenyl, R.sup.3 is H, halogen or lower alkyl, R.sup.4 is H, lower alkyl, lower alkoxy or lower alkoxymethyl, R.sup.5 is lower alkyl, lower hal lk(en)yl or lower haloalkynyl, R.sup.6 and R.sup.7 are each lower alkyl or halogen, A is halogen, lower alkyl, lower alkoxy, lower haloalkyl, lower haloalkoxy, CN or NO.sub.2, m is 0 to 4, n is 1 to 3, B is lower alkyl, lower alkenyl, lower alkynyl or cycloalkyl, and X is H, halogen, lower haloalkyl, lower thioalkyl, lower alkoxy or lower alkyl, and halogen can be fluorine, chlorine or bromine and, in the case of R.sup.2, may furthermore be iodine, a process for their manufacture, and their use as pesticides.

It has been disclosed that 
2,2-dimethyl-3-(2',2'-dimethylvinyl)-cyclopropane carboxylates whose ester 
group is a substituted vinylbenzyl radical possess insecticidal activity 
(GB Pat. No. 2,065,475 and BE Pat. No. 0,738,112). 
The combination of such benzyl alcohols with specific carboxylic acids 
leads to pesticides having a particularly good action. 
We have found that novel esters of the formula I 
##STR3## 
where R.sup.1 is 
##STR4## 
R.sup.2 is H, CN, lower alkyl, lower alkenyl, lower alkynyl, lower 
haloalkyl or lower haloalkenyl, R.sup.3 is H, halogen or lower alkyl, 
R.sup.4 is H, lower alkyl, lower alkoxy or lower alkoxymethyl, R.sup.5 is 
lower alkyl, lower haloalk(en)yl or lower haloalkynyl, R.sup.6 and R.sup.7 
are each lower alkyl or halogen, A is halogen, lower alkyl, lower alkoxy, 
lower haloalkyl, lower haloalkoxy, CN or NO.sub.2, m is 0 to 4, n is 1 to 
3, B is lower alkyl, lower alkenyl, lower alkynyl or cycloalkyl, and X is 
H, halogen, lower haloalkyl, lower thioalkyl, lower alkoxy or lower alkyl, 
and halogen can be fluorine, chlorine or bromine and, in the case of 
R.sup.2, may furthermore be iodine, possess particularly good insecticidal 
activity. 
In formula I, R.sup.1 is trisubstituted or polysubstituted cyclopropyl, in 
particular 3-(2,2-dihalovinyl)-2,2-dimethylcyclopropyl, eg. 
3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropyl, 
3-(2,2-dibromovinyl)-2,2-dimethyl-cyclopropyl or 
3-(2,2-difluorovinyl)-2,2-dimethylcyclopropyl; 
3-(2-haloethynyl)-2,2-dimethylcyclopropyl, eg. 
3-(2-chloroethynyl)-2,2-dimethylcyclopropyl or 
3-(2-bromoethynyl)-2,2-dimethylcyclopropyl; 
3-alkoxy-2,2-dimethylcyclopropyl, eg. 3-ethoxy-2,2-dimethylcyclopropyl, 
3-alkoxymethyl-2,2-dimethylcyclopropyl, eg. 
3-methoxymethyl-2,2-dimethylcyclopropyl; tetraalkylcyclopropyl, in 
particular tetramethylcyclopropyl; 3,3-dihalo-2,2-dialkylcyclopropyl, in 
particular 3,3-dichloro-2,2-dimethylcyclopropyl or 
3,3-dibromo-2,2-dimethylcyclopropyl; or 
3-(haloalkyl)-2,2-dimethylcyclopropyl, eg. 
3-(tetrabromoethyl)-2,2-dimethylcyclopropyl or 
3-(2,2-dichloro-1,2-dibromoethyl)-2,2-dimethylcyclopropyl, or a radical of 
the formula 
##STR5## 
where R.sup.8 is propen-2-yl, isobutenyl or 3-methylbuten-2-yl. 
R.sup.1 may furthermore be a radical of the formula 
##STR6## 
where n is 1 to 3, preferably 1, and substituents A are identical or 
different where there are two or three of these. In this case, A can be, 
for example, fluorine, chlorine or bromine, halomethyl, eg. 
trifluoromethyl, difluoromethyl or trichloromethyl, halomethoxy, eg. 
difluoromethoxy or trifluoromethoxy, cyano, nitro, or straight-chain or 
branched alkyl or alkoxy of not more than 3 carbon atoms, eg. methyl, 
methoxy, ethyl, ethoxy, n-propyl, isopropyl, n-propoxy or isopropoxy. 
Where it occurs in substituent R.sup.1, A is preferably haloalkoxy or 
halogen in the 4-position. 
B can be straight-chain or branched alkyl, alkenyl or alkynyl of not more 
than 4 carbon atoms, eg. methyl, ethyl or, in particular, isopropyl, and 
furthermore tert.-butyl, isobutyl, allyl, isopropenyl, propargyl or an 
alicyclic radical of, for example, 3 to 7 carbon atoms, eg. cyclohexyl or, 
in particular, cyclopropyl or a heterocyclic radical containing not more 
than 3 heteroatoms (N or O). 
R.sup.2 is hydrogen, cyano, straight-chain or branched alkyl, alkeny, 
alkynyl, haloalkyl or haloalkenyl of not more than 3 carbon atoms, eg. 
methyl, ethyl, n-propyl, isopropyl, vinyl, allyl, n-propenyl, isopropenyl, 
ethynyl, n-propynyl, isopropynyl, trifluoromethyl, trichloromethyl, 
difluorovinyl or halogen, in particular iodine. 
In formula I, A is hydrogen, radicals A.sub.m are not more than four 
substituents selected independently of one another, and radicals A.sub.n 
are not more than 3 such substituents, ie. halogen, such as fluorine, 
chlorine or bromine, straight-chain or branched alkyl, alkoxy, alkenyl or 
alkynyl of not more than 5, preferably not more than 3, carbon atoms, eg. 
methyl, ethyl, propyl, isopropyl, n-butyl, tert.-butyl, isobutyl or 
pentyl; methoxy, ethoxy, n-propoxy, isopropoxy, butoxy or pentyloxy; 
vinyl, allyl, n-propenyl, isopropenyl, n-butenyl, n-pentenyl, 
1-methyl-n-propenyl, or 1-methyl-n-butenyl; ethynyl, n-propynyl, 
isopropynyl, n-butynyl, n-pentynyl, 1-methylpropynyl or 1-methylbutynyl; 
or CN or NO.sub.2. 
R.sup.3 is, in particular, hydrogen, but may furthermore be halogen, such 
as fluorine, chlorine or bromine, or methyl, ethyl, propyl or isopropyl. 
X is hydrogen or, preferably, halogen, such as fluorine or, in particular, 
chlorine or bromine, and may furthermore be, for example, methyl, ethyl, 
propyl, isopropyl, methoxy, ethoxy, thiomethyl, chloromethyl, bromomethyl, 
trifluoromethyl or trichloromethyl. 
In each case, the compounds of the formula I can of course occur as one or 
more pairs of optical antipodes, and in many case also in the form of a 
large number of diastereomers; these occur in pure form or as mixtures, 
depending on the starting materials and the reaction conditions. The 
mixtures can be separated into their sterically pure components in a 
conventional manner; in specific cases, their biological action depends on 
their steric configuration. 
The esters of the formula I can be obtained by reacting the corresponding 
acyl halides with appropriate halovinylbenzyl alcohols in the presence of 
an acid acceptor. 
The esters can of course also be prepared from the corresponding carboxylic 
acids and the corresponding halovinylbenzyl halides in the presence of an 
acid acceptor. 
Finally, the novel esters may also be obtained from the free carboxylic 
acids and alcohols under esterification conditions, or by reacting 
available esters with appropriate carboxylic acids or alcohols under 
transesterification conditions. 
Some of the carboxylic acid halides or free carboxylic acids or carboxylic 
acids required are disclosed in British Pat. No. 1,446,304 and U.S. Pat. 
No. 3,981,903. Where in a specific case they are novel, they may be 
prepared in a conventional manner using the halovinylbenzyl compounds 
which are required and essential according to the invention (cf. German 
Laid-Open Applications DOS 2,633,551 and DOS 3,329,288), for example in 
order to introduce the halovinyl radical into the benzyl radical, by 
reaction of an aldehyde with an appropriate Wittig reagent or by 
hydroboration or hydroaluminum or hydrogen halide addition at alkynes 
(Houben-Weyl, Methoden der organischen Chemie, 4th edition, Vol. V/1 b, 
page 795 et seq.). Some of the intermediates required for the preparation 
of the active ingredients are known and some are novel; they can in any 
case be prepared by a conventional process. In this context, reference may 
be made to, for example, U.S. Pat. Nos. 3,979,519 and 3,981,903, Belgian 
Pat. No. 801,946 and German Laid-Open Applications DOS 2,365,555 and DOS 
2,231,312. 
Some or all of the benzyl halides, alcohols and aldehydes required for the 
novel esters of the formula I are novel. 
They can be prepared from the corresponding haloaromatics, toluenes or 
benzoic acids, some of which are known, by a conventional method, for 
example halogenation with N-bromosuccinimide, reduction of acids or 
esters, or oxidation of alcohols. 
The preparation of these haloaromatics, toluenes or benzoic acids is 
described in, for example, GB Pat. No. 2,078,238; JA Pat. No. 4,791,900-Q; 
U.S. Pat. No. 3,336,335; EP Pat. No. 53,687; EP Pat. No. 35,724; Z. org. 
Chim. 1965, 1998-2002; Liebigs Ann. Chem. 1980, 2061-2071; J. Org. Chem. 
36, 1438-1440 (1971); J. Am. Chem. Soc. 1983, 2388-93.