CA1155132A - Dichlorocyclobutanones and processes for their manufacture - Google Patents

Abstract

Abstract of the Disclosure Novel dichlorocyclobutanones of the formula:

(A) in which Z is hydrogen and Z1 is chlorine, or Z1 is hydrogen and Z is chlorine or a group of the formula

Description

~15513Z

The present invention relates to novel dichlorocyclobutanone inter-mediates and processes for their manufacture.
Accordingly one aspect of the invention provides a compound of the formula:
z H - C - C = O (A) CH3 - C - C - Cl in which Z is hydrogen and zl is chlorine, or zl is hydrogen and Z is chlorine or a group of the formula -wherein Rl and R2 each independently represents hydrogen, halogen, methyl, methoxy, trifluoromethyl or cyano, or Rl and R2 together represent methylene-dioxy or a group -CH=CH-CH=CH-.
Another aspect of the invention provides a process for manufacturing a compound of the formula:
z ~1 - C - C = O tA) C~13 - C - C - Cl in which Z is hydrogen and zl is chlorine, or zl ;5 hydrogen and Z is chlorine or a group of the formula:

q~

115513~

~o_ wherein R1 and R2 each independently represents hydrogen~ halogen, methyl, methoxy, trifluoromethyl or cyano, or Rl and R2 together represent methylene-dioxy or a group -CH=CH-CH=CH-.
which process comprises a) for the manufacture of a compound of formula ~A) in which Z represents hydrogen and zl represents chlorine, reacting dichloroacetyl chloride with di-butylene in the presence of a catalyst;
b) for the manufacture of a compound of formula (A) in which Z represents chlorine and zl represents hydrogen, rearranging a compound of formula (A) in which Z represents hydrogen and zl represents chlorine, in the presence of a catalyst; or c) for the manufacture of a compound of formula (A) in which zl is hydro-gen and Z is a group of the formula:

:3~o-wherein R1 and R2 are as defined above reacting a compound of the formula (A) in which one of Z and zl is hydrogen and the other is chlorine, with a phenol of the formula-- la -il55~2 / ~ _ OH

wherein Rl and R2 are as defined aboveJ in the presence of a base.
The compounds ~A) of the invention are useful as intermediates in the production of pesticidally active cyclopropanecarboxyl acid esters of the formula:

--O - CH - CH - COOC~o ~ (I) wherein each of Rl and R2 represents hydrogen, halogen methyl, methoxy, tri-fluoromethyl or cyano, or Rl and R2 together represent methylenedioxy or the fragment -CH=CH-CH=CH-. These compounds (I) are the subject of our copending application Serial No. 323,529, filed March 14, 1979, of which the present application is a divisional.
The term "halogen" used aboué is to be understood as meaning fluorine, chlorine, bromine or iodine, especially fluorine and chlorine.
The compounds of the Formula I can also be obtained by methods which are known per se, for example as follows:

- lb -1) ~30-C~ _Cooll ~ X-C11 CH3 CH3 ~ acid acceptor (~) (IIII

Rl .
: R ~ O-CH -~CH-COX + HO-C ~ O ~

CH3 C~3 acid acceptor ~ (IVI ~ (V) : ~1 3) ~ O-CH - C~-CCX~H + HO ~ ~ ~ O ~

CH3 C~3 hydrophilic agent ~ I :
(Il) (V) .

: Rl ~ ~
~ R o-c5- c~ COOR ~ HO-C~ ~ O ~

2 C~i3 C 3 -ROH
(VI), (V) .

1155~3Z

In the formulae II, IV and VI, Rl and R2 are as defined for formula I.
In the formulae III and IV, X represents a halogen atom, especially a chlcrine or bromine atom, and in formula VI R represents Cl-C4 alkyl, especial-ly methyl or ethyl.
&itable acid acceptors for processes 1 and 2 are in particular terti-ary amines, such as trialkylamine and pyridine, and also hydroxides, oxides, carbonates and bicarbonates of alkali metals and alkaline earth metals, and in addition alkali metal alcoholates, for example potassium tert-butylate and sodi-um methylate. As hydrophilic agent for process 3, dicyclohexylcarbodiimide can for example be used. Processes 1 to 4 are carried out at a reaction temperature between -10 and 120C, usually between 20 and 80C, under normal or elevated pressure and preferably in an inert solvent or diluent. Examples of suitable solvents or diluents are: ether and ethereal compounds, for example diethyl ether, dipropyl ether, dioxane, dimethoxy ethane and tetrahydrofurane; amides, such as N,N-dialkylated carboxamides; aliphatic, aromatic and halogenated hydro-carbons, especially benzene, toluene, xylenes, chloroform and chlorobenzene;
nitriles, such as acetonitrile; dimethyl sulfoxide; and ketones, such as acetone and methyl ethyl ketone.
The starting materials of the formulae II and VI are known or they can be prepared by methods analogous to known ones.
Some of the compounds of the formulae II and VI are known and have been prepared from the corresponding vinyl ethers and diazoacetates (M. Julia and M. Baillage, Bull. soc, chim. France 1966, 734). This process is uneconomic and unacceptable for ecological reasons (diazoacetate is carcinogenic and ex-plosive).
However, it has been found that a more suitable process for the manu-facture of compounds of the formulae II and VI consists in rearranging a com-~ pound of the formula o CH2 - C ~
CH3 - C - C - Cl (B)

3 Cl which is obtainable by a process known per se from dichloroketene and isobutyl-ene, in the presence of a catalyst, to produce a compound of the formula Cl O
CH - C (C) CH3 Cl and converting the compound of the formula (C) with a phenol of the formula Rl ~

wherein Rl and R2 are as defined for formula I, in the presence of a base, into a compound of the formula ~ - O - CH - C
R2 C1~3 - Cj . CH - Cl X

In certain cases it can be advantageous to react the compound of formula (B) direct with a phenol of formula IX, in the presence of a base, to produce the compound of the formula X. The compound of the formula X can be ~55132 converted under known conditions of the Favorski reaction (Organic Reactions II, 261), in the presence of R'OH and a base, into a compound of formu].a R
~ - O - CH - CH - COOR' wherein R' is hydrogen or alkyl. The compound of formula XII is then reacted with an alcohol of the formula CN ~ ~ V

to give a compound of formula I.
Process step 1 As catalysts for the rearrangement of the compound of formula ~B) to produce a compound of formula (C), it is possible to use acids, bases or quaternary ammonium halides.
Suitable basic catalysts are in particular organic bases, such as tertiary amines of the formula Ql N~Q2 wherein Ql represents alkyl of 1 to 8 carbon atoms, cycloalkyl of 5 or 6 carbon atoms, benzyl or phenyl, and Q2 and Q3, each independently of the other, represent alkyl of 1 to 8 carbon atoms, for example triethylamine, tri-n-butylamine, triisopentylamine, tri-n-octylamine, N,N-dimethylcyclohexylamine, N,N-dimethylbenzylami.ne, N,N-dimethyl-2-ethylhexylamine, N,N-diethylaniline; cyclic amines, such as pyridine, ~S5~32 quinoline, lutidine, N-alkylmorpholines, such as N-methylmorpholine, N-alkylpiperidines, such as ~-methylpiperidine and ~-ethylpiperidine, N-alkylpyrrolidines, such as N-methylpyrrolidine and N-ethylpyrrolid-ine; diamines, such as N,N,~',N'-tetramethylethylenediamine, N,N,~',N'-tetramethyl-1,3-diaminobutane, ~,N'-dialkylpiperazines, such as N,N'-dimethylpiperazine; bicyclic diamines, such as 1,4-diaza-bicyclo[2.2.2] octane, and bicyclic amidines, such as 1,5-diazabicyclo ~5.4.0]undec-5-ene and 1,5-diazabicyclo[4.3.0]non-5-ene, and, finally, polymer basic compoùnds, such as p-dimethylaminomethylpolyseyrene.

Suitable acid catalysts which can be used are, for example, inorganic or organic proton acids. Examples of suitable inor$anic proton acids are hydrohalic acids, such as HCl, HBr, HF and ~I, nitric acid, phosphoric acid and sulfuric acid.

Examplesof suitable proton acids are: sulfinic acids, such as benzenesulfinic acid; aliphatic and substituted or unsugstituted aromatic sulfonic acids, such as methanesulfonic acid, benzene-sulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, naphthalene 1,5-disulfonic acids; aliphatic monocarboxylic acids containing preferably 1 to 18 carbon atoms, such as formic acid, acetic acid, propionic acid, butyric acid, lauric acid, palmitic acid, stearic acid; halogen-containing monocarboxylic acids, such as chloroacetic acid, dichloroacetic acid, trichloroacetic scid.tri-fluoroacetic acid; sliphatic ticarboxylic acits containing preeerably 2 to 12 carbon atoms, such as malonic acid, succinic acid, sdipic acid, sebacic acid; substituted or unsubstituted aromatic mono- or dicarboxylic acids, such as benzoic acid, toluic acid, naphthoic acid, phthalic acid and terephthalic acid; aliphatic and aromatic phosphonic and phosphonic acids, such as methylphosphcnic,benzyl-phosphonic and phenylphosphonic acid or dimethylphosphonic and diethylphosphonic acid or diethylphosphinic and benzenephosphinic acid.

1~55~32 If an excess of base or acid is used, then the base or acid can also act as solvent.

It is furthermore also possible to use salts of p}oton acids, in particular hydrohalic acids, with ammonia or a nitrogen-containing organic base, and also quaternary ammonium salts. Suitable nitrogen-containing organic bases are aliphatic, cycloaliphatic, araliphatic and aromatic primary, secondary and tertiary amines and heterocyclic nitrogen bases. Examples are: primary aliphatic amines containing up to 12 carbon atoms, such as methylamine, ethylamine, n-butylamine, n-octylamine, n-dodecylamine, hexamethylenediamine?
dimethylamine, diethylamine, di-n-propylamine; tertiary aliphatic amines containing 1 to 4 carbon atoms in each of the alkyl moieties, such as triethylamine and tri-n-butylamine; cyclohexylamine, dicyclo-hexylamine; benzylamine; substituted or unsubstituted prim~ry, secon-dary and tertiary aromatic amines, such as aniline, toluidine, naphthylamine, N-methylaniline, diphenylamine and N,N-diethylaniline;
pyrrolidine, piperidine, N-methyl-2-pyrrolidone, piperazine, pyridine, picoline, indoline, quinuclidine, morpholine, N-methylmorpholine, 1,4-diazabicyclo[2.2.0]octane.

Preferred salts are those of the formula Q4 ~ Q6 ' . QZ

wherein M represents fluorine, bromine or iodine, especially chlorine, Q4 represents hydrogen, alkyl of 1 to 18 carbon atoms, cyclohexyl, benzyl, phenyl or naphthyl, and Q5, Q6 and Q7, each independently of the other, represent hydrogen or alkyl of 1 to 18 carbon atoms, and N-alkyl-pyridinium halides containing l to 18 carbon atoms in the 1155~3;~

alkyl moiety, in particular the corresponding chlorides.

Examples of such salts are: ammonium chloride, ammonium bromide, methylamine hydrochloride, cyclohexylamine hydrochloride, aniline hydrochloride, dimethylamine hydrochloride, diisobutylamine hydrochloride, triethylamine hydrochloride, triethylamine hydro-bromide, tri-n-octylamine hydrochloride, benzyldimethylamine hydro-chloride, tetramethylammonium chloride, bromide and iodide, tetraethylammonium chloride, bromide and iodide, tetra-n-propylammonium chloride, brom1de and iodide, tetra-n-butylammonium chloride, bromide and iodide, trimethylhexadecylammonium chloride, benzyldimethylhexadecyl-ammonium chloride, benzyldimethyltetradecylammonium chloride, benzyl-trimethylammonium chloride, benzyltriethylammonium chloride and benzyltri-n-butylammonium chloride, n-butyl-tri-n-propylammonium bromide, octadecyltrimethylammonium bromide, phenyltriethylammonium bromide or phenyltriethylammonium chloride and hexadecylpyridinium bromide and hexadecylpyridinium chloride.

.
Additional co-catalysts which can be used are alkali metal halides, such as potassium iodide, sodium iodide, lithium iodide, potassium bromide, sodium bromide, lithium bromide, potassium chloride, sodium chloride, lithium chloride, potassium fluoride, sodium fluo-ride and lithium fluoride~

The amount of catalyst employed can vary within wide limits, In some cases it suffices if the catalyst is present in traces. In general, however, the catalyst is preferably employed in an amount of about 0.1 to 15 per cent by weight, based on the compound of the formula (B).

~155~32 g The rearrangement can be carried out both in the mel t and in an inert organic solvent. The reaction temperatures for the rearran-gement in the melt are in general between about 60 and 150C, especially between about 80 and 13~C.

Suitable catalysts for the rearrangement in the melt are in particular the above mentioned organic bases, especially trialkyl-amines containing 1 to 8 carbon atoms in each alkyl moiety; and also salts of hydrohalic acids with ammonia or organic nitrogen-containing bases J such as trialkylamine hydrochlorides and hydro-bromides containing 1 to 8 carbon atoms in each alkyl moiety, and most preferably tetraalkylammonium halides, in particular tetra-alkylammonium chlorides, bromides and iodides, containing 1 to 18 carbon atoms in each al~yl moiety.

Examples o~ suitable inert organic solvents are aliphatic, cycloaliphatic or aromatic hydrocarbons which can be nitrated or halogenated, such as n-hexane, n-pentane, cyclohexane, benzene, toluene, xylenes, nitrobenzene, chloroform, carbon tetrachloride, trichloroethylene, 1,1,2,2-tetrachloroethane, nitromethane, chloro-benzene, dichlorobenzenes and trichlorobenzenes; lower aliphatic alcohols, for example those containing up to 6 carbon atoms, such as methanol, ethanol, propanol, isopropanol, butanols and pentanols;
aliphatic diols, such as ethylene glycol and diethylene glycol;
ethylene glycol monoalkyl ethers ant diethylene glycol monoalkyl e~hers containing 1 to 4 carbon atom~ in each o~ the alkyl ~oieties, such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, diethylene glycol monomethyl ether and diethylene glycol monoeehyl ether; cyclic amides, such as N-methyl-~-pyrrolidone, N-acetyl-~-pyrrolidone and N-methyl-~-caprolactam; amides of carbonic acid, such as tetramethylurea and dimorpholinocarbonyl; amides of phosphorous acid, ot phosphoric acid, of phenylphosphonic acid or of aliphatic phosphonic acids containing 1 to 3 carbon atoms in the acid - 10- 1~55~32 moiety, such as phosphoric acid triamide, phosphoric acid tris-(dimethylamide), phosphoric acid trimorpholide, phosphoric acid tripyrrolinide, phosphoric acid bis-(dimethylamide)-morpholide, phosphoric acid dimethylamide-diethylamide-morpholide, phosphorous acid tris-(dimethylamide) and the tetramethyldiamide of methane-phosphonic acid; amides of sulfuric acid and of aliphatic or aromatic sulfonic acids, such as tetra~ethylsulfamide, the dimethylamide of methanesulfonic acid or p-toluenesulfonic acid amide; sulfur-containing solvents, such as organic sulfones and sulfoxides, for example dimethyl sulfoxide and sulfolane; and aliphatic and aromatic nitriles, 3-alkoxypropionitriles, aliphatic ketones, alkyl and alkoxy-alkyl esters of aliphatic monocarboxylic acids, cyclic ethers, dialkyl ethers, N,N-disubstituted amides of aliphatic monocarboxylic acids and ethylene glycol dialkyl ethers and diethylene glycol dialkyl ethers of the type mentioned under process stage 1).

For the rearrangement in the presence of an acid catalyst, it is advantageous to use polar solvents, especially lower alcohols, such as methanol~ ethanol and butanols, N,N-dialkylamides of aliphatic mono-carboxylic acids containing 1 to 3 carbon atoms in the acid moiety, especially N,N-dimethyl formamide, or dialkyl sulfoxides, such as timethyl sulfoxide.

In aprotic, strongly polar solvents, such as the above-mentioned N,N-disubstituted amides of aliphatic monocarboxylic acids, cyclic amides, amides of carbonic acit, amites Oe phosphorous acit, of phosphoric acid, of phenylphosphonic acid or of aliphatic phos-phonic acids, amides of sulfuric acid or of aliphatic or aromatic sulfonic acids, and also dialkyl sulfoxides, such as dimethyl sulfoxide, the reaction als- proceeds withouc the addition of base or acid. In these cases, the solvent acts as catalyst.

1 IS5~3Z

In general, however, when the rearrangement is carried out in the presence of an inert organic solvent a catalyst is added, preferably an organic base having a pK value of more than 9, especially trialkylamines containing 1 to 8 carbon atoms in each alkyl moiety, such as triethylamine, tri-n-butylamine and tri-n-octylamine;
and also hydrohalic acids, especially ~Cl and ~Br, and tetra-alkylammonium halides, especially tetraalkylammonium chlorides, bromides and iodides containing 1 to 18 carbon atoms in each alkyl moiety.

Particularly preferred solvents are aliphatic alcohols containing 1 to 4 carbon atoms, toluene, xylenes, chlorobenzene, dioxane, acetonitrile, 3-methoxypropionitrile, ethylene glycol diethyl ether and diisopropyl ketone.
The reaction temperatures for the rearrangement in the presence of an inert org~nic solvent are in general between about 0 and 150C and preferably between about 80 and 130C.

Process stage 2 The conversion of the dichlorocyclobutanones of the formula (B) or (C) into the compounds of the formula X is carried out with a phenol of the formula IX in the presence of a base. Suitable bases are, for example, organic bases such as tertiary amines, in particular trialkylamines containing 1 to 4, preferably 1 to 2, carbon atoms in each of the alkyl moieties; cyclic amines, such as pyridine, quino-line, N-alkyl pyrrolidines, N-alkyl piperidines, N,N-dialkyl pipera-zines and N-alkyl morpholines or dialkyl anilines containing 1 or 2 carbon atoms in each of the alkyl moieties, such as N-methyl-pyrrolidine, N-ethyl piperidine, N,N'-dimethyl ?iperazine, N-ethyl morpholine and dimethyl aniline, and bicyclic amidines, such as 1,5-diazabicyclo[5.4.0]undec-5-ene and 1,5-diazabicyclo[4.3.0]non-5-ene, and bicvclic diamines, such as 1,4-diazabicyclo~2.2.2]octane.

~155~32 Preferred organic bases are trialkylamines containing 2 to 4 carbon atoms in each of the alkyl moieties, especially triethylamine, and pyridine. The organic base can act simultaneously as solvent.

As organic bases it is possible to use carbonates and bi-carbonates of alkali metals and alkaline earth metals, for example potassium hydroxide, sodium hydroxide, calcium hydroxide and barium hy-droxide, sodium and potassium carbonate and sodium and potassium bi-caxbonate. Sodium and potassium hydroxide and sodium and potassium carbonate are particularly preferred organic bases.

Suitable solvents are, for example, unsubstituted or haloge-nated aromatic or aliphatic hydrocarbons, such as benzene, toluene, xylenes, chlorobenzene, dichloro- and trichlorobenzenes, n-pentane, n-hexane, n-octane, methylene chloride, chloroform, tetrachloromethane, 1,1,2,2-tetrachloroethane and ~richloroethylene; cycloaliphatic hydro-carbons, such as cyclopentane or cyclohexane; cycloaliphatic ketones, such as cyclopentanone and cyclohexanone, and also aliphatic ketones, aliphatic and cyclic ethers, alkyl nitriles and 3-alkoxypropionitriles.

Good results, especially with sodium and potassium hydroxide as bases, are also obtained with two-phase solvent mixtures con-sisting of water and one of the solvents listed above, for example the systen water/chloroform. The base is uset in at least equi~olar amounts, based on the cyclobutanones of the formula ~B) or ~C) The reaction temperatures are in general not crucial and are ordinarily between -20 and +100C, preferably between -lo and +50C.

Process stage 3 The conversion of the cyclobutanones of the formula X into the compounds of the formulae IV and VI with ring contraction is carried out in the presence of a base. Suitable bases are for example hydroxides or alcoholates of the formula XI
, 1155~32 Ml ( R )n XI

wherein ~1 is the cation of an alkali metal or alkaline earth metal and n is l or 2 and R' is as defined for formula II or V, such as sodium hydroxide, potassium hydroxide, calcium hydroxide and barium hydroxide or sodium and potassium methylate, sodium and potassium ethylate, sodium and potassium isopropylate, sodium and potassium sec-butylate, sodium and potassium tert-butylate, magnesium methylate.

Suitable bases are also alkali metal and alkaline earth metal carbonates and alkaline earth metal bicarbonates, such as calcium carbonate, barium carbonate, potassium and sodium carbonate, sodium and potassium bicarbonate.

If desired or necessary, the reaction can also be hastened by the addition of suitable halide acceptors, for example silver nitrate.

At least a stoichiometric amount, but preferably an excess, of these bases is used.

Depending on the nature of the base, the reaction is advanta-geously carried out in aqueous, aqueous-organic or organic medium. If an alkali metal carbonate or alkaline earth metal carbonate is used as base, the react;on is carried out in aqueous or aqueous-organic medium. The reaction in the presence of alkali metal hydroxides or alkaline earth metal hydroxides and alkaline earth metal bicarbonates is also carried out with advantage in aqueous or aqueous-organic medium. After acidifying the reaction mixture, for example by the addition of concentrated hydrochloric acid, compounds of the formula II, in which R' is hydrogen, are obtained. These compounds are con-verted in a manner known per se into derivatives of the formula IV.

~55~32 Suitable organic solvents for the reaction in aqueous-organic medium or organic medium are lower alcohols, for example those containing up to 6 carbon atoms, such as methanol, ethanol, propanol, isopropanol, butanol, sec-butanol, tert-butanol and amyl alcohols;
aliphatic or cyclic ethers, such as diethyl ether, di-n-propyl etherJ
diisoprop91 ether, tetrahydrofurane, tetrahydropyrane and dioxane;
and aliphatic, cycloaliphatic or aromatic hydrocarbons, such as n-pentane, n-hexane, cyclohexane, benzene, toluene and xylenes.

The preferred reaction is that in the presence of hydroxides or alcoholates of the formula XI, wherein n is 1, Ml is the cation of an alkali metal, especially sodium or potassium, and R' is hydrogen or alkyl of 1 to 4 carbon atoms. The most preferred reaction is that for the production of compounds of the formula II in the presence of NaOH
or KOH in aqueous or aqueous-organic medium, for example in an aqueous alcohol, such as aqueous methanol or ethanol, or in aqueous dioxane.

The reaction is ordinarily carried out at the boiling point of the chosen reaction medium. Temperatures between about 40 and 120C are particularly preferred.

The intermediates of the formulae ~B), (C)~and X are new.
These intermediates, and also the end products of the formula I, can be isolated and purified in a manner known per se. A working up o the intermedlates is, however, not absolutely necessary.

The compounds of the formula I are in the form of a mixture of different optically active isomers if individual optically active starting materials are not used in the reaction. The different isomer mixtures can be separated into the individual isomers by known methods.
The compound of the formula I is to be understood as comprising both the individual isomers and the mixtures thereof.

The compounds of the formula I are suitable for controlling a variety of animal and plant pests. In particular, the compounds of the formula I are suitable for controlling insects, phytopatho-genic mites and ticks, for example of the orders: Lepidoptera, Coleoptera, Homoptera, Heteroptera, Diptera, Acarina, Thysanoptera, Orthoptera, Anoplura, Siphonaptera, Mal]ophaga, Thysanura, Isoptera, Psocoptera and Hymenoptera.

In particular, the compounds of the formula I are suitable for controlling insects which are harmful to plants, especially insects which damage plants by eating, in ornamentals and crops of useful plants, especially in cotton plahtations (e.g. Spodoptera littoralis and Heliothis virescens) and in vegetable crops (for example Leptinotarsa decemlineata and M~zus persicae).

The active compounds of the formula I also have a very good action against flies, for example Musca domestica and mosquito larvae.
~;
The insecticldal and/or acaricidal action can be substantially . broadened and adapted to prevailing circumstances by addition of other - insecticides and/or acaricides. Examples of suitable additives include: organic phosphorus compounds, nitrophenols and derivatives thereof, formamidines, ureas,~yrethroids, carbamates,and chlorinated - hydrocarbons.

;~ Compounds of the formula I are also combined with particular advantage with substances which exert a synergistic or potentiating effect on pyrethroids. Examples of such compounds include: piperonyl butoxide, propynyl ether, propynyl oximes, propynyl carbamates and propynyl phosphonates, 2-(3,4-methylenedioxyphenoxy)-3,6,9-trioxa-undecane (Sesamex or Sesoxane), S,S,S,-tributylphosphorotrithioate, 1,2-methylenedioxy-4(2-octylsulphonyl)-propyl)-benzene.

.. , .

" . . : . . ,, : :.' ,. . -:: ,. .
- ~: . ;, ~

~5~32 ~ 16 -The compounds of the formula I may be used as pure active substance or together with suitable carriers and/or adjuvants.
Suitable carriers and adjuvants can be solid or liquid and correspond to the substances conventionally used in the art of formulatio~, for example natural or regenerated substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders and/or fertilisers.

The compositions are ~anufactured in known manner by homogeneously mixing and/or grinding active substances of the formula I with the suitable carriers, with or without the addition of dispersants or solvents which are inert to the active substances.

The compounds of the formula I may be processed to the follow-ing formulationS:
Solid formulations:
Dusts, tracking powders and granules (coated granules, impregnated granules and homogeneous granules).
Liquid formulations:
a) active substances which are dispersable in water: wettable powders, pastes and emulsions;
b) solutions.

The content of active substance in the sbove tescribed composiCions is generally between 0.1% and 95%, though concentrations of up to 99.5% or even pure active substance can also be used if the compositions are applied from an aircraft or other appropriate appli-cation devices.

The compounds (active substances) of the formula I can, for example, be formulated as follows (throughout the present specifi-cation all parts and percentages are by weight):

llS5~32 Dusts The following substances are used to formulate a) a 5% and b) a 2% dust:
a) 5 parts of active substance, 95 parts of talc;
b) 2 parts of active substance, l part of highly dispersed silicic acid, 97 parts of talc.
The active substance is mixed with the carriers and ground.
Granules The following substances are mixed to formulate 5% granules:
5 parts of active substance 0.25 parts of epichlorohydrin, 0.25 parts of cetyl polyglycol ether, 3.50 parts of polyethylene glycol, 91 parts of kaolin (particle size 0.3 - 0.8 mm).
The active substance is mixed with epichlorohydrin and the mixture is dissolved in 6 parts of acetone; the polyethylene glycol and cetyl polyglycol ether are then added. The resultant solution is sprayed on kaolin, and the acetone is subsequently evaporated in vacuo.
Wettable powders:
The following constituents are mixed to formulate a) a 40%, b) and c) a 25%, and d) a 10% wettable powder:
a) 40 parts of active substance, 5 parts of sodium ligninsulfonate 1 part of sodium dibutylnaphthalenesulfonate, 54 parts of silicic acid.

r ~ ~ 17 ~

1~55~3Z

b) 25 parts of active substance,

4.5 parts of calcium ligninsulfonate, 1.9 parts of Champagne chalk/hydroxyethyl cellulose mixture (1 1.5 parts of sodium dibutylnaphthalenesulfonate, 19.5 parts of silicic acid, 19.5 parts of Champagne chalk, 28.1 parts of kaolin, c) 25 parts of active substance, 2.5 parts of isooctylphenoxy-polyoxyethyleneethanol, 1.7 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1), 8.3 parts of sodium aluminium silicate, 16.5 parts of kieselguhr, 46 parts of kaolin;
d) 10 parts of active substance, 3 parts of a mixture of the sodium salts of saturated fatty alcohol sulfates,

5 parts of naphthalenesulfonic acid/formaldehyde condensate, 82 parts oE kaolin.
The active substances are homogeneously mixed with the additives in suitable mixers and the mixture is then ground in appropriate mills and rollers.Wettable powders are obtained which can be diluted with wator to give suspen-sions of the desired concentration.
Emuslifiable concentrates:
The following substances are mixedto formulate a) a 10%, b) a 25%
and c) a 50% emulsifiable concentrate:
a) 10 parts of active substance, 3.4 parts of epoxidised vegetable oil, ~155~3Z

3.4 parts of a combination emulsifier consisting of fatty alcohol polyglycol ether and alkylarylsulfonate/calcium salt, parts of dimethyl formamide, 43.2 parts of xylene;
b) 25 parts of active substance, 2.5 parts of epoxidised vegetable oil, parts of alkylarylsulfonate/fatty alcohol polyglycol ether mixture, parts of dimethyl formamide, 57.5 parts of xylene;
c) 50 parts of active substance, 4.2 parts of tributylphenol-polyglycol ether, 5.8 parts of cylcium dodecylbenzenesulfonate, 20 parts of cyclohexanene, 20 parts of xylene.
By diluting these concentrates with water it is possible to obtain emulsions of the required concentration.
Sprays:
The following ingredients are mixed to formulate a) a 5% spray, and b) a 95% spray:
a) 5 parts of active substance, 1 part of epichlorohydrin, 94 parts of ligroin ~boiling range 160 - 190C);
b) 95 parts of active substance, 5 parts of epichlorohydrin.
The invention is further illustrated by the following Examples, some of which relate to the preparation of compounds of formula I and are included for reference purposes.

~55~3Z

Example 1: Manufacture of 3'-(phenoxy)-a-cyanobenzyl 2,2-dimethyl-3-(4-chlorophenoxy)-cyclopropane carboxylate A mixturP of 4.14g (0.016 mole) of 2,~-dimethyl-3-(4-~hloro-phenoxy)-cyclopropanecarboxylic acid and 4.2 ml of oxalyl chloride is stirred for 30 minutes at 25C and for 15 minutes at 50C. The reaction mixture is concentrated and two 3 ml portions of carbon tetrachloride are added to the residue, which is then concentrated. The crude acid chloride and 4.25 g (0.016 mole) of 3-phenoxy--cyanobenzyl alcohol are added to 8 ml of toluene and then 4 ml of pyridine in 4 ml of toluene are added dropwise such that the temperature does not rise above 0C. The reaction mixture is stirred for 2 hours at room temperature. After addition of 0.5 ml of water, the reaction mixture is stirred for a further 15 minutes and acidified with 6N sulfuric acid, then extracted with ether. The ethereal extract is washed with bicarbonate solution, dried over sodium sulfate and concentrated.
The crude product is chromatographed on silica gel with hex~ne/ether (volume ratio 10:1) as eluant, affording the compound of the formula Cl~O~ - C~-COOC~I~O~

C~3 C~3 in the form of an oil with a refractive index o~ nD ~ 1.5732.
The following co~pounds are also obtained in analo~ous manner ~O-C ~- CR-COOCR~0~3 nD ~ 1.5680 1~5S~3Z

3~0-CH - C~-COOCH~0~3 n20~= 1.5643 C~3 CX3 Cl Cl~O-CH - C13-COO-CH~O~ n20 = 1,S769 Cl cl~30-ca - CH-C00-C ~0~ n20 ~ 1,5780 CX3 C~3 ~o-ca - CH-C00-C ~0~ n20 ~ 1~5936 0-CH - CEI-C00-CH~0~
J dlastereoisomers CH CH CN ~ mp. 86-88C
NC 3 3 and 137-138~C
respec~ively CH3 CH3 CN n20 = 1~5553 CH3~ 0-C~ - CH-C00-Cr3-~0~ nD = 1,5631 1~55~2 L__3 C~3 C~3 CN ~ nD = 1,5293 .

p ~ O~C~ ~--COO-C~~ O ~ nD = 1,5498 O
2 - 0 ~ 0-C~ ~ C~-C00-CH ~ 0 ~ n20 = 1,5745 Manufacture of 2,2-dichloro-3,3-dimethyl cvclobutanone A G.3 litre autoclave is charged with 295 g (2 moles) of dichloroacetyl chloride and 800 ml of pentane. The autoclave is then c10s2d and 1120 g of isobutylene (20 moles) are forced in and the contents are heated to 70C. A solution consisting of 202 g (2 moles) of triethylamine and 800 ml of pentane is then forced in over the course of 4 hours and the reaction mi~ture is stirred for a further 4 hours at 70C (ma~imum pressure: 9 bar). After cooling, the mi~ture is filtered with suction. After washing with three 300 ml of pentane, the mother liquor is distilled. The pentane is then removed under normal pressure and subsequently the compound of ~he ~ormula o --f C ~ Cl C~3 Cl distills at b.p. 73-74C/ll mm and crystallises in a refrigerator.

2,~-Dichloro-3,3-dime~hvlcyclobutanone ...... . _ _ _ 501 g ~3 moles) of 2,2-dichloro-3,3-dimethylcyclobutanone ~55~32 are heated to reflux in 200 ml of toluene. Them 15.2 g of triethyl-amine in 30 ml of toluene are added in the course of 2 L/2 hours. The reaction mixture is stirred overnight at room temperature, filtered clear and concentrated. The residue is distilled under reduced pressure, affording the compound of the formula Cl 0 ~ Cl c~3 with a boiling point of 85C/14 mm.

~anufacture of 2-(p-chlorophenoxy)-3,3-dimethyl-4-chlorocyclobutanone from 2,2-dichloro-3,3-dimethylcyclobutanone 41.8 g (0.25 mole) of 2,2-dichloro-3,3-dimethylcyclobutanone, 32.1 g (0.25 mole) of p-chlorophe".ol and 5 g of tetrabut~la3~0nium chloride are charged into 100 ml of chloroform. The light brown solution is cooled to 5C and then 100 ml of 10~ aqueous sodium hydroxide are added dropwise at 5-9C in the course of 55 minutes.
Stirring is continued at this temperature for 15 minutes. The mixture is extracted with four 75 ml portions of ether and the com-bined extracts are washed with 100 ml of saline solution, dried over sodium sulfate and concentrated. The crude product is chromatographed on silica gel with toluene/hexane (volume ratio 1:1) as eluant, affording the compound of the formula Cl ~0 0 H3C Cl 1155~32 in the form of white crystals with a melting point of 72-75C.

Manufacture of 2-(p-methylphenoxy)-3,3-dimethy1-4-chlorocyclobutanone from 2,4-dichloro-3,3-dimeth~lcvclobutane ....
16.7 g (0.1 mole) of 2,4-dichloro-3,3-dimethylcyclobutanone in 30 ml of chloroform are cooled to about 5C and then 10.1 g (105mnoles) of p-cresol and a solution consisting of 2 g of eetra-b~tylammonium chloride and 10 ml of chloroform are added at this temperature. Then 40 ml of 10% aqueous sodium hydroxide are added dropwise at about 5C in the course of 45 minutes and the reaction mixture is subsequently stirred for a further 45 minutes at room temperature. The reaction mixture is extracted with two 60 ml portions of ether and the combined organic phases are washed with saline solution, dried over sodium sulfate and concentrated. The crude product is chromatographed on silica gel with petroleum ether/toluene (4:1) as eluant, affording the compound of the formula H3C ~ `rf' ~3C--~\Cl C;I3 in the for~ of crystals with a melting point of 61-61,5C, Manufacture of 2,2-dimethyl-3-(p-methylph~no~y)-cyclopropanecar~oxylic acid 40 ml of 10% aqueous sodium hydroxide are cooled to about -8C. ~lith stirring, a solution consisting of 7.16 g (30 mmoles) of 2-chloro-3,3-dimethyl-4-(p-methylpheno~y)-cyclobucanone and 16 ml of dioxane is added dropwise at -S~ to -10C in the course of 3; minutes.
The reaction mixture is then stirred for a further half hour at -5C and then allowed to scand overnight at room temperatur~. Then 30 ml of ether are added to the slightly turbid yellow solution and, ~155~32 after brief st;rring, the phases are separated. The aqueous phase is acidified with 6N sulfuric acid and extracted with three 30 ml portions of ether. The ethereal extracts are washed with saline solution, dried over sodium sulfate and concentrated, affording the compound of the formula ~3C ~ O COOH
/\ca3 in the form of white crystals with a melting point of 122-124C.

Example 2: Insecticidal stomach poison action Cotton plants were sprayed with a 0.05% aqueous emulsion of active substance (obtained from a 10% emulsifiable concentrate).
After the spray coating had dried, the cotton plants were populated with Spodoptera littoralis and Heliothis virescens in the L3-stage.
The test was carried out at 24C and 60~ relative humidity.
In this test, the compounds of Example 1 exhibited a good insecticidal stomach poison action against Spodoptera and Heliothis larvae.

Example 3- Acaricidal action Twelve hours before the test for acaricidal action, Phase-olus vulgaris plants were populated with an infested piece of leaf from a mass culture of Tetranychus urticae. The mobile stages which had migrated to the plants were sprayed with the emulsified test preparations from a chromatography atomiser in such a way that the spray broth did not run off. The number of living and dead larvae, adults and eggs was evaluated under a stereoscopic microscope after 2 and 7 days and the result expressed in percentage values.
During the test run, the plants Were kept in greenhouse compartments at 25C.
~ .~
.~

1~55132 In this test, the compounds of Example 1 acted against adults, larvae and eggs of Tetranychus urticae.

Example 4: Action_against ticks A) Rhipicephalus bursa Five adult ticks and 50 tick larvae were counted into each of a number of test tubes and immersed for 1 to 2 minutes in 2 ml of an aqueous emulsion containing a concentration of 100, 10, 1 or 0.1 ppm of test subst~ance. Each test tube was then sealed with a cottonwool plug and iDwerted to enable the cotton wool to absorb the active substance emulsion. Evaluation of the action against adults was made after 2 weeks and of that against larvae after 2 days. Each test was repeated twice.
.

B) Boophilus microplus (larvae) Testswere carried out with 20 OP-sensitive and 20 OP-resistant larvae using aqueous emulsions similar to those used in Test A. (The resistance refers to the tolerance towards diazinone). The compounds of E~ample 1 acted in these tests against adults and larvae of Rhipicephalus bursa and OP-sensitive and OP-resistant larvae of Boophilus microplus.

Claims (5)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A compound of the formula:

(A) in which Z is hydrogen and Z1 is chlorine, or Z1 is hydrogen and Z is chlorine or a group of the formula wherein R1 and R2 each independently represents hydrogen, halogen, methyl, methoxy, trifluoromethyl or cyano, or R1 and R2 together represent methylene-dioxy or a group -CH=CH-CH=CH-.

2. A compound of the formula:

(B)

3. A comp und of the formula:

(C)

4. A compound of the formula:

(D) wherein R1 and R2 are as defined in claim 1.

5. A process for manufacturing a compound of the formula:
(A) in which Z is hydrogen and Z1 is chlorine, or Z1 is hydrogen and Z is chlor-ine or a group of the formula:

wherein R1 and R2 each independently represents hydrogen, halogen, methyl, methoxy, trifluoromethyl or cyano, or R1 and R2 together represent methylene-dioxy or a group -CH=CH-CH=CH-.
which process comprises (a) for the manufacture of a compound of formula (A) in which Z represents hydrogen and Z1 represents chlorine, reacting dichloroacetyl chloride with dibutylene in the presence of a catalyst;
(b) for the manufacture of a compound of formula (A) in which Z represents chlorine and Z1 represents hydrogen, rearranging a compound of formula (A) in which Z represents hydrogen and Z1 represents chlorine, in the presence of a catalyst; or (c) for the manufacture of a compound of formula (A) in which Z1 is hydro-gen and Z is a group of the formula:

wherein R1 and R2 are as defined above reacting a compound of the formula (A) in which one of Z and Z1 is hydrogen and the other is chlorine, with a phenol of the formula:

wherein R1 and R2 are as defined above, in the presence of a base.