GB2142634A - Intermediates useful for the preparation of pyrethroids - Google Patents

Intermediates useful for the preparation of pyrethroids Download PDF

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GB2142634A
GB2142634A GB08418032A GB8418032A GB2142634A GB 2142634 A GB2142634 A GB 2142634A GB 08418032 A GB08418032 A GB 08418032A GB 8418032 A GB8418032 A GB 8418032A GB 2142634 A GB2142634 A GB 2142634A
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acid
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Guiseppe Caprara
Franco Gozzo
Guiseppe Paparatto
Roberti Lamberto
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Montedison SpA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
    • C07C53/15—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen containing halogen
    • C07C53/19—Acids containing three or more carbon atoms
    • C07C53/21—Acids containing three or more carbon atoms containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/44—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by addition reactions, i.e. reactions involving at least one carbon-to-carbon double or triple bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/62—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by introduction of halogen; by substitution of halogen atoms by other halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/65—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/385—Saturated compounds containing a keto group being part of a ring
    • C07C49/457—Saturated compounds containing a keto group being part of a ring containing halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C67/347—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/04—Systems containing only non-condensed rings with a four-membered ring

Abstract

Compounds which are intermediates suitable for the preparation of 2,2-dimethyl-3-( beta -fluoro- beta -trifluoro-methyl-vinyl)-cyclopropanecarboxylic acid which itself is a useful intermediate for the preparation of pyrethroids, the compounds having the general formula: <IMAGE> in which: X represents a chlorine or bromine atom, one of Y and Y<1> represents a chlorine or bromine atom and the other of Y and Y<1> represents a hydrogen atom.

Description

1 GB 2 142 634 A 1
SPECIFICATION
Intermediates useful for the preparation of pyrethrolds This invention relates to intermediates suitable for the preparation of 2, 2-dimethyi-3-(p-fluoro-ptrifluoromethyi-vinyi)-cyclopropanecarboxylic acid which itself is a useful intermediate for the preparation of pyrethroids.
2,2-dimethy]-3-(p-fluoro-p-trifluoromethyi-vinyi)-cyclopropanecarboxylic acid of the formula:
H 3 C CH 3 W 3\ / C \ / C=CH - CH- CH - COOH (I) F is an intermediate for the preparation of pyrethroid insecticides endowed with a high pesticidal activity. Such pyrethroid insecticides are disclosed in British Patent Application No. 7906851 (Serial No 2 015 519A) In the preparation of these pyrethroids, a compound of formula (1) is converted to the corresponding acylic 20 chloride which is then condensed with suitable alcohols, e.g. 3-phenoxy- benzylic alcohol, eL-cyano-3 phenoxy-benzyl alcohol or 2-methyi-5-benzyi-3-furyimethyi-alcohol. The degree of pesticide activity developed by these pyrethroids depends on the isomery on the cyclopropane ring.
The trans-isomer, although possessing a good insecticide activity, has a lower insecticide activity than that of the cis-isomer. British Patent Application No. 7906851 (Serial No. 2 015 519A) discloses two processes for 25 the preparing of compounds of formula (1). These processes may be summarised by the following reaction schemes:
Scheme 1:
a) CF3-CF13r2 + CH2 = CH - C(C1-13)2 - CH2 - COOR- ---> CF3-CFBr-CH2-CHBr-C(CH3)2-CH2-COOR (A) H 3 C CH 3 C W 3-CF=CH-CH CH-COOR (B) b) (A) bases > (-2HBr) hydrolysis c) (B) (1) R represents a lower alkyl group.
Reaction (a) comprises the addition 1,1 -dibromotetrafluoroethane to an ester of 3,3-dimethy]-4-pentenoic acid.
Adduct (A) thus obtained is then treated with bases (reaction (M and undergoes two consecutive 50 dehydrohalogenations with the simultaneous closing of the cyclopropane ring. This reaction yields the lower alky esters (B) of the compound of formula (1), which are then subjected to hydrolysis to obtain the free acid (reaction (0).
Scheme 2:
(a') CF3-CF13r2 + CH2 = CH - C(CH3)2 - CH(COOR)2_---> --> CF3-CFBr-CH2-CHBr-C(CH3)2-CH(COOR)2 (C) 2 GB 2 142 634 A 2 H3C \ /CH 3 c bases W) (C) -2HBr CF3-CF=CH-CH- (D) 5 COOR cl (D) hydrolysis 10 -C02,-R6H R represents a lower alkyl group.
Reaction (al comprises the addition of 1,1-dibromo-tetrafluoroethane to an ester of 2-alkoxycarbonyl-3,3 dimethyl-4-pentenoic acid. The treatment of adduct (C) with bases (reaction (b')) leads to the formation of 15 1,1-cyclopropane dicarboxylic ester (D) which is subjected to hydrolysis, under particular conditions and at a high temperature to yield the compound of formula (1) (reaction (c')).
The processes of reaction schemes 1 and 2 yield compounds of formula (1) as an isomeric mixture on the cyclopropane ring in an approximately equal cis and trans ratio.
Our copending British Patent Application No. 8202785 (Serial No. 2092578A) discloses a process for the 20 preparation of 2,2-dimethyi-3-(0-fiuoro-p-trifluoromethyi-vinyl)- cyclopropanecarboxylic acid of the formula:
H 3 c CH 3 CP c / 25 C=CH - CH- CH - COOH 30 in which a halide of 2,4-dihalo-4,5,5,5-tetrafluoropentanoic acid of the formula:
CF, - CF - CH2 - CH - C - Z (11) 1 1 11 35 X Y 0 in which X, Y and Z may be the same or different and each represent a chlorine or bromine atom, is reacted with isobutene in the presence of a base and an inert solveritto yield 2halo-2-(2'-halo-2',3',3',3'tetrafluoropropyi)-3,3-dimethyi-cyclobutanone of the formula:
H 3 C\ CH 3 F 3 C - W - CH 2 - c / c \ CH 2 (111) 45 X Y. c 11 0 50 in which X and Y are as defined above, which is heated in an inert solvent and in the presence of a quaternary ammonium salt or a tertiary aliphatic amine, to yield 2-(2'-halo-2',3',3',3'-tetrafluoropropyi)-3,3dimethyi-4halo-cyclobutanone of the formula:
H 3 c / CH 3 c F 3 C - CP - CH 2 - CH CH-Y (IV) 60 1 X c 11 0 in which X and Y are as defined above, which is treated with an alkaline base in an inert solvent to yield the compound of formula (1).
3 GB 2 142 634 A 3 The compounds of formula (11) may be prepared directly by reacting 1,1- dihalo-tetrafluoroethane with an acryloyl halide (reaction 1, scheme 3 hereinafter) or by reaction of the same perhaloethane with an acrylic ester, and by the successive conversion of the ester thus obtained to the corresponding acyl halide (reactions 2a), 2b) and 2c), scheme 3 hereinafter).
A further alternative consists in reacting the perhaloethane with ally] alcohol, oxidising the product thus obtained to carboxylic acid and finally in preparing the corresponding acyl chloride (reactions 3a), 3b) and 3c), scheme 3 hereinafter).
With respect to the two prior processes described above (reaction schemes 1 and 2), the process of this invention exhibits considerable advantages in economy, in as much as it uses starting products (derivatives of acrylic acid and isobutene) which are inexpensive and readily available. The various steps of the process are simple to expedite and give high yields. A further considerable advantage is that the compound of formula (1) is obtained as an isomeric mixture on the cyclopropane ring in a cis:trans ratio greater than 4: 1.
The reactions employed in the process of the invention as described above are summarised in the following reaction scheme 3:
Scheme 3:
1) CF3-CMY + C1-12=CH-C - Z catalyst, CF3-CF-CH2 - CH-C - Z (11) 0 1 11 A Y0 2a) CF3-CM+Cl-12=CH-C-OR catalyst, CF3-CF-CH2-CH-C-OR (A) 0 2b) (A)-CF3-CF-CH2-CH-C-OH (B) 1 1 11 X Y 0 2c) (B) halogenating gent (11) 1 1 11 X Y 0 3a) CF3-CFXY+CH2=CH-CH2-OH catalyst, CF3 - CF-CH2-CH-CH201-1 (C) 1 1 X Y 3b) (C) oxi ation CF3-CF-CH2-CH-COOH (B) 1 1 X Y halogenating 9,qent 3c) (B) (11) H3C CH 3 c base:, - 4) (11) + CH 2 =C (CH 3)2 CF 3-CF-CH 2 CH 2 (111) X Y H 3 c CH 3 5) (111) talyst c 11 0 / c \ CF 3-CF-CH 2-CH CH - Y (IV) X c 11 0 4 GB 2 142 634 A 4 H 3 c CH 3 base 2 6) (IV) _HX U 3-CP=CH-CH-CH - COOH (I) 5 -HY X, Y and Z may be the same or different and each represent Cl or Br and R represents an alkyl group having from 1 to 4 carbon atoms.
Reaction 1) of Scheme 3 represents the addition of a 1,1 -dihalotetrafluoroethane to an acryloyl halide 10 (either chloride or bromide) in order to obtain the compound of formula (11), the halide of a 2,4-dihalo-4,5,5,5-tetrafluoropentanoic acid.
When the starting perhaloethane is 1,1 -dibromotetraf luoroethane (X=Y=Br), the reaction is conveniently conducted in an autoclave and in the presence of iron-pentacarbonyl and dimethylformamide (DMF) in a catalytic amount. It is not necessary to use solvents.
Reactions 2a), 2b) and 2c) represent an alternative procedure to reaction 1) to yield a compound of formula (11).
Reaction 2a), analogous to reaction 1), is conducted using an alkyl ester instead of a halide of an acrylic acid and consequently the corresponding ester (A) is obtained instead of acyl halide (11).
This ester (A) is then converted to the corresponding carboxylic acid (B) (reaction 2b)) which is converted 20 to acyl chlorine (11) (reaction 2c)). Both reactions 2b) and 2c) follow conventional routes in organic chemistry.
It is preferable to carry out reaction 2b) by means of a transesterification in order to avoid possible dehydrohalogenation products, in case the hydrolysis is conducted in a basic medium. Reactions 3a), 3b) and 3c) represent another alternative to the process of reaction 1). Reaction 3a), analogous to reaction 1), consists in reacting a perhaloethane with allyl alcohol to yield a polyhalogenated pentyl alcohol (C). The alcholic group of compound (C) is then oxidised (reaction 3b)) according to conventional techniques used in organic chemistry, to yield carboxylic acid (B) (equivalent to the compound obtained by reaction 2b)) which is then converted to the corresponding acyl halide (reaction 3c)) in the same manner as in reaction 2c).
The acyl halide (11) obtained according to one of the above procedures is reacted with isobutene to obtain cyclobutanone (111) according to reaction 4). This reaction is carried out by reacting an excess of isobutene 30 with the acyl halide (11) in an autoclave in the presence of an inert solvent and a stoichiometric quantity with respect to acyl halide (11) of a tertiary amine.
Reaction 5) represents an example of the so-called "kine-substitution" reaction, in which a halogen atom enters the 4-position of a 2-halo-cyclobutanone simultaneously eliminating the halogen atom in the 2-position. When the reaction is conducted catalytically and the atom which enters the 4-position is the same 35 halogen atom which is removed from the 2-position, the reaction is defined as a -kine-rearrangement".
Reaction 5) may be conducted using as catalyst, tertiary amines or quaternary ammonium salts, or by heating the 2-ha lo-cyclo buta none in aprotic polar solvents.
Reaction 6) is conducted by simply treating the compound of formula (IV) with bases in inert solvents.
M) The above described reactions may be effected by various operational techniques.
A practical embodiment of the process, which summarises the results obtained from the study of the various phases of the process is as follows.
Reactions 1) and 2a), (Scheme 3) may conveniently be conducted by loading 2 to 3 moles of CF3-CM and a catalytic amount of dimethylformamide (DMF), e.g. up to 4% by weight, into a glass autoclave. The temperature is raised to about 140'C and then one mole of CF3-CM, into which there is dissolved about 1% by weight of iron-pentacarbonyl and one mole of the derivative of acrylic acid (respectively chloride or ester), are loaded separately and gradually into the autoclave. The mixture is then stirred to 3 to 7 hours whilst maintaining the same temperature, thereupon compound of formula (11) or (A) is isolated by distillation in high yields (85 to 90% with respect to the acrylic derivative).
Reaction 3a) may conveniently be carried out using iron-pentacarbonyl as a catalyst, either in bulk or in 50 alcohol as a solvent.
Reaction 2b) may be effected with good results by means of transesterification, e.g. with formic acid in the presence of a small amount of a mineral acid, according to conventional techniques employed in organic chemistry.
The oxidisation of alcohol (C) in carboxylic acid (B) (reaction 3b)) is readily achieved by means of the 55 standard oxidising systems useful for such reactions, e.g. concentrated nitric acid, in the presence of copper salts and vanadium pentoxide (V205). Also reaction 2c) (and 3c)) consisting in the conversion of carboxylic acid (B) to the corresponding acyl halide is carried out according to conventional techniques. A suitable halogenating agent is thionyl chloride, which results in the compounds of formula (11) in which Z is Cl.
Reaction 4) is conveniently carried out by loading isobutene and compound of formula (11) in an inert solvent, e.g. an aliphatic or aromatic hydrocarbon, and a stoichiometric amount, with respect to compound of formula (11) of a tertiary amine into an autoclave. After some hours of stirring at about 60'C for the reaction to proceed the compound of formula (111) is isolated by distillation.
The rearrangement of the compound of formula (111) to that of formula (IV) (reaction 5)) may be effected with good results by heating at about 100 to 11 O'C a solution of the compound of formula (111) in an inert GB 2 142 634 A 5 solvent, e.g. an aromatic hydrocarbon or dimethylformamide, in the presence of a quaternary ammonium salt or an aliphatic tertiary amine, as catalyst. The compound of formula (R) is then isolated by distillation. Finally, the compound of formula (IV) is treated in an inert solvent with alkaline bases (reaction 6)), to yield the desired compound of formula (1) which may be separated by acidification, extraction and distillation, or it 5 may be converted to the corresponding acyl halide, and isolated by distillation, in this form. If desired, the acyl halide derived from the compound of formula (1) may readily be converted to a free acid. However, for the preparation of pyrethroids, for which the compound of formula (1) is primarily intended, in general it will be useful to convert the corresponding acyl chloride, e.g. by reaction with a suitable alcohol. The process yields compounds of formula (1) with an isomeric ratio cis:trans (on the cyclopropane ring) greater than 4: 1; The cyclobutanones of formulae (111) and (IV) are also new compounds and form the subject of this 10 invention.
Therefore according to the present invention there is provided a compound of the general formula:
H3 c \ H3 c CF CF CH - c CH - Y 3 2 \ / Y C 11 0 in which: X represents a chlorine or bromine atom, one of Y and Y1 represents a chlorine or bromine atom and the other of Y and Y1 represents a hydrogen 25 atom.
The inventionwill nowbe illustrated bythefollowing Examples.
Example 1
Preparation of the methyl ester of 2,4-dibromo-4,5,5,5-tetrafiuoropentanoic acid (reaction 2a), scheme 3).
CF3 - Mr - CH2 - CHBr - COOCH3 780 g (3 moles) of 1,1-dibromo-tetrafluoroethane (CF3-CF13r2) and 40 g of DWwere introduced into an autoclave equipped with a mechanical stirrer.
The autoclave was closed and heated to 14WC under constant stirring. Over a period of 4 to 6 hours a 35 solution of:
1 mole of methylacrylate (CH2=CH-COOCH3), moles of iron-pentacarbonyl [Fe(C0)51, 260 g of CF3-CF13r2 was fed into the autoclave by a metering pump.
Once the addition had been completed, the stirring was continued at the same temperature for a further two hours. After cooling, the reaction mass was subjected to fractioned distillation and the following fractions were gathered:
fraction (1) - 874 g (3.36 moles) of unreacted CF3-CF&2; fraction (11) 0.32 moles of unreacted acrylic ester; fraction (111) - 0.56 moles of the desired product (boiling point = MC at 4.5 mmHg) (conversion of acrylic ester = 68%; yield of desired product based on reacted acrylic ester = 82%).
The structure of the product obtained was confirmed by the IR analysis and by mass-spectroscopy.
Example 2
Adopting the same procedures as in Example 1 the following compounds were prepared:
ethyl ester of 2,4-dibromo-4,5,5,5-tetrafluoro-pentanoic acid (boiling point = WC at 3 mmHg) n-butylester of 2,4-dibromo-4,5,5,5-tetrafluoro-pentanoic acid (boiling point = WC at 0.2 mmHg).
The IR analysis and mass-spectroscopic data were consistent with the assigned structure of each compound.
Example 3
Preparation of 2,4-dibromo-4,5,5,5-tetrafiuoro-pentanoic acid (reaction 2b)):
CF3 - CF13r - CH2 - CHBr - COOH The preparation was effected by trans-esterification of one of the esters prepared in Examples 1 and 2. 1 mole of ethylester of 2,4-dibromo-4,5,5,5-tetrafluoropentanoic acid, 1 mi of concentrated H2S04 and 138 g (3 moles) of formic acid were introduced into a reactorfitted with a fractioning column (34 theoretical plates).
The reaction mixture was heated up to boiling point and maintained at that temperature for 8 to 10 hours, 65 6 GB 2 142 634 A drawing from the head of the column the ethyl formiate that had formed. Once the ethyl formiate was completely removed the formic acid in excess was also removed to leave as a residue a practically stoichiometric amount of the desired acid (boiling point = 650C at 3 mmHg).
Example 4
Preparation of 2,4-dibromo-4,5,5,5-tetrafluoro-l-pentanol (reaction 3a)).
CF3 - Mr - CH2 - CHBr - CH20H.
6 lo 58 9 (1 mole) of allyl alcohol (CH2=CH-CH2OH) and 520 g of C173CI7Br2were introduced into a glass 10 autoclave washed with nitrogen. The autoclave was closed and heated up to 1300C and a solution of 2 M1 of FE(C0)s in 60 m[ of isopropanol was fed in over a period of four hours. The resulting mixture was allowed to rest for another hour at 1300C. After the mixture had cooled, it was subjected to fractioned distillation and the fraction that boiled at WC at a pressure of 2 mmHg was gathered to yield the desired product (170 g), 15 exhibiting a gas-chromatographic titre of 93%.
The data of IR, NMR and mass-spectroscopy were consistent with the assigned structure.
Example 5 Preparation of 2,4-dibromo-4,5,5,5-tetrafluoro-pentanoic acid (reaction 3b)) CF3 - C17Br - CH2 -CHBr - COOH 182 mi of concentrated HN03A.8 g of copper and 0.2 g OfV205 were introduced into a thermostatic reactor. The mixture was heated to 7WC and then additioned under vigorous stirring and over a period of 15 minutes with a solution of 25.6 9 of 2,4-dibromo-4,5,5,5- tetrafluoropentan-l-ol (obtained as described in Example 4) in 40 m] of glacial acetic acid. The reaction mixture Was maintained under stirring at 7WC for another 90 minutes, after which it was allowed to cool to room temperature and was then extracted with 300 mI of methylene chloride (CH2C12).
The extract was washed with water (2 x 250 mi) and dried on anhydrous Na2S04. The solvent was then removed by distillation under reduced pressure to yield 27 g of a residue consisting of the desired product 30 (GLC titre greater than 75%).
Example 6 Preparation of 2,4-dibromo-4,5,5,5-tetrafluoro-pentanoic acid chloride (reaction 2c) or 3c)) CF3 - CFBr - CH2 - CHBr - C - Cl 11 U 1 mole of 2,4-dibromo-4,5,5,5-tetrafluoro-pentanoic acid (prepared as described in Example 3 or Example 40 5) was reflux-heated together with 2 moles of thionyl chloride. After 4 hours the mixture was allowed to cool and was then subjected to fractioned distillation, gathering the fraction that boiled at WC under a pressure of 7 mmHg, and which consisted of the desired acyl chloride (330 g). IR: 1790 - 10 ern' (v C=O).
Example 7
Preparation of 2-bromo-2-(2'-bromo-2',3',3',3'-tetrafluoropropyi)-3,3dimethyl-eyclobutanon e (reaction 0:
H 3 C / CH 3 50 C CF 3 - CPBr - CH 2 - C CH 2 Br C 11 55 0 320 9 (5.71 moles) of isobutene [CH2=C(CH3)21 and 400 m] of n-hexane were successively introduced into an autoclave, fitted with a mechanical stirrer. The reaction mixture was heated to 1 OWC under constant stirring, and a solution of 100 g (0.2853 moles) of chloride of 2,4-dibromo-4,5,5,5-pentanoic acid (prepared as described in Example 6) in 150 mi of n-hexane, and a solution of 29 g (0. 2853 moles) of triethylamine in 160 mi of n-hexane were separately introduced. On completion of the addition the reaction mixture was allowed to cool to room temperature, whereupon it was filtered to separate triethylamine hydrochloride.
After removal of the isobutene in excess, and of the n-hexane, by evaporation, 103 g of a residue were 7 GB 2 142 634 A 7 obtained which was distilled and thefraction that boiled at 70 to 72'C at 01 mmHg gathered which consisted of the desired product (85 g, GCLtitre greaterthan 90%).
IR: 1791 1 cm-1 (v C=O).
Mass-fragmentation: 326 (W-CH2=C=Q main peak) 312 [M--CH2=C(CH3)21 147 1() 133 69 5)):
Example 8 Preparation of 2-(2'-bro m o-2',3',3',3'-tetrafl uoropropyi)-3, 3-d i methyl-4-bromo-cyclo buta none (reaction H 3 c / CH 3 c CP WBr CH CH \C - Br 3 2_ \ c / H 11 0 9 of the cyclobutanone obtained in Example 7 were added over a period of 10 minutes to a solution of 1 9 of tetrabutylammonium bromide 1(C4H9)4NOBrel in 30 m] of DIVIF at a temperature of 1 WC. On completion of the addition, the reaction mixture was allowed to rest at the same temperaturefor one hourwhereupon it was allowed to cool to room temperature, after which it was diluted with 50 mi of CH2C12 and washed with water until all the DIVIF had been removed. The organic solution was dried on anhydrous Na2S04 and the solvent removed by evaporation under reduced pressure, to yield 24 9 of a residue consisting of two products which were separated by fractional distillation. The fraction that boiled between 72 to 74'C at 0.5 mmHg (15 g), proved to consist of the desired product.
IR: 1788 1 cm-1 (v C=O).
Mass-fragmentation:
288 W-1-IBr) 260 W-1-IBr-CO) 248 W-CHBr=C=O) 134 [CHBr=C(CH36 main peak] 69 (CF3'I 55 (C41-171 The fraction that boiled at 43 to 47'C at 0.4 mmHg (4 g), proved to consist of the product of the formula:
IR: 1786 --L 1 cm-1 (v C=O) Mass-fragmentation:
248 W-Cl-12=C=O) 211 W-Br) 69 (main peak) 56 H 3 c CH 3 W 3 - CPBr - CH 2 - CH CH 2 c 11 0 8 GB 2 142 634 A Example 9
Preparation of 2-(2'-bromo-2',3',3',3'-tetrafl uoro-pro pyl)-3,3-d imethyi-4-bromo-cyclobuta none (reaction 5)).
A solution of 5 m] of tri-n-butyl-amine [(n.C4H9)3N] in 10 mi of toluene was added dropwise over a period of 1 hourto a solution of 25 g of the cyclobutanone obtained as described in Example 7, and dissolved in 50 mi of toluene at a temperature of 11 OOC. On completion of the addition the reaction mixture was reflux-heated for one hour whereupon it was allowed to cool to room temperature and was then washed with acidified water and dried on anhydrous Na2S04.
After removal of the solvent, under reduced pressure, the raw productwas distilled and the fraction that 10 boiled at7WC atO.4 mmHg (22 g) was gathered which consisted of the desired product (M and mass-spectroscopy were consistent with the assigned structure).
Example 10
Preparation of 2,2-dimethyi-3-(p-fluoro-p-trifluoromethyl-vinyi)cyclopropanecarboxylic acid (reaction 61l):
8 15 H 3C\ /CH3 c CF 3 - W = CH - CH-CH - COOH 20 g of the 4-bromo-cyclobutanone obtained as described in Example 8 or Example 9 was added to a solution of 4 g of NaOH in 60 m[ of water. This mixture was maintained under stirring at room temperature 25 for 2 hours and then for a further 2 hours at 1 OWC. After cooling to room temperature, the mixture was acidified with hydrochloric acid at 10% concentration, and was then extracted with CH2C12 (3 x 50 mi). The organic phase was dried on anhydrous Na2S04 and the solvent removed by evaporation at reduced pressure.
9 g of a raw product were obtained which was purified by distillation and the fraction boiling at 63 to WC 30 at 0.2 mmHg (89) was gathered which proved to consist of the desired product.
The gas-chromatographic and NMR analyses of the product showed the following isomeric composition on the cyclopropane ring:
cis isomer: 92% trans isomer: 8%.

Claims (6)

1. A compound of the general formula:
H 3 c \ / CH 3 c CP 3 - W - c CH - Y 45 1 1\ / X Y C 11 0 50 in which: X represents a chlorine or bromine atom, one of Y and Y1 represents a chlorine or bromine atom and the other of Y and Y1 represents a hydrogen atom.
2. A compound as claimed in Claim 1 of the formula:
H 3 c CH 3 c W _CF-CH 2 CH (Iii) 3 1; \ / 2 X Y c 11 0 9 in which X and Y may be the same or different and each represent Cl or Br.
3. 2-bromo-(2'-bromo-2',3',3',3'-tetrafluoropropyi)-3,3-dimethyicyclobutanone.
4. A compound as claimed in Claim 1 of the formula:
GB 2 142 634 A 9 H 3C \/ CH 3 5 C W 3-CF-CH 2-CH \ CH - Y (1 V) X C 10 11 0 in which X and Y may be the same or different and each represent Cl or Br.
5. 2-(2'-bromo-2',3',3',3'-tetrafluoropropyi)-3,3-dimethyi-4-bromocyclobutanon e.
6. A compound as claimed in Claim 1 substantially as herein described with reference to anyone of Examples 7 to 9.
New claims or amendments to claims filed on 5-9-84 Superseded claim 1 New or amended claims:- 1. A compound of the general formula:
in whijh:
X represents a chlorine or bromine atom, H 3 C / CH 3 C W 3 - CP - CH 2 C CH - Y 1 i\ / X Y C 11 0 one of Y and Y1 represents a chlorine or bromine atom and the other of Y and Y1 represents a hydrogen atom.
Printed in the UK for HMSO, D8818935, 11184, 7102. Published by The Patent Office, 25 Southampton Buildings, London, WC2A lAY, from which copies may be obtained.
GB08418032A 1981-02-02 1984-07-16 Intermediates useful for the preparation of pyrethroids Expired GB2142634B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
IT19462/81A IT1135265B (en) 1981-02-02 1981-02-02 PROCESS FOR THE PREPARATION OF INTERMEDIATES FOR PYRETROIDS

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CH (1) CH651009A5 (en)
DE (1) DE3203379A1 (en)
FR (2) FR2499070A1 (en)
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DE2638356A1 (en) * 1976-08-26 1978-03-02 Bayer Ag METHOD FOR PRODUCING VINYL-SUBSTITUTED CYCLOPROPANCARBONIC ACID ESTERS
DE2813337A1 (en) * 1977-03-31 1978-10-05 Ciba Geigy Ag PROCESS FOR THE PREPARATION OF 2- (2 ', 2', 2'-TRIHALOGENAETHYL) -4-HALOGENCYCLOBUTAN1-ONE
US4255351A (en) * 1978-03-14 1981-03-10 Ciba-Geigy Corporation Sulfonic acid esters of 2,2,2-trichloroethylhydroxycyclobutanones
GB2031871B (en) * 1978-10-23 1983-01-19 Ciba Geigy Ag Process for the production of 2-(2'2'2'-tribromoethyl)-4-chlorocyclobutan-1-ones

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FR2508031B1 (en) 1984-01-20
GB2142634B (en) 1985-09-04
DE3203379A1 (en) 1982-10-21
FR2499070A1 (en) 1982-08-06
CH651009A5 (en) 1985-08-30
GB2092578A (en) 1982-08-18
GB2092578B (en) 1985-03-13
IT1135265B (en) 1986-08-20
IT8119462A0 (en) 1981-02-02
JPS57146733A (en) 1982-09-10
FR2508031A1 (en) 1982-12-24
FR2499070B1 (en) 1985-02-01
GB8418032D0 (en) 1984-08-22

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