JPS6043062B2 - Production method of esters - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for the preparation of esters of carboxylic acids, particularly esters containing a cyan group bonded to an Ars carbon atom in the alcohol portion of the ester molecule.

Esters with cyano groups in such positions are prepared by reacting acids with appropriate cyanohydrins.

According to U.S. Pat. No. 3,835,176, the reaction is carried out by treating the acyl halide with a mixture of the appropriate aldehyde and aqueous sodium or potassium cyanide, optionally in an aprotic solvent. is also carried out. For example, Chrysanthemoilcro? It is disclosed that 3-phenoxy α-cyanobenzyl chrysanthemer is prepared in a yield of 64% by reacting an aqueous solution of hydride, 3-phenoxybenzaldehyde, and sodium cyanide at 0° C. for 1 hour. It would be of great commercial interest if this and other alpha cyano esters could be made by reacting acyl halides with aldehydes and cyanides to reduce reaction times and increase yields.

Insecticidal alpha sialic esters whose preparation would be amenable include α-cyano 3-phenoxybenzyl 3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylate and α-cyano 3-phenoxybenzyl 3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylate. -phenoxybenzyl 3-(2,2-dipromoethenyl)-2,2-dimethylcyclopropanecarboxylate. Other insecticidal alpha cyano esters of particular interest are α-cyano 3-phenoxybenzyl 3-(2-chloro-3,3,3-trifluoropropenyl) 2,2-dimethylcyclopropanecarboxylate, α-cyano 3-phenoxybenzyl -phenoxybenzyl 2,2,3,3
-tetramethylcyclopropanecarboxylate, alpha cyano 3-phenoxybenzyl 2-(4-chlorophenyl)-3-methylbutanoate, cyano(3-phenoxyphenyl)methyl 4-fluoromethoxy alpha-(1-
methyl ethyl)benzene acetate, cyano(4-fluoro-3-phenoxyphenyl)methyl 3-(2,2-
dichloroethenyl)-2,2-dimethylcyclopropanecarboxylate, cyano(6-phenoxypyrido 2
-yl)methyl 3-(2,2-dichloroethenyl)-2
, 2-dimethylcyclopropanecarboxylate and cyano(3-phenoxyphenyl)methyl 2-[(2-chloro4-trifluoromethylphenyl)amino]-3
-methylbutanoate and cyano[3-(4-halofenoxy)phenyl]methyl 3-(2,2-dichloroethenyl)-2,2-dimethelcyclopropanecarboxylate, where halo is fluorine, chlorine or It is bromine. One advantage of the present invention is that it provides a method for producing alpha cyano esters in very high yields and in a short time.

Another advantage of the present invention is that it provides an esterification process in which the product does not require time-consuming and expensive purification. Accordingly, the present invention provides a method for preparing an acyl compound in a mixture of a substantially water-immiscible neutral solvent and an aqueous solution of a water-soluble cyanide salt in the presence of a catalytic amount of a rate promoter selected from aminoalkylsulfonic acids. A method for producing an alpha cyano ester by reacting a halide with an aldehyde is provided.

Acyl halides or aldehydes can exhibit optical or geometric isomerism, which is not influenced by the reaction.
In a preferred embodiment, a compound of formula [ where x is chlorine or bromine, and R is 3-(2,2-dicycloethenyl)-2,2-dimethylcyclopropyl, 3-(2,2-dipromoethenyl)
-2,2-dimethylcyclopropyl, 3-(2-chloro3,3,3-trifluoropropenyl)-2,2dimethylcyclopropyl, 2,2,3,3-tetramethylcyclopropyl, 1-(4 -chlorophenyl)-2-methylpropyl, 1-(4-difluoromethoxyphenyl)
-2-methylpropyl and 1-[(2-chloro4-trifluoromethylphenyl)amino]-2-methylpropyl acyl halide], 3-phenoxybenzaldehyde, 4-fluoro3-phenoxybenzaldehyde, 3 -(4-halofenoxy)benzaldehyde or 6-phenoxy2-pyridylcarboxaldehyde, wherein R is as defined above and R1 is 3-phenoxyphenyl, 4-fluoro(3-phenoxy)
phenyl, 3-(4-halofenoxy)phenyl and 6
- phenoxy 2-pyridyl] is provided.

The method of the invention provides that the rate enhancer is an amphoteric surfactant selected from aminoalkylsulfonic acids and R is 3-
(2,2-dichloroethenyl)-2,2-dimethylcyclopropyl or 1-(4-chlorophenyl)-2-methylpropyl, the insecticidal α-cyano 3-phenoxybenzyl ester can be produced in a short time with high yield. This is particularly effective when manufacturing on time.

Significant results are obtained when R is 3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropyl. Although the process of the invention is particularly advantageous when R is selected from the above group, the process can also be applied to other groups where R is an aliphatic or aromatic group optionally carrying various substituents. It is also effective in the production of alpha cyano ester.

The process of the invention is preferably used to prepare α-cyano 3-phenoxybenzyl ester by using 3-phenoxybenzaldehyde as a reactant, but by varying the type of aldehyde used in the process. The process is equally suitable for the production of other alpha cyano esters. A variety of neutral solvents that are substantially water-immiscible can be used in the process.

When the alkyl, haloalkyl, aryl, haloaryl, aralkyl, haloaralkyl or cyclic hydrocarbon is liquid at a temperature between about 0°C and 5°C and mixed with water, a second phase separates. As long as it forms
Can be used. Such solvents include iso-hexane, 3
-Methylpentane, 2,3-dimethylbutane, 2,2-
Dimethyl butane, n-heptane, n-octane, petroleum ether, ligroin, n-propyl bromide, n-propyl iodide, n-butyl chloride, n-butyl bromide, n-pentyl chloride, n-pentyl bromide, diethyl ether , dipropyl ether, dibutyl ether, benzene, toluene and xylene. Among these solvents,
N-heptane is preferred because it is easily available and inexpensive. A number of water-soluble cyanide salts can be used, for example the salt can be an alkali metal cyanide such as lithium cyanide, sodium cyanide, potassium cyanide, rubidium cyanide or cesium cyanide or mixtures thereof.

Among these, sodium cyanide is generally preferred. The cyanide salt is dissolved in water, and the amount of water used is relatively small, but preferably sufficient to keep all the cyanide salt in solution under the reaction conditions.

When the salt is sodium cyanide, a suitable molar ratio of water to sodium cyanide is between about 3.5 and 6, preferably about 4.5. The process of the invention is carried out in the presence of a catalytic amount of a rate enhancer selected from aminoalkylsulfonic acids. For the purposes of the present invention, the catalytic amount of rate promoter is in the range of 1 to 5 mole %, preferably about 2 mole %, based on the aldehyde. For the purposes of this invention, the term 1-aminoalkylsulfonic acid is defined as having the structural formula [wherein n is 2 or 3] wherever it appears in the specification or claims.
and R1 and R2 are substituents jointly selected to render the aminoalkylsulfonic acid soluble in a water-immiscible neutral solvent.

Suitable substituents jointly containing hydrocarbon units are present in the following individual aminoalkylsulfonic acids; 1,4-piperazinebisethanesulfonic acid, 4-pyridinethanesulfonic acid, 2- [N,N-di(2-hydroxy)monoethyl]aminoethanesulfonic acid, 3-(
cyclohexylamino)propanesulfonic acid, 2-[4
-(2-hydroxyethyl)piperidin-1-yl]ethanesulfonic acid, 2-(N-morpholino)ethanesulfonic acid, N-tris(hydroxymethyl)methyl-2-aminoethanesulfonic acid, 2-(N-morpholino)ethanesulfonic acid, Propanesulfonic acid and N-tris(hydroxymethyl)methyl-2-aminoethanesulfonic acid. Among these compounds, 1,4-piperidinebisethanesulfonic acid and 3-tris(hydroxymethyl)methyl-2-aminoethanesulfonic acid.
(Cyclohexylamino)propanesulfonic acid is preferred, and 3-(cyclohexylamino)-propanesulfonic acid is particularly effective. The process of the present invention is carried out between an aqueous solution of approximately equimolar amounts of an acyl halide, preferably an acyl chloride, an aldehyde and a cyanide salt, in a water-immiscible neutral solvent, but typically with a slight excess. Amounts of acyl halide and cyanide salts are used. The acyl halide can finally be added, preferably dropwise, to the stirred reaction mixture, but the solution containing the aldehyde and acyl halide is mixed with the aqueous cyanide salt and a stirred water-immiscible neutral solvent. It is preferable to add it to a compound that is Although the reaction can be carried out over a wide temperature range, in most cases a range of 0°C to 50°C is satisfactory and the reaction is carried out at room temperature since no external heating or cooling is required at room temperature. is preferred. The method will be more easily understood by reference to the Examples below which illustrate it. Temperatures are in degrees Celsius.
The reactions of the examples were monitored in most cases by gas-liquid partition chromatography (g'Pc), and the time required for the limiting reagent to disappear after the start of the acyl halide addition was followed by the alpha cyano ester formed. was measured together with the amount of Reference Example 1 α-Cyano 3-phenoxybenzyl 3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylate A using diazabicyclo[2,2,2]octane (1) 3-phenoxylene in a flask Sibenzaldehyde (1.98 g 110.0 mmol), sodium cyanide (4). 59 g 112 mmol), 20 ml n-heptane, 1 ml water and diazabicyclo[2,
2,2]Octane (0.022g..0.2mmol)
filled with.

The mixture was stirred vigorously and 3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarbonichloride (2.38 g 110.5 mmol) was added in one portion. Stirring was continued for 1 hour at room temperature, at which time Gfp
c showed a 94% yield of the desired alpha cyanoester. The mixture was filtered. 10m filter cake
Washed twice with t portions of diethyl ether. The filtrate was dried over magnesium sulfate and the butane was stripped under reduced pressure to remove the desired ester from the residual oil (4.1
0g). Use of optically active (IRl cis)carbonyl chloride in the above method gave the corresponding optically active ester in 96% yield within a reaction time of 1 hour.

(2) Sodium cyanide (5.
9g10.12mol) and 1,4-diazabicyclo[2
,2,2]Octane (0.22g..0.002mol)
A mixture of 10 g of water was stirred at room temperature.

3-phenoxybenzaldehyde (20.
6g. ．． 0.1 mol) and 120 mt of 3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarbonyl chloride (24.1 g 10.105 mol)
A solution in On-octane was added to the reaction mixture.

After complete addition, the reaction mixture was stirred for 1 hour. 20%
of sodium carbonate was added to the reaction mixture and the whole was warmed to 600 ℃.

The organic phase was separated, washed with water, dried over anhydrous magnesium sulfate and filtered. The solvent was removed from the filtrate under reduced pressure to give α-cyano-phenoxybenzyl 3-(2,
2-dichloroethenyl)-2,2-dimethyl-cyclopropanecarboxylate was produced. Add 3-phenoxybenzalde to the flask using B2,6-dimethyl-2,6-diazaheptane. A solution of humans (1.98 g 110 mmol) in 10 ml n-heptane was charged.

The solution was cooled to 101 ml and then 2,6-dimethyldiazaheptane (26 mg, 0.2 mmol), sodium cyanide (0.59 g 112 mmol) and 1 ml of water were added. 3-(2,2-dichloroethenyl)-2,
2-dimethylcyclopropanecarbonyl chloride (2
．． 38 g (110.5 mmol) were then added in one portion with stirring and the temperature of the reaction mixture was maintained at 8-17.

After 45 minutes, g'Pc showed a 93% yield of the desired alpha cyano ester.

The reaction mixture was filtered after a total of 1.2 hours. The filter cake was washed with ether and the solvent was evaporated from the filtrate to give the desired ester (4.3g). 2
, 5,8,11-tetramethyl-2,5,8,11-tetraazadodecane In a flask equipped with a stirrer, an addition funnel and an inlet for nitrogen gas, sodium cyanide (0.59 g 10 .012 mol),
2,5,8,11-tetramethyl-2,5,8,11-tetraazadodecane (4) in 3 ml of heptane. 04
8 g 10.2 mmol) and 3-3 in 7 ml heptane
Phenoxybenzaldehyde (1.98g 10.01 mole) was charged.

The reactions were mixed under nitrogen atmosphere. 3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarbonyl chloride (2.38g) in 10ml heptane
10.0105 mol) was added dropwise in two portions to the stirred mixture.

After two passes, a total of 40 minutes, g'Pc showed a 93% yield of the desired ester.

The reaction mixture was stirred for an additional 4 pulses, then poured into a separatory funnel, diluted with 40 ml of diethyl ether, and washed once with a 1N aqueous solution of sodium hydroxide, three times with water, and once with a saturated aqueous solution of sodium chloride. did. After phase separation, the separated ether layer was dried over magnesium sulfate and the solvent was evaporated to give the ester as a pale yellow oil (4.02 g
) was given as. j (4,7,13,16,21-pentaoxer 1,10-diazabicyclo[8,8,5]
Use of tricosane 3-phenoxybenzaldehyde (1.98 g 110 mmol), 10 mt (7) was added to the flask.
n-heptane, 4,7,13,16,21-pentaoxer 1,10-diazabicyclo[8,8,5]tricosane (6.6 m9, 0.2 mmol), sodium cyanide (0.59 g 112 mmol), 1 wL1 water and 3
-(2,2-dichloroethenyl), -2,2-dimethyl-cyclopropanecarbonyl chloride (2.38g1
10.5 mmol) in 10 ml of n-heptane.

When the reaction mixture is stirred, heat generation (approximately 40°C) occurs after two stirrings.
was seen. After 50 minutes, Gepc showed a 99% yield of the desired ester.

The reaction mixture was filtered, diluted with ether, dried over magnesium sulphate and the solvent was evaporated to give the desired ester (3.90g).

E Use of tetramethylethylenediamine 3-(2,2
-dichloroethenyl)-2,2-dimethyl-cyclopropanecarbonyl chloride (114 g 10.315 mol) and -phenoxybenzaldehyde (61.9 g...
About 40 t of sodium cyanide (0.3 mol) in 275 ml of n-heptane was added under nitrogen for 1 hour.
18g. ．． 0.36 mol), tetramethylethylenediamine (a). 7 g (10.006 mol) and 30 g of water was added dropwise to a stirred mixture.

After the addition, the reaction mixture was stirred at about 40°C. The reaction mixture was processed as in Example 1A(2) to produce the desired ester. F Use of Tetramethyl-1,6-hexanediamine By the method of Example 1E above, but using tetramethyl-1,6-hexanediamine in place of tetramethylenediamine, α-cyano-3-phenoxybenzyl 3-(2,2 -dichloroethenyl)-2,2-
Dimethyl cyclopropane carboxylate was produced.

α-cyano 3-phenoxybenzyl 3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylate using other tertiary amines or polyamines and cryptate rate enhancers and under otherwise similar conditions. Preparation of the rate gave the results shown in Table 1.

Reference Example 2 Production of α-cyano 3-phenoxybenzyl (2,2-dipromoethenyl)-2,2-dimethylcyclopropanecarboxylate using diazabicyclo[2,2,2]octane 3-phenoxybenzaldehyde (1.98g110 .0 mmol), 10 ml of n-
Heptane, diazabicyclo[2,2,2]octane (2
2m110.2 mmol), sodium cyanide (a)
．． 59 g (112 mmol) and 1 ml of water were charged.

3-(2,2-dipromoethenyl)-2,2-dimethylcyclopropanecarbonyl chloride (3.32g11
A solution of 0.5 mmol) in 10 ml of n-heptane was added with stirring.

After 2 hours, the reaction mixture was filtered, the filter cake was washed with 30 ml of ether, and the filtrate was dried over magnesium sulphate.

Stripping of the solvent gave the desired ester as a yellow oil. (4.4g 196% yield) Reference example 3 α using 2,7-dimethyl-2,7-diazaoctane
-cyanophenoxybenzyl-3-(2-chloro-3,
Production of 3,3-trifluoropropenyl)-2,2-dimethylcyclopropanecarboxylate.
Phenoxybenzaldehyde (1.98 g 110 mmol), 10 ml n-heptane, 2.7-dimethyl-2
．． 7-diazaoctane (29m9, 0.2 mmol),
Sodium cyanide (4). 59g, s12 mmol)
and 177! 1 of water was added.

3-(2-
chloro-3,3,3-trifluoropropenyl)-2
．． 2 dimethyl cyclopropane carbonyl chloride (2
．． 0 g 110.5 mmol) was then added in one portion.

Conversion was complete after 1.3 hours. 4. Reaction mixture. Stir for an hour, at which time 5 mt diethyl ether and 5 ml
of IN aqueous sodium hydroxide solution was added. The resulting mixture is 1. Stir for an hour and separate the two phases. The organic phase was washed once with IN aqueous sodium hydroxide solution, once with water and once with saturated aqueous sodium chloride solution, then dried over magnesium sulfate, filtered and the solvent was distilled off under reduced pressure. Desired ester (4.1g 191% yield)
gave. Reference Example 42.6 α-cyano-3-phenoxybenzyl 2 using dimethyl-2,6-diazaheptane
, 2,3,3-tetramethylcyclopropanecarboxylate Into a flask, 3-phenoxybenzaldehyde (3.16 g 116 mmol), 10 ml of n-heptane, 2.6-dimethyl-2.6-diazaheptane (2
6m9, 0.2 mmol), sodium cyanide (a)
．． 94 g (119.2 mmol) and 1 mt of water were charged.

2,2,3 dissolved in 10ml(7)n-heptane
, 3-tetramethylcyclopropanecarbonyl chloride (2.6 g 116.7 mmol) was then added once.

An exotherm (to about 38°C) was observed upon addition of the acid chloride. Analysis showed a 74% yield of the desired ester within 4 hours. After cooling, the reaction mixture was filtered, diluted with diethyl ether, dried over magnesium sulfate, and distilled under reduced pressure to give an orange residual oil. The oil was dissolved in 25 ml of diethyl ether and the resulting ethereal solution was mixed with captive aqueous sodium hydroxide solution over a period of 2 hours. After phase separation, the ether phase was washed once with water and once with saturated aqueous sodium chloride solution, dried over magnesium sulfate, and the solvent was distilled under reduced pressure to give the desired ester (3.0 g). Reference Example 5 Production of α-cyano 3-phenoxybenzyl 2-(4-chlorophenyl)-3-methylbutanoate A Use of diazabicyclo[2,2,2]octane 3-phenoxybenzaldehyde (1.98 g 110 mmol) in a flask 10ml of n-heptane, diazabicyclo[2,2,
2] Octane (22 mg, 0.2 mmol), sodium cyanide (0.59 g 112 mmol) and 1 ml of water were charged and stirring started.

Then 2-(4-chlorophenyl)-3-methylptanoyl chloride (2.4
2 g (110.5 mmol) was added in one portion. The reaction mixture was stirred at room temperature for 1 hour, at which time Gfpc showed a 74% yield of the desired ester. Stirring was continued overnight, then the reaction mixture was filtered, diluted with diethyl ether, and the solvent was distilled under reduced pressure to give the desired ester as a residue (4.
02g). Use of B2,5,8,ll-tetramethyl-2,5,8,11-tetraazadodecane 3-phenoxybenzaldehyde (1.9 modified,
10 mmol), 20 mL (7) n-heptane, 2,5
, 8,11-tetramethyl-2,5,8,11-tetraazadodecane (a). 046g), sodium cyanide (a). 59 g (112 mmol) and 1 ml of water were charged.

2-(4-chlorophenyl)-3-methylptanoyl chloride (2.42 g 110.5 mmol) was added dropwise over 6 minutes while stirring. The reaction mixture was stirred at room temperature. Analysis by Gepc showed a 67.7% yield of the desired ester after addition of the acyl chloride. . Stirring was continued overnight and the desired ester (3.4 g) was isolated as described in the previous example. Example 1 Using 1,4-piperazine bisethanesulfonic acid as a production rate accelerator for α-cyano 3-phenoxybenzyl 3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylate. - phenoxybenzaldehyde (1.98 g, .10 mmol),
10 Tnt(7) n-heptane, 1,4-piperazinebisethanesulfonic acid (60 y, 0.2 mmol), sodium cyanide (0.59 g 112 mmol), 1 ml water, and 3-(2,2-dichloroethenyl) )-2,2-
Dimethylcyclopropane carbonyl chloride (2.3
8g. ．． 4.5 mmol) of a solution of 10 ml (7) in n-heptane. Stir for hours (g′Pc showed 91% yield after 1 hour and 5 millings),
Dilute with 30 ml of diethyl ether, then once with IN aqueous sodium hydroxide (20 ml) and water (20 ml).
once, and a saturated aqueous solution of sodium chloride (20ml)
Washed once with

After separation, the clear yellow ethereal solution was dried over magnesium sulfate and the solvent was then evaporated to give the desired ester (4.05g). B Use of 3-(cyclohexylamino)propanesulfonic acid as rate accelerator (1)
In the method of Example A above, 3-(cyclohexylamino)propanesulfonic acid (44m9, 0.2 mmol) was substituted for 1,4-piperazinebisethanesulfonic acid.
Using Gepc, the yield of the desired ester was 97.2% after 9 millings and isolated to give the desired ester (3.49 g).

In similar experiments, g'Pc gave a 99% yield of the desired ester within 2 hours.

(2) 300TI of sodium cyanide (18.0g.s0.36mol) and 3-(cyclohexylamino)propanesulfonic acid (1.34g..0.006mol)
The stirred mixture in L1 water was warmed to 406 ml.

Cis-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarbonyl chloride (71.7 g, .
0.315 mol) and 262.2 g (7) n- of 3-phenoxybenzaldehyde (61.9 g 10.3 mol)
A solution in heptane was added. The mixture was then stirred with 40 g for a further hour, after which it was washed with an aqueous solution containing 20% sodium carbonate and then with water. The organic phase is separated from the mixture and the solvent removed by vacuum distillation to give α-cyano-3-phenoxybenzylcis-3-(2
, 2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylate. Use of other rate promoters under otherwise similar conditions gave the following yields (Gepc) after the indicated reaction times.

Example 2 Preparation of α-cyano 3-phenoxybenzyl 2-(4-chlorophenyl)-3-methylbutanoate using 3-(cyclohexylamino)propanesulfonic acid as rate accelerator 3-(cyclohexylamino)propane was added to a flask. Charged were sulfonic acid (42 m9), 3-phenoxybenzaldehyde (1.90 g 19.6 mmol), sodium cyanide (0.56 g 112 mmol), 1 ml water and 15 ml (7) n-heptane.

2-(4-chlorophenyl)-3-methylptanoyl chloride (2.34gl) in 5mt(7)n-heptane
10.1 mm. ) was added dropwise to the stirred mixture over a period of 24 minutes.

After 3C@ of complete addition, ie after a total of 4 powders, Mlpc showed a yield of 95.6% of the desired ester. After stirring overnight, the reaction mixture was filtered and extracted with ether. Ether was evaporated from the extract to give α-cyano 3-phenoxybenzyl 2-(4-chlorophenyl)-3-methylbutanoate (3.47g).
Reference Example 6 Production of α-cyano-3-phenoxybenzyl 3-(2,2-dichloroethenyl)2,2-dimethylcyclopropanecarboxylate using diazabicyclo[2,2,2]octane dihydrochloride as a rate accelerator (1) ) 3-phenoxybenzaldehyde (1.98g110
．． 0 mmol), 10 mL (7) n-heptane, diazabicyclo[2,2,2]octane dihydrochloride (30 m9,
0.2 mmol), sodium cyanide (a). 59g
1 WLt water and 2.38 g (2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarbonyl chloride) (110.5 mmol)
of the solution in n-heptane.

Stir the reaction mixture and 1. After hours Gepc showed a 96% yield of the desired ester. After a total of 1 h, the reaction mixture was filtered, diluted with ether, the phases were separated, the ether phase was dried over magnesium sulfate, and the ether phase was dried over magnesium sulphate.
The solvent was then evaporated and the desired ester (3.98g
) was given. 2) Sodium cyanide (
18.1g10.36mol) and diazabicyclo[2,
2,2] Add a stirred mixture of octane dihydrochloride to 4
It warmed up to 00.

3-(2,2-dichloroethenyl)- over 1 hour
102 ml of 2,2-dimethylcyclopropanecarbonyl chloride (77.6 g 10.33 mol) and 3-phenoxybenzaldehyde (61.5 g 10.3 mol)
(7) A solution in n-heptane was added to the reaction mixture.

After the addition was complete, the reaction mixture was stirred for 40 minutes and another 3.5 g. 0.15 mol) of acyl chloride was added. The reaction mixture was stirred for an additional 4 minutes and 10 minutes.
Washed in 0 g of 10% aqueous sodium carbonate solution and then with water, the organic phase was separated from the mixture and the solvent was removed by vacuum distillation to give α-cyano-3-phenoxybenzyl 3-(2,2-dichloroethenyl). -2,2-dimethylpropanecarboxylate was obtained. Preparation of α-cyano-3-phenoxybenzyl-3-(2,2-dichloroethenyl)-2,2-dimethylcyclo-pancarboxylate under otherwise similar conditions using other rate accelerators yields the following result: Gave.

2,7-dimethyl-2,7-diazaoctane dihydrochloride 1. Hashirama 96% 2, 3, 4
, 6,7,8,10-octahydropyrimide[1.2-a]Azepine Hydrochloride 4 hours 99% Quinuclidine Hydrochloride 1. S! Space%
Table 1 α-cyano-3-phenoxybenzyl-3-(2,2-dichloroethenyl)-2,2- with other tertiary amines or polyamines and cryptate rate enhancers
Production process of diethyl cyclopropane carboxylate Speed accelerator Reaction time Yield tri-n-hexylamine 4 hours 82% triethylamine
2 hours 89% 2,4-dimethyl-2,4-diazapentane 2 hours 96% 2,5-dimethyl-2,5-diazahexane 0.
Time 91% 2,9-dimethyl-2,9-diazadecane
1. Shoma 96% 1, Choichi (1,2-
ethanediyl)bis[piperidine] 1. Shouting 94% 1,4-
Dimethyl-1,4-diazacyclohexane 1. Time 86%N,N,
N'',N'-tetramethyl-1,2-diaminocyclohexane 1. time 96% 1,4
,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane

Claims (1)

Claims: 1. In a mixture of a substantially water-immiscible neutral solvent and an aqueous solution of a water-soluble cyanide salt, in the presence of a catalytic amount of a rate promoter selected from aminoalkylsulfonic acids, Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, X is chlorine, and R is 3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropyl,
3-(2,2-dibromotenyl)-2,2-dimethylcyclopropyl, 3-(2-chloro-3,3,3-trifluoropropenyl)-2,2-dimethylcyclopropyl, 2,2,3 ,3,-tetramethylcyclopropyl, 1
-(4-chlorophenyl)-2-methylpropyl, 1-
Acyl halide selected from (4-difluoromethoxyphenyl)-2-methylpropyl and 1-[(2-chloro-4-trifluoromethyl)amino]-2-methylpropyl], 3-phenoxybenzaldehyde, 4-
Fluoro-3-phenoxybenzaldehyde, 3-(4
By reacting -halofenoxy)benzaldehyde or 6-phenoxy-2-pyridylcarboxaldecede, the formula ▲mathematical formula, chemical formula, table, etc.▼ [wherein R is as defined above, and R_1 is 3-phenoxyphenyl, 4-fluoro-(3
-phenoxy)phenyl, 3-(4-halofenoxy)
A method for producing insecticidal α-cyano-3-phenoxybenzyl esters selected from phenyl and 6-phenoxy-2-pyridyl. 2 The rate accelerator is 1,4-piperazinebisethanesulfonic acid, 4-pyridinethanesulfonic acid, 2-[N,N-
selected from di-(2-hydroxy)-ethyl]aminoethanesulfonic acid, 3-(cyclohexylamino)propanesulfonic acid and 2-[4-(2-hydroxyethyl)piperidin-1-yl]ethanesulfonic acid Process according to claim 1, characterized in that it is an aminoalkylsulfonic acid. 3. Process according to claim 2, characterized in that the rate accelerator is selected from 1,4-piperidine-bisethanesulfonic acid and 3-(cyclohexylamino)propanesulfonic acid. 4. Process according to claim 3, characterized in that the rate accelerator is 3-(cyclohexylamino)propanesulfonic acid. 5 R is 3-(2,2-dichloroethenyl)-2,2-
5. Process according to any one of claims 2 to 4, characterized in that it is dimethylcyclopropyl or 1-(4-chlorophenyl)-2-methylpropyl. 6 R is 3-(2,2-dichloroethenyl)-2,2-
5. Process according to any one of claims 2 to 4, characterized in that it is dimethylclopropyl. 7. The method according to any one of claims 2 to 4, characterized in that the water-immiscible neutral solvent is n-heptane. 8. The method according to any one of claims 2 to 4, characterized in that the water-soluble cyanide salt is sodium cyanide. 9 R is 1-(4-difluoro-methoxyphenyl)-
According to any one of claims 2 to 8, selected from 2-methylpropyl and 1-[(2-chloro-4-trifluoromethyl)amino]-2-methylpropyl. Method described. 10 Claims 2 to 8, characterized in that the acyl halide is reacted with 4-fluoro-3-phenoxybenzaldehyde, 3-(4-halofenyxybenzaldehyde or 6-phenoxy-2-pyridylcarboxaldehyde) The method described in any one of paragraphs.