SU685145A3 - Method of synthesis of alpha-cyano-3-phenoxybenzylcarboxylates - Google Patents

Description

3 R, R, R, - independently of each other alkyl y-atom of chlorine, bromine or iodine. The yield of the target product is up to 96. The proposed method is carried out as follows. A suitable temperature for conducting the process is a temperature in the range of from 15 to. Suitable aprotic solvents which are practically immiscible with water are alkanes, cycle alkanes or their mixture, in particular n-hexane; n-heptane, n-octane; n-nonane; n-decane and their isomers (for example, 2-methylpentane; 3-methylpentane, 2-methylhexane, 3-methylhexane and 2,4,4-trimethylpentane) and cyclohexane and methylcyclohexane. The gasolines contained in the canals are also suitable, for example, those that have a boiling point in the range from 40 to 65 ° C; from 60 to 80 ° C or from 80 to 110 ° C at atmospheric pressure o Very good results are obtained with n-heptane and cyclohexane. Other very suitable aproton / 1 and solvents that are practically immiscible with water are aromatic hydrocarbons and chlorinated hydrocarbons, for example benzene, toluene, o-pM- and p-xylene, three methylbenzenes, dichloromethane, 1, -2-dichloromethane, Chloroform, monochlorobenzene and If 2- and 1,3-dichlorobenzolo. Very good results are obtained with toluene and xylene. The process can be carried out with an outcome and saturated aqueous solutions of water-soluble cyanide and in the latter case in the presence or in the absence of solid water-soluble cyanium. With some solvents it has been found that the presence of solid water-soluble cyanide increases the yield and reaction time. The use of alkanes or cycloalkanes in combination with cyanide aqueous solutions in the absence of solid water-soluble cyanide makes it possible to reduce time to a minimum “The use of aromatic hydrocarbons or chlorinated carbohydrates the combination with aqueous solutions of cyanide in the absence of solid water-soluble cyanide leads to a slight increase in reaction time, but nevertheless it is sometimes beneficial because the resulting reaction mixture can be used directly to prepare a paste without further separating the ether from the solvent. The use of aromatic hydrocarbons and chlorinated hydrocarbons in combination with solid cyanide 54 leads to a yiiie.HbilieHHro reaction time. However, solid water-soluble cyanide can also be used in the presence of cycloalkanosis. The required reaction time is reached when the molar ratio of the amount of water to the total amount of water-soluble cyanide is above 0.05. Other examples of aprotic solvents p practically immiscible with water include dialkyl ethers and practically immiscible alkanones, diethyl ether, diisopropyl ether, and liisobene tin tone. You can use mixtures of solvents, for example, from alkanes and aromatic hydrocarbons, for example from n-heptane, containing up to 10% by weight% of benzene and / or toluene. The molar ratio of the amount of a phase transformation catalyst to the amount of banzaldehyde of the general formula III can vary within wide limits, but it can be: the ratio is from Is5 to Is 500. The use of lower molar ratios will require more time to complete the reaction, while the use of high molar ratios leads to an increase in the cost of producing ether of the desired quality. Thus, the choice of the reaction time of the molar composition of the catalyst to benzaldehyde mutually depends on both the utilized reagents and the eco-chemical factors. Very good results are usually obtained with molar ratios from IslO to 1: 100. Another advantage of the process is TOf that the molar ratio of carbonyl halide to benzaldehyde is 1; 1 or a slight excess is used. The most desirable mol of pKfc3viK ratios are ratios from lflsl, 0 to IfOslfO. A suitable molar ratio of D is the amount of cyanide soluble in architecton to the amount of aromatic aldehyde is from l, 5sl to 1, -0; 1.0, and preferably from 1 , 3; 1 to 1.02; 1.00. The term “water-soluble cyanide” means the cyanic acid salt soluble in water. Of the bovine soluble cyanides, alkaline and alkaline earth metal cyanides are most desirable. Sodium cyanide is particularly preferred, since it results in esters of general formula 1 in a short reaction time. . A suitable temperature at which the process is conducted is a temperature higher, preferably from 10 to 50 ° C. Very good results are obtained at temperatures in the range from 15 to. This Real TJecc can also be carried out at room temperature. Examples of suitable downstream compounds are tetra-n-butylammonium bromide, tetra-n-butylammonium chloride, trimethyl-2-methylphenylammonium chloride, tetramethylphosphonium iodide, tetra-n-buttklfononiumbromide. Other suitable catalysts for phase transformations are macrocyclic polyesters, in particular 1,4,7, 16 - hexoxy-C loocadiene, or a surfactant, in particular poly (ethylenoxy) derivative of C, -C alcohols Example 1. Preparation of c6 i - cyano-3-phenoxybenzyl-2- (4-chlorophenyl) -3-methylbutanoate in the presence of n-heptane. In a .50 ml round bottom flask equipped with a magnetic stirrer, 10 mmol of 3-phenoxybenzal dehydrate, 10 mmol of 2- (4-chlorophenyl) -3 | -methylbutanoyl chloride, 12 mmol of qi: sodium anide, water, catalyst, and 20 ml of n-heptane are charged. . The mixture thus obtained is stirred. Seven experiments were performed in this way, the results of which are presented in Table 1. Example 2. Preparation of o6-cyano-3-phenoxybenzyl 2- (2,2-dichlorovinyl) -3,3-dimethylcyclopropanecarboxylate in the presence of n-heptane. A 50 ml round-bottomed flask with a magnetic stirrer was charged with 10 mmol of 3-phenoxybenzaldehyde, a quantity of 2- (2,2-dichlorovinyl) -3,3-dimethylcyclopropanecarbonyl chloride, 12 mmol of sodium cyanide, water, catheshizator, and 20 ml of n-heptane. The mixture was mixed . Conducted six experiments. The data are given in table 2. Example 3. Preparation of cC-ci ano-3-phenoxybenzyl 2,2,3,3-tetramethylcyclopropanecarboxylate in the presence of n-heptane To obtain this ester, methods A and B are used, as described below. The gradual addition of carbonyl chloride to the reaction over a period of 0.5-2 hours leads to a significant increase in yield at the end of the addition. Method A. A 50 ml round-bottomed flask equipped with a magnetic stirrer was charged with 10 mmol of 3-phenoxybenzal degide, 10 mmol of 2,2,3,3-tetramethyl cyclopropanecarbonyl chloride, 12 mmol of sodium cyanide, 1.00 ml of water, catalyst, 20 ml of n - heptane. The molar ratio of water to NaCN is 4.64, with no solid NaCN. The catalyst is added in an amount of 0.20 mmol. The resulting mixture is stirred for 1.5 hours and analyzed. Method B. (gradual addition of carbonyl chloride). A flask of the same type as in Method A was charged with 10 mmol of 3-phenoxybenzaldehyde, 12 mmol of sodium cyanide, 10 ml of n-heptane, 1.00 ml of water and 0.20 mmol of catalyst, if necessary. Moreover, the molar ratio of water in NaCN was 10 4.64, 10 mmol of 2,2,3,3-tetramethylcyclopropanecarbonyl chloride, dissolved in 10 ml of n-heptane and: charged to the flask for 70-75 minutes. At the end of this loading period, the ether yield is determined. Five experiments were performed. Table 3 shows the catalysts that are used, and the yield of the target ester. The amount of catalysts used is 2 mol.% In experiments 2-4 and 10 mol.% In experiment 5, based on 3-phenoxybenzaldehyde. The reaction mixture obtained in Experiment 4 using Method B was filtered and the filtrate was washed twice with 20 ml of TM aqueous sodium bicarbonate solution and once with 20 ml of water. The washed filtrate is dried and the n-heptane is evaporated from the dried filtrate to give the ester as a light yellow oil. This oil is dissolved in 2.5 ml of methanol at 23c. The resulting solution is cooled to (-) temperature until ether precipitates. Ether is filtered, its purity is more than 98%. Example 4. Preparation of cC-cyano-3-phenoxybenzyl-2- (4-chlorophenyl) -3-methyl butanoate. To obtain the desired ester, it compares methods A (according to a known method), B and C. Method A. (there is no catalyst for phase transformation). A 500 ml paddle flask with a paddle stirrer was charged with 100 mmol of 3-phenoxybenzaldehyde, 10.0 ml of 2- (4-chlorophenyl) -3-methylbutanoyl chloride, 1200 mmol of sodium cyanide, 10 ml of water (in which all sodium cyanide was dissolved) and 200 ml of n-heptane . After stirring for 45 hours, the mixture is heated to 40-50 and filtered. The filtrate is washed twice with 50 ml of an IM sodium bicarbonate aqueous solution, once with 50 ml of water, dried and the n-heptane is evaporated from the dried solution to give ether in 99% yield and 96% purity. Method B. (in the presence of an onium compound). The experiment described in part A of the example was carried out in the presence of mol% tetra-n-butylammonium chloride, calculated on 3-phenoxybenzaldehyde. After 2 hours, ester 2 was obtained in 99% yield and 94% purity. Method, (in the presence of neonic surfactant in the substance). The experiment described in part h of the example is repeated in the presence of 10 mol.% Tobartoe 91-6 based on 3-phenoxybenzaldehyde. After stirring for 3 hours, the reaction mixture is heated to 40-50 seconds and filtered. Added 50 ml of ethanol (to form an emulsion to disperse), filter and wash the filtrate twice with 50 ml of 1M aqueous sodium carbonate b, once with 50 ml of water. dried and evaporated from the dried solution of n-heptane to obtain ether with a yield of 98%, purity of 97%. The results are summarized in table 4, Example 5. Preparation of α-cya-3-phenoxy-benzyl-2- (4-chlorophenyl) -3-methyl butanoate in the presence of various solvents and solid cyanide. A 50 ml round bottom flask equipped with a magnetic stirrer is charged with 10 mmol of 3-phenoxybenzaldehyde, 10.0 or 10.5 mmol of 2- (4-chlorophenyl) -3-methylbutanoyl chloride, 12 mmol of sodium cyanide, 9.02 ml of water and 20 ml of aprtone solvent. The molar ratio of water to sodium cyanide is 0.105 ,. and the process contains solid NaCN. The reaction mixture is stirred and analyzed. Therefore, thirteen experiments were carried out (see Table 5, which lists the solvents used). Experiments 2,3,4,8 and 9 were carried out with 10.0, and other experiments with 10 mmol of 2- (4-chlorophenyl) -3-methylbutanoyl chloride. The petroleum ether used in Experiment 3 consists of 97 wt.% Alkanes and 3 wt.% Benzene and has a boiling range at atmospheric pressure 58 from 62 to. In experiments 3 and 4, the ester remains in solution during the reaction. The reaction mixture obtained in Experiment 4 was filtered and the cyclohexane was evaporated from the filtrate to give the desired ester as a colorless oil in quantitative yield. In table.5, in addition, presents the outputs of the desired ether. When comparing yields, it turns out that alkanes and cyclohexane are the best solvent. Example 6. Obtaining ci6-cyano-Z-phenoxybenzyl-2- (4-chlorophenyl) -3-methylbutanoate in the presence of solid cyanide. In a 50 ml round-bottom flask equipped with a magnetic stirrer, 10 mmol of 3-phenoxybenzaldehyde, 10.5 mmol of 2- (4-chlorophenyl) -3-methylbutanoyl chloride, 12 mmol of sodium cyanide, 20 ml of toluene, a phase transformation catalyst, and water are charged. The mixture thus obtained is stirred for various times and subsequently analyzed. In this way, six experiments were conducted, and the results are shown in Table 6. depending on the type of catalyst and the amount of water used. Catalysts are used in an amount of 0.20 mmol. The sodium cyanide used consists of particles whose size is 0.5 mm and contains 0.44% by weight. The molar ratio of water to sodium cyanide is calculated for the amount of water contained in sodium cyanide and the amount of water added, if necessary. For comparison, it can be determined that the molar ratio of water to sodium cyanide in a saturated aqueous solution of sodium cyanide at a temperature of 4.1. Table 1

Trimethyl-2-methyl-heptiammonium chloride

Reed

tetra-n-butylammonium chloride 2

86

3

More than 99

18 96

2

99

2.0

99

n-hexadecyldimethylsulfo

NII YODID

Have

trimethyl-2-methylheptylammonium chloride

an anion exchange resin containing a copolymer of styrene with divinylbenzene as the polymer matrix and a quaternary ammonium residue (as resin in the form of chloride).

a) containing on average about 6 ethylene oxide groups; a mixture of alcohols consists of 85% n-alcohols and 15% 2-alkylalka97

1.0

Table

49

10.2

21

94 99 44

1.0 10.2 1 96 ve ionoactive group (use

trade mark from a mixture of alcohols, nols.

x) (by a known method).

Table 3

Table 4

13x) For comparison, in these two experiments solid cyanide.

685145 14

Continued tabl, 5

Claims (1)

Table 6 is not present. 15 Formula of the invention. Preparation of d-cyano-3-phenoxy-beieel carboxylates of the general formula; where R is 1- (4-chlorophenyl) -2-methylpropyl, 2- {2,2-dihalovinyl) -3, 3-dimethylcyclopropyl- or 2,2,3,3-tetramethylcyclopropyl group by reacting 3-phenoxybene-aldehyde with correspondence carbonyl halide in the presence of sodium cyanide or potassium and water in an environment of a water-immiscible aprotic solvent, about 5 because, in order to increase the consumption, the process is carried out in the presence of a catalyst 1,4,7,10,13,16-hexoxacyclo-octalecan or a poly (ethyleneoxy) derivative of alcohols f or an onium compound of the formula G 1 is J / where X is a nitrogen atom or phosphorus; , R, R, independently of one another, alkyl V is a chlorine atom, 6t.t "5a and. and Jodas Sources of information taken into account during the examination 1. Published for Germany 2231) 3, CFL20, 25/00, published. 1962.