JPS6147825B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing hydroxybenzonitrile. More specifically, the present invention relates to a novel method for producing hydroxybenzonitrile by reacting α,α,α-trihalomethyl phenyl ester with ammonia or aqueous ammonia (hereinafter referred to as ammonia). It is well known that hydroxybenzonitriles are extremely useful compounds as intermediates in the production of insecticides, herbicides, fungicides, dyes, liquid crystals, and the like. Conventionally, the method for producing it is (a) a method of reacting hydroxybenzoic acid or its derivative with phosphoric acid amide or phosphoric acid imide (Japanese Patent Publications No. 7937-1983, Japanese Patent Publication No. 26290-1972, Japanese Patent Publication No. 40072-1972) (b) Sandmeyer reaction of aminophenols (J.Chem.Soc., Journal of Chemical Society, 1942, p. 103), (c) Reaction of halophenols with copper cyanide (J. Am.Chem.Soc.
, Journal of the American Chemical Society, 80, p. 3271 (1958), U.S. Patent No.
3259646 specification, (d) Dehydration of hydroxybenzaldoxime (Japanese Patent Publication No. 1983-3372), (e) Method by ammoxidation of methylphenols (German Patent No. 2020866 specification, German Patent No. 2037495 specification) (book) etc. are known. However, method (a) has disadvantages in that the reaction requires a high temperature of around 250°C, and that high temperature and high pressure are required to produce the raw material hydroxybenzoic acid. In addition, methods (b), (c), and (d) require the use of expensive raw materials and are industrially disadvantageous, such as complicated manufacturing methods, and method (e) has low yields. It has drawbacks such as a low value and is extremely unsatisfactory as an industrial manufacturing method. The present inventors have conducted intensive research on a method for producing hydroxybenzonitrile without the above-mentioned drawbacks, and have found that trihalomethyl The inventors discovered that the production of nitrile groups from groups and the decomposition reaction of ester groups occur all at once, producing hydroxybenzonitrile compounds in high yields, leading to the completion of the present invention. That is, the present invention is based on the general formula () [In the formula, R is the same or different, a hydrogen atom,
Halogen atom or nitro group, X is the same or different halogen atom, Y is an organic or inorganic acid residue, m and n are positive integers of m+n=5, P is Y
represents a positive integer according to the bond valence of . ] General formula () resulting from the reaction of α,α,α-trihalomethyl esters shown by and ammonia or aqueous ammonia [In the formula, R, m and n represent the same meanings as in the general formula (). ] A method for producing hydroxybenzonitrile represented by the following is provided. The method of the present invention will be explained in detail below. Examples of α,α,α-trihalomethylphenyl esters represented by the general formula () used in the method of the present invention include α,α,α-trichloromethylphenol, α,α,α-tribromomethylphenol , α,α,α-trichloromethylfluorophenol, α,α,α-trichloromethylchlorophenol, α,α,α-trichloromethylbromophenol, α,α,α-trichloromethyliodophenol, α,α,α -Tribromomethylchlorophenol, α,α,α-trichloromethylnitrophenol, α,α,α-tribromomethylnitrophenol, α,α,α-trichloromethyldifluorophenol, α,α,α-trichloromethyl Dichlorophenol, α, α, α
-Trichloromethyldibromophenol, α,
α,α-trichloromethyldiiodophenol,
α,α,α-Trichloromethylbromochlorophenol, α,α,α-trichloromethyliodochlorophenol, α,α,α-trichloromethylbromoiodophenol, α,α,α-trichloromethylfluoronitrophenol, α, α、α―
Trichloromethylchlornitrophenol, α,
Esters of organic or inorganic acids of each isomer of phenols such as α,α-trichloromethylbromnitrophenol, α,α,α-trichloromethyliodonitrophenol, and di(α,α,α-trichloromethyl)phenol. Examples include esters of organic acids such as acetic acid, and inorganic acids such as chlorocarbonic acid, carbonic acid, phosphoric acid, and boric acid. To give a more specific example, di(2-α, α, α
-trichloromethylphenyl) carbonate, di(3-α,α,α-trichloromethylphenyl)
carbonate, di(4-α,α,α-trichloromethylphenyl)carbonate, di(3-α,
α, α-Tribromomethylphenyl) carbonate, di(4-α, α, α-tribromomethylphenyl) carbonate, tri(2-α, α, α-trichloromethylphenyl) phosphate, tri(3 -α,α,α-trichloromethylphenyl)
Phosphate, tri(4-α,α,α-trichloromethylphenyl)phosphate, 3-α,α,
α-Trichloromethylphenylchlorocarbonate, 4-α,α,α-trichloromethylphenylchlorocarbonate, 4-α,α,α-trichloromethylphenylacetate, tri(4-α,
α,α-trichloromethylphenyl)borate,
Di(4-fluoro-2-α,α,α-trichloromethylphenyl)carbonate, di(2-fluoro-2-α,α,α-trichloromethylphenyl)carbonate
5-α,α,α-trichloromethylphenyl)carbonate, di(3-fluoro-4-α,α,α-
trichloromethylphenyl) carbonate, tri(3-fluoro-4-α,α,α-trichloromethylphenyl)phosphate, tri(5-chloro-
2-α,α,α-tribromomethylphenyl) phosphate, tri(4-chloro-2-α,α,α
-trichloromethylphenyl)borate, di(4
-Chlor-2-α,α,α-trichloromethylphenyl) carbonate, tri(4-chloro-2-
α, α, α-Trichloromethylphenyl) phosphate, di(4-chloro-3-α, α, α-trichloromethylphenyl) carbonate, tri(2
-Chlor-5-α,α,α-trichloromethylphenyl)phosphate, di(2-chloro-4-
α,α,α-Trichloromethylphenyl) carbonate, tri(3-chloro-4-α,α,α-tribromomethylphenyl)borate, 4-bromo-2-α,α,α-trichloromethylphenyl enylchlorocarbonate, di(5-bromo-2-α,
α,α-Trichloromethylphenyl) carbonate, 4-bromo-3-α,α,α-trichloromethylphenylacetate, di(2-bromo-4-
α, α, α-Trichloromethylphenyl) carbonate, tri(2-bromo-4-α, α, α-trichloromethylphenyl) phosphate, di(3
-bromo-4-α,α,α-trichloromethylphenyl) carbonate, tri(4-iodo-2-
α,α,α-Trichloromethylphenyl)borate, di(2-iodo-5-α,α,α-trichloromethylphenyl)carbonate, di(2-iodo-4-α,α,α-trichloromethyl) phenyl) carbonate, tri(2-iodo-4-α,
α,α-Trichloromethylphenyl) phosphate, di(4-nitro-2-α,α,α-trichloromethylphenyl)carbonate, tri(4-nitro-2-α,α,α-trichloromethylphenyl) ) phosphate, di(5-nitro-2-α,
α,α-trichloromethylphenyl) carbonate, tri(5-nitro-2-α,α,α-trichloromethylphenyl)phosphate, 4-nitro-3-α,α,α-trichloromethylphenyl acetate, Di(2-nitro-5-α,α,α-trichloromethylphenyl)carbonate, tri(2-nitro-5-α,α,α-trichloromethylphenyl)phosphate, di(2-nitro-4
-α,α,α-trichloromethylphenyl)carbonate, tri(2-nitro-4-α,α,α-
trichloromethylphenyl) phosphate, tri(3-nitro-4-α,α,α-tribromomethylphenyl)borate, di(2,6-difluor-
4-α,α,α-trichloromethylphenyl) carbonate, tri(3,4-dichloro-2-α,
α,α-Trichloromethylphenyl) phosphate, 2,4-dichloro-6-α,α,α-tribromomethylphenylacetate, di(2,4-dichloro-5-α,α,α-trichloromethyl) phenyl) carbonate, di(2,6-dichloro-4)
-α,α,α-trichloromethylphenyl) carbonate, tri(2,6-dichloro-4-α,
α,α-Trichloromethylphenyl) phosphate, di(3,5-dichloro-4-α,α,α-trichloromethylphenyl)carbonate, tri(3,5-dichloro-4-α,α,α- trichloromethylphenyl) phosphate, 2,4-dibromo-6-α,α,α-trichloromethylphenylacetate, di(2,4-dibromo-5-α,
α,α-Trichloromethylphenyl) carbonate, di(2,6-dibromo-4-α,α,α-trichloromethylphenyl)carbonate, tri(2,6-dibrom-4-α,α,α- trichloromethylphenyl) phosphate, tri(2,4
-diiodo-6-α,α,α-tribromomethylphenyl)borade, di(2,4-diiodo-5
-α,α,α-trichloromethylphenyl) carbonate, di(2,6-diiodo-4-α,α,
α-trichloromethylphenyl) carbonate,
Tri(2,6-diiodo-4-α,α,α-trichloromethylphenyl)carbonate, Tri(2,6-diiodo-4-α,α,α-trichloromethylphenyl)phosphate, Di(2- Chlor-4-bromo-5-α,α,α-trichloromethylphenyl) carbonate, tri(2-bromo-4-iodo-6-α,α,α-trichloromethylphenyl)phosphate, di(3- Chlor-5
-nitro-4-α,α,α-trichloromethylphenyl)carbonate, di(2-chloro-4-nitro-6-α,α,α-trichloromethylphenyl)carbonate, di(2,3,6 -Trichlor-4-α,α,α-trichlormethylphenyl)
carbonate, di[3,4-di(α,α,α-trichloromethyl)phenyl]carbonate, tri[2,5-di(α,α,α-trichloromethyl)]
Phenyl]phosphate, di[2,4-di(α,
α,α-Trichloromethyl)phenyl] carbonate, etc., and α, α, α
-Trihalomethyl phenyl esters are not limited to these as long as they do not go beyond the gist of the present invention, but carbonic acid esters of α,α,α-trichloromethylphenol are particularly preferably used. The above esters usually have the general formula () [In the formula, R, m and n represent the same meanings as in the general formula (). ] It can be easily produced from the methylphenols shown in the following, but it can also be used as a by-product when producing other products. To explain the preferred method for producing α,α,α-trihalomethylphenyl esters of the above general formula (), first, methylphenols represented by the general formula () are treated with an organic acid, an inorganic acid, or a derivative thereof. esterification using When performing esterification, (1) an organic or inorganic acid and a methylphenol represented by the general formula () are directly reacted without a catalyst or in the presence of an acid catalyst. (2) Anhydrides, halides, etc. of organic or inorganic acids are reacted with methylphenols represented by the general formula () without a catalyst or in the presence of a catalyst such as an acid or an alkali. (3) An organic or inorganic acid ester and a methylphenol represented by the general formula () are transesterified without a catalyst or in the presence of a catalyst such as an acid or an alkali. The types of methylphenols and organic or inorganic acids represented by the general formula () are appropriately selected as necessary. Subsequently, the methyl group in the methylphenol ester is halogenated. Halogenation can be carried out by introducing a halokene into the methylphenol ester produced as described above in the presence or absence of a photo or radical initiator. Halogenation can be carried out in the absence of a solvent or in the presence of a polyhalogenated hydrocarbon solvent such as carbon tetrachloride, chloroform, or trichlorobenzene. As a light source, a high-pressure mercury lamp, a tungsten lamp, sunlight, etc. can be used, and as a radical initiator, an azo compound such as α, α'-azo-bis-isobutyronitrile, benzoyl peroxide, lauroyl peroxide, t - Peroxides such as butyl hydroperoxide can be used. The reaction temperature is usually 50
℃~200℃ is adopted. According to the method described above, α,α,α-trihalomethyl phenyl esters represented by the general formula () can be easily produced in high yield. When carrying out the method of the present invention, gaseous or liquid ammonia or aqueous ammonia can be used as ammonia. When aqueous ammonia is used, it is sufficient to use a commercially available aqueous ammonia with a concentration of about 10 to 30% by weight, but it is also possible to use aqueous ammonia outside this range. The amount of ammonia used is 5 to 1 mole of α,α,α-trihalomethylphenyl ester represented by the general formula ().
~300 times by mole, preferably 6 to 200 times by mole.
If the amount of ammonia is small, the yield will decrease, and using too much ammonia is disadvantageous from an industrial standpoint. The reaction temperature is generally -20~200℃, preferably 0
~130℃. If the reaction temperature is higher than the above-mentioned temperature, side reactions will occur, whereas if it is lower than the above temperature, it is undesirable that a long time is required for the reaction to be completed. The reaction time depends on the reaction temperature, but is usually 0.5 to 10
About an hour is enough. In carrying out the process of the present invention, in some cases there may be no reaction at all with the reactant, or during the reaction,
Substantially inert solvents can be used.
Examples of such solvents include hydrocarbons such as hexane, heptane, benzene, toluene and xylene, aromatic hydrocarbons such as chlorobenzene and dichlorobenzene, and ethers such as diphenyl ether. By the method of the present invention, α of the general formula (),
The method of reacting α,α-trihalomethylphenyl esters with ammonia is as follows: 1. A method of adding α,α,α-trihalomethylphenyl of the general formula () to ammonia or aqueous ammonia and allowing the reaction to occur. . 2. A method in which ammonia or aqueous ammonia is added to the α,α,α-trihalomethyl phenyl ester of the general formula () and reacted. 3. A method in which α,α,α-trihalomethyl phenyl esters of the general formula () and ammonia or aqueous ammonia are simultaneously mixed and reacted. etc., and which method to adopt is selected as appropriate. After the reaction is completed, the desired product can be obtained by separating excess ammonia from the reaction mixture, making it acidic using a mineral acid such as hydrochloric acid or sulfuric acid, and extracting with a suitable organic solvent. The hydroxybenzonitrile obtained here has sufficient purity to be used in the next step as it is, but if necessary, it can be further purified and used by distillation, recrystallization or other known methods. The advantages of the method for producing hydroxybenzonitrile by the method of the present invention detailed above are as follows: 1. The reaction temperature proceeds at a relatively low temperature and the operation is simple. 2. The reaction is extremely selective, and highly pure hydroxybenzonitrile can be produced in high yield. This method is extremely advantageous in industrially producing hydroxybenzonitrile compounds compared to conventional methods such as hydroxybenzonitrile. Hereinafter, the method of the present invention will be specifically explained with reference to Examples. Example 1 162 g of 4-methylphenol and 61.2 g of sodium hydroxide were dissolved in 870 g of water, and 1,2-dichloroerthane 545- and 0.86 g of trimethylbenzylammonium chloride were added as a catalyst, and then phosgene gas was added to the solution while stirring. 75 g were introduced over a period of 2 hours and 30 minutes at a temperature of 30°C. After stirring at the same temperature for 30 minutes after the introduction, the aqueous layer was separated.
The organic layer was washed twice with 500 g of water. 1,2-dichloroethane was distilled off from the organic layer under reduced pressure to obtain di(4-
180.5 g of crystals of methylphenyl carbonate were obtained. 48.4 g of the obtained di(4-methylphenyl) carbonate was dissolved in 436 g of carbon tetrachloride, and 98 g of chlorine gas was introduced at 50 to 60° C. over 3 hours and 40 minutes under irradiation with a 100 W high-pressure mercury lamp. Carbon tetrachloride was distilled off from the reaction mixture under reduced pressure to obtain 90.0 g of white crystals of di(4-α,α,α-trichloromethylphenyl)carbonate. Melting point: 98.5-99.5℃, elemental analysis: C13.32%, H1.81%, Cl47.33%, (theoretical value;
C13.38%, H1.79%, Cl47.38%) 45.0 g of di(4-α,α,α-trichloromethylphenyl) carbonate produced as above and 25
Pour 105.0g of ammonia water (wt%) into a stainless steel autoclave equipped with a stirrer, seal it, and heat it at 100℃.
The mixture was heated and stirred for 1 hour to react. Excess ammonia was then separated at the same temperature, cooled, and the reaction mixture was taken out, adjusted to pH 1 with concentrated hydrochloric acid, and extracted twice with 100 ml of ether. The ether layers were combined, dried over magnesium sulfate, the ether was distilled off, and the purity was determined to be 98.0 by gas chromatography analysis.
% 4-hydroxybenzonitrile crystals 23.7g
I got it. The melting point of this substance is 110°C to 113°C,
The elemental analysis values were C70.6%, H4.3%, and N11.7% (theoretical values C70.58%, H4.23%, N11.75%). 4
-Hydroxybenzonitrile di(4-α, α,
The yield based on α-trichloromethylphenyl) carbonate was 97.5%. Example 2 324 g of 3-methylphenol and 10 g of anhydrous aluminum chloride were mixed, and phosphorus oxychloride was added with stirring.
159 g was added while controlling the temperature to be around 30°C. After the addition was completed, the temperature was raised to 80°C to 120°C, and the reaction was carried out while blowing _N2 gas. After the generation of hydrochloric acid gas was no longer observed, the temperature was cooled to 60°C, and 300 g of a 10% by weight NaOH aqueous solution was added once.
It was then washed twice with 500 g of water. The resulting reaction mixture was separated by distillation under a reduced pressure of 5 mmHg at a temperature below 200°C to obtain 347 g of tri(3-methylphenyl) phosphate. Obtained tri(methacresyl) phosphate
73.7g was dissolved in 570g of carbon tetrachloride, 1.4g of α,α'-azobisisobutyronitrile was added as a catalyst, and 179g of chlorine gas was heated at 75°C to 78°C while stirring.
℃ for 5 hours and 30 minutes. Carbon tetrachloride was distilled off under reduced pressure from the reaction product to obtain tri(3-α,
136 g of α,α-trichloromethylphenyl)phosphate were obtained. Elemental analysis value; C37.0%, H1.5
%, Cl47.2% (theoretical value; C37.18%, H1.78%,
Cl47.03%). 67.8 g of tri(3-α,α,α-trichloromethylphenyl)phosphate produced as above,
122 g of liquid ammonia and 5 g of water were placed in a stainless steel autoclave, the autoclave was sealed, and the autoclave was heated and stirred at 100° C. for 1 hour. Next, excess ammonia was separated at the same temperature, and after cooling, the reaction product was poured into 300 g of water, and the same operation as in Example 1 was carried out. As a result, the purity was 98.1 as determined by gas chromatography analysis.
% 3-hydroxybenzonitrile crystals 34.7g
I got it. The melting point of this material is 80°C to 82°C, and the elemental analysis values are C70.5%, H4.20%, N11.5% (theoretical values: C70.58%, H4.23%, N11.76%). It was hot.
3-hydroxybenzonitrile tri(3-α,
The yield based on α,α-trichloromethylphenyl) phosphate was 95.3%. Example 3 Di(2-chloro-4-α,α,α-trichloromethylphenyl)carbonate produced using 2-chloro-4-methylphenol as a starting material and performing the same method and operation as in Example 1 51.8g,
70 g of toluene and 10 g of water were placed in a glass reactor equipped with a gas blowing tube, a stirrer, a thermometer, and a reflux condenser, and 34 g of ammonia gas was added to the reactor at 50°C while stirring.
introduced over time. Next, the reaction mixture after distilling and separating toluene, ammonia, and water was poured into 300 g of water, and the same operation as in Example 1 was performed to determine the purity by gas chromatography analysis.
28.6 g of 98.0% 3-chloro-4-hydroxybenzonitrile was obtained. The melting point of this thing is 152℃~154
℃, and the elemental analysis values are C54.8%, H2.3%, N9.3
%, Cl22.7% (theoretical value; C54.75%, H2.63%,
N9.12%, Cl23.09%). 3-Chlor-4
-Hydroxybenzonitrile di(2-chloro-
The yield based on 4-α,α,α-trichloromethylphenyl) carbonate was 91.3%. Example 4 Using the same equipment as in Example 3, 2-nitro-5
-Produced using the same method and operation as in Example 2 using methylphenol as a starting material. 23.1 g of tri(2-nitro-5-α,α,α-trichloromethylphenyl)phosphate was added little by little to 105 g of 25% by weight aqueous ammonia at 0° C. with stirring over 30 minutes. Thereafter, the temperature inside the reactor was raised from 0°C to 90°C over 3 hours. Thereafter, the same operation as in Example 1 was carried out to obtain 13.1 g of crystals of 3-hydroxy-4-nitrobenzonitrile with a purity of 94.8% as determined by gas chromatography analysis.
I got it. The melting point of this substance is 116°C to 119°C,
The elemental analysis values were C51.9%, H2.3%, N17.3% (theoretical values; C51.23%, H2.46%, N17.06%).
The yield of 3-hydroxy-4-nitrobenzonitrile based on tri(2-nitro-5-α,α,α-trichloromethylphenyl phosphate) is 86.0%.
It was hot. Examples 5 to 19 Various α, α, α- produced in the same manner as in Example 1 using various methylphenols as starting materials.
Table 1 shows the results of reacting trihalomethylphenol carbonate with 25% by weight aqueous ammonia and then carrying out the same operation as in Example 1. In Table 1, all yields are based on α, α, α-trihalomethyl phenyl ester.

【table】

【table】

[Table] Examples 20 to 25 Various α, α, α- produced in the same manner as in Example 2 using various methylphenols as starting materials.
Phosphate esters of trihalomethylphenols
It was reacted with 25% by weight aqueous ammonia, and then the same operation as in Example 1 was performed. The results are shown in Table 2. In Table 2, all yields are based on α, α, α-trihalomethyl phenyl ester.

[Table] Examples 26 to 28 4-α,
Various organic and inorganic acid esters of α,α-trichloromethylphenol were reacted with aqueous ammonia. The results are shown in Table 3. In Table 3, the yields are all 4-α, α, α
-Based on trichloromethyl phenyl ester.

【table】

Claims (1)

[Claims] 1 General formula () [In the formula, R is the same or different, a hydrogen atom,
Halogen atom or nitro group; represents. ] General formula () characterized by reacting α, α, α-trihalomethyl phenyl esters with ammonia or aqueous ammonia [In the formula, R, m and n represent the same meanings as in the general formula (). ] A method for producing hydroxybenzonitrile. 2 It is represented by the general formula (). A method for producing hydroxybenzonitrile according to claim 1, characterized in that α,α,α-trihalomethyl phenyl ester is reacted with ammonia or aqueous ammonia at -20° to 200°C. 3 5 to 1 mole of α, α, α-trihalomethyl phenyl ester represented by the general formula ()
The method for producing hydroxybenzonitrile according to claim 1, characterized in that 300 moles of ammonia or aqueous ammonia is used. 4. Hydroxybenzo according to claim 1, wherein in the general formula (), Y is an acid residue represented by the chemical formula [Formula] [Formula] [Formula] [Formula] or [Formula] Method for producing nitriles.