JP3149985B2 - Method for producing 2,4-dichloro-3-alkyl-6-nitrophenol - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improved method for producing 2,4-dichloro-3-alkyl (excluding ethyl) -6-nitrophenol which is useful as an intermediate of a cyan color former for color photography.

[0002]

2. Description of the Related Art 2,4-Dichloro-3-alkyl-6
As a method for producing nitrophenol, JP-A-63-4455
No. 2 and JP-A-64-47774, 3,5-dichloro-4-ethyl-nitrobenzene is nitrated to give 3,5
A method is described in which -dichloro-4-ethyl-1,2-dinitrobenzene is obtained by hydrolyzing a nitro group at the 2-position with an alkali metal hydroxide.

JP-A-61-60634 discloses that p-alkylnitrobenzene is chlorinated with chlorine to form 2,3,5
-Trichloro-4-alkylnitrobenzene was obtained and hydrolyzed to give 2,4-dichloro-3-alkyl-6-
Methods for obtaining nitrophenol are described.

Japanese Patent Application Laid-Open No. 60-205447 discloses a method of obtaining a 5-alkyl-2-nitrophenol by chlorination with sulfuryl chloride using a catalyst.

JP-A-1-228943 discloses that a p-alkylbenzenesulfonic acid is chlorinated to obtain a 2,3,5-trichloro-4-alkylbenzenesulfonic acid, which is desulfonated and then nitrated to give 2,2 3,5-trichloro-
A method is described in which 4-alkylnitrobenzene is used, and chlorine is hydrolyzed to obtain 4,6-dichloro-3-alkyl-6-nitrophenol.

Japanese Patent Application Laid-Open No. 61-57536 discloses 4-
Chloro-3-ethylphenol or 3-ethylphenol is sulfonated in a halogenated hydrocarbon solvent using an anhydrous sulfuric acid complex or in an excess of concentrated sulfuric acid to give 5-
Chloro-4-ethyl-2-hydroxybenzenesulfonic acid or 4-ethyl-2-hydroxybenzenesulfonic acid, which is chlorinated with chlorine gas or sulfuryl chloride to give 3,5-dichloro-4-ethyl-2- A method is described for obtaining 2,4-dichloro-3-ethyl-6-nitrophenol by obtaining hydroxybenzenesulfonic acid and then replacing the sulfone group with a nitro group with nitric acid.

[0007]

The above-mentioned known methods have various problems to be solved in order to carry out them industrially. For example, 3,5-dichloro-4-alkyl-nitrobenzene In the production of p-alkylnitrobenzene as a starting material, according to a known method, an alkylbenzene is nitrated with a mixed acid, so that the product becomes a mixture of ortho and para isomers. Requires purification and can only be produced in low yields. In addition, isomerization is also generated in dichlorination, and complicated purification is required in practice.

[0008] On the other hand, the method for trichlorinating p-alkyl-nitrobenzene has the same disadvantages as described above.

Furthermore, the method using 5-alkyl-2-nitrophenol as a starting material is not practical because it is difficult to produce this starting material. That is, since nitration of the m-alkylphenol results in a mixture of isomers, a step of removing by-products is required.

Furthermore, the method using p-alkylbenzenesulfonic acid as a starting material also relates to a method using p-alkylbenzenesulfonic acid as a starting material.
When obtaining alkylbenzenesulfonic acid, it is necessary to separate it from the o, m-form. Chlorination is carried out in a large amount of sulfuric acid. However, in the case of industrial production, low volumetric efficiency and sulfuric acid treatment pose problems.

Further, the method using m-alkylphenol as a starting material is not preferable as an industrial production method since the isomer is formed at the time of sulfonation and the yield becomes low.

The method described in JP-A-61-57536 is
This method uses chlorine gas or sulfuryl chloride for chlorination.If chlorine gas is used, it requires special safety equipment due to its properties.If sulfuryl chloride is used, the reagent is expensive. Further, the reaction must be carried out in an organic solvent, which is disadvantageous for implementation on an industrial scale.

The present inventors have been keen to find an industrially advantageous process for producing the desired 2,4-dichloro-3-alkyl (excluding ethyl) -6-nitrophenol.
As a result of the study, the inventors have found a method of the present invention having few of the above problems, and have completed the present invention.

[0014]

SUMMARY OF THE INVENTION The present invention provides 5-chloro-
3,5-dichloro-hydrochlorinating 4-alkyl (excluding ethyl) -2-hydroxybenzenesulfonic acid with hydrogen chloride and hydrogen peroxide in the presence or absence of a catalyst. This is a method for producing 4-alkyl (but excluding ethyl) -2-hydroxybenzenesulfonic acid.

The present invention also relates to a method for producing 5-chloro-4-alkyl (excluding ethyl) -2-hydroxybenzenesulfonic acid by hydrogen chloride and hydrogen peroxide in the presence or absence of a catalyst. 3,5-dichloro-4-
2,4-dichloro-3-alkyl (excluding ethyl), wherein alkyl (excluding ethyl) is 2-hydroxybenzenesulfonic acid, and then the sulfonic acid group is replaced with nitro group using nitric acid. This is a method for producing -6-nitrophenol.

Further, the present invention relates to a method for producing 5-chloro-4-alkyl (excluding ethyl) -2 by sulfonating 4-chloro-3-alkyl (excluding ethyl) phenol with a sulfonating agent. -Hydroxybenzene sulfonic acid, which is then present in the presence or absence of a catalyst,
Chlorinating with hydrogen chloride and hydrogen peroxide to 3,5-dichloro-4-alkyl (excluding ethyl) -2-hydroxybenzenesulfonic acid, and then substituting sulfonic acid groups with nitro groups using nitric acid. 2, characterized by
4-dichloro-3-alkyl (excluding ethyl) -6
-A method for producing nitrophenol.

Furthermore, the present invention relates to a 3,5-dichloro-
4-Alkyl (excluding ethyl) -2-hydroxybenzenesulfonic acid is replaced with 2,4-dichloro-3-alkyl (excluding ethyl) -6- by converting a sulfonic acid group to a nitro group using nitric acid. A method for producing nitrophenol, characterized in that 3,5-dichloro-4-alkyl (excluding ethyl) -2-hydroxybenzenesulfonic acid is dropped into an aqueous nitric acid solution to replace the sulfonic acid group with a nitro group. 2,4-dichloro-3-alkyl (excluding ethyl) -6-nitrophenol.

Furthermore, the present invention relates to a 3,5-dichloro-4
An alkyl (excluding ethyl) -2-hydroxybenzenesulfonic acid aqueous solution and a nitric acid aqueous solution for producing 2,4-dichloro-3-alkyl (excluding ethyl) -6-nitrophenol by a nitration reaction; After the nitration reaction, the resulting filtrate or aqueous layer obtained by filtering or separating 2,4-dichloro-3-alkyl (excluding ethyl) -6-nitrophenol produced is subjected to the above-mentioned 3,5-dichlorophenol. -2-alkyl (excluding ethyl) -2- reused as part or all of the medium for the nitration reaction of hydroxybenzenesulfonic acid and nitric acid
-Dichloro-3-alkyl (excluding ethyl) -6-
This is a method for producing nitrophenol.

Hereinafter, the method of the present invention will be described in more detail. As described above, the process of the present invention comprises three steps of sulfonation, chlorination and nitration, using 4-chloro-3-alkyl (excluding ethyl) phenol as a starting compound. In the process for producing 4-dichloro-3-alkyl (excluding ethyl) -6-nitrophenol, 2,4-dichloro-3-alkyl (excluding ethyl) -6--6 which is particularly characterized in the chlorination step The main feature is a method for producing nitrophenol.

2,4-dichloro-3-object of the present invention
As the alkyl (excluding ethyl) -6-nitrophenol, specifically, 2,4-dichloro-3-methyl-6
-Nitrophenol and 2,4-dichloro-3-isopropyl-6-nitrophenol.

As the hydrogen chloride used in the present invention, an industrially available hydrochloric acid solution is preferably used.
% Hydrochloric acid solution is most preferably used. However, gaseous hydrogen chloride which is customary in the art of this chlorination reaction may also be introduced into the reaction mixture via a suitable distributor.

The hydrogen chloride is used in an amount of 0.9 mol or more, preferably 1 to 10 mol, per mol of 5-chloro-4-alkyl (excluding ethyl) -2-hydroxybenzenesulfonic acid.
Mole, more preferably in the range of 1 to 4.0 mole.

As the hydrogen peroxide used in the present invention, an aqueous solution of hydrogen peroxide is preferably used as in the case of hydrogen chloride, and a 5 to 60% aqueous solution is most preferably used.
In addition, as this hydrogen peroxide, a high concentration, for example, 98% H ₂ O ₂ can be used.

The hydrogen peroxide is usually used in a stoichiometric amount with respect to the hydrogen chloride, but a slightly excessive amount is more preferable. Therefore, the amount of hydrogen peroxide used is in the range of 0.5 to 2 moles, preferably 1 to 1.2 moles, per mole of hydrogen chloride.

In the chlorination reaction of the present invention, a catalyst can be used. Specific examples of the catalyst used include aluminum chloride and ferric chloride. The amount of the catalyst used is in the range of 0.01 to 10% by weight, preferably 0.1 to 3% by weight, based on 5-chloro-4-alkyl (excluding ethyl) -2-hydroxybenzenesulfonic acid.

The chlorination reaction temperature is generally preferably 80 ° C. or lower.

The reaction mixture is diluted with water to give 3,5-dichloro-4-alkyl (excluding ethyl) -2-hydroxybenzenesulfonic acid as an aqueous solution. Most of the impurities are extracted and removed in the oil layer.

The chlorination reaction of the present invention is industrially excellent in that it can be carried out using water as a solvent.

In the method of the present invention, the sulfonation step is not limited. That is, 4-chloro-3-alkyl (excluding ethyl) phenol is sulfonated with a sulfuric anhydride complex, sulfonated with sulfuric acid, or sulfonated with chlorosulfonic acid in an organic solvent. A method of sulfonation using chlorosulfonic acid in an organic solvent is most industrially preferable. The chlorosulfonic acid used is
Usually, a substance having a purity of 95 to 99.5% is used. The amount of the phenol used is, for example, 0.9 to 1.4 times, preferably 0.95 to 1.20 times, that of 4-chloro-3-alkyl (excluding ethyl) phenol. It is.

Here, as the organic solvent, halogenated hydrocarbons (for example, methylene chloride, chloroform, carbon tetrachloride, dichloroethylene, dichloroethane, trichloroethylene, trichloroethane, tetrachloroethylene,
Tetrachloroethane, dibromoethane, chlorobenzene, o-dichlorobenzene, etc.), nitrated hydrocarbons (nitrobenzene, o-nitrotoluene, etc.), or aromatic hydrocarbons (toluene, xylene, t-butylbenzene, etc.) are used. The reaction temperature of the sulfonation is 0
-80 ° C, preferably 10-50 ° C.

The thus obtained 5-chloro-4-alkyl (excluding ethyl) -2-hydroxybenzenesulfonic acid is then chlorinated by the method of the present invention to give 3,5
-Dichloro-4-alkyl (excluding ethyl) -2-
It can lead to hydroxybenzene sulfonic acid.

In this chlorination reaction, it has been found that a method using hydrogen chloride and hydrogen peroxide is the most excellent industrially. Further, it has been found that it is preferable to use a sulfonic acid solubilizing solvent such as acetic acid for dissolving, for example, 5-chloro-4-alkyl (excluding ethyl) -2-hydroxybenzenesulfonic acid.

The chlorination reaction of the present invention is particularly industrially superior in that it can be carried out using water as a solvent, but this is the case in the case of the method of sulfonation using chlorosulfonic acid. There is an advantage that chlorination can be carried out in an aqueous solvent without isolating the sulfonic acid by using the aqueous layer after pouring into water after sulfonation.

The thus obtained 3,5-dichloro-4-alkyl (excluding ethyl) -6-hydroxybenzenesulfonic acid is then nitrated with nitric acid to give the desired 2,2 4-Dichloro-3-alkyl (excluding ethyl) -6-nitrophenol can be produced.

The nitration reaction is usually carried out by adding nitric acid dropwise to an aqueous solution of 3,4-dichloro-4-alkyl (excluding ethyl) -2-hydroxybenzenesulfonic acid obtained by the chlorination reaction. .

The present inventors have reported that the so-called nitration reaction of the present invention for substituting a sulfonic acid group with a nitro group is carried out by adding a 3,5-dichloro-4-alkyl (excluding ethyl) -2-hydroxy compound in an aqueous nitric acid solution. It has been found that, by dropping an aqueous solution of benzenesulfonic acid, the induction period can be shortened, so that the safety can be significantly improved and the yield can be significantly improved.

The concentration of the nitric acid used is not particularly limited, but is preferably in the form of a 2-70% by weight aqueous nitric acid solution.

The amount of nitric acid used is 0.9 mol or more, preferably 1 mol, per mol of 3,5-dichloro-4-alkyl (excluding ethyl) -2-hydroxybenzenesulfonic acid.
The range is from 10 to 10 mol, and more preferably from 1 to 4 mol.
The temperature of the nitration reaction is usually 80 ° C. or lower, preferably 60 ° C. or lower.

The objective compound of the present invention, for example, 2,4-dichloro-3-methyl-6-nitrophenol can be easily obtained by filtering the crystals after the reaction. If necessary, before filtration, aromatic hydrocarbons such as benzene, toluene, xylene, monochlorobenzene and orthodichlorobenzene, chloroform, methylene chloride, ethane dichloride,
It can be extracted with a solvent such as chlorinated hydrocarbons such as ethane trichloride to remove water-soluble impurities. It is also possible to wash or recrystallize using alcohols such as methanol and isopropanol.

The present inventors have found that a 3,5-dichloro-4-alkyl (excluding ethyl) -2-hydroxybenzenesulfonic acid aqueous solution and a nitric acid aqueous solution are subjected to nitration reaction.
In producing 2,4-dichloro-3-ethyl-6-nitrophenol, after the nitration reaction, the resulting 2,4-dichloro-3-alkyl (excluding ethyl) -6-nitrophenol is filtered or The filtrate or the aqueous layer obtained by the separation is subjected to part or all of the medium for the nitration reaction between the 3,5-dichloro-4-alkyl (excluding ethyl) -2-hydroxybenzenessulfonic acid and nitric acid. It has been found that by reusing as, the induction period can be shortened, so that the safety can be remarkably improved and the yield can be remarkably improved.

In the nitration reaction of the present invention, the filtrate or aqueous layer to be reused may be an aqueous solution of nitric acid and an aqueous solution of 3,4-dichloro-4-alkyl (excluding ethyl) -2-hydroxybenzene, or both. It can be contained in one side.

The concentration of nitric acid in the aqueous nitric acid solution in the nitration reaction of the present invention is not particularly limited, but usually a form of 2 to 70% by weight is most preferably used.

[0043]

According to the method of the present invention, for example, 4-chloro-3-alkyl (excluding ethyl) phenol is converted to 5-chloro-4-alkyl (excluding ethyl) phenol-2-hydroxybenzenesulfone. Acid and 3,5
-Dichloro-4-alkyl (excluding ethyl) -2-
Via hydroxybenzenesulfonic acid, the desired 2,4
-Dichloro-3-alkyl (excluding ethyl) ethyl-6-nitrophenol can be produced industrially and advantageously with high purity and high yield safely.

[0044]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 Into a 1 L glass four-necked flask, 4-chloro-3 was added.
-100 g of methylphenol, 250 g of dichloromethane
Add and dissolve. While maintaining the temperature at 25 to 30 ° C, 80 g of chlorosulfonic acid is added dropwise. After keeping the temperature at the same temperature for 3 hours, 200 g of water is added dropwise while cooling with ice water.

Next, 133 g of 35% hydrochloric acid was added, and the temperature was reduced to 3%.
While maintaining the temperature at 0 ° C., 93 g of 35% hydrogen peroxide solution is added dropwise.
After maintaining at the same temperature for 8 hours, the oil layer is separated. 115 g of 70% nitric acid is charged into a two-liter glass four-necked flask, and the separated aqueous layer is added dropwise while maintaining the temperature at 30 to 35 ° C. After keeping at the same temperature for 1 hour, the mixture is cooled to 15 ° C. and filtered. After washing with water and drying, 2,4-dichloro-3-methyl-6-nitrophenol is obtained. Yield: 132 g (Yield: 85% based on 4-chloro-3-methylphenol) Melting point: 82 to 84 ° C

Example 2 The procedure of Example 1 was repeated, except that 4-chloro-3-isopropylphenol was used as a starting material, except that the desired 2,4-dichloro-3-isopropyl-6 was used.
-Nitrophenol is obtained. Yield; 75% based on 4-chloro-3-isopropylphenol Melting point: 86-88 ° C

Example 3 100 g of 4-chloro-3-methylphenol and 200 g of monochlorobenzene were placed in a 1 L glass four-necked flask and dissolved. While maintaining the temperature at 60 to 65 ° C, 90 g of chlorosulfonic acid is added dropwise. After keeping it at the same temperature for 3 hours,
75.1 g of acetic acid are added. After adding 1.2 g of aluminum chloride and 0.6 g of sulfur chloride, 100 g of sulfuryl chloride is added dropwise at 25 to 30 ° C. After completion of the dropwise addition, the temperature is raised to 35 ° C., and the temperature is kept at that temperature for 5 hours. Water 9 in a 2L flask
60 g are charged, into which the reaction mass is poured under stirring of water. Since the water layer and the oil layer are separated, the lower oil layer is removed.

After cooling the aqueous layer to 20 ° C., it is added dropwise to 168 g of 70% nitric acid while maintaining the temperature at 20 to 25 ° C. After completion of the dropping, the temperature is raised to 45 ° C., and the temperature is kept at that temperature for 4 hours. Cool to 20 ° C. and filter. The desired 2,4-dichloro-3-methyl-6-nitrophenol is obtained by washing with water and drying. Yield: 108 g (Yield; 69% based on 4-chloro-3-methylphenol) Melting point: 85 to 87.7 ° C

Example 4 The procedure of Example 1 was repeated, except that 1,2-dichloroethane was used instead of monochlorobenzene as the solvent, to obtain the desired 2,4-dichloro-3-methyl-
6-Nitrophenol is obtained. Yield: 139 g (yield; 89% based on 4-chloro-3-methylphenol)

Example 5 3,5-Dichloro-4 obtained by the method described in Example 1
The same procedure as in Example 1 was carried out except that a 50% aqueous solution of nitric acid was added dropwise to the aqueous solution of -methyl-2-hydroxybenzenesulfonic acid to obtain the desired 2,4-dichloro-3-methyl-6-nitrophenol. can get. Yield: 119 g (yield; 76% based on 4-chloro-3-methylphenol)

──────────────────────────────────────────────────続 き Continuing on the front page (72) Osamu Kimura Inventor Koji Ito, Examiner, Taoka Chemical Industry Co., Ltd. 4-2-1-11 Nishimikuni, Yodogawa-ku, Osaka (56) References JP-A-61-57536 (JP, A) JP-A-62-223140 (JP, A) JP-A-57-64646 (JP, A) JP-B-53-41138 (JP, B1) (58) Fields investigated (Int. Cl. ⁷ , DB name) ) C07C 205/26 C07C 201/10 C07C 309/39

Claims (14)

(57) [Claims] 1. A method for chlorinating 5-chloro-4-alkyl (excluding ethyl) -2-hydroxybenzenesulfonic acid with hydrogen chloride and hydrogen peroxide in the presence or absence of a catalyst. 3,5-dichloro-4-characteristic
A method for producing an alkyl (excluding ethyl) -2-hydroxybenzenesulfonic acid. 2. Chlorination of 5-chloro-4-alkyl (excluding ethyl) -2-hydroxybenzenesulfonic acid with hydrogen chloride and hydrogen peroxide in the presence or absence of a catalyst to give 3,3 2,4-dichloro-3-alkyl, which is 5-dichloro-4-alkyl (excluding ethyl) -2-hydroxybenzenesulfonic acid, and then the sulfonic acid group is replaced with a nitro group using nitric acid. (However, except for ethyl) A method for producing 6-nitrophenol. 3. A 4-chloro-3-alkyl (excluding ethyl) phenol is sulfonated with a sulfonating agent to give a 5-chloro-4-alkyl (excluding ethyl) phenol.
2-hydroxybenzenesulfonic acid, which is then chlorinated with hydrogen chloride and hydrogen peroxide in the presence or absence of a catalyst to give 3,5-dichloro-4-alkyl (excluding ethyl) -2- A method for producing 2,4-dichloro-3-alkyl (excluding ethyl) -6-nitrophenol, which comprises converting hydroxysulfonic acid to a nitro group using nitric acid and then nitric acid. 4. The method according to claim 1, wherein the chlorination is carried out in an aqueous solvent.
The method according to claim 3. 5. The method according to claim 4, wherein the hydrogen chloride is used in the form of a hydrochloric acid solution. 6. The method according to claim 5, wherein the hydrochloric acid solution is a 5% to 38% hydrochloric acid solution. 7. The method according to claim 4, wherein the hydrogen peroxide is used in the form of an aqueous hydrogen peroxide solution. 8. The method according to claim 7, wherein the aqueous hydrogen peroxide solution is a 5-70% H ₂ O ₂ aqueous solution. 9. The method according to claim 1, wherein aluminum chloride or ferric chloride is used as the chlorination catalyst. 10. The method according to claim 1, wherein 3,5-dichloro-4-alkyl (excluding ethyl) -2-hydroxybenzenesulfonic acid is dropped into an aqueous nitric acid solution to replace the sulfonic acid group with a nitro group. The method for producing 2,4-dichloro-3-alkyl (excluding ethyl) -6-nitrophenol according to any one of claim 2 or claim 3. 11. The nitric acid aqueous solution having a nitric acid concentration of 2 to 70% by weight.
11. The method according to claim 10, wherein 12. A 2,5-dichloro-3-alkyl (excluding ethyl) by a nitration reaction between a 3,5-dichloro-4-alkyl (excluding ethyl) -2-hydroxybenzenesulfonic acid aqueous solution and a nitric acid aqueous solution. To produce -6-nitrophenol after the nitration reaction.
2,4-dichloro-3-alkyl (excluding ethyl)-
The filtrate or the aqueous layer obtained by filtering or separating 6-nitrophenol is subjected to a nitration reaction between the 3,5-dichloro-4-alkyl (excluding ethyl) -2-hydroxybenzenesulfonic acid and nitric acid. 4. The production of 2,4-dichloro-3-alkyl (excluding ethyl) -6-nitrophenol according to claim 2 or 3, which is reused as part or all of the medium. Method. 13. A 3,5-dichloro-4-alkyl (excluding ethyl) -2-hydroxybenzenesulfonic acid,
The sulfonic acid group is replaced with a nitro group using nitric acid to give 2,4
-Dichloro-3-alkyl (excluding ethyl) -6-
A method for producing nitrophenol, characterized in that 3,5-dichloro-4-alkyl (excluding ethyl) -2-hydroxybenzenesulfonic acid is dropped into an aqueous nitric acid solution to replace the sulfonic acid group with a nitro group. 2, 4
-Dichloro-3-alkyl (excluding ethyl) -6-
Method for producing nitrophenol. 14. A 2,5-dichloro-3-alkyl (excluding ethyl) by a nitration reaction between a 3,5-dichloro-4-alkyl (excluding ethyl) -2-hydroxybenzenesulfonic acid aqueous solution and a nitric acid aqueous solution. To produce -6-nitrophenol after the nitration reaction.
2,4-dichloro-3-alkyl (excluding ethyl)-
The filtrate or the aqueous layer obtained by filtering or separating 6-nitrophenol is subjected to a nitration reaction between the 3,5-dichloro-4-alkyl (excluding ethyl) -2-hydroxybenzenesulfonic acid and nitric acid. A method for producing 2,4-dichloro-3-alkyl (excluding ethyl) -6-nitrophenol, which is reused as part or all of a medium. [0001]