JPH03291241A - Production of 2,6-dichloro-substituted phenol - Google Patents

Abstract

PURPOSE:To obtain the title compound useful as an intermediate for agricultural chemical in high purity and in high yield while suppressing formation of by- products, by reacting a p-substituted phenol and/or a 2-chloro-4-substituted phenol with chlorine in an acidic solution having a specific water content. CONSTITUTION:A p-substituted phenol and/or a 2-chloro-4-substituted phenol is reacted with chlorine in an acidic solution having <=15wt.% water content, preferably a liquid acid (e.g. sulfuric acid, phosphoric acid, polyphosphoric acid or acetic acid) not containing water at all, at 0-120 deg.C under <=10kg/cm<2> pressure to give a 2-chloro-4-substituted phenol and a 2,6-dichloro-4-substituted phenol having <1.0wt.% content of resinous substance. Carboxyl group, nitro group, sulfonic group, cyano group, chlorosulfonyl group, chlorocarbonyl group, sulfoamoyl group, carbamoyl group, amino group or halogen atom may be cited as the substituent group of the compound.

Description

[Detailed description of the invention]

[0001] rIndustrial Application Field The present invention relates to p-substituted phenols and/or 2-chloro-
Chlorinating 4-substituted phenols to produce 2- and/or 2-chloro-4-substituted phenols such as 2- and/or 2-chloro-4-ditrophenol useful as agricultural chemical intermediates, etc. Regarding the method. [0002]

[Conventional technology]

2. and/or 2-chloro-4-substituted phenol, such as 2- and/or 2-chloro-4-ditrophenol, can be produced by (1) nitrating 2,6-dichlorophenol with nitric acid; The conventional method (2) is: ■Method of introducing chlorine in hydrochloric acid (4diF 1986-5)
6939), ■ Method of adding hydrogen peroxide in hydrochloric acid (Japanese Patent Publication No. 57-48137), ■ Introducing chlorine in aliphatic halogenated hydrocarbons such as carbon tetrachloride, methylene chloride, chloroform, dichloroethane, etc. Method (Unexamined Japanese Patent Publication No. 5
6-90041, Japanese Patent Application Laid-Open No. 57-70840), A method of reacting an acidic substance with hypochlorous acid and/or hypochlorite (Japanese Patent Laid-Open No. 62-181240), ■ In water A method of acting hypochlorous acid and/or its salt in the presence of a dispersant and/or a Lewis acid (Japanese Unexamined Patent Application Publication No. 1983-1999)
-175429), (2) A method of introducing chlorine in a molten state in the presence of an amine (I# JP-A-63-230660), and the like are known. [0003]

[Problem to be solved by the invention]

In the case of pesticides, if the by-products are 1% by weight or more, teratogenicity tests, toxicity tests, etc. of the compound are required, so pesticide intermediates tend to be required to be highly pure [000
4] However, in the prior art methods, both 2. and/or the purity of 2-chloro-4-ditrophenol is 9
5% by weight or less, and in order to achieve the desired purity,
This required an economically disadvantageous recrystallization operation. [0005] In addition, the above method (1) of nitrating 2,6-dichlorophenol has the problem that 2,6-dichlorophenol is expensive, resulting in high production costs; In the method (2), in the method (1) described in JP-A No. 60-56939 and the method (2) described in JP-A-63-230660, a large amount of resinous substance is produced as a by-product. Therefore, the yield will be low,
■The method described in Japanese Patent Publication No. 57-48137, ■The method described in Japanese Patent Application Laid-Open No. 62-181240, and ■
In the method described in JP-A-62-175429,
The oxidation reaction produces a large amount of 2- and/or 2-chloro-p-benzoquinone, resulting in a low yield, and the need to use a peroxide with a high risk of explosion. Publication No. 56-90041 and Japanese Unexamined Patent Publication No. 1983
The method described in Publication No. 7-70840 had problems such as the need to use a highly toxic solvent [0006]

[Means to solve the problem]

In order to solve these problems, the present inventors have conducted extensive research into methods for producing 2- and/or 2-chloro-4-substituted phenol, particularly 2- and/or 2-chloro-4-ditrophenol. As a result, when an acidic liquid containing a large amount of water, such as hydrochloric acid, is used, a large amount of resinous substances are produced as by-products, resulting in a decrease in yield and purity. When p-nitrophenol and/or 2-chloro-4-ditrophenol is reacted with chlorine, the content of undesirable 2-chloro-4-ditrophenol and resinous substances is reduced to 1.0. 2, and/or 2-chloro-4-ditrophenol can be safely produced with high purity, high yield, and simple operation. It was discovered that the produced scales and this method are also effective for chlorinating other 4-substituted phenols, leading to the completion of the present invention. [0007] That is, the present invention provides p-substituted phenol and/or 2-chloro-4
- It relates to a method for producing a 2- and/or 2-chloro-4-substituted phenol by reacting a substituted phenol with chlorine. [0008] The acidic liquid used in the present invention may have a water content of 15% by weight or less, but liquid acids containing no water at all are preferred, such as sulfuric acid, sulfuric anhydride, phosphoric acid, etc. , polyphosphoric acid, acetic acid, formic acid, etc., among which sulfuric acid is particularly preferred. [0009] The p-substituted phenol and/or 2-chloro-4-substituted phenol used in the present invention may be a substituent that is not chlorinated in the production method of the present invention, such as a carboxyl group, a nitro group, or a sulfone group. Examples include those having an acid group, a cyano group, a chlorosulfonyl group, a chlorocarbonyl group, a sulfamoyl group, a carbamoyl group, an amino group, or a halogen atom. Usually p-nitrophenol and/or 2-chloro-4-ditrophenol, or p-aminophenol and/or 4-amino-2-
Use chlorophenol. Alternatively, an amine salt obtained by neutralizing p-aminophenol and/or 4-amino-2-chlorophenol with an acidic liquid in advance can also be used. [0010] In addition, the amount of acidic liquid used is
Or, it is usually 5 to 20 parts by weight per 1 part by weight of 2-chloro-4-substituted phenol. Chlorine can be gaseous or liquid, but
Usually, a gaseous substance is used. [0011] Since the chlorination reaction is an exothermic reaction, it is necessary to cool it and maintain the temperature within a predetermined range. The reaction is 0-1
It is carried out at a temperature of 20°C. 2. Below 0℃. and/or the production rate of 2-chloro-4-ditrophenol is low, and 2. This is because it involves the decomposition of and/or 2-chloro-4-ditrophenol. [0012] The reaction is carried out under normal pressure or under pressure using chlorine gas. In the case of pressurization, 10 kg/cm2 or less is usually sufficient. If the weight exceeds 10kg/cm2, equipment costs will increase.
Economically unfavorable. [0013] The reaction time varies depending on the temperature, pressure, chlorine supply rate, and concentration of p-nitrophenol and/or 2-chloro-4-ditrophenol during the reaction, but is usually 5 to 20 hours. It is enough. When the raw material is p-nitrophenol, as the reaction progresses, p-nitrophenol becomes 2-chloro-4-ditrophenol, and then 2.
and/or 2-chloro-4-ditrophenol. [0014] After the chlorination is completed, chlorine and hydrogen chloride are removed with nitrogen, the reaction product is filtered, thoroughly washed with water, and then dried at a temperature of 40 to 100°C. In this way, 2, and/or 2-
Needle-shaped crystals of chloro-4-ditrophenol are obtained. 2 and/or from infrared absorption spectroscopy.
or 2-chloro-4-ditrophenol. [0015]

【Example】

The present invention will be specifically explained below by giving Examples and Comparative Examples. In addition, % in an example is weight %. [0016] Example 1 1 with stirrer, thermometer, cooling tube and chlorine supply conduit
750 g of concentrated sulfuric acid and 83 g (0.6 mol) of p-nitrophenol were weighed into a 0100O four-bottle flask. 50g (0.7 mol) of chlorine gas at 30℃ with stirring
was supplied over 4 hours. During this time, heat generation was significant, so the reaction temperature was kept at a temperature not exceeding 30° C. while cooling. Further, 71 g (1.0 mol) of chlorine gas was supplied at 50° C. over 6 hours, and after aging at 50° C. for 2 hours, cooling was performed. [0017] Next, nitrogen gas was supplied for 1 hour to remove chlorine and hydrogen chloride. This reaction product was filtered, thoroughly washed with water, and then dried to obtain 114 g of yellow needle-like crystals of 2- and/or 2-chloro-4-ditrophenol. The yield was 92% based on p-nitrophenol. The melting point was 123°C, and it was confirmed by infrared absorption spectroscopy that it was 2- and/or 2-chloro-4-ditrophenol. As a result of high performance liquid chromatography analysis, the purity was 99.
It was 4%. [0018] Example 2 1 with stirrer, thermometer, cooling tube and chlorine supply conduit
60% oleum in a 000ml four-bottle flask 750ml
g and 104 g of 2-chloro-4-nitrophenol (0
, 6 mol) was weighed out. While stirring, 71 g of chlorine gas (1.0 mol JP-A-3-291241 (7)) was supplied over 10 hours at 40°C, and after aging at 40°C for 2 hours, cooling was performed. [0019] Next, nitrogen gas was supplied for 1 hour to remove chlorine and hydrogen chloride. The reaction product was filtered, thoroughly washed with water, and dried to obtain 115 g of 2,6-diku01nia-4-:)0 phenol in the form of yellow needles. The yield is 2-
It was 93% based on chloro-4-ditrophenol. The melting point was 123°C, and it was confirmed by infrared absorption spectroscopy that it was 2- and/or 2-chloro-4-ditrophenol. As a result of high performance liquid chromatography analysis, the purity was 99.4%. [0020] Example 3 10100 with stirrer, thermometer and chlorine supply conduit
600 g of polyphosphoric acid and 52 g (0.3 mol) of 2-chloro-4-nitrophenol were weighed into a four-bottle flask. While stirring, add 36 g of chlorine gas (0,5
mol) was supplied over 12 hours, aged at 60°C for 2 hours, and then cooled. [00213 Nitrogen gas was then supplied for 1 hour to remove chlorine and hydrogen chloride. The reaction product was filtered, thoroughly washed with water, and dried to produce yellow needle-like crystals. and/or 2-
57 g of chloro-4-ditrophenol was obtained. The yield is
91% based on 2-chloro-4-ditrophenol
Met. The melting point was 123°C, and it was confirmed by infrared absorption spectroscopy that it was 2- and/or 2-chloro-4-ditrophenol. As a result of high performance liquid chromatography analysis, the purity was 99.5%. [0022] Example 4 1 with stirrer, thermometer, cooling tube and chlorine supply conduit
600 g of phosphoric acid and 42 g (0.3 mol) of p-nitrophenol were weighed into a 0100O four-bottle flask. 28 g (0.4 mol) of chlorine gas at 40°C with stirring
was supplied over 4 hours. During this time, since significant heat generation occurred, cooling was performed to prevent the reaction temperature from exceeding 40°C. Furthermore, 341
- JP-A-3-291241 (8) After aging at 60° C. for 2 hours, cooling was performed. [0023] Next, nitrogen gas was supplied for 1 hour to remove chlorine and hydrogen chloride. The reaction product was filtered, thoroughly washed with water, and dried to form yellow needle-like crystals of 2 and/or 2-
58g of chloro-4-ditrophenol was obtained. The yield is
92% based on 2-chloro-p-nitrophenol
Met. The melting point was 123°C, and it was confirmed by infrared absorption spectroscopy that it was 2- and/or 2-chloro-4-ditrophenol. As a result of high performance liquid chromatography analysis, the purity was 99.4%. [0024] Example 5 1 with stirrer, thermometer, cooling tube and chlorine supply conduit
400 g of glacial acetic acid and p-
140 g (1.0 mol) of nitrophenol was weighed out. While stirring, 78 g (1.1 mol) of chlorine gas was fed at 10° C. over a period of 2 hours. During this time, since heat generation was significant, the reaction temperature was kept from exceeding 15° C. while being cooled. Furthermore, 85g of chlorine gas (1,2
mol) was supplied over 6 hours and aged at 15°C for 2 hours. [0025] Next, nitrogen gas was supplied for 1 hour to remove chlorine and hydrogen chloride. The reaction product was filtered, thoroughly washed with water, and dried to produce yellow needle-like crystals. and/or 2-
189g of chloro-4-ditrophenol was obtained. The yield was 91% based on p-nitrophenol. The melting point was 123°C, and it was confirmed by infrared absorption spectroscopy that it was 2- and/or 2-chloro-4-ditrophenol. As a result of high performance liquid chromatography analysis, the purity was 99.5%. [0026] Example 6 1 with stirrer, thermometer, cooling tube and chlorine supply conduit
While stirring, 50 g (0.7 mol) of chlorine gas was added to a pressurized reactor at 15°C at a pressure of 2 kg/cm2 at a gauge pressure of 2 kg/cm2, while stirring to ensure that the reaction temperature did not exceed 15°C. I made it. Further, 71 g (1.0 mol) of chlorine gas was supplied at 35° C. under a constant gauge pressure of 4 kg/cm 2 over 6 hours, and after aging at 35° C. for 2 hours, cooling was performed. [0027] After returning to normal pressure, nitrogen gas was supplied for 1 hour to remove chlorine and hydrogen chloride. The reaction product was filtered, thoroughly washed with water, and dried to produce yellow needle-like crystals of 2 and/or
Alternatively, 119 g of 2-chloro-4-ditrophenol was obtained. The yield was 96% based on p-nitrophenol. The melting point was 123°C, and it was confirmed by infrared absorption spectroscopy that it was 2- and/or 2-chloro-4-ditrophenol. As a result of high performance liquid chromatography analysis, the purity was 99.7%. [0028] Example 7 1 with stirrer, thermometer, cooling tube and chlorine supply conduit
700 g of phosphoric acid and 42 g (0.3 mol) of p-nitrophenol were weighed into a pressurized reactor at 0.0100 O. While stirring, add 36 g (0.5 mol) of chlorine gas at 15°C.
It was supplied over a period of 2 hours under a constant pressure of 3 kg/cm2 gauge pressure. During this time, since heat generation was significant, the reaction temperature was kept from exceeding 15° C. while being cooled. Furthermore, 3
50 g (0.7 mol) of chlorine gas at 5°C, gauge pressure 4
Supplied over 6 hours under a constant pressure of kg/cm2,
After aging at 35° C. for 2 hours, cooling was performed. [0029] After returning to normal pressure, nitrogen gas was supplied for 1 hour to remove chlorine and hydrogen chloride. The reaction product was filtered, thoroughly washed with water, and dried to produce yellow needle-like crystals of 2 and/or
Alternatively, 59 g of 2-chloro-4-ditrophenol was obtained. The yield was 94% based on p-nitrophenol. The melting point is 123°C, and it is determined by infrared absorption spectroscopy to be 2. and/or 2-chloro-4-ditrophenol. As a result of high performance liquid chromatography analysis, the purity was 99.6%. [0030] Example 8 300 g of formic acid and 209 g of p-nitrophenol (1
, 5 mol) was weighed out. While stirring, 113 g (1.6 mol) of chlorine gas was added at 15°C at a gauge pressure of 1 kg/cm.
The mixture was fed under a constant pressure of 2 over a period of 3 hours. During this time, since heat generation was significant, the reaction temperature was kept from exceeding 15° C. while being cooled. Furthermore, at 15°C, chlorine gas 121
g (1.7 mol) was supplied over 5 hours under a constant gauge pressure of 2 kg/cm 2 and ripened at 15° C. for 2 hours. [0031] After returning to normal pressure, nitrogen gas was supplied for 1 hour to remove chlorine and hydrogen chloride. The reaction product was filtered, thoroughly washed with water, and dried to produce yellow needle-like crystals of 2 and/or
Alternatively, 294 g of 2-chloro-4-ditrophenol was obtained. The yield was 94% based on p-nitrophenol. The melting point was 123°C, and it was confirmed by infrared absorption spectroscopy that it was 2- and/or 2-chloro-4-ditrophenol. As a result of high performance liquid chromatography analysis, the purity was 99.6%. [0032] Example 9 1 with stirrer, thermometer, cooling tube and chlorine supply conduit
750 g of concentrated sulfuric acid and 83 g (0.6 mol) of p-hydroxybenzoic acid were weighed into a 0.0100 O four-bottle flask. While stirring, 50 g (0.7 mol) of chlorine gas was fed over 4 hours at 30°C. During this time, since heat generation was significant, the reaction temperature was kept from exceeding 30° C. while cooling. Further, 71 g (1.0 mol) of chlorine gas was supplied at 60° C. over 6 hours, and after aging at 70° C. for 2 hours, cooling was performed. [0033] Next, nitrogen gas was supplied for 1 hour to remove chlorine and hydrogen chloride. This reaction product was filtered, thoroughly washed with water, and dried to form white crystals of 2 and/or 2-
113 g of chloro-4-carboxyphenol was obtained. The yield was 92% based on p-hydroxybenzoic acid. The melting point was 257°C, and it was confirmed by infrared absorption spectroscopy that it was 2- and/or 2-chloro-4-carboxyphenol. As a result of high performance liquid chromatography analysis, the purity was 99.1%. [0034] JP-A-3-291241 (11) Example 10 1 equipped with a stirrer, thermometer, cooling pipe and chlorine supply conduit
750 g of concentrated sulfuric acid and 71 g (0.6 mol) of p-hydroxybenzonitrile were weighed into a 0100O four-bottle flask. While stirring, add 50 g of chlorine gas (0,7
mol) was fed over 4 hours. During this time, since heat generation was significant, the reaction temperature was kept from exceeding 30° C. while cooling. Furthermore, 71g of chlorine gas (1,0
mol) was supplied over 6 hours, and after aging at 70°C for 2 hours,
Cooling was performed. [0035] Next, nitrogen gas was supplied for 1 hour to remove chlorine and hydrogen chloride. This reaction product was filtered, thoroughly washed with water, and dried to form white crystals of 2 and/or 2-
100g of chloro-4-cyanophenol was obtained. The yield was 90% based on p-hydroxybenzonitrile. The melting point was 145°C, and it was confirmed by infrared absorption spectroscopy that it was 2- and/or 2-chloro-4-cyanophenol. As a result of high performance liquid chromatography analysis, the purity was 99.1%. [0036] Example 11 1 with stirrer, thermometer, cooling tube and chlorine supply conduit
675 g of concentrated sulfuric acid and 7 g of water in a 000 ml four-bottle flask
5 g and 83 g (0.6 mol) of p-nitrophenol were weighed out. While stirring, add 50g of chlorine gas (
0.7 mol) was fed over 4 hours. During this time, since heat generation was significant, the reaction temperature was kept from exceeding 30° C. while cooling. Furthermore, 71g of chlorine gas (
1.0 mol) was supplied over 6 hours, and after aging at 60° C. for 2 hours, cooling was performed. [0037] Next, nitrogen gas was supplied for 1 hour to remove chlorine and hydrogen chloride. This reaction product was filtered, thoroughly washed with water, and dried to produce yellow needle-like crystals. and/or 113 g of 2-chloro-4-ditrophenol. The yield was 91% based on p-nitrophenol. The melting point was 122°C, and it was confirmed by infrared absorption spectroscopy that it was 2- and/or 2-chloro-4-ditrophenol. As a result of high performance liquid chromatography analysis, the purity was 99.
It was 2%. 345- [0038] Example 12 1 with stirrer, thermometer, cooling tube and chlorine supply conduit
700g of concentrated sulfuric acid and 50g of water in a 000ml pressurized reactor
and 87 g (0.8 mol) of p-aminophenol were weighed out. While stirring, 78 g (1.1 mol) of chlorine gas was added at 0°C under a constant pressure of 2 kg/cm2 gauge pressure for 30 minutes.
Supplied over time. During this time, since heat generation was significant, the reaction temperature was kept not to exceed 2° C. while cooling. Further, 85 g (1.2 mol) of chlorine gas was supplied at 2° C. under a constant gauge pressure of 3 kg/cm 2 over 6 hours, and aging was carried out at 5° C. for 2 hours. [0039] After returning to normal pressure, nitrogen gas was supplied for 1 hour to remove chlorine and hydrogen chloride. This reaction product was poured into ice water, neutralized with an aqueous sodium hydroxide solution, and then filtered. After thorough washing with water and drying, 135 g of 4-amino-2,6-dichlorophenol in the form of white needle-like crystals was obtained. The yield was 95% based on p-aminophenol. The melting point was 160°C, and it was confirmed by infrared absorption spectroscopy that it was 4-amino-2,6-dichlorophenol. As a result of high performance liquid chromatography analysis, the purity was 99.7%. [00403 Example 13 1 with stirrer, thermometer, cooling tube and chlorine supply conduit
750 g of concentrated sulfuric acid and 87 g (0.8 mol) of p-aminophenol were weighed into a pressurized reactor at 0100O. While stirring, 78 g (1.1 mol) of chlorine gas was supplied at 2° C. under a constant gauge pressure of 2 kg/cm 2 over a period of 3 hours. During this time, since heat generation was significant, the reaction temperature was kept below 5° C. while cooling. Furthermore, 85 g (12 moles) of chlorine gas was added at 2°C at a gauge pressure of 3 kg/cm.
The mixture was fed under a constant pressure of 2 over 5 hours, and aged at 10° C. for 2 hours. [00413 After returning to normal pressure, nitrogen gas was supplied for 1 hour to remove chlorine and hydrogen chloride.
) passed. After thorough washing with water and drying, 136 g of 4-amino-2,6-dichlorophenol in the form of white needle-like crystals was obtained. Yield is 96% based on p-aminophenol
Met. The melting point was 160°C, and it was confirmed by infrared absorption spectroscopy that it was 4-amino-2,6-dichlorophenol. As a result of high performance liquid chromatography analysis, the purity was 99.5%. [0042] Comparative Example 1 1 with stirrer, thermometer, cooling tube and chlorine supply conduit
700 g of methylene chloride in a 000 ml four-neck flask
, 56 g (0.4 mol) of p-nitrophenol, and 2.5 g of aluminum chloride were weighed out. While stirring, 30
36 g (0.5 mol) of chlorine gas were fed over a period of 6 hours. During this time, since heat generation was significant, the reaction temperature was kept from exceeding 30° C. while cooling. Furthermore, 40
57 g (0.8 mol) of chlorine gas while refluxing at °C.
was fed over 12 hours, aged at 40° C. for 4 hours, and then cooled. [0043] Next, nitrogen gas was supplied for 1 hour to remove chlorine and hydrogen chloride. The reaction product was filtered, thoroughly washed with water, and dried to give 2 and/or 2 yellow needle-like crystals.
50 g of -chloro-4-ditrophenol was obtained. The yield was 60% based on p-nitrophenol. The melting point was 117°C, and it was confirmed by infrared absorption spectroscopy that it was 2- and/or 2-chloro-4-ditrophenol. As a result of analysis using high performance liquid chromatography, the purity was 94.5%. [0044] Comparative Example 2 1 with stirrer, thermometer, cooling tube and chlorine supply conduit
600 g (0.97 mol) of a 12% aqueous sodium hypochlorite solution and 42.0 g (0.30 mol) of p-nitrophenol were weighed into a 000 ml four-bottle flask. While stirring, add 86.3 g of concentrated hydrochloric acid (0,27
A mixed solution of 86.3 g of water (mol) and water was added dropwise over 4 hours. After the dropwise addition was completed, aging was performed at a temperature of 50° C. for 1 hour. [0045] 347- After cooling, 25 g of concentrated sulfuric acid was added to make it acidic. The reaction product was filtered, thoroughly washed with water, and dried to obtain 51 g of yellow solid 2 and/or 2-chloro-4-ditrophenol. The yield was 82% based on p-nitrophenol. The melting point is 115°C, and it is determined by infrared absorption spectroscopy that 2, and/or 2-chloro-4
- Confirmed to be ditrophenol. The purity was found to be 92.6% when analyzed by high performance liquid chromatography. [0046] Comparative Example 3 1 with stirrer, thermometer, cooling tube and chlorine supply conduit
750g of 35% concentrated hydrochloric acid in a 0100O four-bottle flask
56 g (0.4 mol) of p-nitrophenol and 0.6 g of iodine were weighed out. While stirring, 42 g (0.6 mol) of chlorine gas was supplied at 30° C. over 4 hours. During this time, since heat generation was significant, the reaction temperature was kept from exceeding 30° C. while cooling. Furthermore, 50 g (0.7 mol) of chlorine gas was supplied at 45 °C over 6 hours, and 45
After aging at ℃ for 2 hours, cooling was performed. [0047] Next, nitrogen gas was supplied for 1 hour to remove chlorine and hydrogen chloride. This reaction product was filtered, thoroughly washed with water, and dried to produce a yellow solid of 2, and/or 2-
65g of chloro-4-ditrophenol was obtained. The yield is
It was 78% based on p-nitrophenol. The melting point is 112°C, and it is determined by infrared absorption spectroscopy to be 2. and/or 2-chloro-4-ditrophenol. As a result of high performance liquid chromatography analysis, the purity was 90.2%. [0048] Comparative Example 4 1 with stirrer, thermometer, cooling tube and chlorine supply conduit
600 g of concentrated sulfuric acid and 1 water in a 000 ml four-bottle flask
50g and p-nitrophenol 83g (0.6 mol)
was weighed. 50g of chlorine gas at 30℃ while stirring
(0.7 mol) was fed over 4 hours. During this time, since heat generation was significant, the reaction temperature was kept from exceeding 30° C. while cooling. Furthermore, 71g of chlorine gas at 60℃
(1.0 mol) was supplied over 8 hours, and after aging at 60° C. for 2 hours, cooling was performed. JP-A-3-291241 (15) [0049] Next, nitrogen gas was supplied for 1 hour to remove chlorine and hydrogen chloride. This reaction product was filtered, thoroughly washed with water, and dried to produce yellow needle-like crystals. and/or 103 g of 2-chloro-4-ditrophenol. The yield was 83% based on p-nitrophenol. The melting point is 116°C, and it is determined by infrared absorption spectroscopy to be 2. and/or 2-chloro-4-ditrophenol. As a result of high performance liquid chromatography analysis, the purity was 92.
It was 2%. [0050]

【Effect of the invention】

According to the method for producing 2, and/or 2-chloro-4-substituted phenol of the present invention, a method for producing 2, and/or 2-chloro-p-benzoquinone, 2,4.6-)dichlorophenol, and the like. [Claim 2 and/or 2
The amount of 2-chloro-4-substituted phenol, resinous substances, etc. contained in the -chloro-4-substituted phenol is less than 1.0% by weight, which is reduced to 176% or less compared to the prior art method. Therefore, there is no need for subsequent purification by recrystallization,
2- and/or 2-chloro-4-substituted phenols can be produced industrially in high yield and purity. Therefore, the obtained 2- and/or 2-chloro-4-substituted phenol can be directly used as a raw material for producing various useful substances.

Claims (7)

[Claims] Claim 1: A process comprising reacting p-substituted phenol and/or 2-chloro-4-substituted phenol with chlorine in an acidic liquid having a water content of 15% by weight or less.
, 6-dichloro-4-substituted phenol. [Claim 2] The substituent of p-substituted phenol and/or 2-chloro-4-substituted phenol is a carboxyl group,
Claim 1: It is a nitro group, a sulfonic acid group, a cyano group, a chlorosulfonyl group, a chlorocarbamoyl group, a sulfamoyl group, a carbamoyl group, an amino group, or a halogen atom.
Manufacturing method described. 3. The method according to claim 2, wherein the substituent is a nitro group. 4. The production method according to claim 2, wherein the substituent is an amino group. 5. The method according to claim 1, wherein the acidic liquid does not contain water and is a liquid acid. 6. The method according to claim 5, wherein the acid is one or more acids selected from the group consisting of sulfuric acid, sulfuric anhydride, phosphoric acid, polyphosphoric acid, acetic acid, and formic acid. 7. The method according to claim 6, wherein the acid is sulfuric acid.