JPS5936983B2 - Method for producing sulfuric acid half ester compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improved process for making sulfuric acid half ester compounds.

More specifically, the present invention relates to the general formula (■) B-NH-ASO2CH2CH2OH)n(■) (wherein A is a residue of an aromatic or heterocyclic compound, and B is a residue of a hydrogen or acid hydrolyzed (n is an integer of 1 to 4) and sulfamic acid, chlorsulfonic acid, or these in a molar ratio of 1 to 3 per β-hydroxyethylsulfonyl group and sulfuric acid in an organic solvent. to react in the presence or absence of general formula (I) NH2
-A-f-SO2CH2CH2OSO3H)n(I)(
This is a method for producing a sulfuric acid half ester compound, characterized in that the compound is a compound represented by the formula (wherein A and n have the above-mentioned meanings).

Conventional methods for converting the compound of general formula (■) into the compound of general formula (I) generally require complicated operations and use a large excess of sulfuric acid in order to obtain the desired product in good yield.

For example, aminoaryl-β-sulfatoethylsulfone is produced by hydrolyzing acetylaminoaryl-β-hydroxyethylsulfone in hydrochloric acid or dilute sulfuric acid to isolate it as aminoaryl-β-hydroxyethylsulfone, which is then dried. After that, it was obtained by esterification in concentrated sulfuric acid.

However, this method has disadvantages in that the isolation yield of aminoaryl-β-hydroxyethylsulfone is low and the operation is complicated due to the necessity of drying, so it cannot be said to be industrially advantageous. Furthermore, Japanese Patent Publication No. 16617/1983 describes a method of hydrolyzing and simultaneously converting 4-acetylaminophenyl-β-hydroxyethylsulfone into a sulfuric acid ester using concentrated sulfuric acid or a mixture of concentrated sulfuric acid and an organic solvent. ing. However, this method actually hydrolyzes 4-acetylaminophenyl-β-hydroxyethylsulfone as described in the Examples, and the resulting 4-aminophenyl-β-hydroxyethylsulfone and 4-aminophenyl In order to convert mono-β-acetoxyethyl sulfone to 4-aminophenyl-β-sulfatoethyl sulfone, it is necessary to further add a large amount of oleum to the reaction solution. Therefore, the obtained 4-aminophenyl-β-sulfatoethyl sulfone can be obtained as a large amount of concentrated sulfuric acid solution or fuming sulfuric acid solution, and can be used as is or isolated by dilution. A large amount of acid must be handled, the cost of an alkali agent required to treat excess sulfuric acid, and the problem of separation of the resulting sulfate are extremely complicated, which is extremely disadvantageous in industrial production. In addition, the special public service 45-2709
Publication No. 6 describes a method for producing aminoaryl-β-sulfatoethylsulfone by hydrolyzing acetylaminoaryl-β-sulfatoethylsulfone in 50% or less sulfuric acid water at 45°C. .

However, this method has the drawback that the reaction requires a long time, and the yield decreases because hydrolysis of the sulfate ester in the β-sulfatoethyl sulfone group occurs simultaneously with the hydrolysis of the acetylamino group. have Furthermore, conventionally known methods require a large amount of sulfuric acid in order to obtain a sulfuric acid ester in good yield.

For example, in Japanese Patent Publication No. 42-16617, the amount of sulfuric acid used is as large as 8.4 to 15.6 molar ratio to the raw material acetylaminophenyl-β-hydroxyethylsulfone, and is relatively small. Even in the method of Japanese Patent Publication No. 45-27096, which is an example of the use of 4
．． An amount as high as 9 molar ratio is used. As a solution to this problem, West German Patent Application No. 14438
No. 77 describes a method for producing a sulfuric acid half-ester compound using 3 to 4 molar ratios of amidosulfonic acid in a water-soluble organic solvent such as pyridine/picoline.

Although this method is excellent in that it can reduce the amount of esterifying agent that has conventionally been used in excess, it has the disadvantage that the water-soluble organic solvent used must be thoroughly distilled off under reduced pressure afterwards. Nevertheless, approximately - of the water-soluble organic solvent used in that case is still contained in the sulfuric acid half-ester, and it is therefore necessary to recover the water-soluble organic solvent by some method before this wastewater reaches the drain. Or it must be removed. Another drawback is that in the case of water-soluble organic solvents, it is difficult to achieve a completely anhydrous state, and as a result, the reaction temperature is relatively high, making hydrolysis of amidosulfonic acid more likely to occur, which may reduce the amount of esterifying agent. However, it is essential to use a considerable amount of the esterifying agent in excess. As a result of various studies to improve the various drawbacks of the above-mentioned known manufacturing methods, the present inventors found that
To produce the desired sulfuric acid half-esterified product in a highly pure state, using a nearly stoichiometric amount of a sulfuric acid esterifying agent, and without producing wastewater that pollutes the environment, which is advantageous for industrial production, and with a nearly quantitative yield. We have found an improved method that allows this, and have completed the present invention.

A feature of the present invention is that in producing the sulfuric acid half ester compound of general formula (1) from the compound of general formula (9), the esterification is carried out using a specific sulfuric acid esterifying agent in an amount close to the theoretically required amount. Therefore, the target sulfuric acid half ester compound can be obtained in a high purity state and in a high yield in an apparatus that can remove volatile components by vaporization or evaporation, and it is also advantageous for industrial production. Since the amount of sulfuric acid used is small, there is little contamination of wastewater, which is extremely advantageous from the viewpoint of wastewater treatment.

Next, the present invention will be explained in more detail.

In the present invention, the compound of the raw material general formula () is a benzene-based compound substituted with a β-hydroxyethylsulfonyl group,
It is an aromatic or heterocyclic compound such as naphthaliga,
These may further have various other substituents.

Specific examples include the following compounds. 4-(amino or acetylamino)phenyl-β-hydroxyethylsulfone 2-methoxy-5-(
2-Methyl-4-(amino or acetylamino)-5-methoxyphenyl-β-hydroxyethylsulfone 3-(amino or acetylamino)-
4-methoxyphenyl-β-hydroxyethylsulfone 3-aminophenyl-β-hydroxyethylsulfone 4
-(amino or acetylamino)-2,5-dimethoxyphenyl-β-hydroxyethylsulfone 5-(amino or acetylamino)-2,4-dimethoxyphenyl-β-hydroxyethylsnorrefone 3-chloro-4-
(amino or acetylamino)-phenyl-β-hydroxyethylsulfone 3-(amino or acetylamino)-4-chlorophenyl-β-hydroxyethylsulfone 2-methyl-5-(amino or acetylamino)
Phenyl-β-hydroxyethylsulfone 3-carboxy-4-(amino or acetylamino) phenyl-β
-Hydroxyethylsulfone 3-hydroxy-4-(amino or acetylamino)phenyl-β-hydroxyethylsulfone 3-amino-4-sulfophenyl-β-
Hydroxyethylsulfone 2-(amino or acetylamino)phenyl-β-hydroxyethylsulfone 5-(
amino or acetylamino)-1-naphthyl-β-hydroxyethylsulfone 4-(amino or acetylamino)-1-naphthyl-β-hydroxyethylsulfone 5-(amino or acetylamino)-2-naphthyl-
β-Hydroxyethylsulfone 2-(amino or acetylamino)-1-naphthyl-6-(β-
3-(3 or 4-aminobenzoyl)aminophenyl-β-hydroxyethylsulfone 3-(3 or 4-hydroxyethylsulfonyl)-1-naphthalenesulfonate
-aminobenzoyl)amino-4-methoxyphenyl-β-hydroxyethylsnolephon 3-(4-acetylaminophenylsulfonyl)aminophenyl-β-hydroxyethylsulfone 3-(4-aminophenylsulfonyl)aminophenyl-β- Hydroxyethyl sulfone 4
-(4-acetylaminophenoxy)phenyl-β-hydroxyethylsulfone 4-(4-aminophenoxy)
phenyl-β-hydroxyethylsulfone 4-(ureido or benzoylamino) phenyl-β-hydroxyethylsulfone 2-methoxy-5-(ureido or benzoylamino) phenyl-β-hydroxyethylsulfone 3-(ureido or benzoylamino)- 4-methoxyphenyl-β-hydroxyethylsulfone 2-methyl-4-(ureido or benzoylamino)-5-
Methoxyphenyl-β-hydroxyethylsulfone 4-
(ureido or benzoylamino)-2,5-dimethoxyphenyl-β-hydroxyethylsulfone 3-chloro-4-(ureido or benzoylamino)-phenyl-β-hydroxyethylsulfone 2-methyl-5-(
ureido or benzoylamino)-phenyl-β-hydroxyethylsulfone 3-(ureido or benzoylamino)-4-sulfophenyl-β-hydroxyethylsulfone 2-(ureido or benzoylamino)phenyl-β-hydroxyethylsulfone 5-(ureido or benzoylamino)-1-naphthyl-β-hydroxyethylsulfone 4-(ureido or benzoylamino)-1-naphthyl-β-hydroxyethylsulfone 4-(ureido or benzoylamino)-1 naphthyl-β-hydroxyethylsulfone 5 -(ureido or benzoylamino)-2-naphthyl-β-hydroxyethylsulfone (ureido or benzoylamino)
-1-naphthyl-β-hydroxyethylsulfone 2-(
ureido or benzoylamino)-6-(β-hydroxyethylsulfonyl)-1-naphthalenesulfonate N,
N'-bis(4-β-hydroxyethylsulfonylphenyl)urea N,NI-bis(4-methoxy-3-β-
hydroxyethylsulfonylphenyl) urea N,N
/-bis(2-methoxy-5-β-hydroxyethylsulfonylphenyl)urea N,N'-bis(2-methoxy-5-methyl-4-β-hydroxyethylsulfonylphenino(c)urea N,N/-bis(2-sulfo-5-β-hydroxyethylsulfonylphenyl)urea N,NLbis(4-β-hydroxyethylsulfonyl-1-naphthyl)ureaN,NLbis(6-β- hydroxyethylsulfonyl-1-naphthyl)urea N,N
7-bis(8-β-hydroxyethylsulfonyl-2-
naphthyl) urea N,N/-bis(1-sulfo-6-β
-Hydroxyethylsulfonyl-2-naphthyl)urea These compounds can also be used in a water-containing state, which is advantageous compared to conventional methods because it does not require complicated operations such as drying and pulverization.

In the present invention, as the sulfuric acid esterification agent, sulfamic acid or crosssulfonic acid, or a combination of these and sulfuric acid is used. The combined use of sulfuric acid and sulfamic acid not only allows the reaction to proceed particularly advantageously depending on the type of raw material compound, but also can be carried out significantly more advantageously than using sulfuric acid alone due to the material of the reaction equipment. can.

The amount of the esterifying agent used is 1 to 3 per β-hydroxyethylsulfonyl group in the compound of general formula ().
It is a molar ratio, and is preferably used in a range of 1 to 2 molar ratios. When sulfuric acid is used in combination as a sulfuric acid esterification agent, the concentration of sulfuric acid used varies depending on the type and state of the compound of general formula (), but is usually 20 to 100%.
In some cases, fuming sulfuric acid or sulfuric anhydride is used.
The reaction temperature is 40-250°C, preferably 40-200°C.
The temperature is determined as appropriate depending on the properties of the raw material compound and the equipment used. Although higher temperatures are preferable in order to facilitate the reaction, excessively high temperatures tend to cause side reactions and deteriorate the target product. In addition, when using an apparatus capable of carrying out the reaction in a short time, the reaction is carried out at a relatively high temperature. In the present invention,
In order to facilitate the reaction, an organic emulsion that is inert to the esterifying agent and can be easily separated from the sulfuric acid half-ester compound after the reaction may be used.

Examples of the organic vehicle that can be used include hydrocarbons, halogenated hydrocarbons, nitrated hydrocarbons, ketones, and the like. More specific examples include cyclohexane, heptane, benzene, toluene, xylene, solvent naphtha, trichloroethane, dichloropropane, trichloroethylene, tetrachloroethane, nomer chloroethylene, chlorobenzene, dichlorobenzene, nitrobenzene, methylisobutylcaine, and the like. The amount used is preferably 0.1 to 10 times, particularly 0.1 to 8 times, the weight of the raw material compound. Inert materials such as diatomaceous earth, activated clay, activated carbon, silica gel, charcoal, etc. may also be used to improve heat transfer. Further, in some cases, the reaction may be carried out under reduced pressure to facilitate distillation of by-product components. As the reaction apparatus used in the present invention, an apparatus capable of removing volatile components by vaporization or evaporation is particularly preferable, and the reaction can be carried out using a conventional batch-type or continuous-type tank, kettle, evaporator, concentrator, or dryer. .

It can also be carried out using a batch-type or continuous-type kneading machine that is capable of kneading with strong force. Evaporator,
Specific examples of thickeners, dryers or kneaders include shelf dryers, spray dryers, flash dryers, rotary dryers, tunnel and band dryers, drum dryers, cylinder dryers, Continuous ventilation dryer, infrared dryer, high frequency dryer, long tube evaporation concentrator, stirring type evaporator, rotary concentrator, ribbon mixer, 'mag mill, double-arm kneader (e.g. dispersion type kneader) 1), a reed co-container, an auger extruder, etc.
In the present invention, the raw material compound can be mixed with the esterifying agent and reacted immediately, but in some cases, pretreatment may be necessary.

For example, when using sulfamic acid as an esterifying agent, if the raw material compound is in a water-containing state, it is preferable to perform a dehydration treatment to prevent decomposition of the sulfamic acid. Further, when obtaining aminoaryl-β-sulfatoethylsulfone from acylaminoaryl-β-hydroxyethylsulfone, it is necessary to hydrolyze the acylamino group, and in this case, sulfuric acid and sulfamic acid are used in combination. The sulfuric acid half ester compound obtained by the method of the present invention can be obtained by injecting the reaction mixture into ice water and then isolating it from the diluted solution.
Alternatively, by neutralizing the diluted solution, it can be used as it is as an intermediate for reactive dyes.

Next, the method of the present invention will be specifically explained using examples.

Parts and e in the examples represent parts by weight or % by weight, respectively, unless otherwise specified. Example 1 49.5 parts of 4-acetylaminophenyl-β-hydroxyethyl sulfone (purity 98.2%) was added to 24.5 parts of 40% sulfuric acid (molar ratio 0.5) with stirring, and
Incubate at ~115°C for 1 hour.

Then, this was heated under reduced pressure (400 mmHg) to 110 to 11
Water and acetic acid are distilled off at 5°C. The resulting mixture was placed in an evaporating dish, and 15.52 parts (0.8 parts) of sulfamic acid was added thereto.
molar ratio) and thoroughly mixed, the mixture was kept warm for 8 hours in a hot air circulation dryer (manufactured by Nishiyama Seisakusho) at 120 to 125°C. During this time water and acetic acid are distilled off. When the obtained reaction product was analyzed by liquid chromatography, the production rate of 4-aminophenyl-β-sulfatoethylsulfone was 96? It also contained small amounts of 4-aminophenyl-β-hydroxyethyl sulfone and 4-aminophenyl-β-acetoxyethyl sulfone. Reference example 1
The reaction mixture obtained in Example 1 was placed in ice water and diazotized in a conventional manner with hydrochloric acid and sodium nitrite without isolating the product, and then 38.9 parts (purity 80%) of 1 -Amino-8-naphthol-3,6-disulfonic acid in a conventional manner.

By spray drying this reaction solution, a black dye known as Reactive Black 5 by Color Index was obtained as a highly concentrated product with a low inorganic salt content. In addition, the solution obtained by adding 0.8 parts of diethylene glycol monobutyl ether to the reaction solution before spray drying without separating the sodium sulfate is a concentrated aqueous solution of the dye with a low content of sodium sulfate, and is kept for a long time at low temperature. Even when left to stand, there was no precipitation of crystals and the product had excellent storage stability. Furthermore, the obtained dye had excellent solubility, and cellulose fibers were dyed black by a conventional reactive dye dyeing method using an alkali, and the dyed products obtained had good fastness properties.

Example 2 3-aminophenyl-β-hydroxyethylsulfone 304 was produced while operating a two-shaft double-arm kneader (manufactured by Inoue Seisakusho) at 60 revolutions per minute with a heating and cooling jacket.

Prepare 5 parts (purity 66%) of wet cake and make 100
Water is distilled off at ~105°C under reduced pressure (600 mmHg).

To this was added 135.8 parts of sulfamic acid (molar ratio 1.4), and the mixture was kept at 90 to 95°C for 6 hours. When the obtained reaction product was analyzed by liquid chromatography, it was found that 3-
The production rate of aminophenyl-β-sulfatoethylsulfone was 95%.

Example 3 57.3 parts of 2-methoxy-5-ureidophenyl-β-hydroxyethyl sulfone (purity 95%) was added to 22.4 parts of 70% sulfuric acid (molar ratio 0.8) with stirring.
Insulate at 10-115°C for 2 hours.

Next, this was poured into 200 parts of perchlorethylene at 115-120°C to which 13.58 parts (0.7 molar ratio) of sulfamic acid had been added, while water was being distilled off, and then at 115-120°C for 1 hour. The reaction was completed by incubating at ℃.
2-Methoxy-5-aminophenyl-β-sulfatoethyl sulfone was obtained with a yield of 93%.

Reference Example 2 The reaction product obtained in Example 3 was poured into ice water, neutralized with sodium carbonate, perchloroethylene was separated, and the product was treated with hydrochloric acid and sodium nitrite in a conventional manner without isolating the product. Perform diazotization of

Thereafter, 1,05 times the molar amount of 8-acetylamino-1-
By coupling with naphthol-3,5-disulfonic acid in a conventional manner and spray-drying the entire amount without taking out the product, the red dye known in Example 3 of Japanese Patent Publication No. 43-124789 can be produced in a good yield. I was able to get it.

Further, a solution to which 0.8 parts of diethylene glycol monobutyl ether was added without spray drying could be used as a concentrated aqueous solution with good storage stability and no precipitation of sodium sulfate even when left under low vortexing. Furthermore, the obtained dye has excellent solubility and dyes cellulose fibers in a bright red color with excellent color fastness by a conventional reactive dye dyeing method using an alkali.

Example 4 3-acetylamino-4-
Methoxyphenyl-β-hydroxyethyl sulfone 28
6.

8 parts (purity 95.2%) were charged, and 49 parts of 40% sulfuric acid (molar ratio 0.2) was added thereto.

This is then kept warm at 120-125°C for 2 hours, and then water and acetic acid are distilled off at 120-125°C under reduced pressure (500 mmHg).

To this, 126.1 parts of sulfamic acid (molar ratio 1.3)
was added and kept at 120-125°C for 5 hours to complete the reaction. 3-Amino-4-methoxyphenyl-β-sulfatoethyl sulfone was obtained with a production rate of 93%.

Reference Example 3 The reaction product obtained in Example 4 was placed in ice water and diazotized using a conventional method using hydrochloric acid and sodium nitrite. Couple with acetylaminonaphthol using a conventional method and spray dry the entire amount without removing it.

C. I. A red-orange dye known as Reactive Orange 16 could be obtained in good yield. In addition, a solution obtained by adding 4.0 parts of diethylene glycol monobutyl ether to the reaction solution before spray drying has a low sodium sulfate content and does not precipitate crystals even when left at low temperatures, so it can be used as a concentrated aqueous solution with good stability in town storehouses. did it. Furthermore, the obtained dye has excellent solubility and dyed cellulose fibers in a reddish-orange color with excellent color fastness by a conventional reactive dye dyeing method using an alkali. Example 5 58.6 parts of 2-methyl-4-acetylamino-5-methoxyphenyl-β-hydroxyethylsulfone (purity 98%) was added to 44.1 parts of 40% sulfuric acid (molar ratio 0.9) with stirring. ) and keep warm at 110-115°C for 2 hours.

Next, this was mixed with 11.6 parts of sulfamic acid (molar ratio 0.6
) and 20 parts of diatomaceous earth were added to 100 parts of toluene at 105 to 110°C over 2 hours while water and acetic acid were distilled off. The reaction was then kept at 105-110° C. for 1 hour to complete the reaction. 2-Methyl-4-amino-5-methoxyphenyl-β-hydroxyethylsulfone was obtained with a yield of 90%.

Example 6 514 parts of 3-(4-aminobenzoyl)aminophenyl-β-hydroxyethylsulfone (purity 95%) was added to a pug mill (manufactured by Kurimoto Iron Works) operating at 80 revolutions per minute.
) and injected 255.2 parts (1.1 molar ratio) of chlorosulfonic acid at 50 to 60°C over 2 hours while cooling externally.
4 Thereafter, hydrogen chloride was distilled off at 30 to 40°C to complete the reaction.

3-(4-aminobenzoyl)aminophenyl-β-sulfatoethyl sulfone was obtained with a production rate of 97%.

Example 7 318.5 parts of 7-acetylamino-1-naphthyl-β-hydroxyethyl sulfone (purity 92%) was added to 310 parts of 30% sulfuric acid (molar ratio 0.95) with stirring,
Insulate at 110-115°C for 2 hours.

The resulting mixture was then cooled to 30°C, 38.8 parts of sulfamic acid (molar ratio 0.4) was added, and this was spray-dried using a spray dryer with an inlet temperature of 200°C and an outlet temperature of 120°C. do. Water and acetic acid were removed to obtain powdered 7-amino-1-naphthyl-β-sulfatoethyl sulfone with a yield of 92%. Example 8
~13 When the reaction was carried out in the same manner as in Example 2 except that the raw material compound, the type and amount of the sulfuric acid esterification agent, and the reaction temperature were changed as shown in the following table, the following results were obtained.

Claims (1)

[Claims] 1 General formula (II) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (II) (In the formula, A is a residue of an aromatic or heterocyclic compound, and B is a residue hydrolyzed by hydrogen or an acid. (n represents an integer of 1 to 4) and sulfamic acid in a molar ratio of 1 to 3 per β-hydroxyethylsulfonyl group,
By reacting chlorosulfonic acid or these with sulfuric acid in the presence or absence of an organic solvent, the general formula (I)▲mathematical formula,
There are chemical formulas, tables, etc. ▼ (I) A method for producing a sulfuric acid half-ester compound, characterized in that the compound is a compound represented by the following (in the formula, A and n have the meanings described above). 2. The manufacturing method according to claim 1, wherein sulfamic acid and sulfuric acid are used as the sulfuric acid esterifying agent.