CN102558004B - Chemical synthesis method for S-(4-tolyl)benzene sulfonate - Google Patents
Chemical synthesis method for S-(4-tolyl)benzene sulfonate Download PDFInfo
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Abstract
The invention discloses a chemical synthesis method for S-(4-tolyl)benzene sulfonate which is shown as a formula (I). According to the method, sodium benzene sulphinate which is shown as a formula (II) and bis(4-tolyl)disulfide which is shown as a formula (III) are used as raw materials; and the S-(4-tolyl)benzene sulfonate is obtained by the steps of fully reacting the sodium benzene sulphinate and the bis(4-tolyl)disulfide in an organic solvent at the temperature of between -40 and 120 DEG C under the action of N-halogenate succinimide, and treating a reaction solution. The process is reasonable, reaction conditions are mild, reaction yield is high, production cost is low, three wastes (waste water, waste gas and residues) are few, and the method has great implementation value and social and economic benefit.
Description
(1) technical field
The present invention relates to the chemical synthesis process of a kind of S-(4-tolyl) benzene sulfonate.
(2) background technology
S-(4-tolyl) benzene sulfonate is a kind of important medicine and chemical intermediate, is often used as benzene sulfuration reagent; S-(4-tolyl) benzene sulfonate can be used as the blocker of mercapto groups in protein chemistry, also can be used as synthetic raw material with bioactive compounds and polymeric material, is the important source material of medicine, material etc., in industrial middle extensive application.
Before the present invention provides, prior art is document [Journal of Sulfur Chemistry (2004) for example, 25 (5), 347-350] described take benzene sulfonyl acid with thiophenol as raw material, condensation reaction under cyanuric chloride and N-methylmorpholine existence prepares S-(4-tolyl) benzene sulfonate as solvent with methylene dichloride.The method has adopted that toxicity is large, volatility is large and what have foul smell is raw material to methylbenzene phenyl-sulfhydrate, and to having relatively high expectations of equipment, and in production process, danger coefficient is large.
For the above industrial unfavorable factor of considering, be necessary existing technique is improved, develop a kind of synthetic method with advantages such as reaction conditions gentleness, efficient, production cost is low, new technology is provided for S-(4-tolyl) benzene sulfonate is synthetic.
(3) summary of the invention
The technical problem to be solved in the present invention is to provide the chemical synthesis process of the S-that a kind of technique is reasonable, reaction conditions is gentle, reaction yield is high, production cost is low, the three wastes are few (4-tolyl) benzene sulfonate.
For solving the problems of the technologies described above, the technical solution adopted in the present invention is as follows:
A kind of chemical synthesis process suc as formula the S-shown in (I) (4-tolyl) benzene sulfonate, take two (4-tolyl) disulfides shown in the benzene sulfinic acid sodium salt shown in formula II and formula (III) as raw material, fully reaction under-40～120 ℃ in organic solvent under the imido effect of N-halogenated succinimide, the gained reaction solution carries out aftertreatment and obtains described S-(4-tolyl) benzene sulfonate; Reaction equation is as follows:
In the present invention, described N-halogenated succinimide imide is one of following: 1. N-chlorosuccinimide triethylamine, 2. N-bromo-succinimide pyridine, 3. N-N-iodosuccinimide; Be preferably N-bromo-succinimide pyridine.
In the present invention, described organic solvent is one of following: 1. chlorobenzene, 2. DMF, 3. toluene, 4. ethanol, 5. tetrahydrofuran (THF), 6. Isosorbide-5-Nitrae-dioxane, 7. ethyl acetate, 8. tetracol phenixin, 9. methylene dichloride, 10. acetonitrile; Preferred organic solvent is tetrahydrofuran (THF) or acetonitrile; Acetonitrile more preferably.
In the present invention, the ratio of described two (4-tolyl) disulfides, benzene sulfinic acid sodium salt, the imido amount of substance that feeds intake of N-halogenated succinimide is 1: 2.0～5.0: 1.0～4.0; Be preferably 1: 3.0～4.0: 2.0～3.0.
In the present invention, the total mass consumption of described organic solvent is 5～50 times of two (4-tolyl) disulfide quality, is preferably 10～30 times.Described total mass consumption refers to for two (4-tolyl) disulfides of dissolving consumption total with being used for dissolving benzene sulfinic acid sodium salt and the imido organic solvent of N-halogenated succinimide.
In the present invention, preferable reaction temperature is-10～50 ℃, and the reaction times is 2～10h.Further, more preferably temperature of reaction is 20～50 ℃, and the reaction times is 5～10h.
Concrete, the chemical synthesis process of described S-(4-tolyl) benzene sulfonate carries out in accordance with the following steps: benzene sulfinic acid sodium salt and N-halogenated succinimide imide are dissolved in organic solvent, stir and drip two (4-tolyl) the disulfide solution with same organic solvent dissolution under certain temperature, dropwise rear insulation reaction to reacting completely, the gained reaction solution first steams and desolventizes, add again saturated aqueous common salt, separate and get organic layer, be described S-(4-tolyl) benzene sulfonate after the rotation evaporate to dryness.
The present invention compared with prior art, beneficial effect is embodied in:
(1) processing condition are reasonable, safety simple to operate; (2) reaction conditions is gentle, and reaction yield is high; (3) raw material used is cheap and easy to get and environmentally friendly, and production cost is low, and the three wastes are few; Therefore the present invention has larger implementary value and economic results in society.
(4) embodiment
The invention will be further described below in conjunction with embodiment, but protection scope of the present invention is not limited to this.
Embodiment 1
Be to feed intake at 1: 4.0: 2.0 by two (4-tolyl) disulfides of the molar ratio that feeds intake, benzene sulfinic acid sodium salt, N-halogenated succinimide imide, two (4-tolyl) disulfide 24.6g (0.1mol); Benzene sulfinic acid sodium salt 64.8g (0.4mol); N-halogenated succinimide imide is the N-bromo-succinimide, the quality that feeds intake 35.6g (0.2mol); Organic solvent is acetonitrile 369g, and its total consumption is 15 times of two (4-tolyl) disulfide quality.
Benzene sulfinic acid sodium salt and N-halogenated succinimide imide are dissolved in organic solvent (consumption of organic solvent is 9 times of two (4-tolyl) disulfide quality).Two (4-tolyl) disulfides are dissolved in organic solvent (consumption of organic solvent is 6 times of two (4-tolyl) disulfide quality), slowly drop in benzene sulfinic acid sodium salt and the imido solution of N-halogenated succinimide, temperature of reaction is 50 ℃, 6 as a child afterreaction end.
React complete after, add saturated aqueous common salt, extracting and separating is got organic layer.Rotate the evaporate to dryness organic solvent after the organic layer drying and reclaim, namely getting S-(4-tolyl) benzene sulfonate 45.4g, yield 86%, purity 98.7%.
Nucleus magnetic resonance:
1H NMR (CDCl
3, 500MHz): δ 7.59-7.56 (m, 3H), 7.44-7.41 (m, 2H), 7.23-7.22 (m, 2H), 7.14-7.13 (m, 2H), 2.37 (s, 3H);
13C NMR (CDCl
3, 125MHz): δ 143.1,142.1,136.5,133.5,130.2,128.8,127.6,124.4,21.4.
Embodiment 2
Be to feed intake at 1: 3.0: 2.0 by two (4-tolyl) disulfides of the molar ratio that feeds intake, benzene sulfinic acid sodium salt, N-halogenated succinimide imide, two (4-tolyl) disulfide 24.6g (0.1mol); Benzene sulfinic acid sodium salt 48.6g (0.3mol); N-halogenated succinimide imide is the N-bromo-succinimide, the quality that feeds intake 35.6g (0.2mol); Organic solvent is acetonitrile 369g, and its total consumption is 15 times of two (4-tolyl) disulfide quality.
Temperature of reaction is 25 ℃, and in 6 hours reaction times, other operates with example 1, S-(4-tolyl) benzene sulfonate 39.1g, yield 74%, purity 98.8%.
Embodiment 3
Be to feed intake at 1: 2.0: 2.0 by two (4-tolyl) disulfides of the molar ratio that feeds intake, benzene sulfinic acid sodium salt, N-halogenated succinimide imide, two (4-tolyl) disulfide 24.6g (0.1mol); Benzene sulfinic acid sodium salt 32.4g (0.2mol); N-halogenated succinimide imide is the N-bromo-succinimide, the quality that feeds intake 35.6g (0.2mol); Organic solvent is acetonitrile 369g, and its total consumption is 15 times of two (4-tolyl) disulfide quality.
Temperature of reaction is 25 ℃, and in 10 hours reaction times, other operates with example 1, S-(4-tolyl) benzene sulfonate 28.2g, yield 53%, purity 98.3%.
Embodiment 4
Be to feed intake at 1: 4.0: 2.0 by two (4-tolyl) disulfides of the molar ratio that feeds intake, benzene sulfinic acid sodium salt, N-halogenated succinimide imide, two (4-tolyl) disulfide 24.6g (0.1mol); Benzene sulfinic acid sodium salt 64.8g (0.4mol); N-halogenated succinimide imide is the N-bromo-succinimide, the quality that feeds intake 35.6g (0.2mol); Organic solvent is tetrahydrofuran (THF) 369g, and its total consumption is 15 times of two (4-tolyl) disulfide quality.
Other operates with example 1, S-(4-tolyl) benzene sulfonate 40.7g, yield 77%, purity 98.9%.
Embodiment 5
Be to feed intake at 1: 4.0: 3.0 by two (4-tolyl) disulfides of the molar ratio that feeds intake, benzene sulfinic acid sodium salt, N-halogenated succinimide imide, two (4-tolyl) disulfide 24.6g (0.1mol); Benzene sulfinic acid sodium salt 64.8g (0.4mol); N-halogenated succinimide imide is the N-bromo-succinimide, the quality that feeds intake 35.6g (0.2mol); Organic solvent is acetonitrile 369g, and its total consumption is 15 times of two (4-tolyl) disulfide quality.
Other operates with example 1, S-(4-tolyl) benzene sulfonate 45.9g, yield 87%, purity 98.6%.
Embodiment 6
Be to feed intake at 1: 4.0: 1.0 by two (4-tolyl) disulfides of the molar ratio that feeds intake, benzene sulfinic acid sodium salt, N-halogenated succinimide imide, two (4-tolyl) disulfide 24.6g (0.1mol); Benzene sulfinic acid sodium salt 64.8g (0.4mol); N-halogenated succinimide imide is the N-bromo-succinimide, the quality that feeds intake 35.6g (0.2mol); Organic solvent is acetonitrile 369g, and its total consumption is 15 times of two (4-tolyl) disulfide quality.
Other operates with example 1, S-(4-tolyl) benzene sulfonate 33.3g, yield 63%, purity 98.9%.
Embodiment 7
Be to feed intake at 1: 3.0: 3.0 by two (4-tolyl) disulfides of the molar ratio that feeds intake, benzene sulfinic acid sodium salt, N-halogenated succinimide imide, two (4-tolyl) disulfide 24.6g (0.1mol); Benzene sulfinic acid sodium salt 48.6g (0.3mol); N-halogenated succinimide imide is the N-bromo-succinimide, the quality that feeds intake 35.6g (0.2mol); Organic solvent is acetonitrile 369g, and its total consumption is 15 times of two (4-tolyl) disulfide quality.
Other operates with example 1, S-(4-tolyl) benzene sulfonate 37.5g, yield 71%, purity 98.5%.
Embodiment 8
Be to feed intake at 1: 4.0: 2.0 by two (4-tolyl) disulfides of the molar ratio that feeds intake, benzene sulfinic acid sodium salt, N-halogenated succinimide imide, two (4-tolyl) disulfide 24.6g (0.1mol); Benzene sulfinic acid sodium salt 64.8g (0.4mol); N-halogenated succinimide imide is the N-chlorosuccinimide, the quality that feeds intake 26.7g (0.2mol); Organic solvent is acetonitrile 369g, and its total consumption is 15 times of two (4-tolyl) disulfide quality.
Other operates with example 1, S-(4-tolyl) benzene sulfonate 20.1g, yield 38%, purity 98.9%.
Embodiment 9
Be to feed intake at 1: 4.0: 2.0 by two (4-tolyl) disulfides of the molar ratio that feeds intake, benzene sulfinic acid sodium salt, N-halogenated succinimide imide, two (4-tolyl) disulfide 24.6g (0.1mol); Benzene sulfinic acid sodium salt 64.8g (0.4mol); N-halogenated succinimide imide is the N-N-iodosuccinimide, the quality that feeds intake 45.0g (0.2mol); Organic solvent is acetonitrile 369g, and its total consumption is 15 times of two (4-tolyl) disulfide quality.
Other operates with example 1, S-(4-tolyl) benzene sulfonate 24.3g, yield 46%, purity 98.9%.
Embodiment 10
Be to feed intake at 1: 4.0: 2.0 by two (4-tolyl) disulfides of the molar ratio that feeds intake, benzene sulfinic acid sodium salt, N-halogenated succinimide imide, two (4-tolyl) disulfide 24.6g (0.1mol); Benzene sulfinic acid sodium salt 64.8g (0.4mol); N-halogenated succinimide imide is the N-bromo-succinimide, the quality that feeds intake 35.6g (0.2mol); Organic solvent is acetonitrile 246g, and its total consumption is 10 times of two (4-tolyl) disulfide quality.
Other operates with example 1, S-(4-tolyl) benzene sulfonate 42.8g, yield 81%, purity 98.4%.
Embodiment 11
Be to feed intake at 1: 4.0: 2.0 by two (4-tolyl) disulfides of the molar ratio that feeds intake, benzene sulfinic acid sodium salt, N-halogenated succinimide imide, two (4-tolyl) disulfide 24.6g (0.1mol); Benzene sulfinic acid sodium salt 64.8g (0.4mol); N-halogenated succinimide imide is the N-bromo-succinimide, the quality that feeds intake 35.6g (0.2mol); Organic solvent is acetonitrile 246g, and its total consumption is 10 times of two (4-tolyl) disulfide quality.
Temperature of reaction is 80 ℃, and in 5 hours reaction times, other operates with example 1, S-(4-tolyl) benzene sulfonate 39.6g, yield 75%, purity 98.6%.
Embodiment 12
Be to feed intake at 1: 4.0: 2.0 by two (4-tolyl) disulfides of the molar ratio that feeds intake, benzene sulfinic acid sodium salt, N-halogenated succinimide imide, two (4-tolyl) disulfide 24.6g (0.1mol); Benzene sulfinic acid sodium salt 64.8g (0.4mol); N-halogenated succinimide imide is the N-bromo-succinimide, the quality that feeds intake 35.6g (0.2mol); Organic solvent is acetonitrile 246g, and its total consumption is 10 times of two (4-tolyl) disulfide quality.
Temperature of reaction is 0 ℃, and in 10 hours reaction times, other operates with example 1, S-(4-tolyl) benzene sulfonate 37.5g, yield 71%, purity 98.5%.
Embodiment 13
Be to feed intake at 1: 4.0: 2.0 by two (4-tolyl) disulfides of the molar ratio that feeds intake, benzene sulfinic acid sodium salt, N-halogenated succinimide imide, two (4-tolyl) disulfide 24.6g (0.1mol); Benzene sulfinic acid sodium salt 64.8g (0.4mol); N-halogenated succinimide imide is the N-bromo-succinimide, the quality that feeds intake 35.6g (0.2mol); Organic solvent is toluene 246g, and its total consumption is 10 times of two (4-tolyl) disulfide quality.
Temperature of reaction is 50 ℃, and in 6 hours reaction times, other operates with example 1, S-(4-tolyl) benzene sulfonate 21.6g, yield 41%, purity 98.1%.
Embodiment 14
Be to feed intake at 1: 4.0: 2.0 by two (4-tolyl) disulfides of the molar ratio that feeds intake, benzene sulfinic acid sodium salt, N-halogenated succinimide imide, two (4-tolyl) disulfide 24.6g (0.1mol); Benzene sulfinic acid sodium salt 64.8g (0.4mol); N-halogenated succinimide imide is the N-bromo-succinimide, the quality that feeds intake 35.6g (0.2mol); Organic solvent is ethanol 246g, and its total consumption is 10 times of two (4-tolyl) disulfide quality.
Temperature of reaction is 50 ℃, and in 6 hours reaction times, other operates with example 1, S-(4-tolyl) benzene sulfonate 22.7g, yield 43%, purity 98.7%.
Claims (6)
1. the chemical synthesis process of S-(4-tolyl) benzene sulfonate as shown in the formula (I), take two (4-tolyl) disulfides shown in the benzene sulfinic acid sodium salt shown in formula (II) and formula (III) as raw material, fully reaction in organic solvent under the imido effect of N-halogenated succinimide, the gained reaction solution carries out aftertreatment and obtains described S-(4-tolyl) benzene sulfonate; Reaction equation is as follows:
Described N-halogenated succinimide imide is one of following: 1. N-chlorosuccinimide; 2. N-bromo-succinimide; 3. N-N-iodosuccinimide;
Temperature of reaction is 20～50 ℃, and the reaction times is 5～10h.
2. the chemical synthesis process of S-as claimed in claim 1 (4-tolyl) benzene sulfonate is characterized in that: described organic solvent is one of following: 1. chlorobenzene; 2. DMF; 3. toluene; 4. ethanol; 5. tetrahydrofuran (THF); 6. Isosorbide-5-Nitrae-dioxane; 7. ethyl acetate; 8. tetracol phenixin; 9. methylene dichloride; 10. acetonitrile.
3. the chemical synthesis process of S-as claimed in claim 1 (4-tolyl) benzene sulfonate, it is characterized in that: described organic solvent is tetrahydrofuran (THF) or acetonitrile.
4. the chemical synthesis process of S-as claimed in claim 1 (4-tolyl) benzene sulfonate, it is characterized in that: described N-halogenated succinimide imide is the N-bromo-succinimide, and described organic solvent is acetonitrile.
5. the chemical synthesis process of S-as described in one of claim 1～4 (4-tolyl) benzene sulfonate is characterized in that: the ratio of described two (4-tolyl) disulfides, benzene sulfinic acid sodium salt, the imido amount of substance that feeds intake of N-halogenated succinimide is 1:2.0～5.0:1.0～4.0; The total mass consumption of described organic solvent is 5～50 times of two (4-tolyl) disulfide quality.
6. the chemical synthesis process of S-as claimed in claim 5 (4-tolyl) benzene sulfonate is characterized in that: the ratio of described two (4-tolyl) disulfides, benzene sulfinic acid sodium salt, the imido amount of substance that feeds intake of N-halogenated succinimide is 1:3.0～4.0:2.0～3.0; The total mass consumption of described organic solvent is 10～30 times of two (4-tolyl) disulfide quality.
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| CN103804249A (en) * | 2014-01-27 | 2014-05-21 | 中国人民解放军63975部队 | Synthetic method of aryl-alkyl thioether compound |
| CN109810037B (en) * | 2019-01-30 | 2020-10-09 | 浙江农林大学暨阳学院 | Method for preparing 2-thiobenzenesulfonylmethyl-3-phenyl methyl acrylate compound by tin catalysis |
| CN113387855B (en) * | 2021-06-10 | 2023-04-14 | 陕西师范大学 | Method for synthesizing disulfide compound by visible light and titanocene complex concerted catalysis |
| CN114230498B (en) * | 2021-12-30 | 2023-11-17 | 湖北华世通生物医药科技有限公司 | Preparation method of beta- (dimethylamino) ethyl p-toluenesulfonate hydrochloride |
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