CN114213298B - Method for preparing thiosulfonate compound by directly oxidizing thiophenol - Google Patents
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- CN114213298B CN114213298B CN202111647096.7A CN202111647096A CN114213298B CN 114213298 B CN114213298 B CN 114213298B CN 202111647096 A CN202111647096 A CN 202111647096A CN 114213298 B CN114213298 B CN 114213298B
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Abstract
The invention relates to a method for preparing thiosulfonate compound by directly oxidizing thiophenol, which comprises the steps of adding thiophenol compound and reaction accelerator into solvent, taking oxygen (air) as oxidant, and carrying out oxidation reaction at room temperature; after the reaction is finished, a crude product is obtained by extraction, drying and distillation, and finally a pure product is obtained by purification. The invention uses oxygen or oxygen in the air as an oxidant, uses NCS as a reaction promoter, has short reaction steps, low temperature, simple operation and higher yield, and is suitable for large-scale industrial production.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a high-efficiency method for preparing a thiosulfonate compound by directly oxidizing thiophenol.
Background
The thiosulfonate and the derivative thereof are sulfonylation reagents which are widely applied to organic synthesis, can be used for synthesizing intermediates of various medicines in the field of medical compounds, and simultaneously have certain biological activity, such as being used as an antimicrobial agent, a fungicide and the like. Due to its wide and important application, a great deal of intensive research has been carried out on the synthesis of thiosulfonate compounds.
In the prior art, for thiosulfonate compounds, the following methods exist: firstly, using benzenesulfonic acid and thiophenol as raw materials, and synthesizing thiosulfonic acid ester in the coexistence of cyanuric chloride and N-methylmorpholine; secondly, synthesizing thiosulfonate by taking sodium benzene sulfinate and thioether as raw materials under the action of iodine; thirdly, sodium benzene sulfinate and disulfide are used as raw materials, and N-bromosuccinimide is used as an accelerator, so that the synthesis of the thiosulfonate compound is realized; fourthly, synthesizing corresponding thiosulfonate by using the catalytic action of metallic copper and ligand and taking sodium benzene sulfinate and thiophenol as raw materials; fifthly, sodium benzene sulfinate and disulfide are used as raw materials in Br 2 The reaction is carried out in the presence of a catalyst to give a thiosulfonate. The aboveSeveral methods for synthesizing the thiosulfonate compounds use transition metal catalysts, ligands or brominating reagents, are not environment-friendly, and cannot realize industrial production.
Therefore, the development of a method for synthesizing thiosulfonate compounds, which is fast, simple, and high in yield and can be applied to industrial production, has become a problem to be solved by those skilled in the art.
Disclosure of Invention
Aiming at the defects and problems in the prior art, the invention aims to provide a high-efficiency method for preparing thiosulfonate compounds by directly oxidizing thiophenol.
The invention is realized by the following technical scheme:
a method for preparing thiosulfonate compounds by directly oxidizing thiophenol comprises the steps of adding thiophenol compounds with a structural formula (I) and a reaction promoter into a solvent, adopting oxygen (air) as an oxidant, carrying out oxidation reaction for a certain time, and then purifying to obtain thiosulfonate compounds with a structural formula (II);
in the formula, R is halogen, nitro or alkyl.
Preferably, the reaction promoter is N-chlorosuccinimide (NCS) or N-bromosuccinimide (NBS).
Preferably, the reaction time is 15-60 min, and the reaction temperature is 15-60 ℃.
Preferably, the solvent is selected from: one or more of dichloromethane, trichloromethane, carbon tetrachloride, dichloroethane, tetrahydrofuran, acetone, acetonitrile, diethyl ether, N-dimethylformamide, 1, 4-dioxane, benzene, toluene, N-hexane and petroleum ether.
Preferably, the charging ratio of the thiophenol compound to the reaction promoter is 1: 1.5-5 in molar parts.
Preferably, the purification method is one or more of extraction, drying, reduced pressure distillation, silica gel column chromatography, recrystallization and filtration.
Compared with the prior art, beneficial effect:
(1) The experiment shows that the yield of the thiosulfonic acid ester compound prepared by the technical scheme provided by the invention can reach 60-90%, and the conversion rate is high.
(2) The method for synthesizing the thiosulfonate has the advantages of short path, high atom utilization rate, cheap and easily-obtained used accelerant, low reaction temperature and short time, and is suitable for large-scale industrial popularization.
(3) The synthetic method of the thiosulfonate compound provided by the invention solves the technical defects that the synthetic method of the thiosulfonate compound in the prior art has great damage to the environment and cannot be applied to industrial production.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of a thiosulfonate compound prepared in example 1 of the present invention;
FIG. 2 is a nuclear magnetic resonance spectrum of a thiosulfonate compound prepared in example 2 of the present invention;
FIG. 3 is a nuclear magnetic resonance spectrum of the thiosulfonate compound prepared in example 3 of the present invention;
FIG. 4 is a nuclear magnetic resonance spectrum of the thiosulfonate compound prepared in example 4 of the present invention;
FIG. 5 is a nuclear magnetic resonance spectrum of a thiosulfonate compound prepared in example 5 of the present invention;
FIG. 6 is a nuclear magnetic resonance spectrum of the thiosulfonate compound prepared in example 6 of the present invention;
FIG. 7 is a NMR spectrum of a thiosulfonate compound prepared in example 7 of the present invention;
FIG. 8 is a nuclear magnetic resonance spectrum of a thiosulfonate compound prepared in example 8 of the present invention;
Detailed Description
The synthetic method of the thiosulfonate compound provided by the invention solves the technical defects that the method for synthesizing the thiosulfonate compound in the prior art has great damage to the environment and cannot be applied to industrial production.
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The present invention will be further described with reference to examples without departing from the spirit or essential characteristics thereof.
Example 1: synthesis of p-toluenesulfo S-p-toluenesulfonate
The reaction substrates p-toluene thiophenol and N-chlorosuccinimide are counted by mol ratio, the feeding ratio of p-toluene thiophenol and N-chlorosuccinimide is 1:3, acetonitrile is used as a solvent, oxygen in air is used as an oxidant, NCS is used as an accelerant, and the specific reaction process of the experiment is as follows:
the method comprises the steps of putting 10mmol (1.24 g) of p-toluenesulfophenol and 30mmol (4 g) of N-chlorosuccinimide into a round-bottom flask under the atmosphere of air at room temperature, adding about 20mL of acetonitrile serving as a solvent, stirring, reacting for half an hour at room temperature, transferring a reaction solution into a 250mL separating funnel after the reaction is completed, extracting with ethyl acetate (30 mL multiplied by 3), combining organic phases at the upper layer, drying, filtering, distilling to obtain a crude product, transferring the crude product into the round-bottom flask, adding ethyl acetate under a heating condition until the crude product is just completely dissolved, fully cooling to separate out a solid, and filtering to obtain the product of p-toluenesulfosulfonic acid S-p-tolyl ester, wherein the yield is 81% (1.13 g). The product is a white solid with a melting point: 72-74 ℃.
As shown in FIG. 1, the nuclear magnetic resonance data of the product p-toluenesulfonyl S-p-toluenesulfonate: 1 h NMR (400MHz, chloroform-d) Δ 7.90-7.84 (m, 4H), 7.41-7.37 (m, 4H), 2.47 (s, 6H) molecular weight (GC-MS determination): 278.
example 2: synthesis of p-fluorophenyl sulfo-sulfonate S-p-fluorophenyl ester
The reaction substrates p-fluorobenzothiophenol and N-chlorosuccinimide are calculated according to the molar ratio, the feeding ratio of p-fluorobenzothiophenol to N-chlorosuccinimide is 1:3, acetonitrile is used as a solvent, N-chlorosuccinimide is used as an accelerating agent, oxygen in the air is used as an oxidizing agent, and the experiment has the following specific reaction process:
putting 10mmol (1.28 g) of p-fluorobenzenethiol and 15mmol (4 g) of N-chlorosuccinimide into a round-bottom flask under the atmosphere of air at room temperature, adding about 20mL of acetonitrile serving as a solvent, stirring, reacting for half an hour at room temperature, transferring a reaction solution into a 250mL separating funnel after the reaction is finished, extracting by using ethyl acetate (30 mL multiplied by 3), combining organic phases at the upper layer, drying, filtering, distilling to obtain a crude product, transferring the crude product into the round-bottom flask, adding the ethyl acetate under a heating condition until the crude product is just completely dissolved, fully cooling to separate out a solid, and filtering to obtain a product of p-fluorobenzenethiosulfonic acid S-p-fluorophenyl ester, wherein the yield is 70% (1.00 g). The product is a white solid with a melting point: 69-70 ℃.
As shown in fig. 2, the nuclear magnetic resonance data of the p-fluorobenzenesulfonic acid S-p-fluorophenyl ester: 1 h NMR (400 MHz, chloroform-d) delta 7.58-7.55 (m, 2H), 7.36-7.32 (m, 2H), 7.12-7.08 (m, 2H), 7.06-7.02 (m, 2H), molecular weight (GC-MS determination): 286.
example 3: synthesis of p-bromophenylthiosulfonate S-p-bromophenyl ester
The reaction substrates are p-bromothiophenol and N-chlorosuccinimide in a feeding ratio of 1:3, acetonitrile is used as a solvent, N-chlorosuccinimide is used as an accelerating agent, and oxygen in the air is used as an oxidizing agent, wherein the molar ratio is calculated as follows:
adding 10mmol (1.88 g) of p-bromothiophenol and 15mmol (4 g) of N-chlorosuccinimide into a round-bottom flask under the atmosphere of room temperature and air, adding about 20mL of acetonitrile solvent, stirring, reacting for half an hour under the condition of room temperature, transferring the reaction liquid into a 250mL separating funnel after the reaction is finished, extracting by using ethyl acetate (30 mL multiplied by 3), combining the organic phases at the upper layer, drying, filtering, distilling to obtain a crude product, transferring the crude product into the round-bottom flask, adding ethyl acetate under the heating condition until the crude product is completely dissolved, fully cooling to separate out a solid, and filtering to obtain the product of p-bromothiophenylsulfonic acid S-p-bromophenyl ester, wherein the yield is 68% (1.39 g). The product is a white solid with a melting point: at the temperature of between 158 and 159 ℃,
as shown in fig. 3, nuclear magnetic resonance data for S-p-bromophenyl p-bromophenylsulfonate: 1 h NMR (400mhz, chloroform-d) δ 7.58 (d, J =8.7hz, 2h), 7.49 (d, J =8.6hz, 2h), 7.41 (d, J =8.7hz, 2h), 7.22 (d, J =8.6hz, 2h) molecular weight (GC-MS determination): 408.
example 4: synthesis of p-methoxybenzenethiosulphonic acid S-p-methoxyphenyl ester
In terms of molar ratio, the feeding ratio of reaction substrates p-methoxythiophenol and N-chlorosuccinimide is 1:3, acetonitrile is used as a solvent, N-chlorosuccinimide is used as an accelerating agent, oxygen in the air is used as an oxidizing agent, and the experiment specifically comprises the following reaction processes:
putting 10mmol (1.4 g) of p-methoxythiophenol and 30mmol (4 g) of N-chlorosuccinimide into a round-bottom flask under the atmosphere of room temperature and air, adding about 20mL of acetonitrile serving as a solvent, stirring, reacting for half an hour at room temperature, transferring a reaction solution into a 250mL separating funnel after the reaction is finished, extracting by using ethyl acetate (30 mL multiplied by 3), combining organic phases at the upper layer, drying, filtering, distilling to obtain a crude product, transferring the crude product into the round-bottom flask, adding the ethyl acetate under the heating condition until the crude product is just completely dissolved, fully cooling to separate out a solid, and filtering to obtain the product of the p-methoxythiophenylsulfonic acid S-p-methoxyphenyl ester, wherein the yield is 83% (1.29 g). The product is a white solid with a melting point: 89 to 90 ℃.
As shown in FIG. 4, the nuclear magnetic resonance data of the product p-methoxybenzene thiophenylsulfonic acid S-p-methoxyphenyl: 1 h NMR (400 mhz, chloroform-d) δ 7.48 (d, J =9.0hz, 2h), 7.24 (d, J =8.8hz, 2h), 6.87-6.80 (m, 4H), 3.84 (s, 3H), 3.81 (s, 3H). Molecular weight (GC-MS determination) was: 310.
example 5: synthesis of p-tert-butylbenzene thiosulfonic acid S-p-tert-butylbenzene ester
The reaction substrates of p-tert-butyl thiophenol and N-chlorosuccinimide are fed in a molar ratio of 1:3, acetonitrile is used as a solvent, N-chlorosuccinimide is used as an accelerating agent, and oxygen in the air is used as an oxidizing agent, and the experiment has the following specific reaction process:
the method comprises the steps of putting 10mmol (1.66 g) of p-tert-butyl thiophenol and 30mmol (4 g) of N-chlorosuccinimide into a round-bottom flask under the air atmosphere at room temperature, adding about 20mL of acetonitrile serving as a solvent, stirring, reacting for half an hour at room temperature, transferring a reaction solution into a 250mL separating funnel after the reaction is completed, extracting with ethyl acetate (30 mL multiplied by 3), combining organic phases at the upper layer, drying, filtering, distilling to obtain a crude product, transferring the crude product into the round-bottom flask, adding ethyl acetate under heating until the crude product is just completely dissolved, fully cooling to separate out a solid, and filtering to obtain the product, namely the p-tert-butyl thiosulfonic acid S-p-tert-butyl phenyl ester, wherein the yield is 90% (1.63 g). The product is a white solid with a melting point: 141-143 ℃.
As shown in FIG. 5, the nuclear magnetic resonance data of the product, p-tert-butyl benzene thiosulfonic acid S-p-tert-butyl benzene ester: 1 h NMR (400mhz, chloroform-d) δ 7.97 (d, J =2.0hz, 2h), 7.95 (d, J =2.0hz, 2h), 7.63 (d, J =2.0hz, 2h), 7.61 (d, J =1.9hz, 2h), 1.37 (s, 18H). Molecular weight (GC-MS determination) was: 362.
example 6: synthesis of p-Nitrophenyl Thiosulfonic acid S-p-Nitrophenyl ester
The reaction substrates p-nitrothiophenol and N-chlorosuccinimide are calculated according to the molar ratio, the feeding ratio of the p-nitrothiophenol to the N-chlorosuccinimide is 1:3, acetonitrile is used as a solvent, the N-chlorosuccinimide is used as an accelerating agent, oxygen in the air is used as an oxidizing agent, and the experiment has the following specific reaction process:
putting 10mmol (1.55 g) of p-nitrobenzothiophenol and 30mmol (4 g) of N-chlorosuccinimide into a round-bottom flask under the air atmosphere at room temperature, adding about 20mL of acetonitrile serving as a solvent, stirring, reacting for half an hour at room temperature, transferring a reaction solution into a 250mL separating funnel after the reaction is finished, extracting by using ethyl acetate (30 mL multiplied by 3), combining organic phases at the upper layer, drying, filtering, distilling to obtain a crude product, transferring the crude product into the round-bottom flask, adding the ethyl acetate under the heating condition until the crude product is completely dissolved, fully cooling to separate out a solid, and filtering to obtain a product of p-nitrobenzenesulfonic acid S-p-nitrophenyl ester, wherein the yield is 60% (1.02 g). The product is a white solid with a melting point: 181-183 ℃.
As shown in fig. 6, nuclear magnetic resonance data of the product p-nitrophenylthio sulfonate S-p-nitrophenyl ester: 1 h NMR (400mhz, chloroform-d) δ 8.50 (d, J =2.0hz, 2h), 8.48 (d, J =2.1hz, 2h), 8.28 (d, J =2.1hz, 2h), 8.26 (d, J =2.0hz, 2h) molecular weight (GC-MS determination) was: 339.
example 7: synthesis of thiosulfonate compound by using 6-chloro-2-mercaptobenzothiazole as raw material
The reaction substrates 6-chloro-2-mercaptobenzothiazole and N-chlorosuccinimide are calculated according to the molar ratio, the feeding ratio of the reactants is 1:3, acetonitrile is used as a solvent, N-chlorosuccinimide is used as an accelerating agent, oxygen in the air is used as an oxidizing agent, and the experiment has the following specific reaction process:
putting 0.5mmol (101 mg) of p-6-chloro-2-mercaptobenzothiazole and 1.5mmol (200 mg) of N-chlorosuccinimide into a round-bottom flask under the atmosphere of air at room temperature, adding about 2mL of acetonitrile serving as a solvent, stirring, reacting for half an hour at room temperature, transferring a reaction solution into a 250mL separating funnel after the reaction is finished, extracting by using ethyl acetate (30 mL multiplied by 3), combining organic phases at the upper layer, drying, filtering, distilling to obtain a crude product, and finally separating by using column chromatography to obtain a product, wherein the column passing ratio is PE: EA = 90: 1, and the product yield is 75% (81 mg). The product was a colorless oily liquid.
As shown in fig. 7, the product nmr data: 1 h NMR (400MHz, chloroform-d) delta 7.89-7.83 (m, 2H), 7.78-7.75 (m, 2H), 7.45-7.42 (m, 2H). Molecular weights (GC-MS measurements) were: 431.
example 8: synthesis of thiosulfonate compound by using 4-methyl-2 mercaptobenzothiazole as raw material
The reaction substrates 4-methyl-2-mercaptobenzothiazole and N-chlorosuccinimide are calculated according to a molar ratio, the feeding ratio of the reaction substrates 4-methyl-2-mercaptobenzothiazole and N-chlorosuccinimide is 1:3, acetonitrile is used as a solvent, N-chlorosuccinimide is used as an accelerating agent, and oxygen in the air is used as an oxidizing agent, and the specific reaction process of the experiment is as follows:
putting 0.5mmol (90 mg) of p-4-methyl-2-mercaptobenzothiazole and 1.5mmol (200 mg) of N-chlorosuccinimide into a round bottom flask under the atmosphere of air at room temperature, adding about 2mL of acetonitrile solvent, stirring, reacting for half an hour under the condition of room temperature, transferring a reaction solution into a 250mL separating funnel after the reaction is finished, extracting by using ethyl acetate (30 mL multiplied by 3), combining organic phases at the upper layer, drying, filtering, distilling to obtain a crude product, and finally separating by using column chromatography to obtain a product, wherein the column chromatography ratio is PE: EA = 90: 1, and the product yield is 79% (77 mg). The product was a colorless oily liquid.
As shown in fig. 8, the product nmr data: 1 H NMR(400MHz，Chloroform-d)δ7.60(d，J＝7.7Hz，2H)，7.30-7.26(m，2H)，7.24(d，J＝7.4Hz，2H)，2.69 (s, 6H). Molecular weight (GC-MS determination) is: 391.
the foregoing merely represents preferred embodiments of the invention, which are described in some detail and detail, and therefore should not be construed as limiting the scope of the invention. It should be noted that, for those skilled in the art, various changes, modifications and substitutions can be made without departing from the spirit of the present invention, and these are all within the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the appended claims.
Claims (5)
1. A method for preparing a thiosulfonate compound by directly oxidizing thiophenol is characterized in that the method comprises the steps of adding the thiophenol compound with a structural formula (I) and a reaction promoter into a solvent, adopting oxygen or air as an oxidant, carrying out oxidation reaction for a certain time, and then purifying to obtain the thiosulfonate compound with a structural formula (II); the reaction promoter is N-chlorosuccinimide or N-bromosuccinimide;
in the formula, R is halogen, nitryl or alkyl.
2. The method for preparing the thiosulfonate compound by the direct oxidation of the thiophenol according to claim 1, wherein: the oxidation reaction time is 15-60 min; the reaction temperature is 15-60 ℃.
3. The method for preparing the thiosulfonate compound by the direct oxidation of the thiophenol according to claim 1, wherein: the molar equivalent ratio of the thiophenol compound to the reaction promoter is 1.5-5.
4. The method for preparing the thiosulfonate compound by the direct oxidation of the thiophenol according to claim 1, wherein: the solvent is one or more of dichloromethane, trichloromethane, carbon tetrachloride, dichloroethane, tetrahydrofuran, acetone, acetonitrile, diethyl ether, N-dimethylformamide, 1, 4-dioxane, benzene, toluene, N-hexane and petroleum ether.
5. The method for preparing the thiosulfonate compound by the direct oxidation of the thiophenol according to claim 1, wherein: the purification method comprises one or more of extraction, drying, reduced pressure distillation, silica gel column chromatography, recrystallization and filtration.
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