CN115521234B - Synthesis method of o-aminothiophenol - Google Patents

Synthesis method of o-aminothiophenol Download PDF

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CN115521234B
CN115521234B CN202211497655.5A CN202211497655A CN115521234B CN 115521234 B CN115521234 B CN 115521234B CN 202211497655 A CN202211497655 A CN 202211497655A CN 115521234 B CN115521234 B CN 115521234B
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reaction
disulfide
aminothiophenol
metal catalyst
water
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CN115521234A (en
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黄忠林
陈玮
卫海浩
徐剑锋
曾淼
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SUZHOU KAIYUAN MINSHENG CHEMICALS TECHNOLOGY CO LTD
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
    • C07C319/06—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols from sulfides, hydropolysulfides or polysulfides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/22—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides
    • C07C319/24—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides by reactions involving the formation of sulfur-to-sulfur bonds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The invention relates to a method for synthesizing o-aminothiophenol, which adopts o-chloronitrobenzene and sulfur-containing mixed solution prepared by sodium sulfide, sulfur and water to obtain disulfide through reaction; the disulfide is 2,2' -dinitro diphenyl disulfide; the disulfide is subjected to hydrogenation reduction reaction under the action of a metal catalyst to obtain o-aminothiophenol. The process of the invention adopts common reagents, and has the advantages of low cost, high reaction yield, less three wastes and simple post-treatment.

Description

Synthesis method of o-aminothiophenol
Technical Field
The invention relates to a synthesis method of o-aminothiophenol, belonging to the technical field of compound preparation.
Background
The o-aminothiophenol is an important intermediate for synthesizing fine chemicals such as medicines, dyes, auxiliaries, organic reagents and the like, and the o-aminothiophenol is a light yellow liquid with the melting point of 23-26 ℃. The common synthetic routes for ortho-aminothiophenols are: (1) The o-nitrochlorobenzene is used as a raw material and is obtained by sulfuration reduction; (2) Is obtained by alkali hydrolysis and neutralization of benzothiazole or 2-aminobenzothiazole. Compared with benzothiazole and 2-aminobenzothiazole, the o-nitrochlorobenzene has large market supply quantity and low price, so the synthetic route (1) is more beneficial to industrialization and market competition.
The synthetic route (1) firstly prepares disulfide intermediate through sulfuration reaction, and then prepares the o-amino thiophenol through reduction reaction. Among them, there are various methods for the reduction of disulfide, for example, purushothama Chayr and the like [1] Using zirconium chloride/sodium borohydride (ZrCl) 4 /NaBH 4 ) Reducing to generate 90 percent of o-aminothiophenol and 10 percent of o-nitrobenzothiophenol; bogert et al [2] Teppema et al [3] With ZnReduction of acetic acid; claasz et al [4] Reduction using tin/acetic acid; sanina et al [5] Reduction using hydrazine hydrate; zhong et al [6] Reducing by using samarium iodide; however, the above methods have some problems: the used reagent is expensive, or more three wastes are generated, or the post-treatment is troublesome.
The applicant filed for the present invention a patent for the preparation of o-aminothiophenol on 13/11/2020 (CN 112062699B), after which the applicant continued further research and obtained research results.
The references referred to above are as follows:
[1] Synthetic Communications, 2000, vol 30, p3905-3911；
[2] JACS，1924，vol46, p1310；
[3] JACS, 1927, vol p1757；
[4] Chemische Berichte, 1912, vol 45, p1031；
[5] Journal of Coordination Chemistry, 2013, vol 66, p3602-3618；
[6] Tetrahedron Letters, 2001, vol 42, p3125-3127。
disclosure of Invention
The main purposes of the invention are: the method for synthesizing the o-aminothiophenol overcomes the problems in the prior art, adopts common reagents, and has the advantages of low cost, high reaction yield, less three wastes and simple post-treatment.
The technical scheme for solving the technical problems of the invention is as follows:
a method for synthesizing o-aminothiophenol is characterized by comprising the following steps:
firstly, reacting o-chloronitrobenzene and a sulfur-containing mixed solution prepared from sodium sulfide, sulfur and water to obtain a disulfide; the disulfide is 2,2' -dinitro diphenyl disulfide, and the structure is shown as a formula I;
Figure DEST_PATH_IMAGE001
and secondly, carrying out hydrogenation reduction reaction on the disulfide under the action of a metal catalyst to obtain o-aminothiophenol.
The method takes o-chloronitrobenzene as a raw material to prepare a disulfide intermediate through a sulfuration reaction: 2,2' -dinitrodiphenyldisulfide; then the disulfide intermediate is hydrogenated and reduced to prepare the o-amino thiophenol. The method adopts common reagents, and has the advantages of low cost, high reaction yield, less three wastes and simple post-treatment.
The further improved technical scheme of the invention is as follows:
preferably, the specific process of the first step is as follows:
adding tetrabutylammonium bromide into N-methylpyrrolidone, heating to a preset temperature, dropwise adding molten o-chloronitrobenzene, dropwise adding a sulfur-containing mixed solution, carrying out heat preservation reaction, cooling the reaction solution to an ambient temperature after the reaction is finished, carrying out suction filtration to obtain a filter cake, washing with water, and drying to obtain the disulfide which is a yellow solid.
More preferably, the predetermined temperature is 90 ℃ ± 5 ℃; the dripping process is finished within 2 plus or minus 0.5 hours; stirring is continuously carried out during the heat preservation reaction, and the heat preservation reaction time is 1-1.5 hours.
More preferably, the ratio of tetrabutylammonium bromide to N-methylpyrrolidone is 1:3-10 g/ml, wherein the weight ratio of the o-chloronitrobenzene to the tetrabutylammonium bromide is 50 +/-10: 1.
the above preferred embodiment is the first preferred embodiment of the first step, and disulfide as an intermediate can be obtained in a high yield.
Preferably, the specific process of the first step is as follows:
adding o-chloronitrobenzene into ethanol, heating to reflux, dropwise adding a sulfur-containing mixed solution, carrying out heat preservation reaction, concentrating the reaction solution after the reaction is finished, adding water, carrying out suction filtration to obtain a filter cake, and washing and drying to obtain the disulfide which is yellow solid.
More preferably, the weight ratio of o-chloronitrobenzene to ethanol is 1:4 plus or minus 1; the reflux temperature is 78 +/-2 ℃; the dripping process is finished within 2 plus or minus 0.5 hours; stirring is continuously carried out during the heat preservation reaction, and the heat preservation reaction time is 2-2.5 hours.
The above preferred embodiment is the second preferred embodiment of the first step, and disulfide as an intermediate can be obtained in a higher yield.
More preferably, when preparing the sulfur-containing mixed solution, the ratio of sodium sulfide to water is 360 ± 20:1 mg/ml, sulphur to water ratio 14.6 ± 1:1 mg/ml, the weight ratio of sodium sulfide to sulfur is 4.1 +/-0.5: 1.
by adopting the preferred scheme, the specific proportioning composition of the sulfur-containing mixed liquor can be further optimized.
Preferably, the specific process of the second step is as follows:
adding a solvent, a disulfide and a metal catalyst into a high-pressure reaction kettle, performing hydrogen replacement after the kettle is combined, and then starting heating reaction; and after the reaction is finished, filtering the reaction liquid to collect the metal catalyst, pouring the filtrate into water, extracting with dichloromethane, concentrating an organic phase to obtain a crude product, and rectifying the crude product to obtain the finished product of the o-aminothiophenol.
More preferably, the metal catalyst is selected from Raney nickel, palladium on carbon, platinum on carbon, pd (OH) 2 /C、Pd/Al 2 O 3 (ii) a The solvent is selected from methanol, ethanol, isopropanol, THF, water, petroleum ether, dichloromethane, dichloroethane, and toluene; the reaction temperature is 30-90 ℃, the reaction pressure is 0.3-2MPa, and the reaction time is 4-9 hours.
More preferably, the weight ratio of the solvent, disulfide, metal catalyst is 300 ± 70:100 +/-50: 2-5; alternatively, the metal catalyst is selected from raney nickel, palladium carbon, platinum carbon.
By adopting the preferable scheme, the specific technical characteristics of the second step can be further optimized.
Compared with the prior art, the process takes o-chloronitrobenzene as a raw material, and prepares the disulfide intermediate through a vulcanization reaction: 2,2' -dinitro diphenyl disulfide, and then carrying out catalytic hydrogenation reduction on the disulfide intermediate by using a metal catalyst to obtain an o-amino thiophenol finished product; the whole route adopts common reagents, the cost is low, the reaction yield is high, the three wastes are less, and the post-treatment is simple.
Drawings
FIG. 1 is a reaction scheme of the present invention.
FIG. 2 shows a flowchart of example 1 of the present invention 1 H NMR chart.
Detailed Description
As shown in FIG. 1, the method for synthesizing o-aminothiophenol of the present invention comprises the following steps:
firstly, reacting o-chloronitrobenzene and a sulfur-containing mixed solution prepared from sodium sulfide, sulfur and water to obtain a disulfide; the disulfide is 2,2' -dinitro diphenyl disulfide, and the structure is shown in a formula I.
Figure 409558DEST_PATH_IMAGE001
The specific process of the first step is as follows:
first preferred embodiment: adding tetrabutylammonium bromide into N-methylpyrrolidone, heating to a preset temperature, dropwise adding molten o-chloronitrobenzene, dropwise adding a sulfur-containing mixed solution at the same time, carrying out heat preservation reaction, cooling the reaction solution to the ambient temperature after the reaction is finished, carrying out suction filtration to obtain a filter cake, and washing and drying to obtain the disulfide which is a yellow solid.
Wherein the preset temperature is 90 +/-5 ℃; the dripping process is finished within 2 plus or minus 0.5 hours; stirring is continuously carried out during the heat preservation reaction, and the heat preservation reaction time is 1-1.5 hours. The ratio of tetrabutylammonium bromide to N-methylpyrrolidone is 1:3-10 g/ml, the weight ratio of o-chloronitrobenzene to tetrabutylammonium bromide is 50 +/-10: 1.
second preferred embodiment: adding o-chloronitrobenzene into ethanol, heating to reflux, dropwise adding a sulfur-containing mixed solution, carrying out heat preservation reaction, concentrating the reaction solution after the reaction is finished, adding water, carrying out suction filtration to obtain a filter cake, and washing and drying to obtain the disulfide which is yellow solid.
Wherein the weight ratio of o-chloronitrobenzene to ethanol is 1:4 plus or minus 1; the reflux temperature is 78 +/-2 ℃; the dripping process is finished within 2 plus or minus 0.5 hours; stirring is continuously carried out during the heat preservation reaction, and the heat preservation reaction time is 2-2.5 hours.
In addition, when preparing the sulfur-containing mixed solution, the ratio of sodium sulfide to water is 360 ± 20:1 mg/ml, sulphur to water ratio 14.6 ± 1:1 mg/ml, the weight ratio of sodium sulfide to sulfur is 4.1 +/-0.5: 1.
and secondly, carrying out hydrogenation reduction reaction on the disulfide under the action of a metal catalyst to obtain o-aminothiophenol.
The second step comprises the following specific processes:
adding a solvent, a disulfide and a metal catalyst into a high-pressure reaction kettle, performing hydrogen replacement after the kettle is closed, and then starting heating reaction; and after the reaction is finished, filtering the reaction liquid to collect the metal catalyst, pouring the filtrate into water, extracting with dichloromethane, concentrating an organic phase to obtain a crude product, and rectifying the crude product to obtain the finished product of the o-aminothiophenol.
Wherein the metal catalyst is selected from Raney nickel, palladium carbon, platinum carbon, pd (OH) 2 /C、Pd/Al 2 O 3 (preferably Raney nickel, palladium on carbon, platinum on carbon); the solvent is selected from methanol, ethanol, isopropanol, THF, water, petroleum ether, dichloromethane, dichloroethane, and toluene; the reaction temperature is 30-90 ℃, the reaction pressure is 0.3-2MPa, and the reaction time is 4-9 hours. The weight ratio of the solvent, the disulfide and the metal catalyst is 300 +/-70: 100 +/-50: 2-5.
The present invention will be described in further detail with reference to examples. The invention is not limited to the examples given.
Example 1
This example is a specific example of the preparation of ortho-aminothiophenol.
The basic process of this embodiment is the specific implementation technical solution of the present invention described above.
Some specific details of this embodiment are as follows:
10ml of N-methylpyrrolidone and 1g of tetrabutylammonium bromide were charged into a reaction flask. The reaction solution is heated to 90 ℃, 50g of fused o-chloronitrobenzene is dripped, and a prepared sulfur-containing mixed solution (21.4 g of sodium sulfide/5.2 g of sulfur/60 ml of water) is dripped at the same time, and the dripping is finished within about 2 hours. The heat preservation and stirring are continued for 1 hour. The reaction solution was cooled to room temperature, filtered, the filter cake washed with water and dried to give an intermediate product as a yellow solid with a purity of 98.6% containing 48.1g of disulfide and a yield of 98.4% (theoretical weight 48.9 g).
Adding 300g of methanol, 100g of disulfide and 5g of Raney nickel into a 1L high-pressure reaction kettle, closing the kettle, performing hydrogen replacement, and reacting at the temperature of 30-70 ℃ under the pressure of 1-2MPa. Opening the kettle after 8h, filtering and collecting the catalyst, pouring the filtrate into water, extracting with dichloromethane, and concentrating the organic phase to obtain the crude o-aminothiophenol. The crude product is rectified to obtain a product with the purity of 99.5 percent, wherein the product contains 76.0g of o-aminothiophenol, the yield is 93.6 percent (the theoretical weight is 81.2 g), and the nuclear magnetic hydrogen spectrum of the product 1 H NMR(500MHz，CDCl 3 ) As shown in fig. 2: δ =3.42 (s, 1h, sh), δ =6.31 (s, 2h, nh) 2 )，6.50(d，1H，ArH)，6.62(t，1H，ArH)，6.97(t，1H，ArH)，7.19(d，1H，ArH)。
Example 2
This example is a specific example of the preparation of ortho aminothiophenols.
The basic process of this embodiment is the specific implementation technical solution of the present invention described above.
Some specific details of this embodiment are as follows:
200g of ethanol and 50g of o-chloronitrobenzene are added into a reaction bottle, and the temperature is raised to reflux. The prepared mixed solution (sodium sulfide 21.4 g/sulfur 5.2 g/water 60 ml) is added dropwise, and the dropping is finished within about 2 hours. Stirring for 2h under constant temperature. The reaction solution was concentrated, water was added, suction filtered, the filter cake washed with water and dried to give an intermediate product as a yellow solid with a purity of 98.5% containing 46.2g of disulfide and a yield of 94.5% (theoretical weight 48.9 g).
Adding 300g of methanol, 100g of disulfide and 2g of palladium carbon into a 1L high-pressure reaction kettle, closing the kettle, replacing the mixture by hydrogen, and reacting at the temperature of 30 to 70 ℃ under the pressure of 0.3 to 1MPa. And opening the kettle after 5 hours, filtering and collecting the catalyst, pouring the filtrate into water, extracting with dichloromethane, and concentrating to obtain a crude product of o-aminothiophenol. The crude product was rectified to give a product with a purity of 99.5% containing 76.4g of ortho-aminothiophenol, and a yield of 94.1% (theoretical weight 81.2 g).
Example 3
This example is a specific example of the preparation of ortho-aminothiophenol.
The basic process of this embodiment is the specific implementation technical solution of the present invention described above.
Some specific details of this embodiment are as follows:
3ml of N-methylpyrrolidone and 1g of tetrabutylammonium bromide were charged into the reaction flask. The reaction solution is heated to 90 ℃, 50g of fused o-chloronitrobenzene is dripped, and simultaneously, a prepared mixed solution (22.5 g of sodium sulfide/5.5 g of sulfur/60 ml of water) is dripped, and the dripping is finished within about 2 hours. Stirring for 2h under constant temperature. The reaction solution was cooled to room temperature, filtered, the filter cake washed with water and dried to give an intermediate product as a yellow solid with a purity of 98.6% containing 47.5g of disulfide in a yield of 97.1% (theoretical weight 48.9 g).
Adding 300g of methanol, 100g of disulfide and 2g of platinum carbon into a 1L high-pressure reaction kettle, closing the kettle, replacing the mixture by hydrogen, and reacting at the temperature of between 60 and 90 ℃ under the pressure of between 0.3 and 1MPa. And opening the kettle after 5 hours, filtering and collecting the catalyst, pouring the filtrate into water, extracting with dichloromethane, and concentrating to obtain a crude product of o-aminothiophenol. The crude product was rectified to give a product with a purity of 99.5% containing 77.3g of ortho-aminothiophenol and a yield of 95.2% (theoretical weight 81.2 g).
In addition to the above embodiments, the present invention may have other embodiments. All technical solutions formed by adopting equivalent substitutions or equivalent transformations fall within the protection scope of the claims of the present invention.

Claims (4)

1. A method for synthesizing o-aminothiophenol is characterized by comprising the following steps:
firstly, reacting o-chloronitrobenzene and a sulfur-containing mixed solution prepared from sodium sulfide, sulfur and water to obtain a disulfide; the disulfide is 2,2' -dinitro diphenyl disulfide, and the structure is shown as a formula I;
Figure DEST_PATH_IMAGE002
；
the specific process of the first step is as follows:
adding tetrabutylammonium bromide into N-methylpyrrolidone, heating to a preset temperature, dropwise adding molten o-chloronitrobenzene, dropwise adding a sulfur-containing mixed solution, carrying out heat preservation reaction, cooling the reaction solution to an ambient temperature after the reaction is finished, carrying out suction filtration to obtain a filter cake, and washing and drying to obtain a yellow solid disulfide;
wherein the preset temperature is 90 +/-5 ℃; the dripping process is finished within 2 plus or minus 0.5 hours; stirring continuously during the heat preservation reaction, wherein the heat preservation reaction time is 1-1.5 hours; the ratio of tetrabutylammonium bromide to N-methylpyrrolidone is 1:3-10 g/ml, wherein the weight ratio of the o-chloronitrobenzene to the tetrabutylammonium bromide is 50 +/-10: 1;
secondly, carrying out hydrogenation reduction reaction on the disulfide under the action of a metal catalyst to obtain o-aminothiophenol;
the second step comprises the following specific processes:
adding a solvent, a disulfide and a metal catalyst into a high-pressure reaction kettle, performing hydrogen replacement after the kettle is combined, and then starting heating reaction; after the reaction is finished, filtering the reaction liquid to collect the metal catalyst, then pouring the filtrate into water, extracting with dichloromethane, concentrating an organic phase to obtain a crude product, and rectifying the crude product to obtain a finished product of o-aminothiophenol;
the metal catalyst is selected from Raney nickel, palladium carbon, platinum carbon, pd (OH) 2 /C、Pd/Al 2 O 3 (ii) a The solvent is selected from methanol, ethanol, isopropanol, THF, water, petroleum ether, dichloromethane, dichloroethane, and toluene; the reaction temperature is 30-90 ℃, the reaction pressure is 0.3-2MPa, and the reaction time is 4-9 hours.
2. The method for synthesizing o-aminothiophenol as claimed in claim 1, wherein the ratio of sodium sulfide to water is 360 ± 20:1 mg/ml, sulphur to water ratio 14.6 ± 1:1 mg/ml, the weight ratio of sodium sulfide to sulfur is 4.1 +/-0.5: 1.
3. the method for synthesizing o-aminothiophenol according to claim 1, wherein the weight ratio of said solvent, disulfide and metal catalyst is 300 ± 70:100 +/-50: 2-5.
4. The method as claimed in claim 1, wherein the metal catalyst is selected from Raney nickel, palladium on carbon, and platinum on carbon.
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