CN111087383A - Production method of 2-mercaptothiophene - Google Patents
Production method of 2-mercaptothiophene Download PDFInfo
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- CN111087383A CN111087383A CN201911327392.1A CN201911327392A CN111087383A CN 111087383 A CN111087383 A CN 111087383A CN 201911327392 A CN201911327392 A CN 201911327392A CN 111087383 A CN111087383 A CN 111087383A
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- mercaptothiophene
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D333/30—Hetero atoms other than halogen
- C07D333/34—Sulfur atoms
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Abstract
The invention discloses a production method of 2-mercaptothiophene, which comprises the steps of proportioning 2-bromothiophene, magnesium chips and diethyl ether, carrying out Grignard reaction, adding sulfur, adding acid, layering, heating and distilling, adding water for elution, and carrying out rectification under reduced pressure to obtain the 2-mercaptothiophene. According to the creative design, 2-bromothiophene, magnesium chips and diethyl ether are uniformly mixed and then subjected to Grignard reaction, then sulfur powder and hydrochloric acid are added, the mixture is kept stand to obtain a supernatant, and the supernatant is subjected to heating distillation and reduced pressure rectification treatment to obtain 2-mercaptothiophene; the method has the advantages of simple steps, simple and convenient operation, less material consumption, reduction of production cost, complete reaction guarantee in each step, smooth product obtaining after the reaction is finished, reduction of side reaction, improvement of product yield after the reaction, and suitability for industrial production.
Description
Technical Field
The invention belongs to the technical field of medicines and chemical engineering, and particularly relates to a production method of 2-mercaptothiophene.
Background
The 2-mercaptothiophene is named as 2-thiophenethiol in Chinese, and is named as thiophene-2-thiol, 2-thiophenethiol and 2-thiophenethiol in Chinese, and the molecular formula is C4H4S2Molecular weight is 116.21; the flash point was 54.7 ℃ and the density was 1.23; physical and chemical properties: is colorless or yellowish oily liquid, is easily oxidized in air, is dissolved in water in a trace amount, is dissolved in organic flux such as acetone and has a boiling point of 166 ℃. Sensory characteristics: has an extremely unpleasant burning, burnt and sulfur smell. Mainly for preparing flavouring essences, for confectionery and baked goodsAromatized, at a concentration of about 0.1mg/kg in the final aromatized food product.
At present, the prior art related to 2-mercaptothiophene has some problems, but the 2-mercaptothiophene has poor stability and is easy to oxidize, so that a byproduct is generated, the reaction yield is influenced, the yield of the prepared 2-mercaptothiophene is not high, the operation is complex, the number of steps is more, the loss of each step of reaction is caused, the consumption of raw materials is more, the production cost is increased, and the industrial production is not facilitated.
Disclosure of Invention
The invention provides a production method of 2-mercaptothiophene for solving the technical problems.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method for producing 2-mercaptothiophene, comprising the steps of:
(1) uniformly mixing 2-bromothiophene and first part of diethyl ether to obtain a mixed solution, then adding second part of diethyl ether and magnesium chips into a reaction kettle, dropwise adding the mixed solution into the reaction kettle in a stirring state, and heating and refluxing the mixed solution after dropwise adding is finished to carry out Grignard reaction;
(2) after the Grignard reaction is finished, adding sulfur powder into the solution, heating and refluxing, then dropwise adding hydrochloric acid, standing and layering after the reaction is finished, and collecting supernatant;
(3) and (3) heating and distilling the supernatant, adding water for elution, then carrying out reduced pressure rectification, and recovering the solvent diethyl ether to obtain the 2-mercaptothiophene.
In step (1), the mass ratio of the 2-bromothiophene to the magnesium chips to the diethyl ether is 6-7: 1: 11-12.
Further, in step (1), the mass ratio of the first portion of diethyl ether to the second portion of diethyl ether is 2: 1.
Further, in the step (2), the mass ratio of the 2-bromothiophene to the sulfur powder is 1: 4.5-5.5.
Further, in the step (2), the mass ratio of the 2-bromothiophene to the hydrochloric acid is 1: 0.5-1.
Further, in the step (2), the mass concentration of the hydrochloric acid is 17% to 19%.
Further, in the steps (1) and (2), the temperature of the heating reflux is 36-38 ℃, and the time is 110-130 min.
Further, in the step (3), the temperature of the heating distillation is 55-60 ℃, and the time is 180-200 min.
Further, in the step (3), the pressure of the vacuum rectification is 0.01Mpa to 0.05Mpa, the temperature is 50 ℃ to 60 ℃, and the time is 100min to 120 min.
The application relates to the following reaction formula:
due to the adoption of the technical scheme, the invention has the following beneficial effects:
according to the creative design, 2-bromothiophene, magnesium chips and diethyl ether are uniformly mixed and then subjected to Grignard reaction, then sulfur powder and hydrochloric acid are added, the mixture is kept stand to obtain a supernatant, and the supernatant is subjected to heating distillation and reduced pressure rectification treatment to obtain 2-mercaptothiophene; the method has the advantages of simple steps, simple and convenient operation, less material consumption, reduction of production cost, complete reaction guarantee in each step, smooth product obtaining after the reaction is finished, reduction of side reaction, improvement of product yield after the reaction, and suitability for industrial production.
Drawings
In order to illustrate the embodiments of the present invention or the technical solutions in the prior art more clearly, the drawings needed in the description of the embodiments or the prior art will be briefly introduced below, it is obvious that the drawings in the following description are only some examples of the present invention, and for a person skilled in the art, without inventive step, other drawings can be obtained according to these drawings:
FIG. 1 is a flow chart of the process for producing 2-mercaptothiophene of the present application.
Detailed Description
The following is a detailed description of the embodiments of the present invention, but the present invention is not limited to these embodiments, and any modifications or substitutions in the basic spirit of the embodiments are included in the scope of the present invention as claimed in the claims.
Example 1
A method for producing 2-mercaptothiophene, comprising the steps of:
(1) uniformly mixing 2-bromothiophene and first part of diethyl ether to obtain a mixed solution, then adding second part of diethyl ether and magnesium chips into a reaction kettle, dropwise adding the mixed solution into the reaction kettle in a stirring state, and heating and refluxing the mixed solution after dropwise adding is finished to carry out Grignard reaction;
the mass ratio of the 2-bromothiophene to the magnesium chips to the diethyl ether is 6:1: 11; the mass ratio of the first part of ethyl ether to the second part of ethyl ether is 2: 1;
(2) after the Grignard reaction is finished, adding sulfur powder into the solution, heating and refluxing, then dropwise adding hydrochloric acid, standing and layering after the reaction is finished, and collecting supernatant;
the mass ratio of the 2-bromothiophene to the sulfur powder is 1: 4.5; the mass ratio of the 2-bromothiophene to the hydrochloric acid is 1: 0.5; the mass concentration of the hydrochloric acid is 17%;
(3) heating and distilling the supernatant, adding water for elution, then carrying out reduced pressure rectification, and recovering a solvent diethyl ether to obtain the 2-mercaptothiophene;
in the step (3), the temperature of the heating distillation is 55 ℃, and the time is 180 min; the pressure of the vacuum rectification is 0.01Mpa, the temperature is 50 ℃, and the time is 100 min.
Further, in the steps (1) and (2), the temperature of the heating reflux is 36 ℃ and the time is 110 min.
Example 2
A method for producing 2-mercaptothiophene, comprising the steps of:
(1) uniformly mixing 2-bromothiophene and first part of diethyl ether to obtain a mixed solution, then adding second part of diethyl ether and magnesium chips into a reaction kettle, dropwise adding the mixed solution into the reaction kettle in a stirring state, and heating and refluxing the mixed solution after dropwise adding is finished to carry out Grignard reaction;
the mass ratio of the 2-bromothiophene to the magnesium chips to the diethyl ether is 7:1: 12; the mass ratio of the first part of ethyl ether to the second part of ethyl ether is 2: 1;
(2) after the Grignard reaction is finished, adding sulfur powder into the solution, heating and refluxing, then dropwise adding hydrochloric acid, standing and layering after the reaction is finished, and collecting supernatant;
the mass ratio of the 2-bromothiophene to the sulfur powder is 1: 5.5; the mass ratio of the 2-bromothiophene to the hydrochloric acid is 1: 1; the mass concentration of the hydrochloric acid is 19%;
(3) heating and distilling the supernatant, adding water for elution, then carrying out reduced pressure rectification, and recovering a solvent diethyl ether to obtain the 2-mercaptothiophene;
in the step (3), the temperature of the heating distillation is 60 ℃, and the time is 200 min; the pressure of the vacuum rectification is 0.05Mpa, the temperature is 60 ℃, and the time is 120 min.
Further, in the steps (1) and (2), the temperature of the heating reflux is 38 ℃ and the time is 130 min.
Example 3
A method for producing 2-mercaptothiophene, comprising the steps of:
(1) uniformly mixing 2-bromothiophene and first part of diethyl ether to obtain a mixed solution, then adding second part of diethyl ether and magnesium chips into a reaction kettle, dropwise adding the mixed solution into the reaction kettle in a stirring state, and heating and refluxing the mixed solution after dropwise adding is finished to carry out Grignard reaction;
the mass ratio of the 2-bromothiophene to the magnesium chips to the diethyl ether is 6.2:1: 11.2; the mass ratio of the first part of ethyl ether to the second part of ethyl ether is 2: 1;
(2) after the Grignard reaction is finished, adding sulfur powder into the solution, heating and refluxing, then dropwise adding hydrochloric acid, standing and layering after the reaction is finished, and collecting supernatant;
the mass ratio of the 2-bromothiophene to the sulfur powder is 1: 4.7; the mass ratio of the 2-bromothiophene to the hydrochloric acid is 1: 0.6; the mass concentration of the hydrochloric acid is 17.5%;
(3) heating and distilling the supernatant, adding water for elution, then carrying out reduced pressure rectification, and recovering a solvent diethyl ether to obtain the 2-mercaptothiophene;
in the step (3), the temperature of the heating distillation is 56 ℃, and the time is 185 min; the pressure of the vacuum rectification is 0.02Mpa, the temperature is 52 ℃, and the time is 105 min.
Further, in the steps (1) and (2), the temperature of the heating reflux is increased to 36.5 ℃ for 115 min.
Example 4
A method for producing 2-mercaptothiophene, comprising the steps of:
(1) uniformly mixing 2-bromothiophene and first part of diethyl ether to obtain a mixed solution, then adding second part of diethyl ether and magnesium chips into a reaction kettle, dropwise adding the mixed solution into the reaction kettle in a stirring state, and heating and refluxing the mixed solution after dropwise adding is finished to carry out Grignard reaction;
the mass ratio of the 2-bromothiophene to the magnesium chips to the diethyl ether is 6.9:1: 11.8; the mass ratio of the first part of ethyl ether to the second part of ethyl ether is 2: 1;
(2) after the Grignard reaction is finished, adding sulfur powder into the solution, heating and refluxing, then dropwise adding hydrochloric acid, standing and layering after the reaction is finished, and collecting supernatant;
the mass ratio of the 2-bromothiophene to the sulfur powder is 1: 5.3; the mass ratio of the 2-bromothiophene to the hydrochloric acid is 1: 0.9; the mass concentration of the hydrochloric acid is 18.5%;
(3) heating and distilling the supernatant, adding water for elution, then carrying out reduced pressure rectification, and recovering a solvent diethyl ether to obtain the 2-mercaptothiophene;
in the step (3), the temperature of the heating distillation is 59 ℃, and the time is 195 min; the pressure of the vacuum rectification is 0.04Mpa, the temperature is 58 ℃, and the time is 115 min.
Further, in the steps (1) and (2), the temperature of the heating reflux is 37.5 ℃ for 125 min.
Example 5
A method for producing 2-mercaptothiophene, comprising the steps of:
(1) uniformly mixing 2-bromothiophene and first part of diethyl ether to obtain a mixed solution, then adding second part of diethyl ether and magnesium chips into a reaction kettle, dropwise adding the mixed solution into the reaction kettle in a stirring state, and heating and refluxing the mixed solution after dropwise adding is finished to carry out Grignard reaction;
the mass ratio of the 2-bromothiophene to the magnesium chips to the diethyl ether is 6.5:1: 11.5; the mass ratio of the first part of ethyl ether to the second part of ethyl ether is 2: 1;
(2) after the Grignard reaction is finished, adding sulfur powder into the solution, heating and refluxing, then dropwise adding hydrochloric acid, standing and layering after the reaction is finished, and collecting supernatant;
the mass ratio of the 2-bromothiophene to the sulfur powder is 1: 5; the mass ratio of the 2-bromothiophene to the hydrochloric acid is 1: 0.8; the mass concentration of the hydrochloric acid is 18%;
(3) heating and distilling the supernatant, adding water for elution, then carrying out reduced pressure rectification, and recovering a solvent diethyl ether to obtain the 2-mercaptothiophene;
in the step (3), the temperature of the heating distillation is 57 ℃, and the time is 190 min; the pressure of the vacuum rectification is 0.03Mpa, the temperature is 55 ℃, and the time is 110 min.
Further, in the steps (1) and (2), the temperature of the heating reflux is 37 ℃ and the time is 120 min.
Comparative example 1
The difference from the embodiment 1 is that: the raw materials of 2-bromothiophene, sulfur powder, hydrochloric acid, magnesium chips and ether are added in different proportions, and other conditions are unchanged.
The processes of example 1 and comparative example 1 of the present application were used to prepare 2-mercaptothiophene, respectively, with the process material inputs and outputs shown in table 1 below.
TABLE 1
As shown in the experimental data in Table 1, compared with the prior art, the method disclosed by the application has the advantages that the required cost is lower, the discharged wastewater and waste gas are less, and the energy is saved and the environment is protected when the 2-mercaptothiophene is prepared.
In summary, the creative design of the method is to mix 2-bromothiophene, magnesium chips and ether uniformly and then carry out Grignard reaction, then add sulfur powder and hydrochloric acid, obtain a supernatant after standing, and carry out heating distillation and reduced pressure rectification treatment on the supernatant so as to obtain 2-mercaptothiophene; the method has the advantages of simple steps, simple and convenient operation, less material consumption, reduction of production cost, complete reaction guarantee in each step, smooth product obtaining after the reaction is finished, reduction of side reaction, improvement of product yield after the reaction, and suitability for industrial production.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (9)
1. A production method of 2-mercaptothiophene is characterized by comprising the following steps:
(1) uniformly mixing 2-bromothiophene and first part of diethyl ether to obtain a mixed solution, then adding second part of diethyl ether and magnesium chips into a reaction kettle, dropwise adding the mixed solution into the reaction kettle in a stirring state, and heating and refluxing the mixed solution after dropwise adding is finished to carry out Grignard reaction;
(2) after the Grignard reaction is finished, adding sulfur powder into the solution, heating and refluxing, then dropwise adding hydrochloric acid, standing and layering after the reaction is finished, and collecting supernatant;
(3) and (3) heating and distilling the supernatant, adding water for elution, then carrying out reduced pressure rectification, and recovering the solvent diethyl ether to obtain the 2-mercaptothiophene.
2. The process according to claim 1 for producing 2-mercaptothiophene, wherein: in the step (1), the mass ratio of the 2-bromothiophene to the magnesium chips to the diethyl ether is 6-7: 1: 11-12.
3. The process according to claim 1 for producing 2-mercaptothiophene, wherein: in step (1), the mass ratio of the first portion of diethyl ether to the second portion of diethyl ether is 2: 1.
4. The process according to claim 1 for producing 2-mercaptothiophene, wherein: in the step (2), the mass ratio of the 2-bromothiophene to the sulfur powder is 1: 4.5-5.5.
5. The process according to claim 1 for producing 2-mercaptothiophene, wherein: in the step (2), the mass ratio of the 2-bromothiophene to the hydrochloric acid is 1: 0.5-1.
6. The process according to claim 1 for producing 2-mercaptothiophene, wherein: in the step (2), the mass concentration of the hydrochloric acid is 17-19%.
7. The process according to claim 1 for producing 2-mercaptothiophene, wherein: in the steps (1) and (2), the temperature of the heating reflux is increased to 36-38 ℃ for 110-130 min.
8. The process according to claim 1 for producing 2-mercaptothiophene, wherein: in the step (3), the temperature of the heating distillation is 55-60 ℃, and the time is 180-200 min.
9. The process according to claim 1 for producing 2-mercaptothiophene, wherein: in the step (3), the pressure of the reduced pressure distillation is 0.01Mpa to 0.05Mpa, the temperature is 50 ℃ to 60 ℃, and the time is 100min to 120 min.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101074226A (en) * | 2007-04-12 | 2007-11-21 | 北京精华耀邦医药科技有限公司 | Synthesis of polyzorine intermediate 3-(2-phobic-thiophene) butyric acid |
| CN101293899A (en) * | 2007-04-28 | 2008-10-29 | 中国人民解放军军事医学科学院毒物药物研究所 | Acyclic nucleoside phosphonate derivative and medicine use thereof |
| CN101885720A (en) * | 2010-07-19 | 2010-11-17 | 连云港宏业化工有限公司 | Method for synthesizing 2-thiophene ethylamine |
| CN103896909A (en) * | 2014-04-01 | 2014-07-02 | 安庆丰源化工有限公司 | Synthesis method of 2-thiopheneethanol |
-
2019
- 2019-12-20 CN CN201911327392.1A patent/CN111087383A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101074226A (en) * | 2007-04-12 | 2007-11-21 | 北京精华耀邦医药科技有限公司 | Synthesis of polyzorine intermediate 3-(2-phobic-thiophene) butyric acid |
| CN101293899A (en) * | 2007-04-28 | 2008-10-29 | 中国人民解放军军事医学科学院毒物药物研究所 | Acyclic nucleoside phosphonate derivative and medicine use thereof |
| CN101885720A (en) * | 2010-07-19 | 2010-11-17 | 连云港宏业化工有限公司 | Method for synthesizing 2-thiophene ethylamine |
| CN103896909A (en) * | 2014-04-01 | 2014-07-02 | 安庆丰源化工有限公司 | Synthesis method of 2-thiopheneethanol |
Non-Patent Citations (1)
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| BERT DE BOER等: "Synthesis and Characterization of Conjugated Mono- and Dithiol Oligomers and Characterization of Their Self-Assembled Monolayers", 《LANGMUIR》 * |
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