CN108863865A - A kind of synthetic method of succinimide mercaptans - Google Patents
A kind of synthetic method of succinimide mercaptans Download PDFInfo
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- CN108863865A CN108863865A CN201810947438.9A CN201810947438A CN108863865A CN 108863865 A CN108863865 A CN 108863865A CN 201810947438 A CN201810947438 A CN 201810947438A CN 108863865 A CN108863865 A CN 108863865A
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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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/18—Preparation of halogenated hydrocarbons by replacement by halogens of oxygen atoms of carbonyl groups
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C335/00—Thioureas, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C335/30—Isothioureas
- C07C335/32—Isothioureas having sulfur atoms of isothiourea groups bound to acyclic carbon atoms
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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Abstract
The invention discloses a kind of synthetic methods of succinimide mercaptans, include the following steps：（1）2,3-butanediol and esterifying agent are esterified to obtain intermediate compound I (diester)；（2）Intermediate compound I (diester) reacts to obtain intermediate II (2,3- dibromobutane) with the acetum of hydrogen bromide；（3）Intermediate II and thiocarbamide are condensed to obtain intermediate III；（4）Intermediate III is hydrolyzed through KOH, is acidified to obtain 2,3- succinimide mercaptans, yield is 60.0% or more, the beneficial effects of the invention are as follows using 2,3-butanediol as starting material, price only 100 yuan/kg, cost is lower than 800 yuan, operation is normal pressure, and simple process, respectively walking intermediate can be easily separated, final products only need to be evaporated under reduced pressure, purity is high.
Description
Technical field
The present invention relates to the synthesis technical field of succinimide mercaptans, specially a kind of synthetic method of succinimide mercaptans.
Background technique
In the prior art, Beijing Technology and Business University's patent ZL00100889.7 discloses a kind of preparation of 2,3 one succinimide mercaptans
Method, with 2,3- epoxy butane for raw material, through reacting with thiocarbamide, NaHS open loop addition obtains 2,3- succinimide mercaptans, changes
Learning reaction equation is：
Its react there are the problem of be：
1,2,3- epoxy butane boiling point limits reaction temperature for 56-57 DEG C, and reaction is not thorough, and yield is lower, 65%
Hereinafter, such as to improve reaction yield needs compressive reaction, equipment requirement autoclave, and 2,3- epoxy butane are not easy to prepare, price
Valuableness, seriously increases cost by 800 yuan/kg；
2, NaHS open loop addition step, NaHS are hydrate, and purity is 70% or so, lead to ring opening process
Middle generation side reaction generates 2- hydroxyl -3- sulfydryl butane, causes separation difficult, needs rectification under vacuum to separate, 2,3- succinimide mercaptans
Yield is 55%；
3, two step total recoverys are only 40% or so, and 2,3- succinimide mercaptans costs are 2000 yuan/kg.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the existing defects, provides a kind of synthetic method of succinimide mercaptans, behaviour
Make simple, product yield height, it is at low cost, it can effectively solve the problems in background technique.
To achieve the above object, the present invention provides the following technical solutions：A kind of synthetic method of succinimide mercaptans, reactional equation
Formula is as follows：
Include the following steps：
(1) addition 2,3-butanediol, 2.0~4.0 times of alcohol mole of esterifying agent and 2.0~3.0 times of alcohol mole tie up acid
Agent, 40.0~80.0 DEG C of heating are stirred to react to 2,3-butanediol fully reacting, then wash through 5.0%NaHCO3, is dry, dense
Contract to obtain intermediate compound I (diester), yield 95.0%；
(2) acetum of 2.0~4.0 times of mole of 30.0% hydrogen bromide, room temperature are added into intermediate compound I (diester)
3.0~5.0h is reacted, removed under reduced pressure solvent, obtains intermediate II (2,3- dibromobutane), yield 85.0% after the reaction was completed；
(3) 2.0~2.5 times of mole of thiocarbamide, the ethyl alcohol that 2.0 times of mass ratio, back flow reaction are added into intermediate II
To intermediate II fully reacting, decrease temperature crystalline obtains intermediate III, yield 92.0%；
(4) potassium hydroxide aqueous solution of 2.0~4.0 times of mass ratio of 10.0%-30.0% is added to intermediate III
In, back hydrolysis 2.0~5.0 hours, PH=3.0 is adjusted with concentrated hydrochloric acid after the reaction was completed, ethyl acetate extraction is added, be layered,
It washes, be concentrated to get crude product 2,3- succinimide mercaptans, yield 85.0%；
(5) it is evaporated under reduced pressure, the fraction for collecting boiling point 86.0~87.0 DEG C (50mmHg) obtains product 2,3- succinimide mercaptans, GC
99.0% or more purity, 60.0% or more total recovery.
As a preferred technical solution of the present invention, esterifying agent described in step (1) is acetic anhydride, propionic andydride, to first
One of benzene sulfonyl chloride, maleic anhydride, additional amount are 2.0~4.0 times of alcohol mole.
As a preferred technical solution of the present invention, acid binding agent described in step (1) be pyridine, triethylamine, DIEA,
DMAP, sodium acetate etc., dosage are 2.0~3.0 times of alcohol mole.
As a preferred technical solution of the present invention, the additional amount of the acetum of 30.0% hydrogen bromide in step (2)
It is 2.0~4.0 times of intermediate II, reacts 3.0~5.0h.
As a preferred technical solution of the present invention, the thiocarbamide additional amount in step (3) is intermediate II mole 2.0
~2.5 times.
As a preferred technical solution of the present invention, the mass concentration of potassium hydroxide aqueous solution is in step (4)
10.0%-30.0%, additional amount are 2.0~4.0 times of intermediate III quality, and the back hydrolysis time is 2.0~5.0 hours.
Compared with prior art, the beneficial effects of the invention are as follows：
1, using 2,3-butanediol as starting material, only 100 yuan/kg, total recovery 60%, cost are lower than 800 yuan to price；
2, operation is normal pressure, simple process；
3, respectively step intermediate can be easily separated, and final products only need to be evaporated under reduced pressure, purity is high.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, to this
Invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, not
For limiting the present invention.
Embodiment one
A kind of synthetic method of succinimide mercaptans, includes the following steps：
(1) 2.0 times of 2,3-butanediol, 2.0 times of alcohol mole of esterifying agent and alcohol mole acid binding agents is added, esterifying agent is
One of acetic anhydride, propionic andydride, paratoluensulfonyl chloride, maleic anhydride, additional amount are 2.0 times of alcohol mole, and acid binding agent is
Pyridine, triethylamine, DIEA, DMAP, sodium acetate etc., dosage are 2.0 times of alcohol mole, and 40.0 DEG C of heating is stirred to react to 2,3-
Butanediol fully reacting, then through 5.0%NaHCO3Washing, is concentrated to give intermediate compound I (diester), yield 94.0% at drying；
(2) acetum of 2.0 times of mole of 30.0% hydrogen bromide, 30.0% bromine are added into intermediate compound I (diester)
The additional amount for changing the acetum of hydrogen is 2.0 times of intermediate II, reacts at room temperature 3.0h, after the reaction was completed removed under reduced pressure solvent,
Obtain intermediate II (2,3- dibromobutane), yield 87.0%；
(3) 2.0 times of mole of thiocarbamide is added into intermediate II, thiocarbamide additional amount is 2.0 times of intermediate II mole,
The ethyl alcohol that 2.0 times of mass ratio, for back flow reaction to intermediate II fully reacting, decrease temperature crystalline obtains intermediate III, and yield is
92.0%；
(4) it is added to intermediate III in 2.0 times of mass ratio of the potassium hydroxide aqueous solution of 10.0%-30.0%, hydrogen-oxygen
The mass concentration for changing aqueous solutions of potassium is 10.0%, and additional amount is 2.0 times of intermediate III quality, back hydrolysis 2.0 hours, instead
PH=3.0 should be adjusted with concentrated hydrochloric acid after the completion, ethyl acetate extraction is added, is layered, washes, being concentrated to get crude product 2,3- dibutyl disulfide
Alcohol, yield 88.0%；
(5) it is evaporated under reduced pressure, the fraction for collecting boiling point 86.0 DEG C (50mmHg) obtains product 2,3- succinimide mercaptans, GC purity
99.2%, total recovery 66.2%.
Embodiment two
A kind of synthetic method of succinimide mercaptans, includes the following steps：
(1) 2.5 times of 2,3-butanediol, 3.0 times of alcohol mole of esterifying agent and alcohol mole acid binding agents is added, esterifying agent is
One of acetic anhydride, propionic andydride, paratoluensulfonyl chloride, maleic anhydride, additional amount are 3.0 times of alcohol mole, and acid binding agent is
Pyridine, triethylamine, DIEA, DMAP, sodium acetate etc., dosage are 2.5 times of alcohol mole, and 60.0 DEG C of heating is stirred to react to 2,3-
Butanediol fully reacting, then through 5.0%NaHCO3Washing, is concentrated to give intermediate compound I (diester), yield 93.0% at drying；
(2) acetum of 3.0 times of mole of 30.0% hydrogen bromide, 30.0% bromine are added into intermediate compound I (diester)
The additional amount for changing the acetum of hydrogen is 3.0 times of intermediate II, reacts at room temperature 4.0h, after the reaction was completed removed under reduced pressure solvent,
Obtain intermediate II (2,3- dibromobutane), yield 84.0%；
(3) 2.2 times of mole of thiocarbamide is added into intermediate II, thiocarbamide additional amount is 2.3 times of intermediate II mole,
The ethyl alcohol that 2.0 times of mass ratio, for back flow reaction to intermediate II fully reacting, decrease temperature crystalline obtains intermediate III, and yield is
93.0%；
(4) it is added to intermediate III in 3.0 times of mass ratio of the potassium hydroxide aqueous solution of 20.0%-30.0%, hydrogen-oxygen
The mass concentration for changing aqueous solutions of potassium is 15.0%%, and additional amount is 3.0 times of intermediate III quality, back hydrolysis 3.0 hours,
PH=3.0 is adjusted with concentrated hydrochloric acid after the reaction was completed, ethyl acetate extraction is added, is layered, washes, being concentrated to get crude product 2,3- fourth two
Mercaptan, yield 83.0%；
(5) it is evaporated under reduced pressure, the fraction for collecting boiling point 86.5 DEG C (50mmHg) obtains product 2,3- succinimide mercaptans, GC purity
99.1%, total recovery 60.3%.
Embodiment three
A kind of synthetic method of succinimide mercaptans, includes the following steps：
(1) 3.0 times of 2,3-butanediol, 4.0 times of alcohol mole of esterifying agent and alcohol mole acid binding agents is added, esterifying agent is
One of acetic anhydride, propionic andydride, paratoluensulfonyl chloride, maleic anhydride, additional amount are 4.0 times of alcohol mole, and acid binding agent is
Pyridine, triethylamine, DIEA, DMAP, sodium acetate etc., dosage are 3.0 times of alcohol mole, and 80.0 DEG C of heating is stirred to react to 2,3-
Butanediol fully reacting, then through 5.0%NaHCO3Washing, is concentrated to give intermediate compound I (diester), yield 92.0% at drying；
(2) acetum of 4.0 times of mole of 30.0% hydrogen bromide, 30.0% bromine are added into intermediate compound I (diester)
The additional amount for changing the acetum of hydrogen is 4.0 times of intermediate II, reacts at room temperature 5.0h, after the reaction was completed removed under reduced pressure solvent,
Obtain intermediate II (2,3- dibromobutane), yield 85.0%；
(3) 2.0~2.5 times of mole of thiocarbamide is added into intermediate II, thiocarbamide additional amount is intermediate II mole
2.5 times, the ethyl alcohol that 2.0 times of mass ratio, for back flow reaction to intermediate II fully reacting, decrease temperature crystalline obtains intermediate III, yield
It is 92.4%；
(4) it is added to intermediate III in 4.0 times of mass ratio of 30.0% potassium hydroxide aqueous solution, potassium hydroxide water
The mass concentration of solution is 30.0%, and additional amount is 4.0 times of intermediate III quality, and back hydrolysis 5.0 hours, reaction was completed
PH=3.0 is adjusted with concentrated hydrochloric acid afterwards, ethyl acetate extraction is added, is layered, washes, being concentrated to get crude product 2,3- succinimide mercaptans are received
Rate is 84.2%；
(5) it is evaporated under reduced pressure, the fraction for collecting boiling point 87.0 DEG C (50mmHg) obtains product 2,3- succinimide mercaptans, GC purity
99.3%, total recovery 60.8%.
The present invention is using 2,3-butanediol as starting material, and only 100 yuan/kg, total recovery 60%, cost are lower than 800 yuan to price,
Operation is normal pressure, and simple process, respectively walking intermediate can be easily separated, and final products only need to be evaporated under reduced pressure, purity is high.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding
And modification, the scope of the present invention is defined by the appended.
Claims (6)
1. a kind of synthetic method of succinimide mercaptans, it is characterised in that：Include the following steps：
（1）2.0~3.0 times of 2,3-butanediol, 2.0~4.0 times of alcohol mole of esterifying agent and alcohol mole acid binding agents is added, rises
40.0~80.0 DEG C of temperature is stirred to react to 2,3-butanediol fully reacting, then through 5.0% NaHCO3Washing, is concentrated to give drying
Intermediate compound I（Diester）, yield 95.0%；
（2）To intermediate compound I（Diester）The acetum of middle 30.0% hydrogen bromide for being added 2.0~4.0 times of mole, room temperature reaction
3.0~5.0h, removed under reduced pressure solvent, obtains intermediate II after the reaction was completed（2,3- dibromobutanes）, yield 85.0%；
（3）2.0~2.5 times of mole of thiocarbamide is added into intermediate II, the ethyl alcohol that 2.0 times of mass ratio, back flow reaction is into
Mesosome II fully reacting, decrease temperature crystalline obtain intermediate III, yield 92.0%；
（4）It is added in the potassium hydroxide aqueous solution of 2.0~4.0 times of mass ratio of 10.0%-30.0%, flows back to intermediate III
Hydrolysis 2.0~5.0 hours adjusts PH=3.0 with concentrated hydrochloric acid after the reaction was completed, and ethyl acetate extraction, layering, washing, concentration is added
Obtain crude product 2,3- succinimide mercaptans, yield 85.0%；
（5）Vacuum distillation collects 86.0~87.0 DEG C of boiling point（50mmHg）Fraction obtain product 2,3- succinimide mercaptans, GC purity
99.0% or more, 60.0% or more total recovery.
2. a kind of synthetic method of succinimide mercaptans according to claim 1, which is characterized in that step（1）The esterification
Agent is one of acetic anhydride, propionic andydride, paratoluensulfonyl chloride, maleic anhydride, and additional amount is 2.0~4.0 times of alcohol mole.
3. a kind of synthetic method of succinimide mercaptans according to claim 1, which is characterized in that step（1）Described ties up acid
Agent is pyridine, triethylamine, DIEA, DMAP, sodium acetate etc., and dosage is 2.0~3.0 times of alcohol mole.
4. a kind of synthetic method of succinimide mercaptans according to claim 1, which is characterized in that step（2）In 30.0% bromination
The additional amount of the acetum of hydrogen is 2.0~4.0 times of intermediate II, reacts 3.0~5.0h.
5. a kind of synthetic method of succinimide mercaptans according to claim 1, which is characterized in that step（3）In thiocarbamide add
Entering amount is 2.0~2.5 times of intermediate II mole.
6. a kind of synthetic method of succinimide mercaptans according to claim 1, which is characterized in that step（4）Middle potassium hydroxide
The mass concentration of aqueous solution is 10.0%-30.0%, and additional amount is 2.0~4.0 times of intermediate III quality, back hydrolysis time
It is 2.0~5.0 hours.
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| CN201810947438.9A CN108863865B (en) | 2018-08-20 | 2018-08-20 | Method for synthesizing butanedithiol |
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| CN201810947438.9A CN108863865B (en) | 2018-08-20 | 2018-08-20 | Method for synthesizing butanedithiol |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1834100A (en) * | 2005-11-11 | 2006-09-20 | 浙江大学 | Bisilane coupler contg. sulfur and nitrogen element and prepn. thereof |
| CN1896053A (en) * | 2005-12-02 | 2007-01-17 | 中国医学科学院放射医学研究所 | Improved production of 1, 2-ethanedithiol |
-
2018
- 2018-08-20 CN CN201810947438.9A patent/CN108863865B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1834100A (en) * | 2005-11-11 | 2006-09-20 | 浙江大学 | Bisilane coupler contg. sulfur and nitrogen element and prepn. thereof |
| CN1896053A (en) * | 2005-12-02 | 2007-01-17 | 中国医学科学院放射医学研究所 | Improved production of 1, 2-ethanedithiol |
Non-Patent Citations (3)
| Title |
|---|
| BRAUN, M.: "Synthesis by substitution of oxygen functionalities", 《SCIENCE OF SYNTHESIS》 * |
| BUDING,HARTMUTH等: "Absolute configuration of (+)-tartaric acid", 《ANGEWANDTE CHEMIE》 * |
| DENIS WAHLER等: "Adrenaline profiling of lipases and esterases with 1,2-diol and carbohydrate acetates", 《TETRAHEDRON》 * |
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