CN104177279A - New process for preparing 3,3'-dimethyl thiodipropionate - Google Patents
New process for preparing 3,3'-dimethyl thiodipropionate Download PDFInfo
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- CN104177279A CN104177279A CN201410396510.5A CN201410396510A CN104177279A CN 104177279 A CN104177279 A CN 104177279A CN 201410396510 A CN201410396510 A CN 201410396510A CN 104177279 A CN104177279 A CN 104177279A
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Abstract
The invention belongs to the technical field of organic synthesis, and particularly relates to a new process for preparing 3,3'-dimethyl thiodipropionate. In the invention, methyl acrylate and an inorganic salt sodium hydrosulfide, taken as raw materials, are reacted in a proton solvent, so that the quantitative problem of reactants is solved, reaction raw materials are fully reacted, and the product yield is relatively increased; and a solution subjected to reaction can be applied for multiple times, and no three wastes are produced in the whole reaction process, so that the process is environmental-friendly, low in production cost and more conducive to industrial production.
Description
Technical field
The invention belongs to technical field of organic synthesis, be specifically related to one and prepare 3, the novel process of 3 '-thio-2 acid dimethyl ester.
Technical background
3,3 '-thio-2 acid dimethyl ester is the widely used intermediate of a class, especially as sulphur ester antioxidant and medical intermediate.At present less about the synthetic report of this intermediate.In Chinese patent CN 102503870A, mention a kind of method of synthetic thio-2 acid dialkyl, the method is to adopt alkyl acrylate directly to pass into stink damp precursor reactant to make, in venting process, be difficult to control gasometry problem, if pass into hydrogen sulfide deficiency, can cause raw material propylene acid alkyl ester residue, affect product yield; If hydrogen sulfide passes into excessive impurity mercapto-propionate and the dithio dipropyl dimethyl phthalate of can generating, affect equally product yield, and have a large amount of three wastes to produce.In reaction process, adopt in addition two stills or the series connection of many stills, increased the cost of investment of equipment.
Summary of the invention
For being difficult to control gasometry in prior art, there are the problems such as three wastes generation, the invention provides the preparation 3 that a kind of environmental protection produces without the three wastes, the novel process of 3 '-thio-2 acid dimethyl ester, adopting methyl acrylate and inorganic salt Sodium sulfhydrate is raw material, in proton type solvent, reacts, solve the quantitative problem of reactant, reaction raw materials is fully reacted, and product yield improves relatively, and production cost reduces.
Its concrete steps are:
(1) add phase-transfer catalyst to being equipped with in the reactor of methyl acrylate, mix, under agitation condition, dripping wherein massfraction is the Sodium sulfhydrate proton type solution of 5-10%, controls temperature at 15-30 DEG C, reaction 2-4 hour;
(2) reaction finishes, and extract, revolve and steam to obtain colourless transparent liquid, 3,3 '-thio-2 acid dimethyl ester.
Its reaction equation is:
Reaction mechanism is:
In reaction process, temperature of reaction is controlled at 15-30 DEG C, if temperature is too low, speed of reaction slows down, and has increased the reaction times; If temperature of reaction is too high, the product of generation will be hydrolyzed, and affects reaction yield.In reaction process, sample tracking, calculate with liquid chromatography area normalization method, until content≤0.1% of reaction raw materials methyl acrylate, reaction finishes, and the general reaction times is 2-4 hour.
In the present invention, with the molar ratio computing of pure substance, methyl acrylate: Sodium sulfhydrate=1:0.52-0.6.If Sodium sulfhydrate add-on is very few, make methyl acrylate reaction not exclusively, affect product yield; If Sodium sulfhydrate add-on is too much, last handling process is more complicated.
Proton type solvent of the present invention is the mixture of water or water and alcohol; Described alcohol is methyl alcohol or ethanol.Described water and the mass ratio of alcohol are 1:1.The object that uses this kind of solvent is in order to increase the solubleness of Sodium sulfhydrate in solvent, accelerates speed of reaction.Proton type solvent preferably water.
The massfraction of the proton type solution of described step (1) Sodium sulfhydrate is 5-10%.If massfraction is excessive, can there is hydrolysis reaction in raw material and product; Can increase the reaction times if massfraction is too small.
In described step (1), phase-transfer catalyst is benzyltriethylammoinium chloride or Tetrabutyl amonium bromide or tetrabutylammonium chloride, and its amount adding is the 1%-5% of methyl acrylate used and Sodium sulfhydrate total mass., add the very few effect that does not have catalyzer; Add-on is excessive can cause waste.
For the effect of extracting having reached, the extraction solvent for use in described step (2) is methylene dichloride or hexanaphthene or toluene, is preferably methylene dichloride.
In surplus solution in step (2) after extraction, main component is sodium hydroxide, now passing into wherein hydrogen sulfide to the pH value of system is 9-10, can make sodium hydroxide all be converted into Sodium sulfhydrate, contriver uses the Sodium sulfhydrate proton type solution that the massfraction in this solution alternative steps (1) is 5-10% to react the quality of product of the final acquisition of discovery and the quality of the product of yield and the Sodium sulfhydrate proton type solution acquisition that directly functional quality mark is 5-10% and yield without any difference.
In sum, the present invention synthesizes 3 using methyl acrylate and Sodium sulfhydrate as raw material reaction, and 3 '-thio-2 acid dimethyl ester adopts proton type solvent, and solvent is applied mechanically feasible, simple to operate.In reaction process, use Sodium sulfhydrate to replace hydrogen sulfide, reduced monitoring and the hydrogen sulfide quantitative problem of under meter; Processing in extraction liquid the use of monitoring hydrogen sulfide consumption and avoided equally under meter by pH value, solve hydrogen sulfide quantitative problem; In whole reaction process, produce environmental protection without the three wastes.Products obtained therefrom yield is high, and production cost is low, is more conducive to suitability for industrialized production.
Embodiment
The raw materials used commercially available prod that is of the present invention.Concrete technology step of the present invention is described by the following examples, and only limitation is not interpreted as that the above-mentioned subject area of the present invention only limits to following instance.All technology realizing based on foregoing of the present invention all belong to scope of the present invention.
Embodiment 1
In the 500mL four-hole boiling flask that agitator, thermometer are housed, add methyl acrylate 86.09g and 3.46g catalyzer benzyltriethylammoinium chloride.After airtight, the proton type solution that constant pressure funnel drips 584g Sodium sulfhydrate (is wherein dissolved with 29.2g Sodium sulfhydrate, the quality of water is 292g, the quality of methyl alcohol is 292g), control temperature in the time of 15 DEG C, react after 4 hours, sampling is followed the tracks of the content of methyl acrylate and is less than 0.1%, the methyl alcohol in solution is steamed for subsequent use, toluene extraction three times for surplus solution, each 100ml, merge organic phase, obtain water white transparency product 3,3 '-thio-2 acid dimethyl ester 101.2g after revolving steaming, content 99.0%, yield 98.1%.
Embodiment 2
In the 500mL four-hole boiling flask that agitator, thermometer are housed, add methyl acrylate 86.09g and 1.20g catalyzer benzyltriethylammoinium chloride.After airtight, constant pressure funnel drips the proton type solution (be wherein dissolved with 33.6g Sodium sulfhydrate, the quality of water is 336g) of 336g Sodium sulfhydrate, control temperature in the time of 25 DEG C, react after 3 hours, the content that methyl acrylate is followed the tracks of in sampling is less than 0.1%, by solution dichloromethane extraction three times, each 100ml, merge organic phase, obtain water white transparency product 3,3 '-thio-2 acid dimethyl ester 101.1g after revolving steaming, content 99.3%, yield 98.0%.
Embodiment 3
In the 500mL four-hole boiling flask that agitator, thermometer are housed, add methyl acrylate 86.09g and 5.82g catalyzer Tetrabutyl amonium bromide.After airtight, constant pressure funnel drips the proton type solution (be wherein dissolved with 30.3g Sodium sulfhydrate, the quality of water is 432g) of 432g Sodium sulfhydrate, control temperature in the time of 30 DEG C, react after 2 hours, the content that methyl acrylate is followed the tracks of in sampling is less than 0.1%, by hexanaphthene extraction three times for solution, each 100ml, merge organic phase, obtain water white transparency product 3,3 '-thio-2 acid dimethyl ester 101.3g after revolving steaming, content 99.8%, yield 98.2%.
Embodiment 4
In the 500mL four-hole boiling flask that agitator, thermometer are housed, add methyl acrylate 86.09g and 2.35g catalyzer Tetrabutyl amonium bromide.After airtight, (be wherein dissolved with 31.4g Sodium sulfhydrate, the quality of water is 261.5g to the proton type solution of constant pressure funnel dropping 523g Sodium sulfhydrate, the quality of ethanol is 261.5g), control temperature in the time of 20 DEG C, react after 3 hours, the content that methyl acrylate is followed the tracks of in sampling is less than 0.1%, by solution dichloromethane extraction three times, each 100ml, merges organic phase, after revolving steaming, obtain water white transparency product 3,3 '-thio-2 acid dimethyl ester 101.6g, content 99.1%, yield 98.5%.
Embodiment 5
In the 500mL four-hole boiling flask that agitator, thermometer are housed, add methyl acrylate 86.09g and 4.74g catalyzer tetrabutylammonium chloride.After airtight, constant pressure funnel drips the proton type solution (be wherein dissolved with 32.5g Sodium sulfhydrate, the quality of water is 406g) of 406g Sodium sulfhydrate, control temperature in the time of 30 DEG C, react after 4 hours, the content that methyl acrylate is followed the tracks of in sampling is less than 0.1%, by solution dichloromethane extraction three times, each 100ml, merge organic phase, obtain water white transparency product 3,3 '-thio-2 acid dimethyl ester 101.4g after revolving steaming, content 99.1%, yield 98.3%.
Embodiment 6
Be 9 by passing into hydrogen sulfide to the pH value of system in the surplus solution after the extraction in embodiment 2, acquisition solution quality is 316g, Sodium sulfhydrate proton type solution in alternate embodiment 2 to add wherein massfraction be 10% Sodium sulfhydrate aqueous solution 20g, benzyltriethylammoinium chloride 0.020g reacts, all the other obtain water white transparency product 3 with embodiment 2,3 '-thio-2 acid dimethyl ester 101.2g, content 99.2%, yield 98.1%.
Embodiment 7
Be 10 by passing into hydrogen sulfide to the pH value of system in the surplus solution after the extraction in embodiment 6, acquisition solution quality is 320g, Sodium sulfhydrate proton type solution in alternate embodiment 2 to add wherein massfraction be 10% Sodium sulfhydrate aqueous solution 16g, benzyltriethylammoinium chloride 0.016g reacts, and reacts, and all the other are with embodiment 2, obtain water white transparency product 3,3 '-thio-2 acid dimethyl ester 101.5g, content 99.5%, yield 98.4%.
Embodiment 8
Be 10 by passing into hydrogen sulfide to the pH value of system in the surplus solution after the extraction in embodiment 7, acquisition solution quality is 309g, Sodium sulfhydrate proton type solution in alternate embodiment 2 to add wherein massfraction be 10% Sodium sulfhydrate aqueous solution 27g, benzyltriethylammoinium chloride 0.027g reacts, all the other obtain water white transparency product 3 with embodiment 2,3 '-thio-2 acid dimethyl ester 101.2g, content 99.3%, yield 98.1%.
Embodiment 9
Be 9 by passing into hydrogen sulfide to the pH value of system in the surplus solution after the extraction in embodiment 8, acquisition solution quality is 317g, Sodium sulfhydrate proton type solution in alternate embodiment 2 to add wherein massfraction be 10% Sodium sulfhydrate aqueous solution 19g, benzyltriethylammoinium chloride 0.019g reacts, all the other obtain water white transparency product 3 with embodiment 2,3 '-thio-2 acid dimethyl ester 101.2g, content 99.5%, yield 98.1%.
Embodiment 10
Be 10 by passing into hydrogen sulfide to the pH value of system in the surplus solution after the extraction in embodiment 9, acquisition solution quality is 305g, Sodium sulfhydrate proton type solution in alternate embodiment 2 to add wherein massfraction be 10% Sodium sulfhydrate aqueous solution 31g, benzyltriethylammoinium chloride 0.031g reacts, all the other obtain water white transparency product 3 with embodiment 2,3 '-thio-2 acid dimethyl ester 101.4g, content 99.3%, yield 98.3%.
Can find out by above embodiment 1-10,3 of the present invention's production, 3 '-thio-2 acid dimethyl ester content can reach more than 99%, and yield can reach more than 98%, and extraction after surplus solution after hydrogen sulfide treatment, can directly overlap for reaction, apply mechanically continuously five times on experimental result without any impact, produce without three industrial wastes, environmental protection, yield is higher, cost is lower, can suitability for industrialized production.
Claims (9)
1. prepare 3 for one kind, the novel process of 3 '-thio-2 acid dimethyl ester, is characterized in that: taking methyl acrylate and Sodium sulfhydrate as raw material, in proton type solvent, react and make.
2. one according to claim 1 prepares 3, and the novel process of 3 '-thio-2 acid dimethyl ester, is characterized in that: its concrete steps are:
(1) add phase-transfer catalyst to being equipped with in the reactor of methyl acrylate, mix, under agitation condition, dripping wherein massfraction is the Sodium sulfhydrate proton type solution of 5-10%, controls temperature at 15-30 DEG C, reaction 2-4 hour;
(2) reaction finishes, and extract, revolve and steam to obtain colourless transparent liquid, 3,3 '-thio-2 acid dimethyl ester.
3. one according to claim 2 prepares 3, the novel process of 3 '-thio-2 acid dimethyl ester, it is characterized in that: be 9-10 to passing into hydrogen sulfide to the pH value of system in the surplus solution after extraction in step (2), and the Sodium sulfhydrate proton type solution that massfraction in alternative steps (1) is 5-10% reacts.
4. one according to claim 2 prepares 3, and the novel process of 3 '-thio-2 acid dimethyl ester, is characterized in that: in described step (1), and with the molar ratio computing of pure substance, methyl acrylate: Sodium sulfhydrate=1:0.52-0.6.
5. one according to claim 1 prepares 3, and the novel process of 3 '-thio-2 acid dimethyl ester, is characterized in that: described proton type solvent is the mixture of water or water and alcohol; Described alcohol is methyl alcohol or ethanol.
6. one according to claim 5 prepares 3, and the novel process of 3 '-thio-2 acid dimethyl ester, is characterized in that: described water and the mass ratio of alcohol are 1:1.
7. one according to claim 2 prepares 3, and the novel process of 3 '-thio-2 acid dimethyl ester, is characterized in that: the phase-transfer catalyst in described step (1) is benzyltriethylammoinium chloride or Tetrabutyl amonium bromide or tetrabutylammonium chloride.
8. one according to claim 2 prepares 3, and the novel process of 3 '-thio-2 acid dimethyl ester, is characterized in that: in described step (1), phase-transfer catalyst quality is the 1%-5% of methyl acrylate used and Sodium sulfhydrate total mass.
9. one according to claim 2 prepares 3, and the novel process of 3 '-thio-2 acid dimethyl ester, is characterized in that: the extraction solvent for use in described step (2) is methylene dichloride or hexanaphthene or toluene.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4052440A (en) * | 1973-07-17 | 1977-10-04 | Witco Chemical Corporation | Method for preparing mercapto propionic acid esters and polythio dipropionic acid esters |
| US4231956A (en) * | 1978-08-28 | 1980-11-04 | Exxon Research & Engineering Co. | Process for preparation of thioethers |
| US4433134A (en) * | 1979-08-01 | 1984-02-21 | Phillips Petroleum Company | Preparation of alkyl mercaptoalkanoates from unsaturated carboxylates and CO2 -contaminated H2 S |
| CN102503870A (en) * | 2011-10-14 | 2012-06-20 | 北京加成助剂研究所 | Preparation method of dialkyl thiodipropionate |
-
2014
- 2014-08-13 CN CN201410396510.5A patent/CN104177279B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4052440A (en) * | 1973-07-17 | 1977-10-04 | Witco Chemical Corporation | Method for preparing mercapto propionic acid esters and polythio dipropionic acid esters |
| US4231956A (en) * | 1978-08-28 | 1980-11-04 | Exxon Research & Engineering Co. | Process for preparation of thioethers |
| US4433134A (en) * | 1979-08-01 | 1984-02-21 | Phillips Petroleum Company | Preparation of alkyl mercaptoalkanoates from unsaturated carboxylates and CO2 -contaminated H2 S |
| CN102503870A (en) * | 2011-10-14 | 2012-06-20 | 北京加成助剂研究所 | Preparation method of dialkyl thiodipropionate |
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Effective date of registration: 20200715 Address after: 256500 Boxing Economic Development Zone, Binzhou, Shandong Patentee after: SHANDONG EFIRM BIOCHEMISTRY AND ENVIRONMENTAL PROTECTION Co.,Ltd. Address before: 256500 Boxing Economic Development Zone, Binzhou, Shandong Patentee before: YELLOW RIVER DELTA JINGBO RESEARCH INSTITUTE OF CHEMICAL INDUSTRY Co.,Ltd. |
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Address after: 256500 Boxing Economic Development Zone, Shandong, Binzhou Patentee after: Yifeng New Material Co.,Ltd. Address before: 256500 Boxing Economic Development Zone, Shandong, Binzhou Patentee before: SHANDONG EFIRM BIOCHEMISTRY AND ENVIRONMENTAL PROTECTION Co.,Ltd. |
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