CN100363342C - Method for preparing 2-sulfhydyl alkyl sulfide and 2- sulfhydyl alkyl ether compound - Google Patents
Method for preparing 2-sulfhydyl alkyl sulfide and 2- sulfhydyl alkyl ether compound Download PDFInfo
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- CN100363342C CN100363342C CNB2006100201769A CN200610020176A CN100363342C CN 100363342 C CN100363342 C CN 100363342C CN B2006100201769 A CNB2006100201769 A CN B2006100201769A CN 200610020176 A CN200610020176 A CN 200610020176A CN 100363342 C CN100363342 C CN 100363342C
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Abstract
The present invention relates to a method for preparing 2-sulfhydryl alkyl group thioether and 2-sulfhydryl alkyl group ether. The purpose products having the structure general formula (I) are obtained by sulfhydryl compounds in the corresponding structure, and the sulfhydryl compound is formed by decomposition of the reaction of isothiuronium salt and ammonium carbonate or ammonium hydrogen carbonate water solution. Meanwhile, the structure general formula (I) also represents disulfhydryl diethyl ether or disulfhydryl diethyl thioether. The corresponding dihydric alcohol reacts with thiourea to generate the isothiuronium salt under the condition that inorganic acid, particularly hydrochloric acid exists, and the isothiuronium salt reacts with the ammonium carbonate or ammonium hydrogen carbonate water solution to generate the corresponding disulfhydryl compound. The present invention has the mild reaction, does not generate a large quantity of dicyandiamide by-product precipitate, and is not easy to generate disulfide impurities to influence the chroma and the quality of the products. After the reaction finishes, the water phase pH value is 8 to 9. After the simple separation, the product can be obtained. The purity of the product reaches 98 percent, the chroma is lower than 15, and the yield reaches above 80 percent.
Description
Technical field
The present invention relates to the preparation method of organic compound, particularly, the present invention relates to the preparation method of 2-mercaptoalkyl thioether class and 2-mercaptoalkyl ethers, this method makes the purity of product and colourity quality all obtain effective raising.
Background technology
2-mercaptoalkyl thioether and 2-mercaptoalkyl ether etc. are the organic compound that a class has special unhappy smell, are used as intermediate product when synthesizing other organic compounds containing sulfur, are specially adapted to sulfide synthesis, monothioester, sulfoxide, sulfone etc.
But, because the processing method of existing Synthetic 2-mercaptoalkyl thioether and 2-mercaptoalkyl ether, usually be difficult to obtain satisfied purity and yield, and the preparation of some material usually requires these initial substances that high purity and extremely low colourity are arranged, thereby hindered the commercial use of these compounds.
According to known preparation method, can only obtain highly purified 2-mercaptoalkyl thioether and 2-mercaptoalkyl ether by the method for purifying in the back, as distillation, rectifying or recrystallization etc.The overwhelming majority can not directly obtain highly purified, does not particularly contain the 2-mercaptoalkyl thioether and the 2-mercaptoalkyl ether of disulphide.Its preparation and purifying can only be implemented by complicated apparatus.
Modal preparation method reacts corresponding 2-hydroxyalkyl thioether under the effect of strong acid with thiocarbamide, generate different thiuronium salt, makes its decomposition obtain corresponding sulfydryl thioether with excessive caustic-alkali aqueous solution then.In most cases yield is not high.More difficult is that this process also has Dyhard RU 100 and so on solid by-product to produce, and the sludge that promptly forms indissoluble is carried the separation of sulfydryl thioether product obstruction secretly.These class methods also have analogue in the process that is prepared 2-mercaptoalkyl ether by the 2-halogenated alkyl ether.
In people such as Bergthaller US 4355185 patents of nineteen eighty-two, adopt hydrazine hydrate to replace the decomposition agent of caustic-alkali aqueous solution as different thiuronium salt, can obtain highly purified 2-mercaptoalkyl thioether and 2-mercaptoalkyl ether, and yield can be up to 80～90%, even more than 90%.But hydrazine hydrate is very expensive, and this makes production cost of products significantly increase, and hinders its application too.
The spy who likes people such as beautiful man nineteen ninety in the Japan portion of crossing opens in the flat 2-145561 patent, the different thiuronium salt that adopts sulfohydrate to replace caustic alkali to decompose 2-hydroxyalkyl thioether and thiocarbamide reaction generation is prepared corresponding 2-mercaptoalkyl thioether, can reclaim thiocarbamide reduces cost, but very easily produce disulphide in this process and make product colourity yellow partially, though through rectifying, still be difficult to fully remove foreign pigment, thereby the difficult quality of product is guaranteed.
Summary of the invention
The present invention is intended to overcome above-mentioned defective, provides a kind of and can guarantee product purity and colourity quality, economical and practical 2-mercaptoalkyl thioether class and the preparation method of 2-mercaptoalkyl ethers again.
Concrete technical scheme of the present invention is as follows:
The preparation method of 2-mercaptoalkyl thioether class and 2-mercaptoalkyl ethers, it is characterized in that having the purpose product of following general structure (I), the different thiuronium salt by following chemical structural formula (II) becomes the sulfhydryl compound of corresponding construction to obtain with volatile salt or ammonium bicarbonate aqueous solution reaction decomposes:
Wherein, R represents H (only when n=1) or a kind of n valency organic group that comprises alkyl or aralkyl or aryl, and group hydrocarbon chain or hydrocarbon ring can be mixed sulphur or/and Sauerstoffatom; Also can be by alkyl or the heteroatoms alkyl that sulfydryl or hydroxyl replaced, the positive integer of n=1～4 scopes;
Y represents a Sauerstoffatom or sulphur atom;
Et represents ethylene group, can be replaced by other group, and also can be the part of 5 Yuans or 6 Yuans rings;
R
1To R
4Can be identical can be different substituting groups also, they represent H, the alkyl of 1～6 carbon atom or aryl.
Described different thiuronium salt is obtained with the thiocarbamide reaction by the halides (III) of corresponding molecular structure;
Perhaps the oxy-compound (IV) by corresponding molecular structure obtains with the thiocarbamide reaction in the presence of mineral acid.
Especially, general structure (I) is also represented dimercapto Anaesthetie Ether or dimercapto diethyl thioether, particularly react the different thiuronium salt that generates following structure (V) with thiocarbamide in the presence of the hydrochloric acid by corresponding dibasic alcohol at mineral acid, different thiuronium salt produces corresponding dimercapto compound with volatile salt or ammonium bicarbonate aqueous solution reaction again.
In the different thiuronium salt decomposition reaction of the present invention, used volatile salt mole number is 1～1.5 times of different thiuronium salt group mole number.
In the different thiuronium salt decomposition reaction of the present invention, used bicarbonate of ammonia mole number is 2～3 times of different thiuronium salt group mole number, perhaps 1～1.5 times when different thiuronium salt group mole number, need to add simultaneously caustic alkali with mole numbers such as bicarbonate of ammonia.
The different thiuronium salt decomposition reaction of the present invention is carried out under 20～200 ℃.
The sulfhydryl compound that the present invention makes can obtain by underpressure distillation that purity reaches 98%, colourity is lower than 15 product, and yield reaches more than 80%.
The invention has the advantages that:
1, the present invention decomposes the different thiuronium salt of intermediate with volatile salt or ammonium bicarbonate aqueous solution, make it be converted into corresponding sulfhydryl compound, different with the general caustic alkali that adopts, reaction temperature and and do not produce a large amount of Dyhard RU 100 by product precipitation, also be not easy to generate disulphide impurity effect product colourity quality.And it is 8～9 that reaction finishes the back ph value of aqueous phase, does not need further neutralization, can obtain the product than high cleanliness after simple separation.
2, in the decomposition reaction of the different thiuronium salt of the present invention, volatile salt or bicarbonate of ammonia are made into the aqueous solution and add, and it is lower that its concentration can make wastewater flow rate drop to when saturated, can increase wastewater flow rate on the contrary.
3, the different thiuronium salt decomposition reaction of the present invention is carried out under 20～100 ℃, both can avoid producing more impurity, can reach speed of response faster again.
Embodiment
Below listed reference example, embodiment and comparative example as the more detailed specific description of the present invention, but data shown in it are not represented the restriction to characteristic range of the present invention.
Reference example 1 (preparation example of different thiuronium salt)
In reactor, add thiocarbamide 265g (3.5 moles) and 36～38% hydrochloric acid 343g (3.5 moles), after heat is dissolved thiocarbamide fully a little, be added dropwise to 3 normal oxy-compound in 15 minutes, constantly stir simultaneously, being warmed up to 90 to 110 ℃ then refluxed 3 hours, promptly obtain the different thiuronium salt aqueous solution of intermediate, be cooled to below 30 ℃ standby.
Reference example 2 (preparation example of different thiuronium salt)
In reactor, add thiocarbamide 182g (2.4 moles) and be dissolved in the 1000ml water, keep refluxing 4 hours after adding 2 normal 2-chloroethylation compounds, promptly obtain the different thiuronium salt aqueous solution of intermediate, be cooled to below 30 ℃ standby.
Embodiment 1
Press the different thiuronium salt of reference example 1 preparation with 183g (1.5 moles) sulfo-glycol ether as the oxy-compound starting raw material.After being cooled to 30 ℃, add 50% aqueous solution that is made into 296g (3.08 moles) volatile salt, stir and be warming up to 80 ℃ of stopped reaction half an hour that reflux, be cooled to room temperature after, isolate water, the about 220g of organic phase dimercapto diethyl sulfide ether products.Promptly obtain 200g purity after the simple distillation up to 98% product under 110～125 ℃, 0.095MPa vacuum tightness, colourity only is 9, and theoretical yield is 86.5%.
Comparative example 1
Press different thiuronium salt same shown in the embodiment 1, replace volatile salt to be made into 50% aqueous solution with 305g (6 moles) sulphur hydrogenation ammonium and carry out different thiuronium salt decomposition reaction, PH=7 after backflow is finished gets yellow crude product 214g.After the rectification under vacuum light yellow product 171g, colourity is about 100, yield only 74%.
Embodiment 2
With 273g (1.5 moles) 1,8-dihydroxyl-3,6-dithio octane is as the oxy-compound starting raw material, prepare corresponding different thiuronium salt by reference example 1 described conditioned response, when adding 50% aqueous solution that is made into 243g (3.08 moles) bicarbonate of ammonia and 123g (3.08 moles) sodium hydroxide, add the 600ml xylene solvent, reflux 1 hour, tell water after the cooling, organic phase is distilled down in normal pressure and is removed xylene solvent, and high vacuum underpressure distillation is then collected 200～210 ℃ and distillated product 1,8-dimercapto-3,6-dithio octane 285g, colourity 15, yield 88.8%.
Embodiment 3
Press reference example 2, with 187g (1 mole) 1,8-two chloro-3,6-dioxo octane are that the different thiuronium salt aqueous solution of starting raw material preparation is cooled to after 30 ℃, 50% aqueous solution and 400ml toluene that adding is made into 198g (2.06 moles) volatile salt, reflux 1 hour is told water after the cooling, organic phase is distilled down in normal pressure and removed toluene solvant, high vacuum underpressure distillation then, collect 105～115 ℃ and distillate product 1,8-dimercapto-3,6-dioxo octane.Yield 81%.
Embodiment 4
The dichloride (molecular weight 370) that is made by commercially available polyoxyethylene glycol with 100g is that initial substance and 60g thiocarbamide are pressed embodiment 3 described methods, prepares the two sulfydryl terminated polyether oily products of 80 grams.Actual measurement sulphur content 15.5% (theoretical value is 16%).
Claims (6)
1.2-the preparation method of mercaptoalkyl thioether class or 2-mercaptoalkyl ethers, it is characterized in that having the purpose product of following general structure (I), the different thiuronium salt by following chemical structural formula (II) becomes the sulfhydryl compound of corresponding construction to obtain with volatile salt or ammonium bicarbonate aqueous solution reaction decomposes:
Wherein, R represents H or a kind of n valency organic group that comprises alkyl or aralkyl or aryl; The assorted sulphur of the hydrocarbon chain of described organic group or hydrocarbon ring is or/and Sauerstoffatom, the positive integer of n=1～4 scopes;
Y represents a Sauerstoffatom or sulphur atom;
Et representative-C
2H
4-;
R
1To R
4Be identical or different substituting group, they represent H, the alkyl of 1～6 carbon atom or aryl.
2. the preparation method of 2-mercaptoalkyl thioether class as claimed in claim 1 or 2-mercaptoalkyl ethers, it is characterized in that described general structure (I) represents dimercapto Anaesthetie Ether or dimercapto diethyl thioether, react the different thiuronium salt that generate following structure (V) with thiocarbamide by corresponding dibasic alcohol in the presence of mineral acid, different thiuronium salt produces corresponding dimercapto compound with volatile salt or ammonium bicarbonate aqueous solution reaction again
Wherein, R
1-R
4All represent H.
3. the preparation method of 2-mercaptoalkyl thioether class as claimed in claim 2 or 2-mercaptoalkyl ethers is characterized in that described mineral acid is a hydrochloric acid.
4. as the preparation method of claim 1,2 or 3 described 2-mercaptoalkyl thioether classes or 2-mercaptoalkyl ethers, it is characterized in that in the reaction of described different thiuronium salt and volatile salt that used volatile salt mole number is 1～1.5 times of different thiuronium salt group mole number.
5. as the preparation method of claim 1,2 or 3 described 2-mercaptoalkyl thioether classes or 2-mercaptoalkyl ethers, it is characterized in that in the reaction of described different thiuronium salt and bicarbonate of ammonia, used bicarbonate of ammonia mole number is 2～3 times of different thiuronium salt group mole number, perhaps 1～1.5 times when different thiuronium salt group mole number, add caustic alkali simultaneously with mole numbers such as bicarbonate of ammonia.
6. as the preparation method of claim 1,2 or 3 described 2-mercaptoalkyl thioether classes or 2-mercaptoalkyl ethers, it is characterized in that being reflected under 20～100 ℃ of described different thiuronium salt and volatile salt or bicarbonate of ammonia carry out.
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| CNB2006100201769A CN100363342C (en) | 2006-01-19 | 2006-01-19 | Method for preparing 2-sulfhydyl alkyl sulfide and 2- sulfhydyl alkyl ether compound |
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| CNB2006100201769A CN100363342C (en) | 2006-01-19 | 2006-01-19 | Method for preparing 2-sulfhydyl alkyl sulfide and 2- sulfhydyl alkyl ether compound |
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| CN102531977B (en) * | 2010-12-10 | 2013-12-04 | 北京英力精化技术发展有限公司 | Synthesis method for bis (2-mercaptoethyl) sulfide |
| CN102584654A (en) * | 2012-02-13 | 2012-07-18 | 锦西化工研究院 | Synthetic method for mercapto ethyl mercapto isopropyl sulfur ether |
| CN107986999A (en) * | 2017-11-29 | 2018-05-04 | 黄河三角洲京博化工研究院有限公司 | A kind of preparation method of thio two sweet mercaptan |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4355185A (en) * | 1979-08-29 | 1982-10-19 | Agfa-Gevaert Aktiengesellschaft | Process for the preparation of 2-mercaptoalkyl-sulphides and 2-mercaptoalkylethers |
| JP2002003475A (en) * | 2000-06-20 | 2002-01-09 | Mitsubishi Chemicals Corp | Method of manufacturing 2-(4-pyridyl) ethanethiol |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4355185A (en) * | 1979-08-29 | 1982-10-19 | Agfa-Gevaert Aktiengesellschaft | Process for the preparation of 2-mercaptoalkyl-sulphides and 2-mercaptoalkylethers |
| JP2002003475A (en) * | 2000-06-20 | 2002-01-09 | Mitsubishi Chemicals Corp | Method of manufacturing 2-(4-pyridyl) ethanethiol |
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Effective date of registration: 20111124 Address after: 610041, No. four, 30 South Renmin Road, Chengdu, Sichuan, Wuhou District Patentee after: China Bluestar Chengrand Research Institute of Chemical Industry Co., Ltd. Address before: 610041 No. four, South Renmin Road, Sichuan, Chengdu province 30 Patentee before: Zhonglan Chenguang Chemical Institute Co., Ltd. |