CN107311901A - A kind of method that water-soluble amino acids catalyze and synthesize two thio-diethylene glycols - Google Patents
A kind of method that water-soluble amino acids catalyze and synthesize two thio-diethylene glycols Download PDFInfo
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Abstract
The invention discloses a kind of method that water-soluble amino acids catalyze and synthesize two thio-diethylene glycols.Water-soluble amino acids are added in reaction vessel first, and add deionized water and are fully dissolved, raw material mercaptoethanol is added after dissolving, oxidant hydrogen peroxide is then added dropwise and is reacted；After reaction terminates, gained reaction solution is extracted, gained reaction solution is washed, dried and filtered successively after extraction, gained filtrate carries out vacuum distillation after filtering, removes the solvent used during extraction, finally obtains the thio-diethylene glycol liquid of product two.Preparation method of the present invention is simple to operate, be easily recycled, and synthesizes two thio-diethylene glycols under conditions of any organic solvent of no use.Two thio-diethylene glycols are prepared using technical solution of the present invention, production cost is low, reaction condition is gentle, and product is easily isolated after reaction, energy-saving.
Description
First, technical field：
The present invention relates to technical field of organic synthesis, and in particular to a kind of water-soluble amino acids catalyze and synthesize two thio diethyls
The method of glycol.
2nd, background technology：
Two thio-diethylene glycols are a kind of industrial value very high compound, its wide market.At present, domestic and international two
The synthetic method of thio-diethylene glycol is with beta -mercaptoethanol (HOCH2CH2SH it is) raw material, using different oxidants and catalysis
Agent, oxidative coupling obtains two thio-diethylene glycols.According to the difference of oxidant used, this method can be roughly divided into dioxygen oxidation again
Method, peroxide oxidation method and other oxidative coupling methods such as lead acetate oxidation, sulphur simple substance oxidation, the oxidation of three bromoquinolines etc..
In existing traditional preparation method, mostly there is heavy metal pollution, catalyst and be difficult to reclaim in the higher reaction of yield
The defect such as utilize；Which part technique simple to operate, then have that preparing for catalyst be complex, solvent for use price is held high
Not high enough the weak point of expensive, products obtained therefrom purity.How to simplify its preparation process, and realize that its industrialized production is still current
The emphasis of research.
(1) dioxygen oxidation method prepares two thio-diethylene glycols：
At present, two thio-diethylene glycol methods of report dioxygen oxidation method preparation are more, substantially there is following several situations：
1st, (M.M.Khodaei, I.Mohammadpoor-Baltork, the K.Nikoofar.Bismuth such as M.M.Khodaei
(III)Nitrate Pentahydrate Bi(NO3)3·5H2O:An Inexpensive and Mild Reagent for
the Efficient and Clean Oxidation of Thiols to Disulfides[J].Bulletin of the
Korean Chemical Society.2003,24(7):885-886.)；The document is added thereto using acetonitrile as solvent
Bi (the NO of beta -mercaptoethanol and 30mol%3)3·5H2O, with the O in air2For oxidant, heating reflux reaction is passed through after reaction
Later handle, the thio-diethylene glycol of product two is made.Although the operating method course of reaction is easily controlled, course of reaction is needed
Take into full account catalyst Bi (NO3)3·5H2O recycling, easily causes the pollution problem of heavy metal ion, is unfavorable for ring
Protect in border；Meanwhile, the usage amount of catalyst is also larger, if cannot rationally reclaim, industrial cost is higher.
2nd, (Makoto Oba, the Kazuhito Tanaka.Aerobic Oxidation of Thiols such as Makoto Oba
to Disulfides Catalyzed by Diaryl Tellurides under Photosensitized Conditions
[J].The Journal of Organic Chemistry.2011,(76):4173-4177.)；The document is with beta -mercaptoethanol
Make solvent, 1mol% double (4- methoxyphenyls) tellurides (An for raw material, dichloromethane2Te) as catalyst, 0.1mmol
Tetraphenylporphyrin (TPP) be emulsion, be placed in reaction vessel and reacted, so that the obtained thio-diethylene glycol of product two.
This method fails to improve with O2Needed during as oxidant it is transition metal-catalyzed so as to exist heavy metal ion pollution problem, and
And react relatively complicated, condition requires the defect such as more.
In alkaline medium, metal phthalocyanine derivative (copper phthalocyanine, cobalt phthalocyanine etc.) can be catalyzed β-sulfydryl as catalyst
Ethanol and O2React, generate two thio-diethylene glycols.Many technical staff have carried out certain grind for this kind of method
Study carefully work (for example：The such as Yao Yuyuan, Lv Wangyang styrene-divinyl benzene resins load catalysis of the Binuclear cobalt phthalocyanine to mercaptoethanol
Performance [J] functional materials .2009.2 (40):271-273；Duan Xixin, Guo Liping binuclear cluster complexes-surfactant are thin
Electrocatalytic oxidation [J] Beihua University journal .2010,11 (5) of the membrane electrode to mercaptoethanol:396-400；Chen Wei, Pang Meiling
Research [J] the chemical industry and engineering technology of copper/mesopore molecular sieve composite catalyst catalysis oxidation coloured glaze base ethanol are write Deng phthaleins
.2013,34(1):1-4.).But, the research of metal phthalocyanine catalysis oxidation mercaptan, at present generally be directed to oil and Industry Waste
The desulfuration-deodorization of water, it is therefore an objective to which conversion and removing mercaptan, are not final purpose to obtain the thio-diethylene glycol of oxidation product two.And
And, the content of mercaptan is not general high in the raw material (oil or industrial wastewater) that this kind of method is used, obtain oxidation product have no compared with
Big economic benefit.Therefore, in the research of this kind of method, usually using the reaction rate of catalysis oxidation as inspection target, without
The yield for pursuing two thio-diethylene glycols is maximized.
(2) peroxide oxidation method prepares two thio-diethylene glycols：
Venkitasamy Kesavan etc. add β-sulfydryl second in containing fluorous solvent (hexafluoroisopropanol or trifluoroethanol)
Alcohol, is stirred at room temperature the lower a certain amount of 30%H of addition2O2, it is reaction end that TLC/GC monitoring beta -mercaptoethanols, which disappear,.Reaction terminates, instead
Answer liquid that fluorous solvent is first evaporated off, residue is extracted three times with ether, and organic phase uses anhydrous MgSO again4After drying, vacuum concentration is obtained
The thio-diethylene glycol of product two.
For hexafluoroisopropanol, reaction only need to carry out 10min, and the yield of two thio-diethylene glycols is to reach 95%；For
Trifluoroethanol, reaction carries out 6h, and yield reaches 96%.Selection hexafluoroisopropanol as solvent be because its in the oxidation reaction by
Proof can provide selectivity well, and it generates the reaction of two thio-diethylene glycols in hydrogen peroxide oxidation beta -mercaptoethanol
In, also show extraordinary selective oxidation effect so that the method has gentle, efficient advantage.But, either six
Fluorine isopropanol or trifluoroethanol, all costly, and react needs substantial amounts of solvent to its price, thus needs to take into full account
The recycling of solvent.In addition, fluorine-containing solvent toxicity is larger, larger pollution is will also result in environment, thus is not suitable for big rule
The industrial production of mould, finds replacement solvent and would is that one of solution.
Rajender S.Varma etc., using ethylenediamine as solvent, exist using ammonium peroxydisulfate as oxidant with beta -mercaptoethanol
20min is ground in mortar, two thio-diethylene glycols are obtained through processing, yield is 71%.
This method is simply gentle, but yield is relatively low.Abdol R.Hajipour etc. by a certain amount of beta -mercaptoethanol,
K2S2O8, the mixing of the methylimidazole bromide ion liquid of 1- butyl -3, in insulation reaction 25min at 65-70 DEG C, product is obtained through processing
Two thio-diethylene glycols, yield reaches 84%.
2011, Wei Jie disclosed a kind of patent of invention of two thio-diethylene glycols, and the patent is former by starting of mercaptan
Material, in bromide ion solution, via potassium persulfate oxidation generation disulfide, method and Abdol R.Hajipour et al. conjunction
It is basically identical into method.Ionic liquid with its low-steam pressure, preferable Thermodynamically stable performance, recoverable, have to many
Machine and inorganic material all have the advantages that good dissolubility energy, and are being increasingly used to substitute conventional organic solvents.
Here, bromide ion liquid also acts certain acid catalyzed effect in addition to as solvent.This method mild condition, instead
It is short between seasonable, but its yield need further raising.
(3) sodium disulfide-chlorethanol method：
2002, Zhang Tianlin etc. utilized two in the research that the thio-diethylene glycol of electroreduction two synthesizes beta -mercaptoethanol
Vulcanized sodium and chlorethanol are that Material synthesis has gone out two thio-diethylene glycols.The research contents is at a certain temperature, to curing
Chlorethanol is instilled in the aqueous solution of sodium, stirring reaction, reaction is finished, and is extracted with ethyl acetate 3-5 times, merge organic phase, distillation
Ethyl acetate is removed, dithiodiglycol is made.And further investigated material proportion, reaction temperature, reaction time and charging
Influence of the mode to dithiodiglycol yield, optimization synthesizes the appropriate process conditions of dithiodiglycol：Vulcanized sodium, sulphur
Powder, the mol ratio of chlorethanol are 1：1.08：1.35, reaction temperature is 80 DEG C, and reaction time 6h, optimal yield can reach 98%
More than.
2004, Wang Zhicai equally synthesized two thio diethyls two using sulphur, vulcanized sodium, ethylene chlorhydrin as initiation material
Alcohol, the research contents is using ethanol as solvent, vulcanized sodium 187mmol, n (ethylene chlorhydrin)：N (sulphur)：N (vulcanized sodium)=1.8：
1.2：1.0, back flow reaction 30min, two thio-diethylene glycol yields are up to 88.5%.In this method, sodium disulfide solution is unstable,
It prepares more crucial.
(4) it is catalyzed light conversion method：
2010, Kheng Yee Desmond Tan etc. used ultra violet lamp CpMn (CO) at 25 DEG C3, β-sulfydryl second
The mixed solution of alcohol and benzene 2.5 hours, obtains two thio-diethylene glycols, and yield reaches 99%.
Unique accessory substance is exactly H in this course of reaction2So that the reaction cleanliness without any pollution, and to numerous species
Mercaptan is all suitable for.This method needs to carry out in inert environments, and if oxygen molecule is present, the yield of disulphide will be very
It is low, reason and CpMn (CO)3Decomposition it is relevant.
(5) oxidative coupling method：
Lamar Field and John E.Lawson are at 25-30 DEG C, by a certain amount of Pb (OAc)4Constantly add in batches
Enter into the benzole soln of beta -mercaptoethanol, finish continuation and stir after 2h, filtering；With the jelly remained in acetonitrile extraction flask,
Gained extract merges with upper step filtrate；Revolving is removed after solvent, and raffinate distills in Hickman type short-distance distillers obtains two
Thio-diethylene glycol, yield is 91%.Reaction equation is as follows：
2RSH+Pb(OAc)4→RSSR+Pb(OAc)2+2HOAc
Using Pb (OAc)4As catalyst, have the advantage that：Stronger oxidability and higher selectivity；It can avoid
The problem of over oxidation or oxidant can further react with product；Benzene as solvent be conducive to the thio-diethylene glycol of product two from
Separation in reaction solution.But benzene solvent toxicity is larger, course of reaction has the deficiency that heavy metal pollution problem is this method
Place.
European patent EP 1428819 utilizes sulphur to be that oxidant and beta -mercaptoethanol reaction preparation two are thio there is provided a kind of
The method of diethylene glycol.This method is the beta -mercaptoethanol and sulfur reaction with excess 1-10mol%, to improve two thio diethyls
The ratio of glycol in the product, the H of process generation2S is then removed by vacuum or nitrogen spray.
2HOCH2CH2SH+S→HOCH2CH2SSCH2CH2OH+H2S
Because remaining beta -mercaptoethanol is difficult to separate with two thio-diethylene glycols in product, so after the completion of reaction,
The dioxygen water process reaction solution that mass fraction is 35%-50% has been used again, so that the content of beta -mercaptoethanol is down to
Below 0.02wt%.The advantage of this method be reaction product water content it is low thus be easy to remove, weak point be reaction generation
H2S is toxic gas, and it removes operation and more bothered.
2007, Mohammad Joshaghani etc. had been not added with the situation of any solvent using three bromoquinolines as oxidant
Under, with beta -mercaptoethanol mixed grinding 5min, two thio-diethylene glycols are obtained through processing, its yield can reach 92%.
This method mild condition, the reaction time is short, but is not suitable for industrial production on a large scale.
In summary, the existing document report on dioxygen oxidation method two thio-diethylene glycol methods of preparation is more, and makes
It is less, it is necessary to using expensive poisonous examination with the method pertinent literature report that hydrogen peroxide is oxidant two thio-diethylene glycols of preparation
Agent, is unfavorable for environmental protection.
3rd, the content of the invention：
The technical problem to be solved in the present invention is：A kind of water-soluble amino acids are provided and catalyze and synthesize two thio-diethylene glycols
Method.Technical solution of the present invention is that water-soluble amino acids catalyze and synthesize two thio-diethylene glycols of preparation using micromolecule catalyst.
Preparation method of the present invention is simple to operate, be easily recycled, and synthesis two is thio under conditions of any organic solvent of no use
Diethylene glycol.Two thio-diethylene glycols are prepared using technical solution of the present invention, production cost is low, reaction condition is gentle, after reaction
Product is easily isolated, energy-saving.
In order to solve the above problems, the technical scheme that the present invention takes is：
The present invention provides a kind of method that water-soluble amino acids catalyze and synthesize two thio-diethylene glycols, the synthetic method bag
Include following steps：
A, using mercaptoethanol as raw material, using water-soluble amino acids as catalyst, hydrogen peroxide is used as oxidant；It is described water-soluble
The molal quantity of acidic amino acid accounts for the 5~10% of mercaptoethanol molal quantity, the mol ratio of the hydrogen peroxide and mercaptoethanol for 0.6~
1.5:1；
B, water-soluble amino acids are added in reaction vessel first, and add deionized water and fully dissolve, added after dissolving
Raw material mercaptoethanol, is then added dropwise oxidant hydrogen peroxide and is reacted, controlling reaction temperature is 20~60 DEG C, and the reaction time is 6
~10h；
C, reaction terminate after, gained reaction solution is extracted, after extraction gained reaction solution washed successively, drying and
Filtering, gained filtrate carries out vacuum distillation after filtering, removes the solvent used during extraction, finally obtains the thio diethyl two of product two
Alcohol liquid.
The method that two thio-diethylene glycols are catalyzed and synthesized according to above-mentioned water-soluble amino acids, the water-soluble amino acids are
Proline, serine, lysine or alanine.
The method that two thio-diethylene glycols are catalyzed and synthesized according to above-mentioned water-soluble amino acids, is controlled anti-described in step b
It is 20~40 DEG C to answer temperature, and the reaction time is 7~9h.
The method that two thio-diethylene glycols are catalyzed and synthesized according to above-mentioned water-soluble amino acids, gained is anti-described in step c
When answering the liquid to be extracted, the solvent used is ethyl acetate, ether or petroleum ether.
Gained after being extracted in the method that two thio-diethylene glycols are catalyzed and synthesized according to above-mentioned water-soluble amino acids, step c
The specific operation process that reaction solution is washed, dried and filtered successively is：Gained organic phase uses sodium carbonate liquor after extraction
Washed, be then dried using anhydrous sodium sulfate, filtered after drying.
The method that two thio-diethylene glycols are catalyzed and synthesized according to above-mentioned water-soluble amino acids, depressurizes described in step c and steams
Control pressure is 0.75MPa when evaporating, and temperature is 45 DEG C.
The synthetic route schematic diagram of technical solution of the present invention refers to accompanying drawing 4.
The positive beneficial effect of the present invention：
1st, technical solution of the present invention is made using small molecule amino acid as catalyst, mercaptoethanol as raw material and hydrogen peroxide
For oxidant, one-step synthesis product of the present invention, product only has two thio-diethylene glycols and water.Two sulphur are prepared using the inventive method
For diethylene glycol, preparation method is simple, be easily isolated purification；And synthesize two under conditions of any organic solvent of no use
Thio-diethylene glycol.Two thio-diethylene glycols are prepared using technical solution of the present invention, production cost is low, reaction condition is gentle, instead
Product is easily isolated after answering, energy-saving, is conducive to environmental protection.
2nd, the catalyst small molecule amino acid that the present invention is used is a kind of amino acid of protein structure, with a variety of work(
Can, wide material sources.Amino acid catalytic effect is good, and reaction system is simple, and reaction is gentle, and building-up process is easy, reacts normal in normal temperature
Pressure is carried out, and energy-saving, product selectivity is good, no coupling product, and subsequent product convenient separation greatlys save product and is separated into
This, two thio-diethylene glycol products of 99% high-purity is can obtain by extraction, washing and vacuum distillation, hence it is evident that better than existing
Method.
3rd, organic solvent is not used in technical solution of the present invention, it is not necessary to expensive solvent is added, so as to effectively drop
Low production cost.Therefore, with significant economic benefit and social benefit.
4th, technical solution of the present invention uses hydrogen peroxide for oxidant, and the wide price in hydrogen peroxide source is low, contributes to reduction to produce
Cost；Reaction, which terminates rear accessory substance, only has water, pollution-free, is an environmentally friendly cleaning route, and industry metaplasia can be achieved
Production.Therefore, technical solution of the present invention has significant economic benefit and social benefit.
4th, illustrate：
The infrared spectrogram of Fig. 1 thio-diethylene glycols of products obtained therefrom two of the present invention；
As shown in Figure 1：3350cm-1The absworption peak at place should correspond to the O-H structures in molecule；2930cm-1The absworption peak at place should
For molecule methylene-CH2Peak；1025cm-1The absworption peak at place should be the peak of primary alconol C-O keys in molecule；629cm-1The suction at place
Receive peak and should be the peak that C-S keys go out；2550-2600cm-1Place should be that going out at this in peak position, but figure for S-H does not absorb
Peak, it is seen that be free of beta -mercaptoethanol in product.Molecular structure with Shangguan's group with two thio-diethylene glycols is corresponding, institute
To be able to demonstrate that products therefrom of the present invention is two thio-diethylene glycols.
Fig. 2 products of the present invention1H-NMR spectrum；
Products obtained therefrom of the present invention is dissolved in deuterated water (D2O in), product of the present invention is respectively obtained1H-NMR spectrum (is referred to
Fig. 2).
As shown in Figure 2：Peak at chemical shift δ=4.7 should be the proton peak of the deuterated water of solvent；Peak at δ=3.7 should generation
The methene proton that table is connected with hydroxyl；Peak at δ=2.8 should be the methene proton being connected with sulphur atom.In addition, δ=3.7
Methylene at place and δ=2.8 is all triplet, and this combination illustrates "-CH2CH2- " presence of structure.Two thio diethyls two
The molecular structure of alcohol is symmetrical, and same type of proton does not repeat appearance, so the result that shows of the figure and two thio diethyls
The structure of glycol is consistent completely.
The typical chromatogram of Fig. 3 product analyses of the present invention；
HPLC conditions are as follows：
Using Shimadzu high performance liquid chromatography (LC-20AT), anti-phase C18 150mm × 4.6mm × 5 μm chromatographic column, using second
Nitrile and water are used as mobile phase.Actual conditions：(volume ratio of acetonitrile and water is 10 to mobile phase acetonitrile-water：90), flow velocity 1.0mL
min-1, sample size 0.5 μ l, Detection wavelength 272nm, 40 DEG C of column temperature.
The thio-diethylene glycol product of product two of the present invention is analyzed under the chromatographic condition.
As shown in Figure 3：Two thio-diethylene glycol 5.91min are two thio-diethylene glycols.It is possible thereby to illustrate ammonia of the present invention
Base acid catalysis synthesizes the technique of two thio-diethylene glycols, and without other accessory substances, subsequent product is isolated and purified simply；
The synthetic route schematic diagram of Fig. 4 technical solution of the present invention.
5th, embodiment：
The present invention is expanded on further with reference to embodiments, but is not intended to limit the technology contents that the present invention is protected.
Embodiment 1：
The method that water-soluble amino acids of the present invention catalyze and synthesize two thio-diethylene glycols, the detailed step of the synthetic method is such as
Under：
A, using beta -mercaptoethanol as raw material, using proline as catalyst, hydrogen peroxide is used as oxidant；The proline
Molal quantity accounts for the 5.0% of beta -mercaptoethanol molal quantity, and the mol ratio of the hydrogen peroxide and beta -mercaptoethanol is 0.6:1；
B, 2.7mmol proline is weighed first add in reaction vessel, and add 5.00mL deionized waters and fully dissolve, it is molten
Dropwise addition 0.033mol hydrogen peroxide under the conditions of 0.054mol beta -mercaptoethanols, room temperature (20~25 DEG C) is added after solution, is opened after dripping
Begin to heat, reaction 6h is stirred under the conditions of being warming up to 30 DEG C；
After c, reaction terminate, gained reaction solution is poured into pear shape separatory funnel, and extracted with ethyl acetate, after extraction
Gained reaction solution (i.e. organic phase) is washed using sodium carbonate liquor, then with anhydrous sodium sulfate drying, is then filtered, and gained filtrate subtracts
Whole ethyl acetate (control pressure is 0.75MPa during vacuum distillation, and temperature is 45 DEG C) are evaporated off in pressure, and it is this to finally obtain liquid
The thio-diethylene glycol of invention product two；Raffinate phase is recycled.
The present embodiment products obtained therefrom is through chromatographic, and its yield is 90.62%.
Embodiment 2：
The method that water-soluble amino acids of the present invention catalyze and synthesize two thio-diethylene glycols, the detailed step of the synthetic method is such as
Under：
A, using beta -mercaptoethanol as raw material, using proline as catalyst, hydrogen peroxide is used as oxidant；The proline
Molal quantity accounts for the 8.5% of beta -mercaptoethanol molal quantity, and the mol ratio of the hydrogen peroxide and beta -mercaptoethanol is 1.4:1；
B, 4.6mmol proline is weighed first add in reaction vessel, and add 5.00mL deionized waters and fully dissolve, it is molten
Dropwise addition 0.076mol hydrogen peroxide under the conditions of 0.054mol beta -mercaptoethanols, room temperature (20~25 DEG C) is added after solution, is opened after dripping
Begin to heat, reaction 9h is stirred under the conditions of being heated to 40 DEG C；
After c, reaction terminate, gained reaction solution is poured into pear shape separatory funnel, and extracted with ethyl acetate, after extraction
Gained reaction solution (i.e. organic phase) is washed using sodium carbonate liquor, then with anhydrous sodium sulfate drying, is then filtered, and gained filtrate subtracts
Whole ethyl acetate (control pressure is 0.75MPa during vacuum distillation, and temperature is 45 DEG C) are evaporated off in pressure, and it is this to finally obtain liquid
The thio-diethylene glycol of invention product two；Raffinate phase is recycled.
The present embodiment products obtained therefrom is through chromatographic, and its yield is 89.48%.
Embodiment 3：
The method that water-soluble amino acids of the present invention catalyze and synthesize two thio-diethylene glycols, the detailed step of the synthetic method is such as
Under：
A, using beta -mercaptoethanol as raw material, using serine as catalyst, hydrogen peroxide is used as oxidant；The serine
Molal quantity accounts for the 10% of beta -mercaptoethanol molal quantity, and the mol ratio of the hydrogen peroxide and beta -mercaptoethanol is 0.9:1；
B, 5.4mmol serines are weighed first add in reaction vessel, and add 5.00mL deionized waters and fully dissolve, it is molten
Dropwise addition 0.049mol hydrogen peroxide under the conditions of 0.054mol beta -mercaptoethanols, room temperature (20~25 DEG C) is added after solution, is opened after dripping
Begin to heat, reaction 6h is stirred under the conditions of being heated to 30 DEG C；
After c, reaction terminate, gained reaction solution is poured into pear shape separatory funnel, and extracted with ethyl acetate, after extraction
Gained reaction solution (i.e. organic phase) is washed using sodium carbonate liquor, then with anhydrous sodium sulfate drying, is then filtered, and gained filtrate subtracts
Whole ethyl acetate (control pressure is 0.75MPa during vacuum distillation, and temperature is 45 DEG C) are evaporated off in pressure, and it is this to finally obtain liquid
The thio-diethylene glycol of invention product two；Raffinate phase is recycled.
The present embodiment products obtained therefrom is through chromatographic, and its yield is 88.87%.
Embodiment 4：
The method that water-soluble amino acids of the present invention catalyze and synthesize two thio-diethylene glycols, the detailed step of the synthetic method is such as
Under：
A, using beta -mercaptoethanol as raw material, using serine as catalyst, hydrogen peroxide is used as oxidant；The serine
Molal quantity accounts for the 7.4% of beta -mercaptoethanol molal quantity, and the mol ratio of the hydrogen peroxide and beta -mercaptoethanol is 1.5:1；
B, 4.0mmol serines are weighed first add in reaction vessel, and add 5.00mL deionized waters and fully dissolve, it is molten
Dropwise addition 0.081mol hydrogen peroxide under the conditions of 0.054mol beta -mercaptoethanols, room temperature (20~25 DEG C) is added after solution, is opened after dripping
Begin to heat, reaction 8h is stirred under the conditions of being heated to 50 DEG C；
After c, reaction terminate, gained reaction solution is poured into pear shape separatory funnel, and extracted with ethyl acetate, after extraction
Gained reaction solution (i.e. organic phase) is washed using sodium carbonate liquor, then with anhydrous sodium sulfate drying, is then filtered, and gained filtrate subtracts
Whole ethyl acetate (control pressure is 0.75MPa during vacuum distillation, and temperature is 45 DEG C) are evaporated off in pressure, and it is this to finally obtain liquid
The thio-diethylene glycol of invention product two.
The present embodiment products obtained therefrom is through chromatographic, and its yield is 89.22%.
Embodiment 5：
The method that water-soluble amino acids of the present invention catalyze and synthesize two thio-diethylene glycols, the detailed step of the synthetic method is such as
Under：
A, using beta -mercaptoethanol as raw material, using alanine as catalyst, hydrogen peroxide is used as oxidant；The alanine
Molal quantity accounts for the 6.7% of beta -mercaptoethanol molal quantity, and the mol ratio of the hydrogen peroxide and beta -mercaptoethanol is 0.7:1；
B, 3.6mmol alanine is weighed first add in reaction vessel, and add 5.00mL deionized waters and fully dissolve, it is molten
0.054mol beta -mercaptoethanols are added after solution, 0.038mol hydrogen peroxide is added dropwise under the conditions of room temperature (20~25 DEG C), after dripping
Reaction 7h is stirred under the conditions of 20 DEG C；
After c, reaction terminate, gained reaction solution is poured into pear shape separatory funnel, and extracted with ethyl acetate, after extraction
Gained reaction solution (i.e. organic phase) is washed using sodium carbonate liquor, then with anhydrous sodium sulfate drying, is then filtered, and gained filtrate subtracts
Whole ethyl acetate (control pressure is 0.75MPa during vacuum distillation, and temperature is 45 DEG C) are evaporated off in pressure, and it is this to finally obtain liquid
The thio-diethylene glycol of invention product two.
The present embodiment products obtained therefrom is through chromatographic, and its yield is 85.07%.
Embodiment 6：
The method that water-soluble amino acids of the present invention catalyze and synthesize two thio-diethylene glycols, the detailed step of the synthetic method is such as
Under：
A, using beta -mercaptoethanol as raw material, using alanine as catalyst, hydrogen peroxide is used as oxidant；The alanine
Molal quantity accounts for the 9.1% of beta -mercaptoethanol molal quantity, and the mol ratio of the hydrogen peroxide and beta -mercaptoethanol is 1.5:1；
B, 4.9mmol alanine is weighed first add in reaction vessel, and add 5.00mL deionized waters and fully dissolve, it is molten
Dropwise addition 0.081mol hydrogen peroxide under the conditions of 0.054mol beta -mercaptoethanols, room temperature (20~25 DEG C) is added after solution, is opened after dripping
Begin to heat, reaction 9h is stirred under the conditions of being heated to 40 DEG C；
After c, reaction terminate, gained reaction solution is poured into pear shape separatory funnel, and extracted with ethyl acetate, after extraction
Gained reaction solution (i.e. organic phase) is washed using sodium carbonate liquor, then with anhydrous sodium sulfate drying, is then filtered, and gained filtrate subtracts
Whole ethyl acetate (control pressure is 0.75MPa during vacuum distillation, and temperature is 45 DEG C) are evaporated off in pressure, and it is this to finally obtain liquid
The thio-diethylene glycol of invention product two；Raffinate phase is recycled.
The present embodiment products obtained therefrom is through chromatographic, and its yield is 89.84%.
Claims (6)
1. a kind of method that water-soluble amino acids catalyze and synthesize two thio-diethylene glycols, it is characterised in that the synthetic method bag
Include following steps：
A, using mercaptoethanol as raw material, using water-soluble amino acids as catalyst, hydrogen peroxide is used as oxidant；The water-soluble ammonia
The molal quantity of base acid accounts for the 5~10% of mercaptoethanol molal quantity, and the mol ratio of the hydrogen peroxide and mercaptoethanol is 0.6~1.5:
1；
B, water-soluble amino acids are added in reaction vessel first, and add deionized water and fully dissolve, raw material is added after dissolving
Mercaptoethanol, is then added dropwise oxidant hydrogen peroxide and is reacted, controlling reaction temperature is 20~60 DEG C, the reaction time for 6~
10h；
After c, reaction terminate, gained reaction solution is extracted, gained reaction solution is washed, dried and mistake successively after extraction
Filter, gained filtrate carries out vacuum distillation after filtering, removes the solvent used during extraction, finally obtains the thio-diethylene glycol of product two
Liquid.
2. the method that water-soluble amino acids according to claim 1 catalyze and synthesize two thio-diethylene glycols, it is characterised in that：
The water-soluble amino acids are proline, serine, lysine or alanine.
3. the method that water-soluble amino acids according to claim 1 catalyze and synthesize two thio-diethylene glycols, it is characterised in that：
Controlling reaction temperature described in step b is 20~40 DEG C, and the reaction time is 7~9h.
4. the method that water-soluble amino acids according to claim 1 catalyze and synthesize two thio-diethylene glycols, it is characterised in that：
When gained reaction solution described in step c is extracted, the solvent used is ethyl acetate, ether or petroleum ether.
5. the method that water-soluble amino acids according to claim 1 catalyze and synthesize two thio-diethylene glycols, it is characterised in that：
The gained reaction solution specific operation process being washed, dried and filtered successively is after being extracted in step c：Gained is organic after extraction
Mutually washed, be then dried using anhydrous sodium sulfate using sodium carbonate liquor, filtered after drying.
6. the method that water-soluble amino acids according to claim 1 catalyze and synthesize two thio-diethylene glycols, it is characterised in that：
Control pressure is 0.75MPa during vacuum distillation described in step c, and temperature is 45 DEG C.
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| US20040116748A1 (en) * | 2002-11-27 | 2004-06-17 | Chevron Phillips Chemical Company | Production of dithiodiglycol |
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| US20040116748A1 (en) * | 2002-11-27 | 2004-06-17 | Chevron Phillips Chemical Company | Production of dithiodiglycol |
| CN101838228A (en) * | 2010-06-11 | 2010-09-22 | 郑州大学 | Clean synthesis method for di-tert-butyl disulfide |
| CN106633183A (en) * | 2016-10-17 | 2017-05-10 | 美轲（淮安）化学有限公司 | Multi-thioether PVC (polyvinyl chloride) co-stabilizer, method for preparing same and application of multi-thioether PVC co-stabilizer |
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