CN101845006B - Beta-alkyl sulfide substituted vinyl propionate sulfur compound and preparation method thereof - Google Patents

Beta-alkyl sulfide substituted vinyl propionate sulfur compound and preparation method thereof Download PDF

Info

Publication number
CN101845006B
CN101845006B CN2010101425119A CN201010142511A CN101845006B CN 101845006 B CN101845006 B CN 101845006B CN 2010101425119 A CN2010101425119 A CN 2010101425119A CN 201010142511 A CN201010142511 A CN 201010142511A CN 101845006 B CN101845006 B CN 101845006B
Authority
CN
China
Prior art keywords
alkyl
preparation
ionic liquid
beta
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN2010101425119A
Other languages
Chinese (zh)
Other versions
CN101845006A (en
Inventor
娄凤文
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huaiyin Normal University
Original Assignee
Huaiyin Normal University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Huaiyin Normal University filed Critical Huaiyin Normal University
Priority to CN2010101425119A priority Critical patent/CN101845006B/en
Publication of CN101845006A publication Critical patent/CN101845006A/en
Application granted granted Critical
Publication of CN101845006B publication Critical patent/CN101845006B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Landscapes

  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a beta-alkyl sulfide substituted vinyl propionate sulfur compound and a preparation method thereof. The preparation method comprises the following steps: firstly adding a certain amount of basic ionic liquid into a reactor, then adding a sulfydryl reagent into the reactor, and sufficiently mixing the basic ionic liquid with the sulfydryl reagent for a certain time to make the sulfydryl reagent and the basic ionic liquid react with each other to convert into alkyl sulfide negative ions; adding a certain amount of an addition receptor vinyl acrylate compound into the reactor, oscillating the reactor at a speed of 200rev./min in a constant temperature oscillating box and monitoring the reaction process by using a TLC; when the reaction is completed, adding a certain volume of extracting agent into mixed solution to extract, after the extract liquid is combined, reducing pressure, distilling and recycling the extracting agent, and separating a crude product by a chromatographic column; or carrying out pressure reduction and distilling on the mixed solution after the reaction to obtain a product, wherein the residual basic ionic liquid is continuously used after being washed. The preparation method is carried out at room temperature, has good yield and has practical industrial operability.

Description

A kind of Beta-hydrocarbyl-sulphur replaces propionate class sulfocompound and preparation method thereof
Technical field
The present invention relates to compound of chemical field and preparation method thereof, be specifically related to a kind of method that promotes SR and vinyl acrylate analog derivative prepared in reaction Beta-hydrocarbyl-sulphur replacement propionate class sulfocompound with alkali ionic liquid.
Technical background
Many synthetic or natural organic compounds containing sulfur be biologically active all.The building-up reactions of transition metal-catalyzed C-S key is for the sulphur organic chemistry has been opened up new developmental stage.But transition metal complex generally exists preparation difficulty, costs an arm and a leg, is prone to run off, difficultly reclaim, can produce shortcoming such as environmentally harmful material.These deleterious materials seriously influence bad can the causing according to survival environment and human health of the mankind.Becoming increasingly conspicuous of problem of environmental pollution, an urgent demand development is to the chemistry of human health and the less harm of environment.To fundamentally address these problems, must adopt green compound method.The environmental friendliness chemistry promptly is to go to reduce or eliminate those generation and application to human health or the deleterious raw material of environment, product, by product, solvent and reagent etc. with the technology and the method for chemistry.
Addition reaction is one type of very important atomic economy reaction in the organic synthesis.Such addition reaction comes activation nucleophilic reagent or acceptor with highly basic, strong acid usually, and this has brought deleterious residual and some side reactions to environment.For fear of the problem that these catalyzer produce, use more gentleness efficiently catalyzer to come the catalysis Michael reaction be a present hot research field.Ionic liquid at room temperature has attracted people's attention as a kind of " green catalyst ", and ionic liquid can the many chemical reactions of catalysis.Acidic ion liquid has been used for the scission reaction of catalytic esterification and ehter bond.Neutral ion liquid also successfully has been used for catalytic alkylation reaction, aldol reaction, epoxidation reaction and Michael addition reaction.Alkali ionic liquid not only has ion liquid general aspects; And has an alkaline functional of mineral alkalis such as sodium hydroxide; Good substrate intermiscibility, catalytic and alkalescence are arranged; Alkali ionic liquid has very big potentiality in conduct aspect environmental friendliness " clean basic solvent and catalyzer ", at aspects such as organic synthesis, industrial reactions higher using value is arranged.
Summary of the invention
The objective of the invention is to: provide a kind of Beta-hydrocarbyl-sulphur to replace propionate class sulfocompound and preparation method thereof; Adopt alkali ionic liquid rapid absorption SR to make it be converted into the stronger sulfydryl negative ion of nucleophilicity; The synthetic Beta-hydrocarbyl-sulphur of highly selective reaction rapidly and efficiently takes place and replaces propionate class sulfocompound in sulfydryl negative ion and vinyl propionate ester compound; This preparation method carries out at ambient temperature, and earning rate is good, has actual industrial operability.
Technical solution of the present invention is: it is that chemical structural formula is the sulfur-bearing vinyl propionate ester derivative that following general formula is represented that a kind of Beta-hydrocarbyl-sulphur replaces propionate class sulfocompound,
Figure GSB00000211504800031
R 1Represent 4-12 carbon atom alkyl; R 2Represent the alkyl of Wasserstoffatoms or 1-3 carbon atom; R 3Represent the alkyl of Wasserstoffatoms or 1-3 carbon atom; R 4Represent the alkyl of Wasserstoffatoms or 1-3 carbon atom.
Wherein, The preparation method that a kind of Beta-hydrocarbyl-sulphur replaces propionate class sulfocompound may further comprise the steps: at first; In reactor drum, add a certain amount of alkali ionic liquid earlier, add SR again; Behind the certain hour thorough mixing, SR and alkali ionic liquid effect are converted into alkyl sulphur negative ion; Then, add a certain amount of addition acceptor vinyl acrylate compounds, in the constant-temperature shaking case, with the velocity fluctuation of 200rev./min, TLC monitors reaction process; At last, when reaction finishes, in mixed liquid, add the extraction agent extraction of certain volume, extraction liquid merges the back underpressure distillation and reclaims extraction agent, and crude product separates with chromatography column; Perhaps reacted mixed liquid underpressure distillation is obtained product, residual alkali ionic liquid continues to use through washing.
Wherein, described SR is a mercaptan compound, the butyl sulfhydryl of alkane thiol, hexylmercaptan, spicy thioalcohol, decyl mercaptan, Dodecyl Mercaptan; The thiophenol of aromatic thiol, to methylbenzene thiophenol, a methylbenzene thiophenol, o-methyl-benzene thiophenol, to ethyl thiophenol, an ethyl thiophenol, adjacent ethyl thiophenol, to propylbenzene thiophenol, a propylbenzene thiophenol, adjacent propylbenzene thiophenol, p-isopropyl thiophenol, a different basic thiophenol, adjacent different basic thiophenol, to the butylbenzene-thiophenol, to the amylbenzene thiophenol, to the hexyl benzene thiophenol; Benzyl mercaptan, phenyl sulfur alcohol, phenyl propylmercaptan, the phenyl hexylmercaptan of fragrance substituted alkyl mercaptan, benzyl mercaptan; Or the compound represented of following general formula:
Figure GSB00000211504800041
In this formula, R 1Represent 4-12 carbon atom alkyl, preferred 4, twelve carbon atom alkyl or 6,7 carbon atom aryl perfume bases.
Wherein, the vinyl acrylate compound is the compound that following general formula is represented:
Figure GSB00000211504800042
R 2Represent the alkyl of Wasserstoffatoms or 1-3 carbon atom; R 3Represent the alkyl of Wasserstoffatoms or 1-3 carbon atom; R 4Represent the alkyl of Wasserstoffatoms or 1-3 carbon atom.
Wherein, preferred positive vinyl acrylate, different vinyl acrylate, Vinyl crotonate.
Wherein, the anionic monomer of described alkali ionic liquid is hydroxide radical OH -, cationic monomer is the substituted imidazol ion of alkyl or substituted pyridinium ion of alkyl or quaternary ammonium alkyl ion.The substituted imidazol ion of alkyl has: [1-methyl-3-Methylimidazole], [1-ethyl-3-Methylimidazole], [1-butyl-3-Methylimidazole], [1-methyl-3-ethyl imidazol(e)]; [1-ethyl-3-propyl imidazole], [1-butyl-3-NSC 158165], [1-methyl-2-methyl-3-Methylimidazole], [1-ethyl-2-methyl-3-Methylimidazole]; [1-propyl group-2-methyl-3-Methylimidazole], [1-butyl-2-methyl-3-ethyl imidazol(e)], [1-butyl-2-methyl-3-propyl imidazole], [1-butyl-2-methyl-3-NSC 158165]; [1-methyl-2-ethyl-3-NSC 158165], [1-ethyl-2-ethyl-3-Methylimidazole], [1-propyl group-2-propyl group-3-Methylimidazole], [1-butyl-2-propyl group-3-Methylimidazole]; [1-butyl-2-propyl group-3-ethyl imidazol(e)], [1-butyl-2-propyl group-3-propyl imidazole], [1-ethyl-1-methylpyrrole ammonium], [1-propyl group-1-methylpyrrole ammonium]; [1-butyl-1-methylpyrrole ammonium], [1-ethyl-1-N-ethyl pyrrole N-ammonium], [1-propyl group-1-N-ethyl pyrrole N-ammonium], [1-butyl-1-N-ethyl pyrrole N-ammonium]; [1-butyl-pyridinium], [1-butyl-3-picoline], [1-butyl-4-picoline], [1-ethyl-3-(methylol) ethylpyridine]; [1-ethylpyridine], [1-ethyl-3-picoline], [cyclohexyl trimethyl ammonium]; [methyl trioctylammonium], [methyl trioctylammonium], [TBuA].
Wherein, preferred hydroxide of alkali ionic liquid [1-alkyl-3-Methylimidazole] or [C 4Mim] OH.
Wherein, prepare in the substituted vinyl acrylate compound of β-sulphur at mercaptan and vinyl acrylate addition, the mercaptan of 1mol can obtain the adduct of 1mol with excessive vinyl acrylate usually; Specifically, every mole of mercaptan uses the 1-1.5mol vinyl acrylate, preferred 1.1-1.3mol; If it is excessive that vinyl acrylate uses, it has no adverse effect to reaction, but will increase removal process.
Wherein, temperature of reaction is 20-50 ℃, preferred 20-25 ℃; The alkali ionic liquid catalytic activity of using in the method is high, and being reflected at room temperature or normal temperature can carry out smoothly; Reaction pressure is 1-3kg/cm 2, preferred 1kg/cm 2Oxidized in order to prevent mercaptan in reaction process, be adapted at carrying out under the airtight condition, excessive vinyl acrylate atmosphere can reduce or avoid the oxidation of mercaptan.
Wherein, in reaction the vinyl acrylate of excessive use can be after reaction through fractionation by distillation, reclaim and recycle.
Wherein, alkali ionic liquid reaches (Fig. 1) more than 6 times through washing can continue to recycle, and the alkali ionic liquid usage quantity is 1-10 a times of SR molar weight, and preferred 4-6 doubly.
Wherein, the alkali ionic liquid preparation method is similar to the preparation method of hydroxide 1-butyl-3-Methylimidazole [bmim] OH: measure 60mL N-Methylimidazole and the 95mL 1-chlorobutane is poured the 250mL three-necked bottle into, put into magneton, logical nitrogen, 75 ℃ of condition refluxed 72h; Reaction stops, and is cooled to room temperature, pours the reaction solution in the three-necked bottle into separating funnel, washes twice with ETHYLE ACETATE earlier, and each 100mL washes once with ether 70mi again, gets product 132g, and productive rate is 69%; Take by weighing ion exchange resin 50g, with the salt soak 12h of 1mol/mL, the NaOH aqueous solution soaking 12h of 1mol/mL, repeatedly after 2 times, upper prop, water is washed till neutrality; Add 23g chlorination 1-butyl-3-Methylimidazole, use water elution, receive alkaline liq; 50 ℃ of underpressure distillation of obtained aqueous solution obtain little yellow transparent liquid 50 ℃ of dryings; [bmim] OH is heated to 200 ℃, and cool to room temperature carries out IR and characterizes (Fig. 2), explains more stable.
The present invention has the following advantages:
1, SR is organic nucleophilic reagent of using always; Multiple organic synthesis can take place; It is the important intermediate of organic synthesis; Yet it has very strong volatility, during use smell bigger and also when containing or containing simultaneously the reagent of a plurality of nucleophilic groups such as amino, hydroxyl the selectivity of mercapto groups reaction undesirable; The method that the present invention solves relates to alkali ionic liquid rapid absorption mercaptan makes it be converted into the stronger sulfydryl negative ion of nucleophilicity as ordorless sulphur reagent and the synthetic Beta-hydrocarbyl-sulphur replacement of vinyl propionate ester reaction propionate class sulfocompound.
2, the present invention has synthesized and has multi-functional Beta-hydrocarbyl-sulphur and replace propionate class sulfocompound, and a lot of chemical reactions can take place, and is with a wide range of applications.
3, the present invention has synthesized and has multi-functional Beta-hydrocarbyl-sulphur and replace propionate class sulfocompound, is the environmental friendliness reaction, has practical industrial application value.
4, the present invention carries out at ambient temperature, in 2-20 minute, can obtain good earning rate, the retortable recycling of excessive vinyl acetate, and alkali ionic liquid also can recycle repeatedly.
5, the present invention relates to make it be converted into the alternative reagent of ordorless sulfydryl negative ion reagent as mercaptan with alkali ionic liquid rapid absorption SR.
6, reacted mixed liquid underpressure distillation is directly obtained product, have actual industrial operability; Perhaps in mixed liquid, add the eco-friendly extraction agent extraction of certain volume, extraction liquid merges the back underpressure distillation and obtains high purity product, the extraction agent reusable edible of recovery.
7, the present invention uses and contains the polymer monomer of the unsaturated carbon-carbon double bond chemical structure of ethene as sulfur-bearing, can form the polymkeric substance with unique function and character.
8, of the present inventionly contain the substrate that the unsaturated carbon-carbon double bond chemical structure of ethene and ester group structure can be used as chemical reaction and proceed the reaction that unsaturated carbon-carbon double bond and ester group has.
9, the sulfide based structural that contains of the present invention can be used as the further oxidation sulfoxide of substrate, comprises partial oxidation products such as chiral sulfoxide, sulfone.
Description of drawings
Fig. 1 is the infrared spectrogram of the circulation 8 times of alkali ionic liquid hydroxide 1-butyl-3-Methylimidazole [bmim] OH;
Fig. 2 is the infrared spectrogram of alkali ionic liquid hydroxide 1-butyl-3-Methylimidazole [bmim] OH through 200 ℃ of processing;
Fig. 3 is the GC color atlas of thiophenol and methacrylic vinyl acetate reaction solution;
Fig. 4 is the infrared spectrogram of the reaction product of thiophenol and methacrylic vinyl acetate;
Fig. 5 is β-thiophenyl-α-Jia Jibingxisuan vinyl acetate 1H nuclear magnetic resonance, hydrogen spectrogram;
Fig. 6 is β-thiophenyl-α-Jia Jibingxisuan vinyl acetate 13C nuclear magnetic resonance, carbon spectrogram;
Fig. 7 is β-thiophenyl-Beta-methyl vinyl acrylate 1H nuclear magnetic resonance, hydrogen spectrogram;
Fig. 8 is β-thiophenyl-Beta-methyl vinyl acrylate 13C nuclear magnetic resonance, carbon spectrogram;
Fig. 9 is β-benzylthio--α-Jia Jibingxisuan vinyl acetate 1H nuclear magnetic resonance, hydrogen spectrogram;
Figure 10 is β-benzylthio--α-Jia Jibingxisuan vinyl acetate 13C nuclear magnetic resonance, carbon spectrogram;
Figure 11 is β-benzylthio--Beta-methyl vinyl acrylate 1H nuclear magnetic resonance, hydrogen spectrogram;
Figure 12 is β-benzylthio--Beta-methyl vinyl acrylate 13C nuclear magnetic resonance, carbon spectrogram;
Figure 13 is β-butane sulfenyl-α-Jia Jibingxisuan vinyl acetate 1H nuclear magnetic resonance, hydrogen spectrogram;
Figure 14 is β-butane sulfenyl-α-Jia Jibingxisuan vinyl acetate 13C nuclear magnetic resonance, carbon spectrogram;
Figure 15 is β-butane sulfenyl-Beta-methyl vinyl acrylate 1H nuclear magnetic resonance, hydrogen spectrogram;
Figure 16 is β-butane sulfenyl-Beta-methyl vinyl acrylate 13C nuclear magnetic resonance, carbon spectrogram;
Figure 17 is β-n-dodecane sulfenyl-α-Jia Jibingxisuan vinyl acetate 1H nuclear magnetic resonance, hydrogen spectrogram;
Figure 18 is β-n-dodecane sulfenyl-α-Jia Jibingxisuan vinyl acetate 13C nuclear magnetic resonance, carbon spectrogram;
Figure 19 is β-n-dodecane sulfenyl-Beta-methyl vinyl acrylate 1H nuclear magnetic resonance, hydrogen spectrogram;
Figure 20 is β-n-dodecane sulfenyl-Beta-methyl vinyl acrylate 13C nuclear magnetic resonance, carbon spectrogram;
Figure 21 is β-(2-hydroxyl ethane sulfenyl)-α-Jia Jibingxisuan vinyl acetate 1HNMR hydrogen nuclear magnetic resonance spectrogram;
Figure 22 is β-(2-hydroxyl ethane sulfenyl)-α-Jia Jibingxisuan vinyl acetate 13CNMR carbon-13 nmr spectra figure;
Figure 23 is β-(2-hydroxyl ethane sulfenyl)-Beta-methyl vinyl acrylate 1HNMR hydrogen nuclear magnetic resonance spectrogram;
Figure 24 is β-(2-hydroxyl ethane sulfenyl)-Beta-methyl vinyl acrylate 13CNMR carbon-13 nmr spectra figure;
Embodiment
Below in conjunction with embodiment technical solution of the present invention is described in further detail, it is the restriction to technical solution that these embodiment should not be construed as.
Embodiment 1:
At the ground Erlenmeyer flask of a 200mL, add 50mL ionic liquid hydroxide [1-butyl-3-Methylimidazole] earlier, add the 0.1mol thiophenol again in Erlenmeyer flask, add 0.12mol methacrylic vinyl acetate behind the thorough mixing, at 1kg/cm 2In pressure, the 20 ℃ of constant-temperature shaking culture casees, with the velocity fluctuation of 200rev./min; TLC monitors reaction process, shows after 10 minutes to react completely, with the component of GC chromatography detection reaction liquid, like Fig. 3; T among Fig. 3 R=5.828 is the chromatographic peak of thiophenol, t R=7.169 is the chromatographic peak of product; Finish the back adds 60mL in reaction solution ethyl acetate extraction 5 times, extraction liquid merges back water pump underpressure distillation and reclaims ETHYLE ACETATE, products therefrom yield 93%, and infrared spectrum characterization such as Fig. 4, nucleus magnetic hydrogen spectrum characterize like Fig. 5, and nuclear-magnetism carbon stave is levied like Fig. 6; Ionic liquid continues to use 8 times through washing.
The addition reaction of catalytic thiophenol of alkali ionic liquid and methacrylic vinyl acetate is shown in following reaction formula:
Figure GSB00000211504800101
Ir spectra spectrogram such as Fig. 4 of product have single-substituted charateristic avsorption band, from 3088cm -1, 3059cm -1The place=C-H stretching vibration absorption and 1583cm -1, 1480cm -1, 1458cm -1The absorption peak of skeletal vibration of phenyl ring, 740cm -1, 691cm -1Phenyl ring=C-H the out-of-plane deformation vibration at place, 1646cm -1It is the absorption peak of vibration of the C=C of vinyl.
Hydrogen nuclear magnetic resonance spectrogram such as Fig. 5 are at 4.88 (dd, J=6.26Hz, 1H ,-CH=C H aH b), 4.59 (dd, J=1.65Hz, 1H ,-CH=CH a H b) appearance of locating absorption peak further specifies-O-CH=CH 2Existence, near 6.00, do not have O=C-CH=CH 2Absorption peak, and 3.29 (d, 1H ,-S-C have appearred H 2-CH-), 2.95 (q, 1H, J=7.00Hz ,-S-CH 2-C H-), 2.75 (d, 1H ,-S-C H 2-CH-) absorption peak is explained the α of methacrylic vinyl acetate, and the Michael reaction has taken place the unsaturated conjugated carbon-carbon double bond of β and the vinyl ester structure division does not change, at 7.39-7.21 (6H, C 6 H 5-,-C H=CH 2) absorption peak explanation thiophenol Michael reaction has taken place.
Carbon-13 nmr spectra figure such as Fig. 6, δ c=172.2ppm ( C=O) absorption peak shows the existence of ester carbonyl group; δ c=141.4 ( CH=CH 2) and δ c=98.3 (CH= CH 2) absorption peak, show the existence of vinyl ester; δ c=135.6～126.9 (C 6H 5-) show the existence of phenyl; δ c=39.8 (S-CH 2- CH-) and δ c=37.4 (S- CH 2-CH-) absorption peak shows α, the sp of the unsaturated conjugated system of β 2Thereby Michael addition has taken place for carbon atom and thiophenol changes sp into 3Carbon atom; δ c=16.7 (CH 3) absorption peak be methyl; Above analytical results has further shown the generation of Michael reaction.
Embodiment 2:
At the ground Erlenmeyer flask of a 200ml, add 50ml ionic liquid hydroxide [1-butyl-3-Methylimidazole] earlier, add the 0.1mol thiophenol again in Erlenmeyer flask, add the 0.12mol Vinyl crotonate behind the thorough mixing, at 1kg/cm 2In pressure, the 20 ℃ of constant-temperature shaking culture casees, with the velocity fluctuation of 200rev./min; TLC monitors reaction process, shows after 10 minutes to react completely, and finishes the back adds 60ml in reaction solution ethyl acetate extraction 5 times; Extraction liquid merges back water pump underpressure distillation and reclaims ETHYLE ACETATE; Products therefrom yield 95%, nucleus magnetic hydrogen spectrum characterize sees Fig. 7, and nuclear-magnetism carbon stave is levied and seen Fig. 8.
Embodiment 3:
At the ground Erlenmeyer flask of a 50ml, add 10ml ionic liquid hydroxide [1-butyl-3-Methylimidazole] earlier, add 0.1mol benzyl mercaptan again in Erlenmeyer flask, add 0.12mol methacrylic vinyl acetate behind the thorough mixing, at 1kg/cm 2In pressure, the 25 ℃ of constant-temperature shaking culture casees, with the velocity fluctuation of 200rev./min; TLC monitors reaction process, shows after 2 minutes to react completely, and finishes the back adds 60ml in reaction solution ethyl acetate extraction 5 times; Extraction liquid merges back water pump underpressure distillation and reclaims ETHYLE ACETATE; Products therefrom yield 91%, nucleus magnetic hydrogen spectrum characterize sees Fig. 9, and nuclear-magnetism carbon stave is levied and seen Figure 10.
Embodiment 4:
At the ground Erlenmeyer flask of a 50ml, add 10ml ionic liquid hydroxide [1-butyl-3-Methylimidazole] earlier, add 0.1mol benzyl mercaptan again in Erlenmeyer flask, add the 0.11mol Vinyl crotonate behind the thorough mixing, at 1kg/cm 2In pressure, the 25 ℃ of constant-temperature shaking culture casees, with the velocity fluctuation of 200rev./min; TLC monitors reaction process, shows after 2 minutes to react completely, and finishes the back adds 60ml in reaction solution ethyl acetate extraction 5 times; Extraction liquid merges back water pump underpressure distillation and reclaims ETHYLE ACETATE; Products therefrom yield 92%, nucleus magnetic hydrogen spectrum characterize sees Figure 11, and nuclear-magnetism carbon stave is levied and seen Figure 12.
Embodiment 5:
At the ground Erlenmeyer flask of a 100ml, add 20ml ionic liquid hydroxide [1-methyl-3-NSC 158165] earlier, adding the 0.1mol butanethiol in Erlenmeyer flask, add 0.11mol methacrylic vinyl acetate behind the thorough mixing, at 3kg/cm 2In pressure, the 30 ℃ of constant-temperature shaking culture casees, with the velocity fluctuation of 200rev./min; TLC monitors reaction process, shows after 5 minutes to react completely, and finishes the back adds 60ml in reaction solution ethyl acetate extraction 5 times; Extraction liquid merges back water pump underpressure distillation and reclaims ETHYLE ACETATE; Products therefrom yield 90%, nucleus magnetic hydrogen spectrum characterize sees Figure 13, and nuclear-magnetism carbon stave is levied and seen Figure 14.
Embodiment 6:
At the ground Erlenmeyer flask of a 100ml, add 20ml ionic liquid hydroxide [1-methyl-3-NSC 158165] earlier, add the 0.1mol butanethiol again in Erlenmeyer flask, add the 0.13mol Vinyl crotonate behind the thorough mixing, at 3kg/cm 2In pressure, the 30 ℃ of constant-temperature shaking culture casees, with the velocity fluctuation of 200rev./min; TLC monitors reaction process, shows after 5 minutes to react completely, and finishes the back adds 60ml in reaction solution ethyl acetate extraction 5 times; Extraction liquid merges back water pump underpressure distillation and reclaims ETHYLE ACETATE; Products therefrom yield 87%, nucleus magnetic hydrogen spectrum characterize sees Figure 15, and nuclear-magnetism carbon stave is levied and seen Figure 16.
Embodiment 7:
At the ground Erlenmeyer flask of a 500ml, add 100ml ionic liquid hydroxide [1-ethyl-3-ethyl imidazol(e)] earlier, add the 0.1mol Dodecyl Mercaptan again in Erlenmeyer flask, add 0.15mol methacrylic vinyl acetate behind the thorough mixing, at 1kg/cm 2In pressure, the 50 ℃ of constant-temperature shaking culture casees, with the velocity fluctuation of 200rev./min; TLC monitors reaction process, shows after 20 minutes to react completely, and finishes the back adds 60ml in reaction solution ethyl acetate extraction 5 times, and extraction liquid merges back water pump underpressure distillation and reclaims ETHYLE ACETATE.Products therefrom yield 82%, nucleus magnetic hydrogen spectrum characterize sees Figure 17, and nuclear-magnetism carbon stave is levied and seen Figure 18.
Embodiment 8:
At the ground Erlenmeyer flask of a 500ml, add 100ml ionic liquid hydroxide [1-ethyl-3-ethyl imidazol(e)] earlier, add the 0.1mol Dodecyl Mercaptan again in Erlenmeyer flask, add the 0.15mol Vinyl crotonate behind the thorough mixing, at 1kg/cm 2In pressure, the 50 ℃ of constant-temperature shaking culture casees, with the velocity fluctuation of 200rev./min; TLC monitors reaction process, shows after 20 minutes to react completely, and finishes the back adds 60ml in reaction solution ethyl acetate extraction 5 times; Extraction liquid merges back water pump underpressure distillation and reclaims ETHYLE ACETATE; Products therefrom yield 82%, nucleus magnetic hydrogen spectrum characterize sees Figure 19, and nuclear-magnetism carbon stave is levied and seen Figure 20.
Embodiment 9:
At the ground Erlenmeyer flask of a 150ml, add 40ml ionic liquid hydroxide [1-butyl-pyridinium] earlier, add 0.1mol beta-hydroxy sulfur alcohol again in Erlenmeyer flask, add 0.14mol methacrylic vinyl acetate behind the thorough mixing, at 2kg/cm 2In pressure, the 20 ℃ of constant-temperature shaking culture casees, with the velocity fluctuation of 200rev./min; TLC monitors reaction process, shows after 15 minutes to react completely, and finishes the back adds 60ml in reaction solution ethyl acetate extraction 5 times; Extraction liquid merges back water pump underpressure distillation and reclaims ETHYLE ACETATE; Products therefrom yield 97%, nucleus magnetic hydrogen spectrum characterize sees Figure 21, and nuclear-magnetism carbon stave is levied and seen Figure 22.
Embodiment 10:
At the ground Erlenmeyer flask of a 150ml, add 40ml ionic liquid hydroxide [1-butyl-pyridinium] earlier, add 0.1mol beta-hydroxy sulfur alcohol again in Erlenmeyer flask, add the 0.14mol Vinyl crotonate behind the thorough mixing, at 2kg/cm 2In pressure, the 20 ℃ of constant-temperature shaking culture casees, with the velocity fluctuation of 200rev./min; TLC monitors reaction process, shows after 15 minutes to react completely, and finishes the back adds 60ml in reaction solution ethyl acetate extraction 5 times; Extraction liquid merges back water pump underpressure distillation and reclaims ETHYLE ACETATE; Products therefrom yield 96%, nucleus magnetic hydrogen spectrum characterize sees Figure 23, and nuclear-magnetism carbon stave is levied and seen Figure 24.
Embodiment 11:
At the ground Erlenmeyer flask of a 250ml, add 80ml ionic liquid hydroxide [1-ethyl-3-picoline] earlier, add the 0.1mol near amino thiophenols again in Erlenmeyer flask, add 0.12mol methacrylic vinyl acetate behind the thorough mixing, at 1kg/cm 2In pressure, the 35 ℃ of constant-temperature shaking culture casees, with the velocity fluctuation of 200rev./min; TLC monitors reaction process, shows after 15 minutes to react completely, and finishes the back adds 60ml in reaction solution ethyl acetate extraction 5 times, and extraction liquid merges back water pump underpressure distillation and reclaims ETHYLE ACETATE, products therefrom yield 90%.
Embodiment 12:
At the ground Erlenmeyer flask of a 250ml, add 80ml ionic liquid hydroxide [cyclohexyl trimethyl ammonium] earlier, add 0.1mol benzoglyoxaline 2-mercaptan again in Erlenmeyer flask, add 0.12mol methacrylic vinyl acetate behind the thorough mixing, at 1kg/cm 2In 40 ℃ of constant-temperature shaking culture casees of pressure, with the velocity fluctuation of 200rev./min; TLC monitors reaction process, shows after 15 minutes to react completely, and finishes the back adds 60ml in reaction solution ethyl acetate extraction 5 times, and extraction liquid merges back water pump underpressure distillation and reclaims ETHYLE ACETATE, products therefrom yield 86%.

Claims (8)

1. one kind β-beta-alkyl sulfide substituted vinyl propionate sulfur compound is characterized in that: this compound is that chemical structural formula is the sulfur-bearing vinyl propionate ester derivative of following general formula,
Figure 584988DEST_PATH_IMAGE001
R 1Represent 4-12 carbon atom alkyl; R 2Represent the alkyl of Wasserstoffatoms or 1-3 carbon atom; R 3Represent the alkyl of Wasserstoffatoms or 1-3 carbon atom; R 4Represent the alkyl of Wasserstoffatoms or 1-3 carbon atom.
One kind according to claim 1 βThe preparation method of-beta-alkyl sulfide substituted vinyl propionate sulfur compound; It is characterized in that this preparation method may further comprise the steps: at first; In reactor drum, add a certain amount of alkali ionic liquid earlier, add SR again; Behind the certain hour thorough mixing, SR and alkali ionic liquid effect are converted into alkyl sulphur negative ion; Then, add a certain amount of addition acceptor vinyl acrylate compounds, in the constant-temperature shaking case, with the velocity fluctuation of 200 rev/min, TLC monitors reaction process; At last, when reaction finishes, in mixed liquid, add the extraction agent extraction of certain volume, extraction liquid merges the back underpressure distillation and reclaims extraction agent, and crude product separates with chromatography column; Perhaps reacted mixed liquid underpressure distillation is obtained product, residual alkali ionic liquid continues to use through washing.
3. according to claim 2 a kind of βThe preparation method of-beta-alkyl sulfide substituted vinyl propionate sulfur compound is characterized in that: the negatively charged ion of described alkali ionic liquid is hydroxide radical OH -
4. according to claim 2 a kind of βThe preparation method of-beta-alkyl sulfide substituted vinyl propionate sulfur compound is characterized in that: the positively charged ion of described alkali ionic liquid is the substituted imidazol ion of alkyl or substituted pyridinium ion of alkyl or quaternary ammonium alkyl ion; The substituted imidazol ion of alkyl is [C 2Mim] +Or [C 4Mim] +Or [C 6Mim] +
5. according to claim 2 a kind of βThe preparation method of-beta-alkyl sulfide substituted vinyl propionate sulfur compound is characterized in that: described SR is the compound that following general formula is represented:
Figure DEST_PATH_IMAGE002
, in this formula, R 1Represent 4-12 carbon atom alkyl.
6. according to claim 2 a kind of βThe preparation method of-beta-alkyl sulfide substituted vinyl propionate sulfur compound is characterized in that described vinyl acrylate compound is the compound that following general formula is represented:
Figure DEST_PATH_IMAGE003
R 2, R 3, R 4Represent the alkyl of Wasserstoffatoms or 1-3 carbon atom.
7. according to claim 2 βThe preparation method of-beta-alkyl sulfide substituted vinyl propionate sulfur compound is characterized in that: wherein, and in mercaptan and vinyl acrylate addition preparation β-In the substituted vinyl acrylate compound of sulphur, every mole of mercaptan uses the 1-1.5mol vinyl acrylate; Wherein, temperature of reaction is between 20-50 ℃; Reaction times is between 2-20 minute; Reaction pressure is 1-3 kg/cm 2The alkali ionic liquid usage quantity is 1-10 a times of SR molar weight.
8. according to claim 2 βThe preparation method of-beta-alkyl sulfide substituted vinyl propionate sulfur compound is characterized in that: wherein, the preparation method of alkali ionic liquid hydroxide 1-butyl-3-Methylimidazole [bmim] OH is following: measure 60mL respectively N-Methylimidazole and 95mL 1-chlorobutane are poured the 250mL three-necked bottle into, put into magneton, logical nitrogen, 75 ℃ of condition refluxed 72h; Reaction stops, and is cooled to room temperature, pours the reaction solution in the three-necked bottle into separating funnel, washes twice with ETHYLE ACETATE earlier, and each 100mL washes once with ether 70ml again, gets product 132g, and productive rate is 69 %; Take by weighing ion exchange resin 50g, with the salt soak 12h of 1mol/mL, the NaOH aqueous solution soaking 12h of 1mol/mL, repeatedly after 2 times, upper prop, water is washed till neutrality; Add 23g chlorination 1-butyl-3-Methylimidazole, use water elution, receive alkaline liq; 50 ℃ of underpressure distillation of obtained aqueous solution obtain little yellow transparent liquid 50 ℃ of dryings.
CN2010101425119A 2010-03-31 2010-03-31 Beta-alkyl sulfide substituted vinyl propionate sulfur compound and preparation method thereof Expired - Fee Related CN101845006B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2010101425119A CN101845006B (en) 2010-03-31 2010-03-31 Beta-alkyl sulfide substituted vinyl propionate sulfur compound and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2010101425119A CN101845006B (en) 2010-03-31 2010-03-31 Beta-alkyl sulfide substituted vinyl propionate sulfur compound and preparation method thereof

Publications (2)

Publication Number Publication Date
CN101845006A CN101845006A (en) 2010-09-29
CN101845006B true CN101845006B (en) 2012-11-21

Family

ID=42769841

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2010101425119A Expired - Fee Related CN101845006B (en) 2010-03-31 2010-03-31 Beta-alkyl sulfide substituted vinyl propionate sulfur compound and preparation method thereof

Country Status (1)

Country Link
CN (1) CN101845006B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102807463A (en) * 2011-06-01 2012-12-05 同济大学 Method for synthesizing chiral sulfocompound by transition metal catalysis
CN105646303A (en) * 2016-03-03 2016-06-08 淮阴师范学院 Preparation method of 2-methyl-3-(2-amino) ethylidenethio-vinylpropionate
CN105968364B (en) * 2016-05-27 2018-08-10 山东师范大学 Imidazoles salt form poly ion liquid cross linking membrane based on Click reactions and its preparation, application
CN111909069B (en) * 2020-08-25 2022-04-19 安徽启威生物科技有限公司 Degradable quaternary ammonium salt compound and preparation method and application thereof
CN113773812B (en) * 2021-09-13 2023-07-04 浙江巨化技术中心有限公司 Composition containing heterocyclic accelerator, application of composition to liquid coolant and immersed liquid cooling system

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3078290A (en) * 1961-04-17 1963-02-19 Carlisle Chemical Works Dihydrocarbontin salts of carboxy mercaptals

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3078290A (en) * 1961-04-17 1963-02-19 Carlisle Chemical Works Dihydrocarbontin salts of carboxy mercaptals

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Candida antarctica Lipase B (CAL-B)-Catalyzed Carbon-Sulfur Bond Addition and Controllable Selectivity in Organic Media;Feng-Wen Lou, et al.;《Adv. Synth. Catal.》;20080813;第350卷;1959-1962 *
Feng-Wen Lou, et al..Candida antarctica Lipase B (CAL-B)-Catalyzed Carbon-Sulfur Bond Addition and Controllable Selectivity in Organic Media.《Adv. Synth. Catal.》.2008,第350卷1959-1962.
Feng-Wen Lou, et al..Highly selective anti-Markovnikov addition of thiols to vinyl ethers under solvent- and catalyst-free conditions.《Tetrahedron Letters》.2007,第48卷8815-8818.
Highly selective anti-Markovnikov addition of thiols to vinyl ethers under solvent- and catalyst-free conditions;Feng-Wen Lou, et al.;《Tetrahedron Letters》;20071022;第48卷;8815-8818 *

Also Published As

Publication number Publication date
CN101845006A (en) 2010-09-29

Similar Documents

Publication Publication Date Title
CN101845006B (en) Beta-alkyl sulfide substituted vinyl propionate sulfur compound and preparation method thereof
WO2019223290A1 (en) Method for preparing thiourethane and producing 2-mercaptoethanol or o-alkyl ethyl xanthate in parallel
CN101306383B (en) Chiral organic micromolecule catalyst loaded by heteropoly acid and preparation method and use thereof
CN103242197B (en) Preparation method of ultraviolet absorbent intermediate etocrilene (ETO)
Wong et al. Recent development in functionalized ionic liquids as reaction media and promoters
CN101863858A (en) Synthetic method of bentazone
CN105777488A (en) Method for catalytically preparing fatty alcohol
CN101456844A (en) Room temperature ion liquid containing sulfonic acid ester base side chain as well as preparation method and use thereof
US20070017151A1 (en) Nucleophilic Acyl Substitutions of Acids or Esters Catalyzed by Oxometallic Complexes, and the Applications in Fabricating Biodiesel
CN109824466B (en) Method for preparing 2-methyl-1, 3-pentadiene
Bandgar et al. Regioselective ring opening of epoxides with thiols under solvent free and mild conditions using heterogeneous catalyst
CN104276987B (en) A kind of preparation method of mercaptan compound
JP7197172B2 (en) Method for producing cinnamic acid ester compound
CN110527076A (en) A kind of preparation method of epoxy resin high-quality polysulfide alcohols curing agent
CN113024364B (en) Efficient green synthesis method of hydroxycitronellal
CN111217694B (en) Method for selectively reducing carbon-carbon double bond in alpha, beta-unsaturated carbonyl compound
CN113582914A (en) Process for preparing hydroxy group-containing hindered amine light stabilizers
CN110878025B (en) Method for reducing aromatic nitro compound into aromatic amine compound
CN103435433A (en) Method for synthesizing isolongifolene by catalytically isomerizing longifolene with solid acid
CN111848476B (en) Preparation method of thiotoluene diiso (thio) cyanate
CN105152946B (en) A kind of method for efficiently, quickly synthesizing o-Aminobenzaldehyde
CN111004176A (en) Synthesis method of 2-aryloxy ethanol compound
CN111072745A (en) Preparation method of 6-methylene-7-ketocholic acid
NL2030589B1 (en) Preparation method of bicalutamide
CN114014757B (en) Synthesis method of tert-butyl crotonate

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20121121

Termination date: 20150331

EXPY Termination of patent right or utility model