CN108863873A - A kind of sulphur allyl carbonate esters compound and preparation method thereof - Google Patents
A kind of sulphur allyl carbonate esters compound and preparation method thereof Download PDFInfo
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- HGPNRTIBBZDVFQ-UHFFFAOYSA-N C=CCOC(Sc(cc1)ccc1[N+]([O-])=O)=O Chemical compound C=CCOC(Sc(cc1)ccc1[N+]([O-])=O)=O HGPNRTIBBZDVFQ-UHFFFAOYSA-N 0.000 description 1
- BLLPXBMVZYUZJB-UHFFFAOYSA-N CC1(C)[BrH]c2c1cccc2 Chemical compound CC1(C)[BrH]c2c1cccc2 BLLPXBMVZYUZJB-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C329/00—Thiocarbonic acids; Halides, esters or anhydrides thereof
- C07C329/02—Monothiocarbonic acids; Derivatives thereof
- C07C329/04—Esters of monothiocarbonic acids
- C07C329/10—Esters of monothiocarbonic acids having sulfur atoms of thiocarbonic groups bound to carbon atoms of six-membered aromatic rings
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C329/00—Thiocarbonic acids; Halides, esters or anhydrides thereof
- C07C329/02—Monothiocarbonic acids; Derivatives thereof
- C07C329/04—Esters of monothiocarbonic acids
- C07C329/06—Esters of monothiocarbonic acids having sulfur atoms of thiocarbonic groups bound to acyclic carbon atoms
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- C07D213/70—Sulfur atoms
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
- C07D277/70—Sulfur atoms
- C07D277/74—Sulfur atoms substituted by carbon atoms
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Abstract
The invention belongs to the technical fields of fine chemistry industry, it is related to a kind of sulphur allyl carbonate esters compound, and the preparation method of above-mentioned sulphur allyl carbonate esters compound, above-mentioned preparation method include that Compound RS H and allyl chlorocarbonate react under phase transfer catalysis (PTC).Sulphur allyl carbonate esters compound provided by the invention, can be used for synthesizing the high molecular material of its copolymer, is applied in optical instrument and national defense industry；The preparation method of sulphur allyl carbonate esters compound provided by the invention, can carry out, step is simple, it is only necessary to which single step reaction can be completed in a mild condition.
Description
Technical field
The invention belongs to the technical field of fine chemistry industry, it is related to a kind of sulphur allyl carbonate esters compound and its preparation side
Method.
Background technique
Diethylene glycol bis-allyl carbonate (ADC) is a kind of diallyl esters unsaturated monomer, and copolymer has height
Translucency and good physical mechanical property have resistance to infrared if light weight, hardness height, strong shock resistance, wear resistance are higher
The performance of line and ultraviolet light, especially its corrosion resistance are higher by 30 times of common organic glass.Excellent optics and physical property makes
ADC is widely used in optical instrument and national defense industry, it may replace optical glass and crystal glass makes various mirrors
Piece and optical lens manufacture the shock resistance screen window of aircraft, tank, warship, submarine.
Diethylene glycol (DEG) diallylcarbonate is commercially referred to as CR-39 and has at home and abroad obtained very since it is widely used
Great development, therefore, analog also largely synthesizes, and obtains the superior structure of performance with it, wherein sulfur-bearing allyl carbonate
Compound is also synthesized to obtain, and Japan Patent JP2009073751, JPH10175947, JPH1149744 report three classes respectively
Sulphur allyl carbonate esters compound, structural formula are as follows：
Above-mentioned sulphur allyl carbonate esters compound shows good high refractive index, low dispersion, impact resistance, heat resistance
And abrasion resistance properties, and show good optical property.Therefore, in order to further find the sulphur allyl carbonates of excellent properties
Ester type compound, the application study for opening up such compound have great importance.
Summary of the invention
The present invention provides a kind of new sulfur allyl carbonate esters compound, structural formula is as follows：
The present invention also provides the preparation methods of above-mentioned sulphur allyl carbonate esters compound, including RSH and chloro-carbonic acid alkene
Propyl ester reacts under phase transfer catalysis (PTC), and reaction equation is as follows：
The molar ratio of RSH, allyl chlorocarbonate and phase transfer catalyst are 1 in above-mentioned reaction:1-3:0.005-0.01.
Above-mentioned reaction carries out in the solution of sodium hydroxide, and the molar ratio of the RSH and sodium hydroxide is 1:1-3.
The reaction temperature of above-mentioned reaction is 0-20 DEG C.
Above-mentioned phase transfer catalyst is positive butylammonium bromide, benzyltriethylammoinium chloride, tetrabutylammonium chloride, tetrabutyl sulphur
One or more of sour hydrogen ammonium, cetyl trimethylammonium bromide.
The time of above-mentioned reaction is 2-12 hours, and the terminal of above-mentioned reaction is detected using thin-layer chromatography, is divided after reaction
For two-phase, wherein organic phase is washed with 2M sodium hydroxide solution, dry with anhydrous sodium sulfate, and solvent is evaporated under reduced pressure later and obtains oil
The crude product of shape object, the crude product pillar layer separation, the sulphur allyl carbonate esters compound purified.
The present invention having the beneficial effect that compared with the existing technology：
1, sulphur allyl carbonate esters compound provided by the invention, can be used for synthesizing the high molecular material of its copolymer,
It is applied in optical instrument and national defense industry.
2, synthetic method provided by the invention can carry out in a mild condition, and step is simple, it is only necessary to which single step reaction can be complete
At.
Specific embodiment
Below by the description of specific embodiment, the invention will be further described, but it is to limit of the invention that this, which is not,
System, those skilled in the art's basic thought according to the present invention, various modifications may be made or improves, but without departing from
Basic thought of the invention, is all within the scope of the present invention.
Various raw materials and reagents used in the embodiment of the present invention are commercially available purchase unless otherwise instructed.
Embodiment 1：The preparation of O- allyl-S-4- tolyl carbon sulfuric ester
Weigh 1 molar part to the 16 of the allyl chlorocarbonate of methylbenzene phenyl-sulfhydrate and 1.2 molar parts and 0.005 molar part
Alkyl trimethyl ammonium bromide mixing, in the presence of 4M sodium hydroxide solution, reaction temperature is 0 DEG C, and the reaction time is 5 hours, is adopted
It is detected with thin-layer chromatography, is divided into two-phase after reaction, wherein organic phase is washed with 2M sodium hydroxide solution, uses anhydrous sodium sulfate
It is dry.Yellow oil is obtained after solvent is evaporated under reduced pressure.Crude product pillar layer separation, the O- allyl-S-4- first purified
Phenyl carbons sulfuric ester, yield 88%.1HNMR(400MHz,CDCl3) δ 7.41 (d, J=7.8Hz, 2H), 7.20 (d, J=7.8Hz,
2H), 6.00-5.85 (m, 1H), 5.40-5.23 (m, 2H), 4.71 (d, J=5.8Hz, 2H), 2.37 (s, 3H)；13CNMR
(101MHz,CDCl3)δ169.90,139.97,134.89,131.37,130.01,124.10,119.28,68.20,21.33；
IR(film)ν:2939,1722,1448,1132,937,812cm-1；HRMS(ESI)calcd for C11H12O2S([M+Na]+):
231.0486；found:231.0487.
Embodiment 2：The preparation of O- allyl-S-4- anisyl carbon sulfuric ester
Weigh 1 molar part to the ten of the allyl chlorocarbonate of methoxybenzenethiol and 1.3 molar parts and 0.007 molar part
The mixing of six alkyl trimethyl ammonium bromides, in the presence of 4M sodium hydroxide solution, reaction temperature is 0 DEG C, and the reaction time is 9 hours,
It is detected using thin-layer chromatography, is divided into two-phase after reaction, wherein organic phase is washed with 2M sodium hydroxide solution, uses anhydrous slufuric acid
Sodium is dry.Yellow oil is obtained after solvent is evaporated under reduced pressure.Crude product pillar layer separation, the O- allyl-S-4- purified
Anisyl carbon sulfuric ester, yield 90%.1H NMR(400MHz,CDCl3)δ7.50–7.39(m,2H),6.96–6.85(m,
2H), 5.97-5.84 (m, 1H), 5.39-5.22 (m, 2H), 4.70 (dt, J=5.8,1.3Hz, 2H), 3.81 (s, 3H)；13C
NMR(101MHz,CDCl3)δ170.25,160.88,136.67,131.40,119.25,118.27,114.83,68.17,
55.37；IR(film)ν:2945,2839,1724,1593,1456,1249,831cm-1；HRMS(ESI)calcd for
C11H12O3S([M+Na]+):247.0405；found:247.0403.
Embodiment 3：The preparation of O- allyl-S-2,6- 3,5-dimethylphenyl carbon sulfuric ester
Weigh the 2,6- thiophenol dimethyl benzene of 1 molar part and the allyl chlorocarbonate of 1.5 molar parts and 0.01 molar part
The mixing of normal-butyl ammonium bromide, in the presence of 4M sodium hydroxide solution, reaction temperature is 5 DEG C, and the reaction time is 3 hours, and use is thin
Layer chromatography detection, is divided into two-phase after reaction, and wherein organic phase is washed with 2M sodium hydroxide solution, dry with anhydrous sodium sulfate
It is dry.Yellow oil is obtained after solvent is evaporated under reduced pressure.Crude product pillar layer separation, O- the allyl-S-2,6- bis- purified
Aminomethyl phenyl carbon sulfuric ester, yield 82%.1H NMR(400MHz,CDCl3)δ7.31–7.17(m,2H),7.16–7.14(m,
1H), 5.96-5.88 (m, 1H), 5.41-5.20 (m, 2H), 4.70 (d, J=5.6Hz, 2H), 2.45 (s, 6H)；13CNMR
(101MHz,CDCl3)δ158.41,143.33,131.46,130.08,128.34,126.81,119.02,68.01,21.91；
IR(film)ν:2954,1722,1460,1136,937,773cm-1；HRMS(ESI)calcd for C12H14O2S([M+H+Na
]+):246.0690；found:246.0692.
Embodiment 4：The preparation of O- allyl-S-4- bromophenyl carbon sulfuric ester
Weigh 1 molar part to the allyl chlorocarbonate of bromo thiophenol and 1.5 molar parts and the hexadecane of 0.01 molar part
The mixing of base trimethylammonium bromide, in the presence of 4M sodium hydroxide solution, reaction temperature is 20 DEG C, and the reaction time is 3 hours, is used
Thin-layer chromatography detection, is divided into two-phase after reaction, and wherein organic phase is washed with 2M sodium hydroxide solution, dry with anhydrous sodium sulfate
It is dry.Yellow oil is obtained after solvent is evaporated under reduced pressure.Crude product pillar layer separation, the O- allyl-S-4- bromobenzene purified
Base carbon sulfuric ester, yield 81%.1HNMR(400MHz,CDCl3) δ 7.52 (d, J=8.4Hz, 2H), 7.39 (d, J=8.4Hz,
2H),5.95–5.87(m,1H),5.37–5.28(m,2H),4.73–4.71(m,2H)；13C NMR(101MHz,CDCl3)δ
168.80,136.26,132.40,131.14,126.79,124.34,119.58,68.52；IR(film)ν:3086,2947,
1726,1471,1132,939,819cm-1；HRMS(ESI)calcd for C10H9BrO2S([M+Na]+):294.9404；
found:294.9402.
Embodiment 5：The preparation of O- allyl-S-2- bromophenyl carbon sulfuric ester
Weigh the hexadecane of the 2- bromo thiophenol of 1 molar part and the allyl chlorocarbonate of 1.5 molar parts and 0.01 molar part
The mixing of base trimethylammonium bromide, in the presence of 4M sodium hydroxide solution, reaction temperature is 20 DEG C, and the reaction time is 5 hours, is used
Thin-layer chromatography detection, is divided into two-phase after reaction, and wherein organic phase is washed with 2M sodium hydroxide solution, dry with anhydrous sodium sulfate
It is dry.Yellow oil is obtained after solvent is evaporated under reduced pressure.Crude product pillar layer separation, the O- allyl-S-2- bromobenzene purified
Base carbon sulfuric ester, yield 83%.1HNMR(400MHz,CDCl3)δ7.73–7.65(m,2H),7.35–7.24(m,2H),6.00–
5.86 (m, 1H), 5.41-5.24 (m, 2H), 4.74 (d, J=5.9Hz, 1H)；13C NMR(101MHz,CDCl3)δ167.86,
137.34,133.62,131.36,131.17,129.94,129.34,128.02,119.40,68.54；IR(film)ν:3086,
2949,1728,1450,1267,1141,1022,939,754cm-1；HRMS(ESI)calcd for C10H9BrO2S([M+Na
]+):294.9404；found:294.9406.
Embodiment 6：The preparation of O- allyl-S-4- chlorphenyl carbon sulfuric ester
Weigh 1 molar part to the allyl chlorocarbonate of chlorothio-phenol and 1.5 molar parts and the hexadecane of 0.005 molar part
The mixing of base trimethylammonium bromide, in the presence of 4M sodium hydroxide solution, reaction temperature is 10 DEG C, and the reaction time is 6 hours, is used
Thin-layer chromatography detection, is divided into two-phase after reaction, and wherein organic phase is washed with 2M sodium hydroxide solution, dry with anhydrous sodium sulfate
It is dry.Grease is obtained after solvent is evaporated under reduced pressure.Crude product pillar layer separation, the O- allyl-S-4- chlorphenyl carbon purified
Sulfuric ester, yield 83%.1H NMR(400MHz,CDCl3)δ7.50–7.42(m,2H),7.40–7.34(m,2H),5.98–5.88
(m, 1H), 5.41-5.25 (m, 2H), 4.72 (dt, J=5.9,1.3Hz, 2H)；13C NMR(101MHz,CDCl3)δ168.97,
136.10,136.06,131.14,129.44,126.15,119.56,68.50；IR(film)ν:3086,2947,1726,
1475,1136,939,825cm-1；HRMS(ESI)calcd for C10H9ClO2S([M+Na]+):250.9909；found:
250.9906.
Embodiment 7：The preparation of O- allyl-S-3- naphthalene carbon sulfuric ester
Weigh three second of benzyl of the 3- thionaphthol of 1 molar part and the allyl chlorocarbonate of 1.2 molar parts and 0.005 molar part
Ammonium chloride mixing, in the presence of 4M sodium hydroxide solution, reaction temperature is 5 DEG C, and the reaction time is 6 hours, using thin layer color
Spectrum detection, is divided into two-phase after reaction, and wherein organic phase is washed with 2M sodium hydroxide solution, dry with anhydrous sodium sulfate.Subtract
Grease is obtained after pressure evaporation solvent.Crude product pillar layer separation, the O- allyl-S-3- naphthalene carbon sulfuric ester purified,
Yield 87%.1H NMR(400MHz,CDCl3)δ8.05(s,1H),7.87–7.80(m,3H),7.58–7.50(m,3H),6.01–
5.84(m,1H),5.38–5.26(m,2H),4.75–4.69(m,2H)；13C NMR(101MHz,CDCl3)δ169.58,
134.70,133.45,133.41,131.32,131.21,128.88,128.02,127.79,127.30,126.67,124.90,
119.41,68.34；IR(film)ν:3053,2922,1624,1587,1425,1226,920,812,742cm-1；HRMS(ESI)
calcd for C14H12O2S([M+Na]+):267.0456；found:267.0455.
Embodiment 8：The preparation of O- allyl-S- benzyl carbon sulfuric ester
Weigh three second of benzyl of the benzyl mercaptan of 1 molar part and the allyl chlorocarbonate of 1.4 molar parts and 0.007 molar part
Ammonium chloride mixing, in the presence of 4M sodium hydroxide solution, reaction temperature is 0 DEG C, and the reaction time is 8 hours, using thin layer color
Spectrum detection, is divided into two-phase after reaction, and wherein organic phase is washed with 2M sodium hydroxide solution, dry with anhydrous sodium sulfate.Subtract
Grease is obtained after pressure evaporation solvent.Crude product pillar layer separation, the O- allyl-S- benzyl carbon sulfuric ester purified are received
Rate 75%.1H NMR(400MHz,CDCl3)δ7.38–7.21(m,5H),5.99–5.83(m,1H),5.42–5.21(m,2H),
4.71 (d, J=5.8,1.4Hz, 2H), 4.11 (s, 2H)；13C NMR(101MHz,CDCl3)δ170.56,137.13,131.45,
128.86,128.64,127.46,119.17,67.97,35.41；IR(film)ν:2927,1710,1452,1136,935,
704cm-1；HRMS(ESI)calcd for C11H12O2S([M+Na]+):231.0456；found:231.0453.
Embodiment 9：The preparation of O- allyl-S- normal-butyl carbon sulfuric ester
Weigh the benzyl three of the butyl mercaptan of 1 molar part and the allyl chlorocarbonate of 1.5 molar parts and 0.01 molar part
Ethyl ammonium chloride mixing, in the presence of 4M sodium hydroxide solution, reaction temperature is 0 DEG C, and the reaction time is 10 hours, using thin layer
Chromatography detection, is divided into two-phase after reaction, and wherein organic phase is washed with 2M sodium hydroxide solution, dry with anhydrous sodium sulfate.
Grease is obtained after solvent is evaporated under reduced pressure.Crude product pillar layer separation, the O- allyl-S- normal-butyl carbon sulfuric acid purified
Ester, yield 73%.1H NMR(400MHz,CDCl3)δ5.99–5.86(m,1H),5.39–5.22(m,2H),4.71–4.69(m,
2H), 2.87 (t, J=7.4Hz, 2H), 1.69-1.56 (m, 2H), 1.44-1.39 (m, 2H), 0.93 (t, J=7.3Hz, 3H)；13C NMR(101MHz,CDCl3)δ171.12,131.60,118.94,67.63,31.80,30.73,21.80,13.54；IR
(film)ν:2960,2873,1712,1458,1138,935cm-1；HRMS(ESI)calcd for C8H14O2S([M+Na]+):
197.0612；found:197.0615.
Embodiment 10：The preparation of O- allyl-S-4- nitrobenzophenone carbon sulfuric ester
Weigh the 16 of the p-Nitrobenzenethiol of 1 molar part and the allyl chlorocarbonate of 1.2 molar parts and 0.009 molar part
Alkyl trimethyl ammonium bromide mixing, in the presence of 4M sodium hydroxide solution, reaction temperature is 10 DEG C, and the reaction time is 5 hours, is adopted
It is detected with thin-layer chromatography, is divided into two-phase after reaction, wherein organic phase is washed with 2M sodium hydroxide solution, uses anhydrous sodium sulfate
It is dry.Grease is obtained after solvent is evaporated under reduced pressure.Crude product pillar layer separation, the O- allyl-S-4- nitrobenzene purified
Base carbon sulfuric ester, yield 82%.1H NMR(400MHz,CDCl3) δ 8.24 (d, J=8.9Hz, 2H), 7.73 (d, J=8.9Hz,
2H), 5.96-5.89 (m, 1H), 5.56-5.18 (m, 2H), 4.77 (d, J=5.9Hz, 2H)；13C NMR(101MHz,CDCl3)δ
167.38,148.16,136.35,134.61,130.82,123.94,120.00,68.97；IR(film)ν:3097,1720,
1512,1344,1161,943,846cm-1；HRMS(ESI)calcd for C10H9NO4S([M+Na]+):262.0150；
found:262.0153.
Embodiment 11：The preparation of O- allyl-S-3- pyridyl group carbon sulfuric ester
Weigh the 16 of the 3- pyridyl group thiophenol of 1 molar part and the allyl chlorocarbonate of 1.3 molar parts and 0.007 molar part
Alkyl trimethyl ammonium bromide mixing, in the presence of 4M sodium hydroxide solution, reaction temperature is 10 DEG C, and the reaction time is 5 hours, is adopted
It is detected with thin-layer chromatography, is divided into two-phase after reaction, wherein organic phase is washed with 2M sodium hydroxide solution, uses anhydrous sodium sulfate
It is dry.Grease is obtained after solvent is evaporated under reduced pressure.Crude product pillar layer separation, the O- allyl-S-3- pyridyl group purified
Carbon sulfuric ester, yield 81%.1H NMR(400MHz,CDCl3)δ8.64–8.56(m,1H),7.77–7.69(m,2H),7.29–
7.25 (m, 1H), 6.00-5.87 (m, 1H), 5.39-5.27 (m, 2H), 4.76 (d, J=5.9Hz, 2H)；13CNMR(101MHz,
CDCl3)δ168.25,151.71,150.16,137.26,131.10,129.38,123.46,119.55,68.42；IR(film)
ν:2949,1724,1570,1450,1145,941,767cm-1；HRMS(ESI)calcd for C9H9NO2S([M+H]+):
196.0432；found:196.0431.
Embodiment 12：The preparation of O- allyl-S-2- benzothiazolyl carbon sulfuric ester
Weigh the ten of the 2-mercaptobenzothiazole of 1 molar part and the allyl chlorocarbonate of 1.2 molar parts and 0.007 molar part
The mixing of six alkyl trimethyl ammonium bromides, in the presence of 4M sodium hydroxide solution, reaction temperature is 0 DEG C, and the reaction time is 3 hours,
It is detected using thin-layer chromatography, is divided into two-phase after reaction, wherein organic phase is washed with 2M sodium hydroxide solution, uses anhydrous slufuric acid
Sodium is dry.Grease is obtained after solvent is evaporated under reduced pressure.Crude product pillar layer separation, the O- allyl-S-2- benzo purified
Thiazolyl carbon sulfuric ester, yield 86%.1HNMR(400MHz,CDCl3)δ8.08–7.95(m,1H),7.94–7.82(m,1H),
7.52-7.40 (m, 2H), 6.02-5.92 (m, 1H), 5.48-5.31 (m, 2H), 4.84 (dt, J=6.0,1.3Hz, 2H)；13C
NMR(101MHz,CDCl3)δ166.00,157.78,152.08,136.51,130.52,126.41,125.62,123.08,
121.14,120.41,69.44；IR(film)ν:3062,1728,1419,1147,1001,1147,759cm-1；HRMS(ESI)
calcd for C11H9NO2S2([M+H]+):252.0153；found:252.0152.
Claims (7)
1. a kind of sulphur allyl carbonate esters compound, which is characterized in that the structure of the sulphur allyl carbonate esters compound
Formula is as follows：
2. a kind of preparation method of sulphur allyl carbonate esters compound described in claim 1, which is characterized in that the preparation
Method includes that RSH and allyl chlorocarbonate react under phase transfer catalysis (PTC), and reaction equation is as follows：
3. the preparation method of sulphur allyl carbonate esters compound according to claim 2, it is characterised in that：The RSH,
The molar ratio of allyl chlorocarbonate and phase transfer catalyst is 1:1-3:0.005-0.01.
4. the preparation method of sulphur allyl carbonate esters compound according to claim 2, which is characterized in that the reaction
It is carried out in the solution of sodium hydroxide, the molar ratio of the RSH and sodium hydroxide is 1:1-3.
5. a kind of preparation method of sulfur-bearing allyl carbonate ester compounds according to claim 2, which is characterized in that described
The reaction temperature of reaction is 0-20 DEG C.
6. the preparation method of sulphur allyl carbonate esters compound according to claim 2, which is characterized in that the phase turns
Shifting catalyst is positive butylammonium bromide, benzyltriethylammoinium chloride, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, cetyl
One or more of trimethylammonium bromide.
7. the preparation method of sulphur allyl carbonate esters compound according to claim 2, which is characterized in that the reaction
Time be 2-12 hours.
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|---|---|---|---|---|
| JP2009073751A (en) * | 2007-09-20 | 2009-04-09 | Showa Denko Kk | Manufacturing method of radically polymerizable compound having dithiocarbonate structure and sulfur-containing allyl carbonate group |
| WO2010008886A2 (en) * | 2008-06-24 | 2010-01-21 | Teva Pharmaceutical Industries Ltd. | Processes for preparing prodrugs of gabapentin and intermediates thereof |
| CN102216257A (en) * | 2008-10-08 | 2011-10-12 | 基菲雅制药公司 | GABA conjugates and methods of use thereof |
| WO2018079693A1 (en) * | 2016-10-27 | 2018-05-03 | 国立大学法人 千葉大学 | Pharmaceutical applications for (s)-norketamine and salts thereof |
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| JP2009073751A (en) * | 2007-09-20 | 2009-04-09 | Showa Denko Kk | Manufacturing method of radically polymerizable compound having dithiocarbonate structure and sulfur-containing allyl carbonate group |
| WO2010008886A2 (en) * | 2008-06-24 | 2010-01-21 | Teva Pharmaceutical Industries Ltd. | Processes for preparing prodrugs of gabapentin and intermediates thereof |
| CN102216257A (en) * | 2008-10-08 | 2011-10-12 | 基菲雅制药公司 | GABA conjugates and methods of use thereof |
| WO2018079693A1 (en) * | 2016-10-27 | 2018-05-03 | 国立大学法人 千葉大学 | Pharmaceutical applications for (s)-norketamine and salts thereof |
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