CN102249962A - Preparation method of 1,1-disulfur-1-olefin - Google Patents
Preparation method of 1,1-disulfur-1-olefin Download PDFInfo
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- CN102249962A CN102249962A CN2011101515637A CN201110151563A CN102249962A CN 102249962 A CN102249962 A CN 102249962A CN 2011101515637 A CN2011101515637 A CN 2011101515637A CN 201110151563 A CN201110151563 A CN 201110151563A CN 102249962 A CN102249962 A CN 102249962A
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Abstract
The invention belongs to the technical fields of organic synthesis medicament, pesticide and functional materials, in particular relates to a preparation method of 1,1-disulfur-1-olefin. According to the invention, the 1,1-disulfur-1-olefin compound is efficiently synthesized in the presence of organic base 1,8-diazabicyclo undecene in a dimethylsulfoxide solvent at the room temperature by taking easily prepared 1,1-dibromine-1-olefin as a raw material without any metal catalyst. The 1,1-disulfur-1-olefin synthesized by the method in the invention can be used as a synthesis intermediate of medicament, pesticide and optical linear materials. Compared with the existing noble metal palladium and nickel catalytic synthesis method, the method has the characteristics of available raw material, cheap cost, mild reaction condition and the like, is simple to operate, is easy to industrialize, and has wide application prospect.
Description
Technical field
The invention belongs to organic synthesis medicine, agricultural chemicals and field of functional materials, be specifically related to a kind of 1, the preparation method of 1-two sulphur-1-alkene.
Background technology
1,1-two sulphur-1-alkene is widely used in fields (Kondo, T. JP2008155201,2008) such as medicine, agricultural chemicals and functional materials as molecular building block important in the organic synthesis.For example; 1; 1-two sulphur-1-alkene is the medicine intermediate (Ikeda, M. JP7061966,1995) of synthetic beta-lactam; its derivative acyl group list sulphur compound is the intermediate (Mukoyama of synthetic various carbohydrates; M. JP5086020,1993), disulfide also is the main raw material (Tanaka of synthetic poly-sulphur class optics linear material in addition; M. WO03089488,2003).
In the past few decades, chemists proposed some 1,1-two sulphur-1-alkene synthetic method.Yet, rare with conveniently be easy to get 1,1-two bromo-1-alkene is the document of raw material.More representational method is 1, and 1-two bromo-1-alkene reacts with alkyl sodium sulphite under 120 ℃ of high temperature under metallic nickel catalysis for a long time, obtains 1,1-two sulphur-1-alkene (Cristau, H. J.
J. Org. Chem. 1986,
51, 875).
In addition, under the acting in conjunction of the transition-metal catalyst palladium and the Xantphos part of costliness, 1,1-two bromo-, 1-alkene and alkyl indium sulfide generation linked reaction obtain 1 under the high temperature, 1-two sulphur-1-alkene (Lee, P. WO 2009069888,2009).
Same under the katalysis of precious metal palladium, 1, linked reaction also can take place in 1-two bromo-, 1-alkene and alkyl lithium sulfide, obtains 1,1-two sulphur-1-alkene, but 10% ~ 20% transformation efficiency (Murahashi, S. are only arranged
J. Org. Chem. 1979,
44, 2408).
To sum up all there is same problem in these methods: use expensive transition metal relative with temperature of reaction higher as catalyzer, these two problems seriously limit the consistency of substrate.Therefore, find a kind of gentleness and effective 1,1-two sulphur-1-alkene is synthetic to be necessary.
Therefore, the present invention is with 1, and 1-two bromo-1-alkene is raw material, does not need to add any metal catalyst, under the effect of organic bases, prepares 1 under the room temperature, 1-two sulphur-1-olefin(e) compound.This method have raw material be easy to get, with low cost, reaction conditions is gentle, simple operation and other advantages, is easy to industrialization, have broad application prospects.
Summary of the invention
The object of the present invention is to provide a kind of 1, the preparation method of 1-two sulphur-1-alkene.
1 of the present invention's proposition, the preparation method of 1-two sulphur-1-alkene, its reaction equation is as follows:
Wherein, R
1For hydrogen, to methyl, p-isopropyl, to methoxyl group, to chlorine, m-chloro, adjacent chlorine, to bromine, in nitro or the naphthalene any.R
2For in phenyl, p-methylphenyl or the benzyl any.
Concrete steps are as follows:
In round-bottomed flask, add methyl-sulphoxide, 1,1-two bromo-1-alkene, thiophenol or mercaptan, 1,8-diazacyclo hendecene (DBU) stirred 5-15 minute under 25 ℃ of room temperatures.Add distilled water after reaction is finished, again with ethyl acetate extraction, organic layer is behind saturated common salt water washing, anhydrous sodium sulfate drying, and underpressure distillation is removed solvent and obtained thick product, and thick product obtains final product 1,1-two sulphur-1-alkene through column chromatography for separation.Wherein, DBU and 1, the mol ratio of 1-two bromo-1-alkene is 1.5:1-4:1.Thiophenol or mercaptan and 1, the mol ratio of 1-two bromo-1-alkene is 2:1-4:1.
Among the present invention, it is eluent that described column chromatography adopts ethyl acetate and sherwood oil.
Among the present invention, described alkali is 1,8-diazacyclo hendecene (DBU).
Among the present invention, described temperature of reaction is 25 ℃ of room temperatures.
Utilize that the inventive method obtains 1,1-two sulphur-1-alkene, its general formula is:
Wherein, R
1For hydrogen, to methyl, p-isopropyl, to methoxyl group, to chlorine, m-chloro, adjacent chlorine, to bromine, in nitro or the naphthalene any.R
2For in phenyl, p-methylphenyl or the benzyl any.
Further, utilize that the inventive method obtains 1,1-two sulphur-1-olefin(e) compound, its structural formula are following any:
Synthetic 1 of the present invention, 1-two sulphur-1-alkene can be used as the synthetic intermediate of medicine, agricultural chemicals and optics linear material.Compare with the nickel process for catalytic synthesis with existing precious metal palladium, the inventive method have raw material be easy to get, with low cost, reaction conditions is gentle, characteristics such as simple to operate, is easy to industrialization, and broad prospect of application is arranged.
Embodiment
Further specify the inventive method below by embodiment, but can not limit content of the present invention.
Embodiment 1:2-(4-aminomethyl phenyl)-1,1-two (4-aminomethyl phenyl) ethyl vinyl sulfide synthetic
In the 25mL round-bottomed flask, add 3mL methyl-sulphoxide, 2-(4-aminomethyl phenyl)-1, and the 1-sym-dibromoethane (83 mg, 0.3mmol), (82mg, 0.66mmol), DBU (160 mg, 1.05 mmol) stirred 10 minutes under 25 ℃ of room temperatures to the methylbenzene thiophenol.After reaction finishes, in reaction, add 3mL distilled water, use ethyl acetate extraction, organic layer is behind saturated common salt water washing, anhydrous sodium sulfate drying, underpressure distillation is removed solvent and is obtained thick product, and thick product obtains final product 2-(4-aminomethyl phenyl)-1 through column chromatography for separation, 1-two (4-aminomethyl phenyl) ethyl vinyl sulfide 92 mg, yield 85%.
Characterization data is as follows:
1H NMR (400 MHz, CDCl
3)
d7.46 (d,
J=8.4 Hz, 2 H), 7.42 (d,
J=8.4 Hz, 2 H), 7.20-7.15 (m, 5 H), 7.07 (d,
J=8.0 Hz, 2 H), 7.02 (d,
J=8.0 Hz, 2 H), 2.38 (s, 3 H), 2.30 (s, 3H), 2.27 (s, 3H);
13C NMR (100 MHz, CDCl
3): 137.6,137.3,136.2,135.8,135.7,131.9,131.3,130.9 130.0,129.6,129.3,129.1,128.5,126.6,21.1,21.1,21.0.
Embodiment 2:2-(4-bromophenyl)-1,1-two (4-aminomethyl phenyl) ethyl vinyl sulfide synthetic
In the 25mL round-bottomed flask, add 3mL methyl-sulphoxide, 2-(4-bromophenyl)-1, and the 1-sym-dibromoethane (102mg, 0.3mmol), (82mg, 0.66mmol), DBU (160 mg, 1.05 mmol) stirred 10 minutes under 25 ℃ of room temperatures to the methylbenzene thiophenol.After reaction finishes, in reaction, add 3mL distilled water, use ethyl acetate extraction, organic layer is behind saturated common salt water washing, anhydrous sodium sulfate drying, underpressure distillation is removed solvent and is obtained thick product, and thick product obtains final product 2-(4-bromophenyl)-1 through column chromatography for separation, 1-two (4-aminomethyl phenyl) ethyl vinyl sulfide 111 mg, yield 87%.
Characterization data is as follows:
1H NMR (400 MHz, CDCl
3)
d7.40-7.32 (m, 6H), 7.18-7.11 (m, 5H), 6.99 (d,
J=8.0 Hz, 2H), 2.36 (s, 3H), 2.24 (s, 3H);
13C NMR (100 MHz, CDCl
3): 137.9,139.8,137.6,136.1,131.4,131.1,130.6,130.1,129.7,128.7,128.3,128.1,121.3,21.1,21.0.
Embodiment 3:2-(4-aminomethyl phenyl)-1,1-hexichol ethyl vinyl sulfide synthetic
In the 25mL round-bottomed flask, add 3mL methyl-sulphoxide, 2-(4-aminomethyl phenyl)-1, and the 1-sym-dibromoethane (83mg, 0.3mmol), (73mg, 0.66mmol), DBU (160 mg, 1.05 mmol) stirred 10 minutes under 25 ℃ of room temperatures thiophenol.After reaction finishes, in reaction, add 3mL distilled water, use ethyl acetate extraction, organic layer is behind saturated common salt water washing, anhydrous sodium sulfate drying, underpressure distillation is removed solvent and is obtained thick product, and thick product obtains final product 2-(4-aminomethyl phenyl)-1 through column chromatography for separation, 1-hexichol ethyl vinyl sulfide 79 mg, yield 79%.
Characterization data is as follows:
1H NMR (400 MHz, CDCl
3):
7.22-7.56 (m, 14H), 7.12 (s, 1H), 2.34 (s, 3H).
Embodiment 4:2-(4-chloro-phenyl-)-1,1-dibenzyl ethyl vinyl sulfide synthetic
In the 25mL round-bottomed flask, add 3mL methyl-sulphoxide, 2-(4-chloro-phenyl-)-1, and the 1-sym-dibromoethane (89mg, 0.3mmol), (82mg, 0.66mmol), DBU (160 mg, 1.05 mmol) stirred 5 minutes under 25 ℃ of room temperatures benzyl sulfhydrate.After reaction finishes, in reaction, add 3mL distilled water, use ethyl acetate extraction, organic layer is behind saturated common salt water washing, anhydrous sodium sulfate drying, underpressure distillation is removed solvent and is obtained thick product, and thick product obtains final product 2-(4-chloro-phenyl-)-1 through column chromatography for separation, 1-dibenzyl ethyl vinyl sulfide 102mg, yield 89%.
Characterization data is as follows:
1H NMR (400 MHz, CDCl
3)
d(7.37-7.24 m, 14 H), 6.86 (s, 1 H), 4.09 (s, 2H), 4.08 (s, 2H);
13C NMR (100 MHz, CDCl
3): 137.6,137.5,135.9,134.6,133.1,132.7,130.5,129.0,128.9,128.6,128.5,128.1,127.3,127.2,38.4,38.3.
Claims (3)
1. one kind 1, the preparation method of 1-two sulphur-1-alkene is characterized in that concrete steps are as follows:
In round-bottomed flask, add methyl-sulphoxide, 1,1-two bromo-1-alkene, thiophenol or mercaptan, 1,8-diazacyclo hendecene at room temperature stirred 5-15 minute; Add distilled water after reaction is finished, again with ethyl acetate extraction, organic layer is behind saturated common salt water washing, anhydrous sodium sulfate drying, and underpressure distillation is removed solvent and obtained thick product, and thick product obtains final product 1,1-two sulphur-1-alkene through column chromatography for separation; Wherein, 1,8-diazacyclo hendecene and 1, the mol ratio of 1-two bromo-1-alkene is 1.5:1-4:1; Thiophenol or mercaptan and 1, the mol ratio of 1-two bromo-1-alkene is 2:1-4:1.
2. according to claim 11, the preparation method of 1-two sulphur-1-alkene is characterized in that gained 1, and the general formula of 1-two sulphur-1-olefin(e) compound is:
Wherein, R
1For hydrogen, to methyl, p-isopropyl, to methoxyl group, to chlorine, m-chloro, adjacent chlorine, to bromine, in nitro or the naphthalene any; R
2For in phenyl, p-methylphenyl or the benzyl any.
3. described 1 according to claim 2, the preparation method of 1-two sulphur-1-alkene is characterized in that gained 1, following any of 1-two sulphur-1-olefin(e) compound:
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104710332A (en) * | 2015-02-17 | 2015-06-17 | 温州大学 | Method for preparing alkenyl sulfide |
| CN106220538A (en) * | 2016-08-02 | 2016-12-14 | 龚小倩 | A kind of synthetic method of diaryl sulfide |
| CN114195690A (en) * | 2021-11-26 | 2022-03-18 | 华南理工大学 | Preparation method of vinyl aryl thioether compound |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008155201A (en) * | 2006-11-29 | 2008-07-10 | Kyoto Univ | New ruthenium-based catalyst and method for producing 1,1-dithio-1-alkene using the same |
| CN101808985A (en) * | 2007-11-28 | 2010-08-18 | 江原大学校产学协力团 | Methods for the synthesis of organic sulfides by using sulfides and organic sulfur-indium complexes |
-
2011
- 2011-06-08 CN CN 201110151563 patent/CN102249962B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008155201A (en) * | 2006-11-29 | 2008-07-10 | Kyoto Univ | New ruthenium-based catalyst and method for producing 1,1-dithio-1-alkene using the same |
| CN101808985A (en) * | 2007-11-28 | 2010-08-18 | 江原大学校产学协力团 | Methods for the synthesis of organic sulfides by using sulfides and organic sulfur-indium complexes |
Non-Patent Citations (2)
| Title |
|---|
| H.J.CRISTAU ET AL.: "Synthesis of Vinyl Selenides or Sulfides and Ketene Selenoacetals or Thioacetals by Nickel(Ⅱ) Vinylation of Sodium Benzeneselenolate or Benzenethiolate", 《J.ORG.CHEM.》, vol. 51, no. 6, 31 December 1986 (1986-12-31), pages 875 - 878 * |
| SHUN-ICHI MURAHASHI ET AL.: "Stereoselective Synthesis of Alkenes and Alkenyl Sulfides from Alkenyl Halides Using Palladium and Ruthenium Catalysts", 《J.ORG.CHEM.》, vol. 44, no. 14, 31 December 1979 (1979-12-31), pages 2408 - 2417, XP002257406, DOI: doi:10.1021/jo01328a016 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104710332A (en) * | 2015-02-17 | 2015-06-17 | 温州大学 | Method for preparing alkenyl sulfide |
| CN104710332B (en) * | 2015-02-17 | 2017-01-04 | 温州大学 | A kind of preparation method of thiazolinyl sulfide |
| CN106220538A (en) * | 2016-08-02 | 2016-12-14 | 龚小倩 | A kind of synthetic method of diaryl sulfide |
| CN114195690A (en) * | 2021-11-26 | 2022-03-18 | 华南理工大学 | Preparation method of vinyl aryl thioether compound |
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