CN104177328A - Synthesis method of 1,2-di(2-thienyl)ethane - Google Patents
Synthesis method of 1,2-di(2-thienyl)ethane Download PDFInfo
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- CN104177328A CN104177328A CN201410372070.XA CN201410372070A CN104177328A CN 104177328 A CN104177328 A CN 104177328A CN 201410372070 A CN201410372070 A CN 201410372070A CN 104177328 A CN104177328 A CN 104177328A
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- C07—ORGANIC CHEMISTRY
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- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
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Abstract
The invention relates to a synthesis method of 1,2-di(2-thienyl)ethane, and particularly relates to a synthesis method of 1,2-di(2-thienyl)ethane by firstly converting 2-penphene as a raw material into thienyl borane, then reacting with p-toluene sulfonate-2-(2-thienyl)ethyl to generate 1,2--di(2-thienyl)ethane. The 1,2-di(2-thienyl)ethane is synthesized by the following steps: by taking 2-penphene as a raw material, firstly converting into thienyl borane, then reacting with p-toluene sulfonate-2-(2-thienyl)ethyl to generate 1,2--di(2-thienyl)ethane. The invention provides a new method for synthesizing 1,2-di(2-thienyl)ethane, and the synthesis method has the characteristics of being mild in reaction conditions, short in reaction route, and high in reaction yield.
Description
Technical field
The present invention relates to a kind of 1, the synthetic method of 2-bis-(2-thienyl) ethane, especially take 2-chlorothiophene as raw material first becomes three thienyl borines, then react the synthetic method that generates 1,2-bis-(2-thienyl) ethane with tosic acid-2-(2-thienyl) ethyl ester.
Background technology
1,2-bis-(2-thienyl) ethane is fine-chemical intermediate, and many investigators are once to its synthetic being studied.Bibliographical information the earliest appears at J. Am. Chem. Soc, 1942,64 (3): P
477-480upper, author be take 2-chloromethyl thiophene as raw material, under magnesium exists, by adding oxyethane to carry out condensation reaction, makes 1,2-bis-(2-thienyl) ethane, and yield is 69%; Similarly method also appears at periodical Polymer, 2000,41:P
5681-5687upper, investigator adopts bimolecular 2-chloromethyl thiophene to carry out condensation reaction under magnesium exists and generates 1 of a part, 2-bis-(2-thienyl) ethane, and yield is 58%; Although above-mentioned two kinds of methods preparation is easier, the production yield of preparing raw material 2-chloromethyl thiophene used is lower (being about 40%) generally, causes its total recovery to be respectively 27.6% and 23.2%, all do not surpass 30%. in addition, also have periodical J. Org. Chem, 1976,41(12): P
2187-2193reported by N-(1-(2-thienyl)-2-thienyl) dimethylamine and iodomethane reaction and obtained corresponding quaternary ammonium salt, then through Lithium Aluminium Hydride reduction, obtain 1,2-bis-(2-thienyl) ethane, the yield of two-step reaction is low to moderate 10%, and starting raw material also needs multistep just can obtain, relatively loaded down with trivial details; And periodical Chemistry Letters, 1981:P
627-630reported that employing organoselenium compound prepares the method for 1,2-bis-(2-thienyl) ethane, yield has reached 32%; Up-to-date bibliographical information is from Macromolecules, 2011,44:P
4711-4720upper, it is raw material that author adopts 2-chloromethyl thiophene, by Wurtz, is reacted and is made 1,2-bis-(2-thienyl) ethane, and yield is only 20%.
summary of the invention
Inventing technical problem to be solved is: how to provide that a kind of reaction conditions is gentle, simple to operate, yield is high 1, the synthetic method of 2-bis-(2-thienyl) ethane.
The technical solution adopted in the present invention is: 1, a kind of 1, the synthetic method of 2-bis-(2-thienyl) ethane, follows these steps to carry out:
Step 1, by 2-(2-thienyl) ethanol, methylene dichloride, tosic acid and chlorination silica gel puts into reaction flask, reaction obtains tosic acid-2-(2-thienyl) ethyl ester;
Step 2, in lithium, toluene mixture, add boric acid three isobutyl esters, 2-chlorothiophene and toluene, after having reacted, isopropylcarbinol is removed in distillation, dilute hydrochloric acid adjusts pH to neutral, filters, vacuum-drying obtains three (2-thienyl) borine;
Step 3, dioxane, tetrakis triphenylphosphine palladium, Tripotassium phosphate, tosic acid-2-(2-thienyl) ethyl ester, three (2-thienyl) borine are mixed after, react complete to the conversion of tosic acid-2-(2-thienyl) ethyl ester, add hexanaphthene, the superoxol that adds again sodium hydroxide solution and 30%, reaction obtains 1,2-bis-(2-thienyl) ethane.
As a kind of optimal way: in step 1, back flow reaction 2h, cooling, filter, remove silica gel, reaction solution washs with distilled water, saturated sodium carbonate solution, salt solution successively, then dichloromethane solvent is removed in underpressure distillation, prepares tosic acid-2-(2-thienyl) ethyl ester.
As a kind of optimal way: in step 2, in lithium, toluene mixture, logical nitrogen temperature to 100 ℃, after dripping boric acid three isobutyl esters, slowly drip the solution that 2-chlorothiophene and toluene form, dropwise at this temperature, to continue to react to 2-chlorothiophene raw material and be substantially exhausted, reaction solution is slowly down to room temperature, adding distil water, isopropylcarbinol is removed in distillation, then with dilute hydrochloric acid, adjust pH to neutral, filter, distillation washing for filter cake, ethyl alcohol recrystallization, vacuum-drying obtains three (2-thienyl) borine;
As a kind of optimal way: in step 3; after dioxane, tetrakis triphenylphosphine palladium, Tripotassium phosphate, tosic acid-2-(2-thienyl) ethyl ester, three (2-thienyl) borine are mixed; under nitrogen protection, in 85 ℃, react complete to the conversion of tosic acid-2-(2-thienyl) ethyl ester; be down to room temperature; add hexanaphthene; the hydrogen peroxide that adds 3.0 mol/L sodium hydroxide solutions and 30% under stirring; reaction 1h; with hexanaphthene, extract; salt water washing, dry, underpressure distillation obtain 1,2-bis-(2-thienyl) ethane.
The invention has the beneficial effects as follows: first reactions steps is few, the 2-chlorothiophene of take has synthesized object product as raw material two steps; Secondly yield is high, take 2-chlorothiophene as raw material total recovery is greater than 65%, exceeds more than 30% final reaction mild condition, easy and simple to handle than the yield of existing bibliographical information.
Embodiment
Below the specific embodiment of the present invention is further described.
Implement provided by the present invention a kind of 1, the synthetic method of 2-bis-(2-thienyl) ethane.It is to take 2-chlorothiophene as starting raw material, through borine glycosylation reaction, obtains three (2-thienyl) borine, further reacts and makes 1,2-bis-(2-thienyl) ethane with tosic acid-2-(2-thienyl) ethyl ester.
It is below a specific embodiment of the present invention (carrying out in laboratory).
1, the preparation of tosic acid-2-(2-thienyl) ethyl ester
By 12.8 g (0.1mol) 2-(2-thienyl) ethanol, 1000 mL methylene dichloride, 21.0 g (0.12mol) tosic acid and 10.0g chlorination silica gel puts into reaction flask, back flow reaction 2h, cooling, filter, remove silica gel.Reaction solution washs with distilled water, saturated sodium carbonate solution, salt solution successively, and then dichloromethane solvent is removed in underpressure distillation, prepares 26.0g tosic acid-2-(2-thienyl) ethyl ester, and yield is 90%.
2, the preparation of three (2-thienyl) borine
6.0 g lithiums, 200 ml toluene are put into reaction flask, logical nitrogen temperature to 100 ℃, drip successively 34.8 g (0.15 mol) boric acid, three isobutyl esters and slowly drip the solution that 2-chlorothiophene and 150 mL toluene by 56.8 g (0.48 mol) form, dropwise and at this temperature, continue to react to 2-chlorothiophene raw material be substantially exhausted (testing by TLC method); Again reaction solution is slowly down to room temperature, adding distil water 250mL, isopropylcarbinol is removed in distillation, then with dilute hydrochloric acid, adjusts pH to neutral, filter, distillation washing for filter cake, ethyl alcohol recrystallization, vacuum-drying obtains 31.2g tri-(2-thienyl) borine, and yield is 80.1%.
3,1,2-bis-(2-thienyl) ethane synthetic
By 200mL dioxane, 1.45g (1.25mmol) tetrakis triphenylphosphine palladium, 10.6g (75mmol) Tripotassium phosphate, 14.1g (50 mmol) tosic acid-2-(2-thienyl) ethyl ester, 14.3g (55 mmol) three (2-thienyl) borine adds in reaction flask, under nitrogen protection, in 85 ℃, react to tosic acid-2-(2-thienyl) ethyl ester conversion complete (testing by TLC method), be down to room temperature, add 400mL hexanaphthene, under stirring, add 25 mL 3.0 mol/L sodium hydroxide solutions, the hydrogen peroxide of 25mL 30%, reaction 1h, with hexanaphthene, extract, salt water washing, dry, underpressure distillation obtains 8.0g 1, 2-bis-(2-thienyl) ethane, yield 82.3%.
Claims (3)
1. one kind 1, the synthetic method of 2-bis-(2-thienyl) ethane, is characterized in that following these steps to carry out:
Step 1, by 2-(2-thienyl) ethanol, methylene dichloride, tosic acid and chlorination silica gel puts into reaction flask, reaction obtains tosic acid-2-(2-thienyl) ethyl ester;
Step 2, in lithium, toluene mixture, add boric acid three isobutyl esters, 2-chlorothiophene and toluene, after having reacted, isopropylcarbinol is removed in distillation, dilute hydrochloric acid adjusts pH to neutral, filters, vacuum-drying obtains three (2-thienyl) borine;
Step 3, dioxane, tetrakis triphenylphosphine palladium, Tripotassium phosphate, tosic acid-2-(2-thienyl) ethyl ester, three (2-thienyl) borine are mixed after, react complete to the conversion of tosic acid-2-(2-thienyl) ethyl ester, add hexanaphthene, the superoxol that adds again sodium hydroxide solution and 30%, reaction obtains 1,2-bis-(2-thienyl) ethane.
2. according to claim 1 a kind of 1, the synthetic method of 2-bis-(2-thienyl) ethane, it is characterized in that: in step 1, back flow reaction 2h, cooling, filter, remove silica gel, reaction solution washs with distilled water, saturated sodium carbonate solution, salt solution successively, and then dichloromethane solvent is removed in underpressure distillation, prepares tosic acid-2-(2-thienyl) ethyl ester.
3. according to claim 1 a kind of 1, the synthetic method of 2-bis-(2-thienyl) ethane, it is characterized in that: in step 2, at lithium, in toluene mixture, logical nitrogen temperature to 100 ℃, after dripping boric acid three isobutyl esters, slowly drip the solution that 2-chlorothiophene and toluene form, dropwise at this temperature, to continue to react to 2-chlorothiophene raw material and be substantially exhausted, reaction solution is slowly down to room temperature, adding distil water, isopropylcarbinol is removed in distillation, then with dilute hydrochloric acid, adjust pH to neutral, filter, distillation washing for filter cake, ethyl alcohol recrystallization, vacuum-drying obtains three (2-thienyl) borine,
According to claim 1 a kind of 1, the synthetic method of 2-bis-(2-thienyl) ethane, it is characterized in that: in step 3, by dioxane, tetrakis triphenylphosphine palladium, Tripotassium phosphate, tosic acid-2-(2-thienyl) ethyl ester, after three (2-thienyl) borine mixes, under nitrogen protection, in 85 ℃, react complete to the conversion of tosic acid-2-(2-thienyl) ethyl ester, be down to room temperature, add hexanaphthene, the hydrogen peroxide that adds 3.0 mol/L sodium hydroxide solutions and 30% under stirring, reaction 1h, with hexanaphthene, extract, salt water washing, dry, underpressure distillation obtains 1, 2-bis-(2-thienyl) ethane.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106866617A (en) * | 2017-01-22 | 2017-06-20 | 山西恒强化工有限公司 | A kind of synthetic method of the thiophene ethyl ester of p-methyl benzenesulfonic acid 2 |
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Non-Patent Citations (4)
| Title |
|---|
| GUPTA, B. D. 等: ""Reactions of organocobaloximes with aryldisulfonyl chlorides"", 《JOURNAL OF ORGANOMETALLIC CHEMISTRY》, vol. 689, no. 7, 1 April 2004 (2004-04-01), pages 1102 - 1109, XP004496410, DOI: doi:10.1016/j.jorganchem.2004.01.001 * |
| MANLEY, DAVID W. 等: ""Unconventional Titania Photocatalysis: Direct Deployment of Carboxylic Acids in Alkylations and Annulations"", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》, vol. 134, no. 33, 7 August 2012 (2012-08-07), pages 13580 - 13583 * |
| SATO, M.-A. 等: ""Soluble polymers with constant π-conjugation length: polymers containing thiophene tetramers and hexamers"", 《POLYMER》, vol. 41, no. 15, 31 July 2000 (2000-07-31), pages 5681 - 5687 * |
| SINGH, GARIMA 等: ""Reactions of hybrid organotellurium ligands......their decomposition"", 《INORGANICA CHIMICA ACTA》, vol. 358, no. 4, 1 March 2005 (2005-03-01), pages 912 - 918 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106866617A (en) * | 2017-01-22 | 2017-06-20 | 山西恒强化工有限公司 | A kind of synthetic method of the thiophene ethyl ester of p-methyl benzenesulfonic acid 2 |
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