CN104177328B - A kind of synthetic method of 1,2-bis-(2-thienyl) ethane - Google Patents
A kind of synthetic method of 1,2-bis-(2-thienyl) ethane Download PDFInfo
- Publication number
- CN104177328B CN104177328B CN201410372070.XA CN201410372070A CN104177328B CN 104177328 B CN104177328 B CN 104177328B CN 201410372070 A CN201410372070 A CN 201410372070A CN 104177328 B CN104177328 B CN 104177328B
- Authority
- CN
- China
- Prior art keywords
- thienyl
- bis
- ethane
- reaction
- ethyl ester
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- 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
- C07D333/08—Hydrogen atoms or radicals containing only hydrogen and carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The present invention relates to a kind of 1, the synthetic method of 2-bis-(2-thienyl) ethane, especially one is with 2-chlorothiophene for raw material first becomes three thienyl borines, then reacts the synthetic method of generation 1,2-bis-(2-thienyl) ethane with tosic acid-2-(2-thienyl) ethyl ester.Three (2-thienyl) borine is obtained for raw material reaction with 2-chlorothiophene, lithium, boric acid three isobutyl ester, then it and tosic acid-2-(2-thienyl) ethyl ester are obtained by reacting 1,2-bis-(2-thienyl) ethane under the catalysis of tetrakis triphenylphosphine palladium.The invention provides a kind of novel method of synthesis 1,2-bis-(2-thienyl) ethane, be characterized in that reaction conditions is gentle, reaction scheme is short, and reaction yield is high.
Description
Technical field
The present invention relates to a kind of 1, the synthetic method of 2-bis-(2-thienyl) ethane, especially one is with 2-chlorothiophene for raw material first becomes three thienyl borines, then reacts the synthetic method of generation 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 were studied its synthesis once.Bibliographical information the earliest appears at J.Am.Chem.Soc, and 1942,64 (3): P
477-480on, author is with 2-chloromethyl thiophene for raw material, and under magnesium exists, carry out obtained 1,2-bis-(2-thienyl) ethane of condensation reaction by adding oxyethane, yield is 69%; Similar method also appears at periodical Polymer, 2000,41:P
5681-5687on, investigator adopts bimolecular 2-chloromethyl thiophene to carry out 1,2-bis-(2-thienyl) ethane that condensation reaction generates a part under magnesium exists, and yield is 58%; Although above-mentioned two kinds of methods preparation is easier, prepares the production yield general lower (being about 40%) of raw material 2-chloromethyl thiophene used, cause its total recovery to be respectively 27.6% and 23.2%, all more than 30%. in addition, also have periodical J.Org.Chem, 1976,41(12): P
2187-2193report and obtain corresponding quaternary ammonium salt by N-(1-(2-thienyl)-2-thienyl) dimethylamine to iodomethane reaction, then 1 is obtained through Lithium Aluminium Hydride reduction, 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 ChemistryLetters, 1981:P
627-630then report the method adopting organoselenium compound to prepare 1,2-bis-(2-thienyl) ethane, yield reaches 32%; Up-to-date bibliographical information from Macromolecules, 2011,44:P
4711-4720on, author adopts 2-chloromethyl thiophene to be raw material, and by obtained 1,2-bis-(2-thienyl) ethane of Wurtz reaction, yield is only 20%.
Summary of the invention
Inventing technical problem to be solved is: the synthetic method how providing 1,2-bis-(2-thienyl) ethane that a kind of reaction conditions is gentle, simple to operate, yield is high.
The technical solution adopted in the present invention is: 1, a kind of synthetic method of 1,2-bis-(2-thienyl) ethane, follows these steps to carry out:
Step one, 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 ester, 2-chlorothiophene and toluene, after having reacted, distillation removing isopropylcarbinol, dilute hydrochloric acid adjusts solution ph to neutral, and filter, vacuum-drying obtains three (2-thienyl) borine;
Step 3, by dioxane, tetrakis triphenylphosphine palladium, Tripotassium phosphate, tosic acid-2-(2-thienyl) ethyl ester, three (2-thienyl) borine mixing after, react complete to the conversion of tosic acid-2-(2-thienyl) ethyl ester, add hexanaphthene, add the superoxol of sodium hydroxide solution and 30% again, reaction acquisition 1,2-bis-(2-thienyl) ethane.
As a kind of optimal way: in step one, back flow reaction 2h, cooling, filter, removing silica gel, reaction solution washs with distilled water, saturated sodium carbonate solution, salt solution successively, and then underpressure distillation removing dichloromethane solvent, 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 DEG C, the solution of 2-chlorothiophene and toluene composition is slowly dripped after dripping boric acid three isobutyl ester, dropwise continuation reaction at such a temperature to be substantially exhausted to 2-chlorothiophene raw material, reaction solution is slowly down to room temperature, adding distil water, distillation removing isopropylcarbinol, then adjust solution ph to neutral with dilute hydrochloric acid, filter, filter cake distillation washing, 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, the mixing of three (2-thienyl) borine; transform complete in 85 DEG C of reactions to tosic acid-2-(2-thienyl) ethyl ester under nitrogen protection; be down to room temperature; add hexanaphthene; the hydrogen peroxide of 3.0mol/L sodium hydroxide solution and 30% is added under stirring; reaction 1h; extract with hexanaphthene; salt water washing, drying, underpressure distillation obtain 1,2-bis-(2-thienyl) ethane.
The invention has the beneficial effects as follows: first reactions steps is few, with 2-chlorothiophene for raw material two step has synthesized object product; Secondly yield is high, in 2-chlorothiophene for raw material total recovery is greater than 65%, exceeds more than 30% than the yield of existing bibliographical information, final reaction mild condition, easy and simple to handle.
Embodiment
Below the specific embodiment of the present invention is further described.
Implement the synthetic method of a kind of 1,2-bis-(2-thienyl) provided by the present invention ethane.It is with 2-chlorothiophene for starting raw material, is obtained by reacting three (2-thienyl) borine through boryl, reacts obtained 1,2-bis-(2-thienyl) ethane further with tosic acid-2-(2-thienyl) ethyl ester.
It is below a specific embodiment (carrying out in laboratory) of the present invention.
1, the preparation of tosic acid-2-(2-thienyl) ethyl ester
By 12.8g (0.1mol) 2-(2-thienyl) ethanol, 1000mL methylene dichloride, 21.0g (0.12mol) tosic acid and 10.0g chlorination silica gel puts into reaction flask, back flow reaction 2h, cooling, filter, removing silica gel.Reaction solution washs with distilled water, saturated sodium carbonate solution, salt solution successively, then underpressure distillation removing dichloromethane solvent, and prepare 26.0g tosic acid-2-(2-thienyl) ethyl ester, yield is 90%.
2, the preparation of three (2-thienyl) borine
6.0g lithium, 200ml toluene are put into reaction flask, logical nitrogen temperature to 100 DEG C, drip 34.8g (0.15mol) boric acid three isobutyl ester successively and slowly drip the solution be made up of 2-chlorothiophene and the 150mL toluene of 56.8g (0.48mol), dropwising continuation reaction at such a temperature and be substantially exhausted (being tested by TLC method) to 2-chlorothiophene raw material; Again reaction solution is slowly down to room temperature, adding distil water 250mL, distillation removing isopropylcarbinol, then adjust solution ph to neutral with dilute hydrochloric acid, filter, filter cake distillation washing, ethyl alcohol recrystallization, vacuum-drying obtains 31.2g tri-(2-thienyl) borine, and yield is 80.1%.
3, the synthesis of 1,2-bis-(2-thienyl) ethane
By 200mL dioxane, 1.45g (1.25mmol) tetrakis triphenylphosphine palladium, 10.6g (75mmol) Tripotassium phosphate, 14.1g (50mmol) tosic acid-2-(2-thienyl) ethyl ester, 14.3g (55mmol) three (2-thienyl) borine adds in reaction flask, complete (being tested by TLC method) is transformed to tosic acid-2-(2-thienyl) ethyl ester under nitrogen protection in 85 DEG C of reactions, be down to room temperature, add 400mL hexanaphthene, 25mL3.0mol/L sodium hydroxide solution is added under stirring, the hydrogen peroxide of 25mL30%, reaction 1h, extract with hexanaphthene, salt water washing, dry, underpressure distillation obtains 8.0g1, 2-bis-(2-thienyl) ethane, yield 82.3%.
Claims (4)
1. the synthetic method of one kind 1,2-bis-(2-thienyl) ethane, is characterized in that following these steps to carrying out:
Step one, 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 ester, 2-chlorothiophene and toluene, after having reacted, distillation removing isopropylcarbinol, dilute hydrochloric acid adjusts solution ph to neutral, and filter, vacuum-drying obtains three (2-thienyl) borine;
Step 3, by dioxane, tetrakis triphenylphosphine palladium, Tripotassium phosphate, tosic acid-2-(2-thienyl) ethyl ester, three (2-thienyl) borine mixing after, react complete to the conversion of tosic acid-2-(2-thienyl) ethyl ester, add hexanaphthene, add the superoxol of sodium hydroxide solution and 30% again, reaction acquisition 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 one, back flow reaction 2h, cooling, filters, removing silica gel, reaction solution washs with distilled water, saturated sodium carbonate solution, salt solution successively, and then underpressure distillation removing dichloromethane solvent, 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 DEG C, the solution of 2-chlorothiophene and toluene composition is slowly dripped after dripping boric acid three isobutyl ester, dropwise continuation reaction at such a temperature to be substantially exhausted to 2-chlorothiophene raw material, reaction solution is slowly down to room temperature, adding distil water, distillation removing isopropylcarbinol, then adjust solution ph to neutral with dilute hydrochloric acid, filter, filter cake distillation washing, ethyl alcohol recrystallization, vacuum-drying obtains three (2-thienyl) borine.
4. 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 the mixing of three (2-thienyl) borine, transform complete in 85 DEG C of reactions to tosic acid-2-(2-thienyl) ethyl ester under nitrogen protection, be down to room temperature, add hexanaphthene, the hydrogen peroxide of 3.0mol/L sodium hydroxide solution and 30% is added under stirring, reaction 1h, extract with hexanaphthene, salt water washing, dry, underpressure distillation obtains 1, 2-bis-(2-thienyl) ethane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410372070.XA CN104177328B (en) | 2014-07-31 | 2014-07-31 | A kind of synthetic method of 1,2-bis-(2-thienyl) ethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410372070.XA CN104177328B (en) | 2014-07-31 | 2014-07-31 | A kind of synthetic method of 1,2-bis-(2-thienyl) ethane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104177328A CN104177328A (en) | 2014-12-03 |
| CN104177328B true CN104177328B (en) | 2016-04-06 |
Family
ID=51958707
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410372070.XA Expired - Fee Related CN104177328B (en) | 2014-07-31 | 2014-07-31 | A kind of synthetic method of 1,2-bis-(2-thienyl) ethane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104177328B (en) |
Families Citing this family (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 |
-
2014
- 2014-07-31 CN CN201410372070.XA patent/CN104177328B/en not_active Expired - Fee Related
Non-Patent Citations (4)
| Title |
|---|
| "Reactions of hybrid organotellurium ligands......their decomposition";Singh, Garima 等;《Inorganica Chimica Acta》;20050301;第358卷(第4期);第912-918页 * |
| "Reactions of organocobaloximes with aryldisulfonyl chlorides";Gupta, B. D. 等;《Journal of Organometallic Chemistry》;20040401;第689卷(第7期);第1102-1109页 * |
| "Soluble polymers with constant π-conjugation length: polymers containing thiophene tetramers and hexamers";Sato, M.-A. 等;《Polymer》;20000731;第41卷(第15期);第5681-5687页 * |
| "Unconventional Titania Photocatalysis: Direct Deployment of Carboxylic Acids in Alkylations and Annulations";Manley, David W. 等;《Journal of the American Chemical Society》;20120807;第134卷(第33期);第13580-13583页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104177328A (en) | 2014-12-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101215235B (en) | Method for synthesizing hindered phenol antioxidants | |
| CN109232178B (en) | Novel method for preparing high-purity hydroxytyrosol | |
| JP2013505898A (en) | Process for the preparation of aromatic boronic ester compounds | |
| CN103304516B (en) | Method for preparing beta-aminoketone, ester and nitrile amide derivatives | |
| CN104177328B (en) | A kind of synthetic method of 1,2-bis-(2-thienyl) ethane | |
| CN104860872A (en) | Bis-(3R,4R)-1-benzyl-N,4-dimethyl piperidin-3-amine L-di-p-toluyl tartrate synthesis method | |
| CN110981779B (en) | Synthesis method of R-2- (2, 5-difluorophenyl) pyrrolidine | |
| KR100881617B1 (en) | Atorvastatin intermediates and method for producing the same | |
| CN101967075B (en) | Method for synthesizing terminal alkyne compound by using 3-aryl-2,3-dibromopropionic acid | |
| CN110818560A (en) | Preparation method of 4-benzyloxy phenyl ethyl n-decanoate | |
| US8981122B2 (en) | Method for producing optically active N-monoalkyl-3-hydroxy-3-arylpropylamine compound | |
| CN104045596A (en) | Novel method for preparing etoricoxib intermediate 1-(6-methylpyridyl-3-yl)-2-[4-(mesyl)-phenyl]-ethyl-one | |
| CN107954872B (en) | Method for synthesizing malonate type compound | |
| CN102127061B (en) | One prepares improving one's methods of fluoro-3, the 4-dihydro-2 H-1-benzopyran-2-epoxy ethanes of 6- | |
| CN103012047A (en) | Simple synthesis method of benzophenanthrene | |
| CN103626791B (en) | A kind of method of synthesizing 3-amino-4-fluorobenzoic boric acid | |
| CN108164561B (en) | Chiral menthyl phenyl phosphonamide compound and preparation method thereof | |
| CN105111229A (en) | Synthetic method for silthiopham | |
| CN102775268B (en) | Preparation method of 1-methyl-1-phenyl-3-phenylpropadiene compounds | |
| CN104591939B (en) | A kind of method preparing xenyl acrylic acid ether compound | |
| CN107759540A (en) | A kind of preparation method of butyrolactone derivative | |
| JP2016517897A (en) | Aminoaryl-boronic acids and esters and methods for producing aminoheteroaryl boronic acids and esters | |
| CN102731236B (en) | Alpha-amino cyclo nitrile compound preparation method | |
| CN110590641B (en) | Green preparation method of 3-hydroxyisoindole-1-ketone series compounds | |
| KR20100121332A (en) | Method for production of cyclopentadiene derivatives and composition for preparing cyclopentadiene derivatives |
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: 20160406 Termination date: 20180731 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |