CN102731371A - Synthesis method of 3-[2-nitroethyl] pyridine - Google Patents
Synthesis method of 3-[2-nitroethyl] pyridine Download PDFInfo
- Publication number
- CN102731371A CN102731371A CN2012102335388A CN201210233538A CN102731371A CN 102731371 A CN102731371 A CN 102731371A CN 2012102335388 A CN2012102335388 A CN 2012102335388A CN 201210233538 A CN201210233538 A CN 201210233538A CN 102731371 A CN102731371 A CN 102731371A
- Authority
- CN
- China
- Prior art keywords
- pyridine
- nitro
- ethyl
- compound method
- thf
- 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.)
- Pending
Links
Abstract
The invention discloses a synthesis method of 3-[2-nitroethyl] pyridine. The synthesis method comprises the following steps of: taking easily obtained 3-formaldehydepyridine as a raw material, and reacting the 3-formaldehydepyridine with nitromethane to generate 2-nitro-1-(3-pyridyl) ethanol; carrying out a dewatering reaction under the existence of acetic anhydride and 4-dimethylamino-pyridine to generate 3-[2-nitrovinyl] pyridine; and then reducing the 3-[2-nitrovinyl] pyridine through sodium borohydride to obtain the 3-[2-nitroethyl] pyridine.
Description
Technical field
The present invention relates to the synthesis technique of a kind of 3-[2-nitro-ethyl] pyridine, belong to medicine, chemical technology field.
Background technology
3-[2-nitro-ethyl] pyridine is a kind of dark solid, is the important chemical midbody.
Summary of the invention
The present invention is a raw material with the 3-carboxaldehyde radicals pyridine that is easy to get; Behind Nitromethane 99Min. reaction generation 2-nitro-1-(3-pyridyl) ethanol; Reaction generates and obtains 3-[2-nitroethylene base] pyridine in the presence of diacetyl oxide and 4-Dimethylamino pyridine again, obtains 3-[2-nitro-ethyl] pyridine through sodium borohydride reduction again.
The compound method of 3-according to the invention [2-nitro-ethyl] pyridine; Be that 3-carboxaldehyde radicals pyridine is dissolved in the cold THF and the trimethyl carbinol; Add Nitromethane 99Min. and potassium tert.-butoxide, zero degree stirs and added water in two hours and concentrate after the extracted with diethyl ether then and obtain 2-nitro-1-(3-pyridyl) ethanol, is dissolved in the methylene dichloride again; Add diacetyl oxide and 4-Dimethylamino pyridine stirring at room and drip sodium hydrogen carbonate solution after two hours; Add separatory, organic phase dry filter concentrating under reduced pressure obtains oily matter, with obtaining 3-[2-nitroethylene base] pyridine solid after the re-crystallizing in ethyl acetate; This solid is dissolved in THF and the alcohol mixed solvent, behind the adding Peng Qinghuana, stirs after two hours and uses dichloromethane extraction behind the adjusting pH to 6 behind the dropping water, obtains 3-[2-nitro-ethyl] pyridine with silica gel column chromatography after concentrating, and three go on foot yields more than 30%.
Above-mentioned with 3-carboxaldehyde radicals pyridine, Nitromethane 99Min., diacetyl oxide, 4-Dimethylamino pyridine and Peng Qinghuana etc. are following for the chemical reaction and the reaction formula of synthetic 3-[2-nitro-ethyl] pyridine of raw material:
(1) 3-carboxaldehyde radicals pyridine is dissolved in the THF and the trimethyl carbinol, with the reaction equation of Nitromethane 99Min. is:
(2) 2-nitro-1-(3-pyridyl) ethanol and 4-Dimethylamino pyridine and acetic anhydride equation are:
(3) 3-[2-nitroethylene base] pyridine and Peng Qinghuana reaction equation are:
Embodiment
Embodiment:
Under the zero degree, Nitromethane 99Min. (40ml, 740 mmoles) and potassium tert.-butoxide (2.9 grams; 25.8 mmole) join dissolved 3-carboxaldehyde radicals pyridine (50 the gram; 467 mmoles) in THF (250 milliliters) and the trimethyl carbinol (250 milliliters) mixing solutions, stir and add 300 milliliters in water after 2 hours, with twice of extracted with diethyl ether; Organic phase dried over mgso after-filtration concentrates and obtains brown oil 2-nitro-1-(3-pyridyl) ethanol (79.4 gram), directly is used for next step reaction.
2-nitro-1-(3-pyridyl) ethanol (78.9 grams that a last step obtains; 469 mmoles), with (50 milliliters of 4-Dimethylamino pyridine (3 gram, 24.56 mmoles) and diacetyl oxides; 530 mmoles) be dissolved in together in the methylene dichloride (1000 milliliters); Stirring at room drips 8% sodium hydrogen carbonate solution and is adjusted to alkalescence after 1 hour, organic phase is dry after the layering obtains 95.3 gram brown oils after concentrating, and this oil obtains 45 gram 3-[2-nitroethylene base] pyridines with re-crystallizing in ethyl acetate.
3-[2-nitroethylene base] pyridine (2 grams that a last step obtains; 13.32 mmole) be dissolved in the THF (23 milliliters); In 15 minutes, be added dropwise to and dissolved Peng Qinghuana (1 gram; 26.4 in THF mmole) (10 milliliters) and ethanol (10 milliliters) mixing solutions, controlled temperature is not higher than 10 ° of C, this reaction mixture adds 10 ml waters in reaction under 5 ° of C after 1.5 hours; With vinegar acid for adjusting pH value to 6; With dichloromethane extraction 3 times, the organic phase saturated nacl aqueous solution of merging washing back concentrates with the dried over mgso after-filtration and obtains 2.5 gram black oil, and silica gel column chromatography obtains 0.92 after with methylene dichloride and methanol-eluted fractions and restrains yellow solid 3-[2-nitro-ethyl] pyridine.
Claims (5)
1. the compound method of 3-according to the invention [2-nitro-ethyl] pyridine; Be that 3-carboxaldehyde radicals pyridine is dissolved in the cold THF and the trimethyl carbinol; Add Nitromethane 99Min. and potassium tert.-butoxide, zero degree stirs and added water in two hours and concentrate after the extracted with diethyl ether then and obtain 2-nitro-1-(3-pyridyl) ethanol, is dissolved in the methylene dichloride again; Add diacetyl oxide and 4-Dimethylamino pyridine stirring at room and drip sodium hydrogen carbonate solution after two hours; Add separatory, organic phase dry filter concentrating under reduced pressure obtains oily matter, with obtaining 3-[2-nitroethylene base] pyridine solid after the re-crystallizing in ethyl acetate; This solid is dissolved in THF and the alcohol mixed solvent, behind the adding Peng Qinghuana, stirs after two hours and uses dichloromethane extraction behind the adjusting pH to 6 behind the dropping water, obtains 3-[2-nitro-ethyl] pyridine with silica gel column chromatography after concentrating, and three go on foot yields more than 30%.
2. the compound method of 3-[2-nitro-ethyl] pyridine as claimed in claim, it is characterized in that: described initial feed is meant that 3-carboxaldehyde radicals pyridine is a raw material.
3. compound method the first step Synthetic 2-nitro-1-(3-pyridyl) ethanol of above-mentioned 3-[2-nitro-ethyl] pyridine, it is characterized in that: solvent is the mixed solvent of the THF and the trimethyl carbinol, and Nitromethane 99Min. is another raw material, and catalyzer is a potassium tert.-butoxide.
4. synthetic 3-[the 2-nitroethylene base] pyridine of compound method second step dehydration of above-mentioned 3-[2-nitro-ethyl] pyridine, it is characterized in that: dehydrated reagent is an acetic anhydride, and catalyzer is the 4-Dimethylamino pyridine, and aftertreatment recrystallization solvent for use is an ETHYLE ACETATE.
5. synthetic 3-[2-nitro-ethyl] pyridine of the 3rd step of compound method of above-mentioned 3-[2-nitro-ethyl] pyridine, it is characterized by reductive agent is Peng Qinghuana, solvent is THF and ethanol mixed solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102335388A CN102731371A (en) | 2012-07-07 | 2012-07-07 | Synthesis method of 3-[2-nitroethyl] pyridine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102335388A CN102731371A (en) | 2012-07-07 | 2012-07-07 | Synthesis method of 3-[2-nitroethyl] pyridine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102731371A true CN102731371A (en) | 2012-10-17 |
Family
ID=46987761
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012102335388A Pending CN102731371A (en) | 2012-07-07 | 2012-07-07 | Synthesis method of 3-[2-nitroethyl] pyridine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102731371A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110357809A (en) * | 2018-04-10 | 2019-10-22 | 新发药业有限公司 | A kind of simple and convenient process for preparing of 4- methyl piperidine -3- ketone and its derivative |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009052078A1 (en) * | 2007-10-19 | 2009-04-23 | Boehringer Ingelheim International Gmbh | Ccr10 antagonists |
-
2012
- 2012-07-07 CN CN2012102335388A patent/CN102731371A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009052078A1 (en) * | 2007-10-19 | 2009-04-23 | Boehringer Ingelheim International Gmbh | Ccr10 antagonists |
Non-Patent Citations (1)
| Title |
|---|
| KUSTER, GEORGE J.T.ET AL: "Novel five/five- and six/five-membered bicyclic nitroso acetals from high-pressure-promoted cyclization reactions of p-methoxybenzyl vinyl ether, 1-nitro-2-heteroaryl ethenes, and mono- and di-substituted olefins", 《EUROPEAN JOURNAL OF ORGANIC CHEMISTRY》, no. 3, 31 December 2001 (2001-12-31), pages 553 - 560 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110357809A (en) * | 2018-04-10 | 2019-10-22 | 新发药业有限公司 | A kind of simple and convenient process for preparing of 4- methyl piperidine -3- ketone and its derivative |
| CN110357809B (en) * | 2018-04-10 | 2020-10-02 | 新发药业有限公司 | Simple preparation method of 4-methylpiperidine-3-one and derivatives thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106495105B (en) | A method of synthesis nanometer selenium material | |
| CN106946707A (en) | A kind of polysubstituted hydrogenation indene derivative and preparation method thereof | |
| CN103694188B (en) | The preparation method of Fu benzene Ni Kao oxazoline intermediate | |
| CN103130719B (en) | A kind of polysubstituted imidazoles Calixarene Derivatives and preparation method | |
| CN103204819B (en) | Deuterated diazepam and preparation method thereof | |
| Ying et al. | C (sp3)–H Peroxidation of 3-Substituted Indolin-2-ones under Metal-Free Conditions | |
| CN102731371A (en) | Synthesis method of 3-[2-nitroethyl] pyridine | |
| CN105037179B (en) | A kind of novel hole transport material and its preparation method and application | |
| CN103772278A (en) | Important tetrahydroisoquinoline derivative midbody and synthesis method thereof | |
| CN102977017A (en) | Method for catalytically preparing 6(5H)-phenanthridine ketone by copper component | |
| CN102617455A (en) | Preparation method of pyridoxal or pyridoxal hydrochloride | |
| CN101575340A (en) | Preparation method of ketorolac tromethamine | |
| CN102382038B (en) | Preparation method for synthesizing carbazoles alkaloid Siamenol | |
| CN104370830A (en) | Synthetic method of 5-trifluoromethyl uracil | |
| CN102516162A (en) | Method for preparing copper-catalyzed nitro aromatic (heterocyclic) compounds | |
| CN103435531A (en) | Method for preparing feed additive DL-tryptophan | |
| CN104402690B (en) | The preparation method of method Buddhist nun's aldehyde and accompany the preparation method of auspicious tretinoin | |
| CN109776409B (en) | Method for synthesizing C-2-bit polyfluoro functional group substituted quinoline by using microchannel reaction device | |
| CN105399718A (en) | Solid phase synthesis method of 2H-benzopyran compounds | |
| CN101921235A (en) | Preparation method of telmisartan | |
| CN106674011B (en) | A method of indenone derivative is synthesized by dimethyl sulfoxide | |
| CN106866324A (en) | A kind of application of carborane radical ammonium perchlorate | |
| CN102643262B (en) | A kind of preparation method of 8-oxyethyl group-2-(to fluorophenyl)-3-nitro-2H-chromene | |
| CN103408481B (en) | The method of the pyrroles-3-formic acid ester compound that microwave radiation one-step synthesis replaces | |
| CN103772177A (en) | Preparation method of p-methoxyacetophenone |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20121017 |