CN102964189A - Improved Huang Minlon reaction - Google Patents
Improved Huang Minlon reaction Download PDFInfo
- Publication number
- CN102964189A CN102964189A CN201210023899XA CN201210023899A CN102964189A CN 102964189 A CN102964189 A CN 102964189A CN 201210023899X A CN201210023899X A CN 201210023899XA CN 201210023899 A CN201210023899 A CN 201210023899A CN 102964189 A CN102964189 A CN 102964189A
- Authority
- CN
- China
- Prior art keywords
- reaction
- nitro
- compound
- carbonyl
- solvent
- 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.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an improved Huang Minlon reaction, which adopts hexamethylphosphoramide as the solvent. By changing the reaction solvent, the reaction temperature is decreased from 200DEG C to 80DEG C, so that the reaction has lower equipment requirements and reduced energy consumption, and is easier for large-scale industrial production. At the same time test, tests find that the reaction not only can well reduce carbonyl compounds, but also can well reduce nitro-compounds and compounds containing nitro and carbonyl groups simultaneously.
Description
Technical field
The present invention relates to a kind of reduction reaction, specifically relate to a kind of huang-Minlon reaction of improvement.
Background technology
Huang-Minlon reduction is an important reaction in the organic chemistry, and it can effectively be reduced to alkylate with carbonyl compound.The method is normally mixed reaction substrate with hydrazine hydrate, ethylene glycol is solvent, and reacting by heating generates hydrazone compounds, then adds potassium hydroxide, and reaction mixture is heated to more than 200 degree, and pyrolytic decomposition obtains corresponding alkylate.Because this reaction is carried out, therefore alkalescence and temperature sensitive compound are not suitable for the method under potassium hydroxide and high temperature.Simultaneously, in actually operating, so that the method is very high to equipment requirements in suitability for industrialized production, increased simultaneously energy consumption up to the temperature more than 200 degree.And the method and be not suitable for the reduction of nitro-compound.
Summary of the invention
The objective of the invention is in order to solve in the huang-Minlon reaction since the temperature of reaction height to equipment requirements the high and large defective that consumes energy.By changing reaction solvent, the invention provides a kind of huang-Minlon reaction of improvement.
Realize that above-mentioned purpose technical scheme of the present invention is, a kind of huang-Minlon reaction of improvement, described reaction is take HMPA (HMPA) as solvent.
This reaction can be used for carbonyl compound, nitro-compound or contains simultaneously the reduction of the compound of carbonyl and nitro.
This reaction may further comprise the steps:
(1) take HMPA as solvent, carbonyl or nitro-compound and excessive hydrazine hydrate 80 ℃ of lower reactions to reacting completely;
(2) reaction solution with step (1) is cooled to 40 ℃, removes excessive hydrazine hydrate and water, and the control temperature is no more than 60 ℃, obtains mixed solution;
(3) KOH is joined in the mixed solution that step (2) makes, be warming up to 80 ℃, reaction is to reacting completely under this temperature.
Wherein, whether fully reaction is to determine by TLC point plate or high performance liquid chromatography.
The present invention compared with prior art has following beneficial effect: (1) yellow ring dragon improvement reaction of the present invention is as solvent take HMPA, replaced traditional ethylene glycol, so that temperature of reaction has been reduced to 80 ℃ from 200 ℃, thereby so that the requirement that should react production unit reduces, it is little to consume energy, and is easier to large-scale industrial production; (2) test finds that method of the present invention is more reducible thermally sensitive compounds also; (3) the present invention is used for huang-Minlon reaction with HMPA first, not only makes the reduction reaction of carbonyl obtain good effect, and well nitro compound reducing or contain nitro and the compound of carbonyl of this reaction is also found in simultaneously test.
Embodiment
For ease of the understanding of technical solution of the present invention, be introduced below in conjunction with concrete embodiment.
Embodiment 1:
In the 2L there-necked flask, add the 165g m-nitroacetophenone, 300mLHMPA, the hydrazine hydrate of 320ml80% is heated to 80 degree reaction 1h.Be cooled to 40 degree, excessive hydrazine hydrate and water are removed in the water pump underpressure distillation, and temperature is no more than 60 degree in the control bottle.Complete rear adding KOH160g is warming up to 80 degree, insulation reaction 3h under this temperature, and cooling is poured into water, and dichloromethane extraction three times merges organic phase, anhydrous magnesium sulfate drying, underpressure distillation gets product 3-ethylaniline 119g, productive rate: 98%.
Please hydrogenation is not composed and mass-spectrometric data.
Embodiment 2:
In the 2L there-necked flask, add 257g 4-nitro-1-naphthalene pentanone, 500mLHMPA, the hydrazine hydrate of 320ml80% is heated to 80 degree reaction 1h.Be cooled to 40 degree, excessive hydrazine hydrate and water are removed in the water pump underpressure distillation, and temperature is no more than 60 degree in the control bottle.Complete rear adding KOH160g is warming up to 80 degree, insulation reaction 3h under this temperature, and cooling is poured into water, and dichloromethane extraction three times merges organic phase, anhydrous magnesium sulfate drying, underpressure distillation gets product 4-amyl group-naphthalidine 200g, productive rate: 93%.
Please hydrogenation is not composed and mass-spectrometric data.
Embodiment 3:
In the 2L there-necked flask, add 260g benzene ten diketone, 500mLHMPA, the hydrazine hydrate of 320ml80% is heated to 80 degree reaction 1h.Be cooled to 40 degree, excessive hydrazine hydrate and water are removed in the water pump underpressure distillation, and temperature is no more than 60 degree in the control bottle.Complete rear adding KOH160g is warming up to 80 degree, insulation reaction 3h under this temperature, and cooling is poured into water, and dichloromethane extraction three times merges organic phase, anhydrous magnesium sulfate drying, underpressure distillation gets product dodecylbenzene 236g, productive rate: 96%.
Please hydrogenation is not composed and mass-spectrometric data.
Technique scheme has only embodied the optimal technical scheme of technical solution of the present invention, and some changes that those skilled in the art may make some part have wherein all embodied principle of the present invention, belong within protection scope of the present invention.
Claims (3)
1. the huang-Minlon reaction of an improvement is characterized in that, described reaction is take HMPA as solvent.
2. reaction according to claim 1 is characterized in that, described reaction is used for carbonyl compound, nitro-compound or contains simultaneously the reduction of the compound of carbonyl and nitro.
3. reaction according to claim 1 and 2 is characterized in that, described reaction may further comprise the steps:
(1) take HMPA as solvent, carbonyl or nitro-compound and excessive hydrazine hydrate 80 ℃ of lower reactions to reacting completely;
(2) reaction solution with step (1) is cooled to 40 ℃, removes excessive hydrazine hydrate and water, and the control temperature is no more than 60 ℃, obtains mixed solution;
(3) KOH is joined in the mixed solution that step (2) makes, be warming up to 80 ℃, reaction is to reacting completely under this temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210023899 CN102964189B (en) | 2012-02-03 | 2012-02-03 | Improved Huang Minlon reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210023899 CN102964189B (en) | 2012-02-03 | 2012-02-03 | Improved Huang Minlon reaction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102964189A true CN102964189A (en) | 2013-03-13 |
| CN102964189B CN102964189B (en) | 2013-08-14 |
Family
ID=47794659
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201210023899 Active CN102964189B (en) | 2012-02-03 | 2012-02-03 | Improved Huang Minlon reaction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102964189B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114085152A (en) * | 2021-12-02 | 2022-02-25 | 华东医药（西安）博华制药有限公司 | Method for preparing 2- (4-nitrophenyl) butyric acid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1850795A (en) * | 2006-05-19 | 2006-10-25 | 西华师范大学 | Bialkylbiphenyl sodium disulfonate, and its preparing method |
| CN102093230A (en) * | 2011-01-28 | 2011-06-15 | 成都金桨高新材料有限公司 | Type I forked biphenyl diamine and preparation method and application thereof |
-
2012
- 2012-02-03 CN CN 201210023899 patent/CN102964189B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1850795A (en) * | 2006-05-19 | 2006-10-25 | 西华师范大学 | Bialkylbiphenyl sodium disulfonate, and its preparing method |
| CN102093230A (en) * | 2011-01-28 | 2011-06-15 | 成都金桨高新材料有限公司 | Type I forked biphenyl diamine and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| ELENA EIEZ-CECILIA ET AL: "One-step double reduction of aryl nitro and carbonyl groups using hydrazine", 《TETRAHEDRON LETTERS》, vol. 52, no. 50, 2011 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114085152A (en) * | 2021-12-02 | 2022-02-25 | 华东医药（西安）博华制药有限公司 | Method for preparing 2- (4-nitrophenyl) butyric acid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102964189B (en) | 2013-08-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2014522413A5 (en) | ||
| Qu et al. | Cu (OTf) 2-catalysed Ritter reaction: efficient synthesis of amides from nitriles and halohydrocarbons in water | |
| CN102701911A (en) | A method for purification and enhanced stability of alkynol compounds | |
| CN104086363B (en) | The energy-saving reclaiming process of N-BUTYL ACETATE and butanols in waste acid water | |
| CN102964189B (en) | Improved Huang Minlon reaction | |
| CN102757312B (en) | High-selectivity and low-energy-consumption preparation method for benzyl alcohol | |
| CN102643213B (en) | Preparation method of 3, 5-dimethyl-4-bromomethylbenzonitrile | |
| CN112552279A (en) | Synthesis method of substituted dibenzothiophene compound | |
| CN104592044A (en) | Low-temperature synthesis method of 2,6-dichloro-4-nitroaniline | |
| CN108084217A (en) | A kind of preparation method of 2,6- dichloros phenyl boric acid | |
| CN103980229A (en) | Preparation method of N-phenyl piperazine | |
| CN105622481A (en) | Process for efficient synthesis of 5-bromoindole | |
| CN104447391A (en) | Methylenebisamide derivative and preparation method thereof | |
| CN103626791B (en) | A kind of method of synthesizing 3-amino-4-fluorobenzoic boric acid | |
| CN102964233A (en) | Synthetic method of 3,5-2-fluoro-(trifluoromethyl)benzophenone | |
| CN105801482A (en) | Method for preparing 1-cyclopropyl-4-oxo-7-bromine-8-difluoromethoxy-1,4-dihydro-quinoline-3-nonanoic acid-ethyl ester | |
| CN104230719B (en) | A kind of method preparing substituted biphenyl | |
| CN106397469A (en) | Continuous cycle preparation method of trimethyl borate | |
| CN104395286A (en) | Method of preparing lactam compound | |
| CN105541560A (en) | TBHQ crude product synthesis process | |
| CN104130092B (en) | A kind of to the reductive coupling method between Methyl benzenesulfonyl oxo-compounds | |
| CN102675120A (en) | Preparation method of 3, 4-dichloronitrobenzene by solid acid catalyst | |
| CN103613526B (en) | A kind of preparation method of meropenem intermediate cyclization compound | |
| CN104370864B (en) | A kind of 2-(6-hydroxyl-2,3-Dihydrobenzofuranes-3-base) cyanide compound and prepare the method for TAK-875 medicine with this compound | |
| EP2980056A1 (en) | Method for producing cycloalkyl alkyl ether compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| DD01 | Delivery of document by public notice |
Addressee: Tianjin Pharmacn Medical Technology Co., Ltd. Document name: Notification of Passing Preliminary Examination of the Application for Invention |
|
| DD01 | Delivery of document by public notice |
Addressee: Tian Dongkui Document name: Notification of Passing Examination on Formalities |
|
| 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 |