CN102964189B - Improved Huang Minlon reaction - Google Patents
Improved Huang Minlon reaction Download PDFInfo
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- CN102964189B CN102964189B CN 201210023899 CN201210023899A CN102964189B CN 102964189 B CN102964189 B CN 102964189B CN 201210023899 CN201210023899 CN 201210023899 CN 201210023899 A CN201210023899 A CN 201210023899A CN 102964189 B CN102964189 B CN 102964189B
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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.This method is normally mixed reaction substrate with hydrazine hydrate, ethylene glycol is solvent, and reacting by heating generates hydrazone compounds, adds potassium hydroxide then, 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 this method under potassium hydroxide and high temperature.Simultaneously, in actually operating, make this method very high to equipment requirements in suitability for industrialized production up to the above temperature of 200 degree, increased energy consumption simultaneously.And this 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 big 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 solvent with HMPA (HMPA).
This reaction can be used for carbonyl compound, nitro-compound or contains the reduction of the compound of carbonyl and nitro simultaneously.
This reaction may further comprise the steps:
(1) with the HMPA be solvent, carbonyl or nitro-compound and excessive hydrazine hydrate 80 ℃ of following 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 to be solvent with the HMPA, replaced traditional ethylene glycol, make temperature of reaction be reduced to 80 ℃ from 200 ℃, thereby make this reaction reduce the requirement of production unit, 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 this reaction nitro compound reducing or contain nitro and the compound of carbonyl is well also found in test simultaneously.
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.Add KOH160g after finishing, be warming up to 80 degree, insulation reaction 3h under this temperature, cooling is poured in the water, and dichloromethane extraction three times merges organic phase, anhydrous magnesium sulfate drying, underpressure distillation gets product 3-ethylaniline 119g, productive rate: 98%.
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.Add KOH160g after finishing, be warming up to 80 degree, insulation reaction 3h under this temperature, cooling is poured in the water, and dichloromethane extraction three times merges organic phase, anhydrous magnesium sulfate drying, underpressure distillation gets product 4-amyl group-1-naphthylamines 200g, productive rate: 93%.
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.Add KOH160g after finishing, be warming up to 80 degree, insulation reaction 3h under this temperature, cooling is poured in the water, and dichloromethane extraction three times merges organic phase, anhydrous magnesium sulfate drying, underpressure distillation gets product dodecylbenzene 236g, productive rate: 96%.
Technique scheme has only embodied the optimal technical scheme of technical solution of the present invention, those skilled in the art to some part wherein some changes that may make all embodied principle of the present invention, belong within protection scope of the present invention.
Claims (2)
1. the method using huang-Minlon reaction reducing carbonyl compound, nitro-compound or contain the compound of carbonyl and nitro simultaneously is characterized in that described method is solvent with the HMPA.
2. the method for claim 1 is characterized in that may further comprise the steps:
(1) with the HMPA be solvent, carbonyl or nitro-compound and excessive hydrazine hydrate 80 ℃ of following 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 CN102964189A (en) | 2013-03-13 |
| CN102964189B true CN102964189B (en) | 2013-08-14 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 201210023899 Active CN102964189B (en) | 2012-02-03 | 2012-02-03 | Improved Huang Minlon reaction |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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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 (2)
| Title |
|---|
| Elena Eiez-Cecilia et al.One-step double reduction of aryl nitro and carbonyl groups using hydrazine.《Tetrahedron Letters》.2011,第52卷(第50期), |
| One-step double reduction of aryl nitro and carbonyl groups using hydrazine;Elena Eiez-Cecilia et al;《Tetrahedron Letters》;2011;第52卷(第50期);6702-6704 * |
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