CN101817747A - Preparation method of 4-acetoxyl-2-methyl-2-butene-1-aldehyde - Google Patents
Preparation method of 4-acetoxyl-2-methyl-2-butene-1-aldehyde Download PDFInfo
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- CN101817747A CN101817747A CN201010166233A CN201010166233A CN101817747A CN 101817747 A CN101817747 A CN 101817747A CN 201010166233 A CN201010166233 A CN 201010166233A CN 201010166233 A CN201010166233 A CN 201010166233A CN 101817747 A CN101817747 A CN 101817747A
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- butene
- methyl
- acetoxyl group
- aldehyde
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Abstract
The invention discloses a preparation method of 4-acetoxyl-2-methyl-2-butene-1-aldehyde, comprising the step of: carrying out catalytic oxidation on 4-acetoxyl-2-butene-1-alcohol as a raw material and pure oxygen or air as an oxidizing agent, the series compound of a tetramethyl-piperidine oxide as a main catalyst and ferric nitrate as an assistant in a solvent under the condition of a certain temperature to obtain the 4-acetoxyl-2-methyl-2-butene-1-aldehyde. The preparation method has the characteristics of high selectivity, mild reaction condition and simple operation; and solid wastes can not be generated in the reaction process, and products are easy to refine.
Description
Technical field
The present invention relates to a kind of preparation method who is used for the 4-acetoxyl group-2-methyl-2-butene-1-aldehyde of synthetic medicine intermediate.
Background technology
4-acetoxyl group-2-methyl-2-butene-1-aldehyde is called five-carbon ring aldehydo again, is one of important intermediate of synthesise vitamins A, and its structural formula is as follows:
The US5527952 report adopts 2,2,6,6-tetramethyl piperidine oxide compound (TEMPO) is a Primary Catalysts, CuCl is an auxiliary agent, at N, in dinethylformamide (DMF) solution, logical oxygen carries out catalytic oxidation to 4-acetoxyl group-2-methyl-2-butene-1-alcohol, obtain 4-acetoxyl group-2-methyl-2-butene-1-aldehyde, but this method selectivity is relatively poor, and side reaction is more, and the trans product content of the product that obtains is lower.And, can produce a large amount of solid giving up in the reaction process owing to being auxiliary agent with CuCl, generation is polluted to environment, is unfavorable for product postprocessing.
Summary of the invention
The present invention has mainly overcome had problems such as poor selectivity, aftertreatment complexity and environmental pollution be serious in 4-acetoxyl group-2-methyl-2-butene-1-aldehyde preparation process, provide can not produce in a kind of selectivity height, reaction conditions gentleness, simple to operate, the reaction process useless admittedly, and the preparation method of product a kind of 4-acetoxyl group-2-methyl-2-butene-1-aldehyde of being easy to purify.
For reaching above-mentioned purpose, the present invention adopts following technical scheme:
The preparation method of a kind of 4-acetoxyl group-2-methyl-2-butene-1-aldehyde, with 4-acetoxyl group-2-methyl-2-butene-1-alcohol is raw material, oxygen-containing gas is as oxygenant, in solvent with the series compound of tetramethyl piperidine oxide compound as Primary Catalysts (general structure is as follows), with do not have in the reaction process that precipitation produces and iron nitrate cheap and easy to get as auxiliary agent, catalyzed oxidation obtains 4-acetoxyl group-2-methyl-2-butene-1-aldehyde under the certain temperature condition.
Z：(-OR，-NHR，-N＝C(R)
2)
R:(hydrogen or C
1-C
6The alkyl of straight or branched)
The series compound of described tetramethyl piperidine oxide compound is a 4-hydroxyl-2,2,6,6-tetramethyl piperidine oxide compound (THMPO), 4-oxygen-2,2,6,6-tetramethyl piperidine oxide compound (4-O-TEMPO), 4-methoxyl group-2,2,6,6-tetramethyl piperidine oxide compound (4-OCH
3-TEMPO), 4-amino-2,2,6,6-tetramethyl piperidine oxide compound (4-NH
2-TEMPO) and 4-acetylaminohydroxyphenylarsonic acid 2,2,6, a kind of in the 6-tetramethyl piperidine oxide compound (4-AcNH-TEMPO).
Described Primary Catalysts preferably adopts 4-hydroxyl-2,2,6,6-tetramethyl piperidine oxide compound (THMPO), 4-oxygen-2,2,6, a kind of in the 6-tetramethyl piperidine oxide compound (4-O-TEMPO).
Described solvent is any one in acetate, methylene dichloride, toluene, the phenylfluoroform; Auxiliary agent is anhydrous or contains a kind of in the iron nitrate of crystal water; Temperature of reaction is 0～120 ℃.
Described solvent is preferably phenylfluoroform; Auxiliary agent is preferably the iron nitrate that contains 9 crystal water; Temperature of reaction is preferably 20～60 ℃.
Described oxygenant is pure oxygen or air, and feeds at normal pressure or near under the atmospheric pressure state.
The mol ratio of described Primary Catalysts and 4-acetoxyl group-2-methyl-2-butene-1-alcohol is 0.01-0.10: 1.
The mol ratio of described Primary Catalysts and 4-acetoxyl group-2-methyl-2-butene-1-alcohol is preferably 0.03-0.07: 1.
The mol ratio of described auxiliary agent and 4-acetoxyl group-2-methyl-2-butene-1-alcohol is 0.01-0.10: 1.
The mol ratio of described auxiliary agent and 4-acetoxyl group-2-methyl-2-butene-1-alcohol is preferably 0.03-0.07: 1.
Beneficial effect of the present invention is: synthetic 4-acetoxyl group-2-methyl-2-butene-1-aldehyde (trans-isomer(ide)) that the catalyzer of use can highly selective, and the reaction conditions gentleness, technological operation is good, and cost is low, and environmental pollution is little; Products obtained therefrom purity height, suitability for mass industrialized production.
Embodiment
Below by specific embodiment, the invention will be further described.
Embodiment 1
In three mouthfuls of round-bottomed flasks of the 100ml that is furnished with magnetic agitation, add 4-acetoxyl group-2-methyl-2-butene-1-alcohol 14.40g (0.10mol) and solvent phenylfluoroform 20ml, stir 3～5min under 40 ℃ of conditions, add THMPO 0.86g (5mmol) and Fe (NO then successively
3)
39H
2O 2.02g (5mmol), and slowly feed pure oxygen.Reaction 3h sampling, GC analyzes and knows: the transformation efficiency of 4-acetoxyl group-2-methyl-2-butene-1-alcohol is 99.3%.
Embodiment 2
In three mouthfuls of round-bottomed flasks of the 100ml that is furnished with magnetic agitation, add 4-acetoxyl group-2-methyl-2-butene-1-alcohol 14.40g (0.10mol) and solvent phenylfluoroform 20ml, stir 3～5min under 20 ℃ of conditions, add 4-O-TEMPO 0.52g (3mmol) and Fe (NO then successively
3)
39H
2O 1.21g (3mmol), and slowly feed pure oxygen.Reaction 6h sampling, GC analyzes and knows: the transformation efficiency of 4-acetoxyl group-2-methyl-2-butene-1-alcohol is 99.6%.
Embodiment 3
In three mouthfuls of round-bottomed flasks of the 100ml that is furnished with magnetic agitation, add 4-acetoxyl group-2-methyl-2-butene-1-alcohol 14.40g (0.10mol) and solvent phenylfluoroform 20ml, stir 3～5min under 60 ℃ of conditions, add 4-OCH then successively
3-TEMPO 0.86g (10mmol) and anhydrous Fe (NO
3)
32.02g (10mmol), and slowly feed pure oxygen.Reaction 5h sampling, GC analyzes and knows: the transformation efficiency of 4-acetoxyl group-2-methyl-2-butene-1-alcohol is 98.8%.
Embodiment 4
In three mouthfuls of round-bottomed flasks of the 100ml that is furnished with magnetic agitation, add 4-acetoxyl group-2-methyl-2-butene-1-alcohol 5.76g (40mmol) and solvent toluene 40ml, stir 3～5min under 0 ℃ of condition, add THMPO 0.43g (2.5mmol) and Fe (NO then successively
3)
39H
2O1.01g (2.5mmol), and slowly feed pure oxygen.Reaction 7h sampling, GC analyzes and knows: the transformation efficiency of 4-acetoxyl group-2-methyl-2-butene-1-alcohol is 98.4%.
Embodiment 5
In three mouthfuls of round-bottomed flasks of the 100ml that is furnished with magnetic agitation, add 4-acetoxyl group-2-methyl-2-butene-1-alcohol 5.76g (42mmol) and methylene chloride 40ml, stir 3～5min under 120 ℃ of conditions, add 4-NH then successively
2-TEMPO 0.52g (3mmol) and Fe (NO
3)
39H
2O 1.21g (3mmol), and slowly feed pure oxygen.Reaction 5h sampling, GC analyzes and knows: the transformation efficiency of 4-acetoxyl group-2-methyl-2-butene-1-alcohol is 99.2%.
Embodiment 6
In three mouthfuls of round-bottomed flasks of the 100ml that is furnished with magnetic agitation, add 4-acetoxyl group-2-methyl-2-butene-1-alcohol 5.76g (40mmol) and solvent acetic acid 40ml, stir 3～5min under 25 ℃ of conditions, add 4-AcNH-TEMPO 0.34g (2mmol) and Fe (NO then successively
3)
39H
2O 0.81g (2mmol).Uncovered reaction 6h sampling, GC analyzes and knows: the transformation efficiency of 4-acetoxyl group-2-methyl-2-butene-1-alcohol is 99.5%.
Embodiment 7
In three mouthfuls of round-bottomed flasks of the 100ml that is furnished with magnetic agitation, add 4-acetoxyl group-2-methyl-2-butene-1-alcohol 5.76g (40mmol) and solvent acetic acid 40ml, stir 3～5min under 80 ℃ of conditions, add THMPO 0.31g (0.4mmol) and Fe (NO then successively
3)
39H
2O0.81g (0.4mmol).Uncovered reaction 6h sampling, GC analyzes and knows: the transformation efficiency of 4-acetoxyl group-2-methyl-2-butene-1-alcohol is 98.7%.
Claims (10)
1. the preparation method of 4-acetoxyl group-2-methyl-2-butene-1-aldehyde, it is characterized in that: with 4-acetoxyl group-2-methyl-2-butene-1-alcohol is raw material, with pure oxygen or air as oxygenant, in solvent with the series compound of tetramethyl piperidine oxide compound as Primary Catalysts, iron nitrate is as auxiliary agent, and catalyzed oxidation obtains 4-acetoxyl group-2-methyl-2-butene-1-aldehyde under the certain temperature condition.
2. the preparation method of 4-acetoxyl group according to claim 1-2-methyl-2-butene-1-aldehyde is characterized in that: the series compound of described tetramethyl piperidine oxide compound is a 4-hydroxyl-2,2,6,6-tetramethyl piperidine oxide compound, 4-oxygen-2,2,6,6-tetramethyl piperidine oxide compound), 4-methoxyl group-2,2,6,6-tetramethyl piperidine oxide compound, 4-amino-2,2,6,6-tetramethyl piperidine oxide compound and 4-acetylaminohydroxyphenylarsonic acid 2,2,6, a kind of in the 6-tetramethyl piperidine oxide compound.
3. the preparation method of 4-acetoxyl group according to claim 1 and 2-2-methyl-2-butene-1-aldehyde is characterized in that: described catalyzer adopts 4-hydroxyl-2,2,6,6-tetramethyl piperidine oxide compound, 4-oxygen-2,2,6, a kind of in the 6-tetramethyl piperidine oxide compound.
4. the preparation method of 4-acetoxyl group according to claim 1-2-methyl-2-butene-1-aldehyde is characterized in that: described solvent is any one in acetate, methylene dichloride, toluene, the phenylfluoroform; Auxiliary agent is anhydrous or contains a kind of in the iron nitrate of crystal water; Temperature of reaction is 0～120 ℃.
5. the preparation method of 4-acetoxyl group according to claim 4-2-methyl-2-butene-1-aldehyde is characterized in that: described solvent is a phenylfluoroform; Auxiliary agent is the iron nitrate that contains 9 crystal water; Temperature of reaction is 20～60 ℃.
6. the preparation method of 4-acetoxyl group according to claim 1-2-methyl-2-butene-1-aldehyde is characterized in that: described oxygenant is pure oxygen or air.
7. the preparation method of 4-acetoxyl group according to claim 1-2-methyl-2-butene-1-aldehyde is characterized in that: the mol ratio of described Primary Catalysts and 4-acetoxyl group-2-methyl-2-butene-1-alcohol is 0.01-0.10: 1.
8. the preparation method of 4-acetoxyl group according to claim 7-2-methyl-2-butene-1-aldehyde is characterized in that: the mol ratio of described Primary Catalysts and 4-acetoxyl group-2-methyl-2-butene-1-alcohol is 0.03-0.07: 1.
9. the preparation method of 4-acetoxyl group according to claim 1-2-methyl-2-butene-1-aldehyde is characterized in that: the mol ratio of described auxiliary agent and 4-acetoxyl group-2-methyl-2-butene-1-alcohol is 0.01-0.10: 1.
10. the preparation method of 4-acetoxyl group according to claim 9-2-methyl-2-butene-1-aldehyde is characterized in that: the mol ratio of described auxiliary agent and 4-acetoxyl group-2-methyl-2-butene-1-alcohol is 0.03-0.07: 1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924276A (en) * | 2011-08-10 | 2013-02-13 | 浙江医药股份有限公司新昌制药厂 | Preparation method and intermediate hemiacetal of 2-methyl-2-acetoxy-3-butenyl-1-aldehyde |
| CN111675613A (en) * | 2020-05-29 | 2020-09-18 | 万华化学集团股份有限公司 | Preparation method of 4-acetoxyl-2-methyl-2-butenal |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5527952A (en) * | 1993-06-14 | 1996-06-18 | Takeda Chemical Industries, Ltd. | Process for producing aldehyde derivatives |
| CN101045686A (en) * | 2006-03-29 | 2007-10-03 | 浙江医药股份有限公司新昌制药厂 | Preparation method of 1-hydroxyl-2-methyl-4-acetoxy-2-buten |
| CN101544548A (en) * | 2008-03-26 | 2009-09-30 | 中国科学院大连化学物理研究所 | Method for preparing aldehydes or ketones by oxidizing alcohols with oxygen |
-
2010
- 2010-05-07 CN CN201010166233A patent/CN101817747A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5527952A (en) * | 1993-06-14 | 1996-06-18 | Takeda Chemical Industries, Ltd. | Process for producing aldehyde derivatives |
| CN101045686A (en) * | 2006-03-29 | 2007-10-03 | 浙江医药股份有限公司新昌制药厂 | Preparation method of 1-hydroxyl-2-methyl-4-acetoxy-2-buten |
| CN101544548A (en) * | 2008-03-26 | 2009-09-30 | 中国科学院大连化学物理研究所 | Method for preparing aldehydes or ketones by oxidizing alcohols with oxygen |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924276A (en) * | 2011-08-10 | 2013-02-13 | 浙江医药股份有限公司新昌制药厂 | Preparation method and intermediate hemiacetal of 2-methyl-2-acetoxy-3-butenyl-1-aldehyde |
| CN102924276B (en) * | 2011-08-10 | 2014-12-17 | 浙江医药股份有限公司维生素厂 | Preparation method and intermediate hemiacetal of 2-methyl-2-acetoxy-3-butenyl-1-aldehyde |
| CN111675613A (en) * | 2020-05-29 | 2020-09-18 | 万华化学集团股份有限公司 | Preparation method of 4-acetoxyl-2-methyl-2-butenal |
| CN111675613B (en) * | 2020-05-29 | 2023-01-13 | 万华化学集团股份有限公司 | Preparation method of 4-acetoxyl-2-methyl-2-butenal |
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Application publication date: 20100901 |