CN101481344B - Preparation of tetradecanal - Google Patents
Preparation of tetradecanal Download PDFInfo
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- CN101481344B CN101481344B CN2008100591006A CN200810059100A CN101481344B CN 101481344 B CN101481344 B CN 101481344B CN 2008100591006 A CN2008100591006 A CN 2008100591006A CN 200810059100 A CN200810059100 A CN 200810059100A CN 101481344 B CN101481344 B CN 101481344B
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Abstract
The invention discloses a method for preparing an important intermediate-myristic aldehyde of vitamin A. Dimethyl sulphide, a fetid solvent, is used in the current reaction, leading to serious environmental pollution, more reaction steps and difficult control. The method has the following steps: 2, 2, 6-trimethyl-1-acetylenyl-1-cyclohexanol is obtained after ethynylation of 2, 2, 6-trimethylcyclohexanone; two isomers are obtained after rearranging the product obtained in the previous step, namely (2, 6, 6- trimethyl-1-cyclohexenyl)-acetaldehyde and (2, 2, 6-trimethyl cyclohexylidene)-acetaldehyde; the final product myristic aldehyde is obtained after the two isomers react with propionaldehyde in the present of catalyst. The method is easy in obtaining the raw materials, low in production cost, easy in controlling the reaction conditions and little side reaction, thus increasing the reaction yield and minimizing the environmental pollution.
Description
Technical field
The invention discloses the preparation method of a kind of important intermediate myristic aldehyde of vitamin A.
Background technology
Myristic aldehyde, molecular formula are C
14H
28O, English Tetradecanal by name, structural formula is following:
It is a kind of key intermediate of preparation vitamin A, generally through reaching Qin Si (Darzens) condensation reaction preparation, is promptly obtained under the sodium methylate effect by methyl chloroacetate and β jononeionone, and synthetic route is following:
The shortcoming of aforesaid method is raw materials used costing an arm and a leg, and like alpha, beta-lonone and sodium methylate etc., and sodium methylate has certain danger in storage, course of conveying.In addition, the yield of this method is on the low side, and the wastewater flow rate of generation is bigger.
4044028 pairs of aforesaid methods of U.S. Pat have been done improvement, and it adopts sulfur ylide as one of reactant and the reaction of β jononeionone, and synthetic route is following:
The reaction yield that this method obtains is higher, but needs with this malodorous solvent of dimethyl sulphide in the reaction, and environmental pollution is serious, and reactions step is many, controls difficult.
Summary of the invention
Technical problem to be solved by this invention is to overcome the defective that above-mentioned prior art exists, and the preparation method that a kind of raw material is easy to get, reaction conditions is prone to the myristic aldehyde of control is provided, and to reduce cost, reduces side reaction, improves reaction yield, reduces environmental pollution.
For this reason, the present invention adopts following technical scheme: a kind of preparation method of myristic aldehyde, and its step is following: 1) raw material 2,2, and 6-trimethylcyclohexanone ethinylation reaction obtains product 2,2,6-trimethylammonium-1-ethynyl-1-hexalin; 2) go up the step product and obtain two kinds of isomer (2,6,6-trimethylammonium-1-cyclohexenyl)-acetaldehyde (a) and (2,2,6-trimethylammonium cyclohexylidene)-acetaldehyde (b) (hereinafter to be referred as aldehyde (a), aldehyde (b)) through rearrangement; 3) described two kinds of isomer products aldehyde (a), aldehyde (b) obtain the final product myristic aldehyde with the propionic aldehyde reaction under catalyst action.Synthetic route of the present invention is following:
As the further of technique scheme improved and replenish, the present invention takes following technical measures:
The preparation method of above-mentioned myristic aldehyde, catalyzer is an alkali metal salt of organic imines carboxylate salt, carboxylic acid or the alkaline earth salt of carboxylic acid.
The preparation method of above-mentioned myristic aldehyde, catalyzer is organic imines carboxylate salt that carboxylic acid and amine reaction generate, and described carboxylic acid is acetate, propionic acid or butyric acid, and described amine is n n dimetylaniline, diethylamine or piperidines.
The preparation method of above-mentioned myristic aldehyde, an alkali metal salt of carboxylic acid is carboxylic acid sodium, carboxylic acid lithium or carboxylic acid potassium, the alkaline earth salt of carboxylic acid is calcium carboxylates or magnesium carboxylates.
The preparation method of above-mentioned myristic aldehyde, the saturated vapo(u)r that is reflected at material in the 3rd step is depressed and is carried out, and temperature of reaction is 200-260 ℃, and the reaction times is 2～20 minutes.The present invention adopts pressurization to react, and can improve temperature of reaction, shortens the reaction times, the bigger catalyst consumption that reduced, and yield is higher than the yield that reaction obtains under normal pressure.
The mol ratio of above-mentioned catalyzer and two kinds of isomer products aldehyde (a), aldehyde (b) is respectively 0.01-0.1: 1, and catalyst consumption is few.
The preparation method of above-mentioned myristic aldehyde, after three-step reaction finishes, with material below 2～5 minutes internal cooling to 50 ℃, thereby side reactions such as self condensation take place in the product that can effectively avoid generating.
The present invention has following beneficial effect: raw material is easy to get, and production cost is low; Reaction conditions is prone to control, and side reaction is few, has improved reaction yield, and is low in the pollution of the environment; Be employed under the pressurized conditions and react, the reaction times is short, and catalyst consumption is few, and yield is higher than the yield that reaction obtains under normal pressure.
Below in conjunction with embodiment the present invention is described further.
Embodiment
Embodiment 1
2,2, the preparation of 6-trimethylammonium-1-ethynyl-1-hexalin
Insert 1000ml liquefied ammonia in the 2000ml four-hole boiling flask, it is warm below-35 ℃ to use dry ice-alcohol bath to keep in the bottle, slowly adds metallic lithium 8.0g; Solution is mazarine, and lithium finishes, and the restir reaction begins after 20 minutes to feed acetylene with 1.5L/min; Solution becomes grey after 40 minutes continues logical acetylene and stopped logical acetylene in 30 minutes, makes ammonia volatilization through indirect heating; Volatilizing begins slowly to add ether 800ml mid-term, the control evaporation rate and the speed that adds diethyl ether, and it is constant basically to keep bottle interior volume of material.Treat that bottle 5 ℃ of continued of interior temperature rise fed acetylene 30 minutes with 0.75L/min; Then in the control bottle temperature-10 ℃ of continued with the logical acetylene of 0.75L/min drip simultaneously the 140.0g precooling to-10 ℃ 2,2, the 6-trimethylcyclohexanone; Drip and finish; Stirring reaction added the ammonium chloride stirring reaction 15 minutes after 1 hour, and reaction product is transferred in the reaction flask of 1000ml (in 400ml water is housed) then, and organic layer is used anhydrous sodium sulfate drying after the washing layering; Often, rectification under vacuum is reclaimed ether and is steamed desired product 157.7g, yield 95%.
The preparation of aldehyde (a), aldehyde (b)
The product 100.0g of embodiment 1 gained is placed the four-hole boiling flask of 500ml belt stirrer, TM, add p-methylbenzoic acid 13.0g, YLENE 130g; Tetrabutyl titanate 2.7g, cuprous chloride 1.1g was warming up to 130 ℃ of insulation reaction 6 hours; Reaction is finished, and material is cooled to 20 ℃ of after-filtration and removes cuprous chloride, and rectification under vacuum obtains 94.0g product (2 then; 2,6 trimethylammonium cyclohexylidenes)-acetaldehyde and (2,6; 6 trimethylammoniums-1-cyclohexenyl)-and the mixture of acetaldehyde, the ratio of the two is 1: 2, yield 94%.
The preparation method of embodiment 2 myristic aldehydes
In the 500ml of belt stirrer, TM four-hole boiling flask, add 83.0g (2,6; 6 trimethylammoniums-1-cyclohexenyl)-acetaldehyde, 58.0g propionic aldehyde, 22.5g n n dimetylaniline, 40g water, 30.0g acetate; Be warming up to 200 ℃, depressed stirring reaction 20 minutes at the saturated vapo(u)r of reaction mass, reaction is finished; In 5 minutes, material is cooled to 30 ℃; Standing demix, organic layer washs the myristic aldehyde 88.6g that once back rectification under vacuum obtains total GC content 94.8%, yield 85.5% with the saturated brine that contains the 1.0g glacial acetic acid.
The preparation method of embodiment 3 myristic aldehydes
In the withstand voltage reaction flask of the 500ml of belt stirrer, TM, add 83.0g (2,6; 6 trimethylammoniums-1-cyclohexenyl)-and acetaldehyde, 58.0g propionic aldehyde, 0.9g n n dimetylaniline, 20.0g water, 1.2g acetate, be warming up to 230 ℃ behind the nitrogen replacement, depress violent stirring reaction 7 minutes at the saturated vapo(u)r of reaction mass; Reaction is finished; In 2 minutes, material is cooled to below 50 ℃, cold complete, standing demix; Organic layer washs the myristic aldehyde 94.4g that once back rectification under vacuum obtains total GC content 96.0%, yield 88.0% with the saturated brine that contains the 0.4g glacial acetic acid.
The preparation method of embodiment 4 myristic aldehydes
In the withstand voltage reaction flask of the 500ml of belt stirrer, TM, add 83.0g (2,6; 6 trimethylammoniums-1-cyclohexenyl)-and acetaldehyde, 58.0g propionic aldehyde, sodium acetate trihydrate 2.72g, 20.0g water, be warming up to 260 ℃ behind the nitrogen replacement, depress violent stirring reaction 5 minutes at the saturated vapo(u)r of reaction mass; Reaction is finished; In 2 minutes, material is cooled to below 50 ℃, cold complete, standing demix; Organic layer washs the myristic aldehyde 96.6g that once back rectification under vacuum obtains total GC content 95.7%, yield 89.8% with the saturated brine that contains the 0.4g glacial acetic acid.
The above only is preferred embodiment of the present invention, is not structure of the present invention is done any pro forma restriction.Every foundation technical spirit of the present invention all falls in protection scope of the present invention any simple modification, equivalent variations and modification that above embodiment did.
Claims (3)
1. the preparation method of a myristic aldehyde, its step is following: 1) raw material 2,2, and 6-trimethylcyclohexanone ethinylation reaction obtains product 2,2,6-trimethylammonium-1-ethynyl-1-hexalin; 2) go up the step product and obtain two kinds of isomer (2,6,6-trimethylammonium-1-cyclohexenyl)-acetaldehyde and (2,2,6-trimethylammonium cyclohexylidene)-acetaldehyde through rearrangement; 3) described two kinds of isomer products obtain the final product myristic aldehyde with propionic aldehyde reaction under catalyst action, and the saturated vapo(u)r that is reflected at material is depressed and carried out, and temperature of reaction is 200-260 ℃, and the reaction times is 2～20 minutes;
Described catalyzer is organic imines carboxylate salt, carboxylic acid sodium, carboxylic acid lithium, carboxylic acid potassium, calcium carboxylates or the magnesium carboxylates that carboxylic acid and amine reaction generate; In organic imines carboxylate salt; Described carboxylic acid is acetate, propionic acid or butyric acid, and described amine is n n dimetylaniline, diethylamine or piperidines.
2. the preparation method of myristic aldehyde according to claim 1 is characterized in that the mol ratio of described catalyzer and two kinds of isomer products is respectively 0.01-0.1: 1.
3. the preparation method of myristic aldehyde according to claim 1, it is characterized in that three-step reaction finishes after, with material below 2～5 minutes internal cooling to 50 ℃.
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| CN2008100591006A CN101481344B (en) | 2008-01-10 | 2008-01-10 | Preparation of tetradecanal |
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| CN2008100591006A CN101481344B (en) | 2008-01-10 | 2008-01-10 | Preparation of tetradecanal |
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| CN101481344B true CN101481344B (en) | 2012-06-13 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111484510B (en) * | 2019-01-25 | 2023-02-03 | 新发药业有限公司 | Preparation method of (2, 6-trimethyl-1-cyclohexenyl) aldehyde |
| CN111440055B (en) * | 2020-04-24 | 2022-11-08 | 万华化学集团股份有限公司 | Synthesis method of beta-damascone |
| CN114409580B (en) * | 2021-12-27 | 2024-06-07 | 厦门金达威维生素有限公司 | Preparation method of vitamin A intermediate tetradecaldehyde |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB627453A (en) * | 1947-07-16 | 1949-08-09 | Glaxo Lab Ltd | Improvements in and relating to the preparation of derivatives of cyclohexene |
| US4250332A (en) * | 1979-10-26 | 1981-02-10 | International Flavors & Fragrances Inc. | Process for preparing acyl trimethyl cyclohexene derivatives and use of intermediates therefor in augmenting or enhancing the aroma or taste of a consumable material |
| US5162552A (en) * | 1986-05-23 | 1992-11-10 | Basf Aktiengesellschaft | Preparation of 4-acetals of butene-1,4-dial and novel acetals of butene-1,4-dial |
| CN1348947A (en) * | 2000-10-18 | 2002-05-15 | 浙江新和成股份有限公司 | Prepn process of vitamin A intermediate |
-
2008
- 2008-01-10 CN CN2008100591006A patent/CN101481344B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB627453A (en) * | 1947-07-16 | 1949-08-09 | Glaxo Lab Ltd | Improvements in and relating to the preparation of derivatives of cyclohexene |
| US4250332A (en) * | 1979-10-26 | 1981-02-10 | International Flavors & Fragrances Inc. | Process for preparing acyl trimethyl cyclohexene derivatives and use of intermediates therefor in augmenting or enhancing the aroma or taste of a consumable material |
| US5162552A (en) * | 1986-05-23 | 1992-11-10 | Basf Aktiengesellschaft | Preparation of 4-acetals of butene-1,4-dial and novel acetals of butene-1,4-dial |
| CN1348947A (en) * | 2000-10-18 | 2002-05-15 | 浙江新和成股份有限公司 | Prepn process of vitamin A intermediate |
Non-Patent Citations (2)
| Title |
|---|
| Pierre CHABARDES.Ti/Cu AND Ti/Ag CATALYSTS FOR THE ISOMERISATION OF α-ACETYLENIC ALCOHOLS INTO α,β-ETHYLENIC CARBONYL DERIVATIVES.《Tetrahedron Letters》.1988,第29卷(第48期),6253-6256. * |
| PierreCHABARDES.Ti/CuANDTi/AgCATALYSTSFORTHEISOMERISATIONOFα-ACETYLENICALCOHOLSINTOα β-ETHYLENIC CARBONYL DERIVATIVES.《Tetrahedron Letters》.1988 |
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Effective date of registration: 20130108 Address after: 312500 No. 4 Zhenjiang North Road, Chengguan County, Zhejiang, Xinchang Patentee after: Zhejiang Xinhecheng Co., Ltd. Patentee after: Shangyu Xinhecheng Bio-Chemical Co., Ltd. Address before: 312500 No. 4 Zhenjiang North Road, Chengguan County, Zhejiang, Xinchang Patentee before: Zhejiang Xinhecheng Co., Ltd. |