Preparing method of 2,6 11,15-tetramethyl2,4,6,8,10,12,14hexadecene heptaene dialdehyde

A technology of carbheptaene dialdehyde and carbheptaene dialdehyde tetramethylene acetal is applied in the field of synthesis of carotenoid intermediates in organic chemistry, and can solve the problems of low yield, cumbersome operation, difficult to obtain raw materials and the like, and achieves The yield is good, the operation is simple, and the effect of avoiding side reactions

Active Publication Date: 2017-08-18
GUANGZHOU LEADER BIO TECH
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  • Abstract
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  • Application Information

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Problems solved by technology

[0018] The object of the present invention is to aim at the problem existing in the above-mentioned route, provide a kind of crocetin dialdehyde preparation method that is main feature with two-step Horner-Wadsworth-Emmons reaction, this two-step reaction can be carried out continuously in a pot, helps To solve the problems in the prior art that the raw materials are not easy to obtain, the operation is cumbersome, and the yield is not high

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  • Preparing method of 2,6 11,15-tetramethyl2,4,6,8,10,12,14hexadecene heptaene dialdehyde
  • Preparing method of 2,6 11,15-tetramethyl2,4,6,8,10,12,14hexadecene heptaene dialdehyde
  • Preparing method of 2,6 11,15-tetramethyl2,4,6,8,10,12,14hexadecene heptaene dialdehyde

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Experimental program
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Effect test

Embodiment 1

[0052] A. Preparation of tetraethyl ethylene diphosphate

[0053] Add 18.8g (0.1mol) dibromoethane, 49.8g (0.3mol) triethyl phosphite and 0.5g tetrabutylammonium iodide to a dry 500ml three-necked flask, and heat at 150-160°C for reflux reaction 4- 5h, the gas phase followed the reaction. Cool down to 100 DEG C afterwards, and the unreacted raw material is steamed out under reduced pressure by the water pump; Yield 86%.

[0054] B. "One-pot" preparation of 2,6,11,15-tetramethyl-2,4,6,8,10,12,14-hexadecadienedial

[0055] Under the protection of nitrogen, 150ml of toluene and 16.8g (0.15mol) of potassium tert-butoxide solid were successively added to a dry 500ml three-necked flask, and the mixture was stirred evenly, and 36.3g (0.12mol) of tetraethyl ethylene diphosphate, 11.8 g (0.1mol) of acetone aldehyde dimethyl acetal and 100ml of toluene mixed solution, about 0.5h to complete the dropwise addition, then react at room temperature. After the gas phase detection of acegu...

Embodiment 2

[0057] A. Preparation of tetraethyl ethylene diphosphate

[0058] Add 18.8g (0.1mol) dibromoethane, 49.8g (0.3mol) triethyl phosphite, 0.5g nickel iodide to a dry 500ml three-necked flask, heat at 150-160°C for 4-5h under reflux, gas phase Follow the reaction as it progresses. Cool down to 100 DEG C afterwards, and the unreacted raw material is steamed out under reduced pressure by the water pump; Yield 76%.

[0059] B. "One-pot" preparation of 2,6,11,15-tetramethyl-2,4,6,8,10,12,14-hexadecadienedial

[0060] Under the protection of nitrogen, 150ml toluene, 10.2g (0.15mol) sodium ethoxide solid were added successively to a dry 500ml three-necked flask, stirred evenly, and 36.3g (0.12mol) tetraethyl ethylene diphosphate, 11.8g ( 0.1mol) of aceguvaldehyde dimethyl acetal and 100ml of toluene, the mixed solution was added dropwise in about 0.5h, and then reacted at room temperature. Gas phase detection After the conversion of acetoaldehyde dimethyl acetal is completed, add 16...

Embodiment 3

[0062] A. Preparation of tetraethyl ethylene diphosphate

[0063] Add 18.8g (0.1mol) dibromoethane, 49.8g (0.3mol) triethyl phosphite, 0.5g sodium iodide to a dry 500ml three-necked flask, heat at 150-160°C for 4-5h, and gas phase Follow the reaction as it progresses. Cool down to 100 DEG C afterwards, and the unreacted raw material is distilled off by water pump decompression; Yield 72%.

[0064] B. "One-pot" preparation of 2,6,11,15-tetramethyl-2,4,6,8,10,12,14-hexadecadienedial

[0065] Under the protection of nitrogen, 150ml of toluene and 8.1g (0.15mol) of sodium methoxide solid were successively added to a dry 500ml three-necked flask, and the mixture was evenly stirred, and 36.3g (0.12mol) of tetraethyl ethylene diphosphate, 11.8g 0.1mol) of aceguvaldehyde dimethyl acetal and 100ml of toluene, the mixed solution was added dropwise in about 0.5h, and then reacted at room temperature. Gas phase detection After the conversion of acetoaldehyde dimethyl acetal is complet...

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Abstract

The invention provides a preparing method of 2,6,11,15-tetramethyl 2,4,6,8,10,12,14 hexadecene heptaene dialdehyde. The preparing method comprises the first step of using 1,2-dihalogenated ethane as a raw material, making 1,2-dihalogenated ethane react with triethyl phosphite under the effect of a catalyst through Michaelis-Arbuzov to obtain tetraethyl ethylenebisphosphonate; the second step of making phosphonate react with pyruvic aldehyde dimethyl acetal under an alkali effect and through Horner-Wadsworth-Emmons to obtain 3-methyl-4,4-dimethoxy-2-butylene-1-diethyl phosphate; the third step of making 3-methyl-4,4-dimethoxy-2-butylene-1-diethyl phosphate directly react with 2,7-dimethyl-2,4,6-octatriene-1,8-dialdehyde through a 'one pot method' without separation to obtain 2,6,11,15-tetramethyl-2,4,6,8,10,12,14-hexadecene heptaene dialdol methanol; the fourth step of making the acetal compound be subjected to hydrolysis protection under an acid condition to obtain the target compound 2,6,11,15-tetramethyl 2,4,6,8,10,12,14 hexadecene heptaene dialdehyde. According to the 'one pot method' processing technology, the raw materials are easy to obtain, and the preparing method is simple and coherent, simple in operation, mild in condition, good in yield, less in three wastes, and is thus suitable for industrialized production.

Description

technical field [0001] The present invention relates to a preparation method of 2,6,11,15-tetramethyl-2,4,6,8,10,12,14-hexadecaheptacenedialdehyde, which belongs to the intermediate carotenoid in organic chemistry body synthesis. Background technique [0002] 2,6,11,15-Tetramethyl-2,4,6,8,10,12,14-Hexadecanedialdehyde (hereinafter referred to as "crocetin dialdehyde"), CAS No. 502-70 -5, its structural formula is as follows: [0003] [0004] It is an important intermediate in the synthesis of carotenoids, and has important applications in the synthesis of β-carotene, astaxanthin, lycopene, β-apo-8′-carotene aldehyde, etc. Carotenoids are widely used in industries such as medicine, food, cosmetics and feed, and their demand is increasing day by day. The research on the synthesis of its intermediate crocetin dialdehyde is particularly valuable. [0005] At present, the synthesis methods of crocetin dialdehyde mainly include enol ether condensation method, sulfone compou...

Claims

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Application Information

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IPC IPC(8): C07C45/42C07C47/21C07F9/40
CPCC07C41/48C07C45/42C07F9/4006C07C47/21C07C43/303
Inventor 朱熇林劲冬陶正国周应芳冼啓志
Owner GUANGZHOU LEADER BIO TECH
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