Method for selective hydrogenation synthesis of nerol and geraniol mixture by using citral in water-organic two-phase system

A citral and selective technology, applied in the preparation of organic compounds, chemical instruments and methods, organic chemistry, etc., can solve problems such as harsh operating conditions, achieve convenient post-processing, simple process, and reduce pollution

Active Publication Date: 2013-10-09
SHANDONG NHU PHARMA +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although the selectivity of the above method is high, it needs to use supercritical CO 2 As a solvent, the operating conditions are relatively harsh; in addition, the use of a fixed bed reactor requires the catalyst to have a long service life

Method used

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  • Method for selective hydrogenation synthesis of nerol and geraniol mixture by using citral in water-organic two-phase system

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0022] 10g of ruthenium acetate and tris-(p-phenoxy-polyoxyethylene ether)-phosphine complex catalyst (mass ratio of ruthenium acetate to tri-(p-phenoxy-polyoxyethylene ether)-phosphine is 0.008:1), Add 500g of water into a 2L autoclave with magnetic stirring and a temperature controller, then add 500g of citral, replace with nitrogen three times, then replace with hydrogen three times, heat to 100°C, pressurize hydrogen to 0.5MPa, stir at 500rpm, Reacted for 2 hours, and the conversion rate of sampling analysis of citral was greater than 98%. Cool with water, press out the reaction solution, leave to stand for stratification, the water phase is the catalyst and can be applied to the next batch of reactions, and the organic phase is a mixture of geraniol and nerol. According to gas chromatography analysis, the conversion rate of citral was 98.85%, and the total selectivity of nerol / geraniol was 99.10%.

Embodiment 2

[0024] Add 20g of rhodium nitrate and sodium triphenylphosphine sulfonate complex catalyst (mass ratio of rhodium nitrate to sodium triphenylphosphine sulfonate is 0.001:1), 1000g of water into a 2L autoclave with magnetic stirring and temperature controller Then add 100g of citral, replace it with nitrogen three times, then replace it with hydrogen three times, heat to 150°C, pressurize the hydrogen to 1.5MPa, stir at 1000rpm, react for 20 hours, take samples and analyze the conversion rate of citral is greater than 98%. Cool with water, press out the reaction solution, leave to stand for stratification, the water phase is the catalyst and can be applied to the next batch of reactions, and the organic phase is a mixture of geraniol and nerol. According to gas chromatography analysis, the conversion rate of citral was 98.68%, and the total selectivity of nerol / geraniol was 99.22%.

Embodiment 3

[0026] With 25g palladium chloride and three-(4-methoxy group-3-sodium sulfonate phenyl)phosphine complex catalyst (palladium chloride and tri-(4-methoxy group-3-sulfonate sodium phenyl)phosphine The mass ratio is 0.01:1), 800g of water was added into a 2L autoclave with magnetic stirring and a temperature controller, and then 200g of citral was added, replaced with nitrogen three times, and then replaced with hydrogen three times, heated to 30°C, and added with hydrogen Pressed to 1.4MPa, stirred at 800rpm, reacted for 12 hours, and the conversion rate of citral was greater than 98% by sampling analysis. Squeeze out the reaction liquid, let it stand for stratification, the water phase is the catalyst and can be applied to the next batch of reactions, and the organic phase is the mixture of geraniol and nerol. According to gas chromatography analysis, the conversion rate of citral was 98.23%, and the total selectivity of nerol / geraniol was 99.52%.

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Abstract

The invention relates to a method for selective hydrogenation synthesis of nerol and geraniol mixture by using citral in a water-organic two-phase system. High selectivity of unsaturated alcohol cannot be easily obtained by the traditional selective hydrogenation method of a plurality of citrals. The method is characterized by comprising the following steps of: taking water soluble complex formed by the VIII-group water soluble metal salt and water soluble ligand as a catalyst, wherein the mass ratio of the water soluble salt of the VIII-group metal to the water soluble ligand is (0.001-0.01):1; carrying out selective hydrogenation on the citral in the water-organic two-phase system, stewing and layering after reaction is ended; continuing to mechanically apply the water phase containing the catalyst to the next reaction, wherein the organic phase is mixture of nerol and geraniol. The method is simple in process, high in conversion ratio of reaction, and high in selectivity; the catalyst has high activity and stability, and can be mechanically applied for a plurality of times in cycle; the cost is reduced when pollution is reduced; the method is suitable for industrial production.

Description

technical field [0001] The invention relates to a method for selectively hydrogenating α,β-unsaturated aldehydes to synthesize unsaturated alcohols, in particular to a method for selectively hydrogenating citral to synthesize a mixture of nerol and geraniol in a water-organic two-phase system method. Background technique [0002] Citral is a typical α,β-unsaturated aldehyde, and its selective hydrogenation product is a mixture of geraniol and nerol. Geraniol and nerol have a mild sweet smell and a rose fragrance, and are widely used in the deployment of various floral flavors. They are raw materials for the manufacture of vanillyl alcohol, vanillin, citral, hydroxyvanillin, ionone and vitamin A. It is widely used in fragrance, medicine and other industries. [0003] [0004] The difficulty in preparing geraniol by hydrogenation of citral is that there are two C=C and one C=O double bonds in the citral molecule, and the middle C=C double bond and the terminal C=O have th...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C33/02C07C29/141
CPCY02P20/584
Inventor 马啸赵文乐郝小雷张玉中俞海东
Owner SHANDONG NHU PHARMA
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