阅读说明：本技术 一种酮、醛加氢还原制备醇类化合物的方法 (Method for preparing alcohol compound by hydrogenation reduction of ketone and aldehyde ) 是由 冯秀娟 陈雨 包明 于 2019-11-06 设计创作，主要内容包括：本发明属于医药和天然化合物化工中间体及相关化学技术领域,提供了一种酮、醛加氢还原制备醇类化合物的方法。本发明以酮、醛及其衍生物为原料、纳米多孔钯为催化剂、氢气为氢源,高效地加氢还原酮、醛化合物,其中氢气的压力为0.1～0.5MPa；酮、醛及其衍生物在溶剂中的摩尔浓度为0.01～2mmol/mL。所采用的催化剂孔骨架大小为1-50nm之间,酮、醛及其衍生物与所用催化剂摩尔比为1：0.01～1：0.5。本发明的有益效果是该产物产率高,反应条件非常温和,操作和后处理简单,催化剂重复性好,且多次使用催化效果没有明显降低,为其实现工业化提供可能。(The invention belongs to the technical field of chemical intermediates of medicines and natural compounds and related chemistry, and provides a method for preparing alcohol compounds by hydrogenation reduction of ketone and aldehyde. The method takes ketone, aldehyde and derivatives thereof as raw materials, nano porous palladium as a catalyst and hydrogen as a hydrogen source, and efficiently hydrogenates and reduces ketone and aldehyde compounds, wherein the pressure of the hydrogen is 0.1-0.5 MPa; the molar concentration of the ketone, the aldehyde and the derivative thereof in the solvent is 0.01-2 mmol/mL. The size of the adopted catalyst pore skeleton is 1-50nm, and the molar ratio of the ketone, the aldehyde and the derivatives thereof to the used catalyst is 1: 0.01-1: 0.5. the method has the advantages of high product yield, very mild reaction conditions, simple operation and post-treatment, good catalyst repeatability, no obvious reduction of the catalytic effect after multiple use, and possibility for realizing industrialization.)

1. A method for preparing alcohol compounds by hydrogenation reduction of ketones and aldehydes is characterized in that the ketones, the aldehydes and derivatives thereof are used as raw materials, nano porous palladium is used as a catalyst, hydrogen is used as a hydrogen source, and the ketones, the aldehydes and the derivatives thereof are efficiently hydrogenated and reduced in an organic solvent to generate alcohol, wherein the reaction route is as follows:

the reaction temperature is 30-80 ℃, and the reaction time is 12-36 h;

R¹one selected from hydrogen, alkyl, methoxy, halogen, hydroxyl and aryl;

R²one selected from hydrogen, alkyl and aryl;

the aperture of the catalyst is 1-50 nm;

the molar ratio of the ketone, aldehyde and derivatives thereof to the catalyst is 1: 0.01-1: 0.5;

the pressure of the hydrogen is 0.1-0.5 MPa;

the molar concentration of the ketone, the aldehyde and the derivatives thereof in the organic solvent is 0.01-2 mmol/mL.

2. The method for preparing alcohol compounds by hydrogenation reduction of ketones and aldehydes according to claim 1, wherein the organic solvent is one or a mixture of two or more of acetonitrile, methanol, triethylamine, tetrahydrofuran, toluene, ethanol, dichloromethane, 1, 4-dioxane, ethyl acetate, acetone, and N, N-dimethylformamide.

Technical Field

The invention belongs to the technical field of chemical intermediates of medicines and natural compounds and related chemistry, and relates to a method for preparing alcohol compounds by hydrogenation reduction of ketone and aldehyde.

Background

Alcohol is used as an important organic chemical raw material and an intermediate for synthesizing a plurality of fine chemicals, and has wide application in industries such as dyes, medicines, pesticides, surfactants, textile auxiliaries, chelating agents, high polymer materials and the like, so that the synthesis of alcohol compounds occupies a very important position. Due to its importance, people pay attention to the research on the synthesis of alcohol compounds, and the research focuses on changing the types of catalysts and hydrogen sources in the reaction process, so as to improve the performance of the synthesis of alcohol compounds.

Although there are many synthetic routes to produce alcohol, the reduction of carbonyl compounds is simple and convenient, and the raw materials are easily available, and because of the advantages, it is more realistic to develop a more green and economical reduction reaction of carbonyl compounds so as to synthesize alcohol compounds. The traditional method for preparing alcohol by reducing ketone and aldehyde is mainly divided into two main categories, one is homogeneous catalyst formed by combining Ru, Ir, Co and other transition metals with ligands, and the catalyst has higher activity but needs higher temperature and pressure (T)>80℃ and H₂>10bar), and the catalyst is expensive, etc。[ALOICE O,STEPHEN O,etal.Dal.Trans.,2014,1228-1237；HE L-P,CHEN T,et al.JOC.,2011,202-206](ii) a And secondly, the research on heterogeneous catalysts is more, such catalysts comprise Pd/C and the like, but the catalysts are difficult to separate and recover, cannot be reused, and have low yield due to over reduction, so that the industrial application is limited. [ SHLOMI E, ARKADI V, et. Adv. Synth. Catal.,2009, 1499-one 1504]. The nano porous palladium catalyst (PdNPore) is a novel nano catalyst, has a unique bicontinuous three-dimensional porous structure, has the pore canal diameter of about 1-50nm, large specific surface area and stable structure, is easy to prepare and recover, can be repeatedly used, and overcomes the defects of the traditional nano structure catalyst [ TANAKAS, KANEKO T, ASAO N, YAMAMOTO Y, CHEN M-W, ZHANG W, INOUE A.chem.Commun.2011, 47, 5985-; KANEKO T, TANAKA S, ASAO N, YAMAMOTO Y, et al, adv, Synth, Catal.,2011,353, 2927-.]。

Disclosure of Invention

The invention provides a method for preparing alcohol compounds by hydrogenation reduction of ketone and aldehyde, which has very mild reaction conditions, the highest yield can reach 99%, the used catalyst has the advantages of high activity, good stability and the like, and the catalytic activity of the catalyst is basically unchanged after repeated use.

The technical scheme of the invention is as follows:

a method for preparing alcohol compounds by hydrogenation reduction of ketones and aldehydes takes the ketones, the aldehydes and derivatives thereof as raw materials, nano porous palladium (PdNPore) as a catalyst, hydrogen as a hydrogen source, and the ketones, the aldehydes and the derivatives thereof are efficiently hydrogenated and reduced in an organic solvent to generate alcohol, wherein the reaction route is as follows:

the reaction temperature is 30-80 ℃, and the reaction time is 12-36 h;

R¹one selected from hydrogen, alkyl, methoxy, halogen, hydroxyl and aryl;

R²one selected from hydrogen, alkyl and aryl;

the aperture of the catalyst is 1-50 nm;

the molar ratio of the ketone, aldehyde and derivatives thereof to the catalyst is 1: 0.01-1: 0.5;

the pressure of the hydrogen is 0.1-0.5 MPa;

the molar concentration of the ketone, the aldehyde and the derivatives thereof in the organic solvent is 0.01-2 mmol/mL.

The organic solvent is one or more of acetonitrile, methanol, triethylamine, tetrahydrofuran, toluene, ethanol, dichloromethane, 1, 4-dioxane, ethyl acetate, acetone and N, N-dimethylformamide.

The separation method uses column chromatography, silica gel or alkaline alumina as stationary phase, and developing agent is polar and nonpolar mixed solvent such as ethyl acetate-petroleum ether, ethyl acetate-n-hexane, dichloromethane-petroleum ether, and methanol-petroleum ether.

The invention has the beneficial effects that: the reaction conditions are very mild, the product yield is high, the operation and the post-treatment are simple, the catalyst has good repeatability, the catalytic effect is not obviously reduced after repeated utilization, and the possibility is provided for realizing industrialization.

Drawings

FIG. 1 is a schematic representation of 1-phenylethyl alcohol in example 1¹H nuclear magnetic spectrum.

FIG. 2 is a schematic representation of 1-phenylethyl alcohol in example 1¹³C nuclear magnetic spectrum.

FIG. 3 is a scheme showing the preparation of 1- (4-methylphenyl) -1-ethanol in example 2¹H nuclear magnetic spectrum.

FIG. 4 is a schematic representation of 1- (4-methylphenyl) -1-ethanol in example 2¹³C nuclear magnetic spectrum.

FIG. 5 is a scheme showing the preparation of 1- (4-methoxyphenyl) ethanol in example 3¹H nuclear magnetic spectrum.

FIG. 6 is a scheme showing the preparation of 1- (4-methoxyphenyl) ethanol in example 3¹³C nuclear magnetic spectrum.

FIG. 7 is a scheme showing the preparation of 1- (4-hydroxyphenyl) ethanol in example 4¹H nuclear magnetic spectrum.

FIG. 8 is a scheme showing the preparation of 1- (4-hydroxyphenyl) ethanol in example 4¹³C nuclear magnetic spectrum.

FIG. 9 shows the preparation of benzhydrol in example 5¹H nucleusAnd (4) a magnetic spectrum.

FIG. 10 shows the preparation of benzhydrol in example 5¹³C nuclear magnetic spectrum.

FIG. 11 is a drawing showing the preparation of 3, 4-dimethylbenzhydrol in example 6¹H nuclear magnetic spectrum.

FIG. 12 is a drawing showing the preparation of 3, 4-dimethylbenzhydrol in example 6¹³C nuclear magnetic spectrum.

FIG. 13 is a scheme showing the preparation of 1- (2-naphthyl) ethanol in example 7¹H nuclear magnetic spectrum.

FIG. 14 is a scheme showing the preparation of 1- (2-naphthyl) ethanol in example 7¹³C nuclear magnetic spectrum.

FIG. 15 is a drawing showing the preparation of 1- (6-methoxy-2-naphthylmethyl) ethanol in example 8¹H nuclear magnetic spectrum.

FIG. 16 is a drawing showing the preparation of 1- (6-methoxy-2-naphthylmethyl) ethanol in example 8¹³C nuclear magnetic spectrum.

FIG. 17 is a scheme showing the preparation of 1- (3-trifluoromethylphenyl) ethanol in example 9¹H nuclear magnetic spectrum.

FIG. 18 is a scheme showing the preparation of 1- (3-trifluoromethylphenyl) ethanol in example 9¹³C nuclear magnetic spectrum.

FIG. 19 is of 9-hydroxyfluorene of example 10¹H nuclear magnetic spectrum.

FIG. 20 is a scheme showing the preparation of 9-hydroxyfluorene in example 10¹³C nuclear magnetic spectrum.

Detailed Description

The ketone and aldehyde hydrogenation reduction method has the advantages that the highest reaction yield reaches 99%, the selected catalyst has good catalytic reaction repeatability, the operation and the post-treatment are simple, the catalytic effect is not obviously reduced after repeated utilization, and favorable conditions are provided for industrial production of the ketone and aldehyde hydrogenation reduction method.

The invention will be further illustrated with reference to the following specific examples. The simple replacement or improvement of the present invention by those skilled in the art is within the technical scheme of the present invention.