CN101214438B

CN101214438B - Aldol condensation catalyst and use thereof

Info

Publication number: CN101214438B
Application number: CN200710300079XA
Authority: CN
Inventors: 胡建立; 冉云根; 贾洪亮; 赵青松; 朱岭军
Original assignee: Zhengzhou University; Henan Tianguan Group Co Ltd
Current assignee: Zhengzhou University; Henan Tianguan Group Co Ltd
Priority date: 2007-12-27
Filing date: 2007-12-27
Publication date: 2010-10-13
Anticipated expiration: 2027-12-27
Also published as: CN101214438A

Abstract

The invention discloses an aldol condensation catalyst and application thereof in synthetization of 4-phenyl-3- butane-2-ketone. The invention is prepared by the weight percent of the following raw materials: 5-15: CaO percent, 3-5: MgO percent, 1-2: La2O3 percent, 0.01 to 0.02: Pt percent, 0.01 to 0.02: Pd percent, and the rest is Al2O3 percent. The aldol condensation catalyst has simple formula, is easy to be prepared and convenient in use, has good catalyst performance; in particular in aldol condensation preparation of the 4-phenyl-3- butane-2-ketone, the yield of the invention can reach above 95 percent, and the post-processing is simple; in addition, the invention has moderate response time, simple process, low production cost and is good for mass production.

Description

Aldol condensation catalyst and application thereof

Technical field:

The present invention relates to catalyst and the application thereof of organic compound intermediate in synthetic, relate in particular to aldol condensation catalyst and the application in 4-phenyl-3-butene-2-ketone is synthetic.

Background technology:

BENZYLIDENE ACETONE is an organic compound of having many uses, and can be used as the raw material of synthetic perfume, the brightener in the electroplating industry, goes back the stabilizing agent in the useful as pesticides; Document " spices and application thereof " Fan Chengyou. Beijing: Chemical Industry Press, 1990,181 and document " synthetic flavor handbook " Jinan City's light industry research institute write. all there is argumentation in China Light Industry Press to this, in addition at " phase transfer catalysis process synthesis of benzylidene acetone " Cheng Jiahao [J]. petroleum technology and application, 1992, (2): also introduced it in 89-92 one literary composition and had strong sweet pea type fragrance, be used to allocate sweet pea series essence and fruital flavoring essence, also be used for essence such as flores aurantii and hyacinth.According to document " Experiment of Organic Chemistry " Fang Zhenfa, Nanjing: publishing house of Nanjing University, introduce among the 1992:194: the synthetic of it mainly is the Claisen condensation of adopting benzaldehyde and acetone, and the BENZYLIDENE ACETONE yield only is about 70%.In recent years, the synthesis catalytic method of 4-phenyl-3-butene-2-ketone mainly contained two kinds: (1) phase transfer catalysis process and load-type solid catalysis method.Though the productive rate of phase transfer catalysis process is higher, phase transfer catalyst costs an arm and a leg, for example, triethyl benzyl ammonia chloride, crown ether-like etc., production cost is very high, is difficult for suitability for industrialized production; (2) the load type solid body base catalyst preparation process is loaded down with trivial details, for example, the preparation of alkaline gama-alumina etc., the post processing trouble, productive rate is lower, also is unsuitable for large-scale production.

Summary of the invention:

In order to improve the production efficiency of aldol condensation, simplify synthesis technique, the objective of the invention is to seek a kind of easy to use, preparation is simple, the aldol condensation catalyst that catalytic efficiency is high.

Another object of the present invention provides a kind of aldol condensation catalyst and produces Jie of 4-phenyl-3-butene-2-ketone.

The specific embodiment:

The invention will be further described below in conjunction with embodiment:

Embodiment one:

Choose the Al that diameter is 0.6mm ₂O ₃Particle is a carrier, with 5%CaO, 4%MgO, the 1%La of powdery ₂O ₃, 0.01%Pt, 0.02%Pd, surplus be Al ₂O ₃, after stirring, add 5% carboxymethylcellulose sodium solution and make adhesive, stir and to make homogeneous granules, oven dry, 200 ℃ of activation 2 hours, be cooled to room temperature naturally after, be put in the drier standby.Common consumption 0.5%.Be called for short: the ZD composite catalyst.

Embodiment two:

Choose the Al that diameter is 0.8mm ₂O ₃Particle is a carrier, with 10%CaO, 3%MgO, the 1.5%La of powdery ₂O ₃, 0.015%Pt, 0.01%Pd, surplus be Al ₂O ₃, after stirring, add an amount of carboxymethylcellulose sodium solution and make adhesive, stir and to make homogeneous granules, oven dry, 300 ℃ of activation 1.5 hours, be cooled to room temperature naturally after, be put in the drier standby.Common consumption 0.5%.Be called for short: the ZD composite catalyst.

Embodiment three:

Choose the Al that diameter is 1mm ₂O ₃Particle is a carrier, with 15%CaO, 5%MgO, the 2%La of powdery ₂O ₃, 0.02%Pt, 0.015%Pd, surplus be Al ₂O ₃, after stirring, add an amount of carboxymethylcellulose sodium solution and make adhesive, stir and to make homogeneous granules, oven dry, 200-300 ℃ of activation 2 hours, be cooled to room temperature naturally after, be put in the drier standby.Common consumption 0.5%.Be called for short: the ZD composite catalyst.

Utilize the Catalyst Production 4-phenyl-3-butene-2-ketone of above-mentioned preparation:

In being housed, the 50ml round-bottomed flask of return duct adds the 100ml benzaldehyde successively, 90ml acetone and 1gZD composite catalyst, and 80 ℃ of water-bath heating, magnetic agitation 6h filters then and obtains light yellow liquid, and decompression is steamed and is produced.

The specific embodiment:

The invention will be further described below in conjunction with embodiment:

Embodiment one:

Embodiment two:

Embodiment three:

In being housed, the 50ml round-bottomed flask of return duct adds the 100ml benzaldehyde successively, 90ml acetone and 1gZD composite catalyst, 80 ℃ of water-bath heating, magnetic agitation 6h filters then and obtains light yellow liquid, and low-boiling point material is removed in decompression distillation, get thick product 139g, productive rate 95%.Use acetone recrystallization, get light yellow acicular crystal, fusing point is 41-42 ℃, 42 ℃ of literature values.

The sign of gained 4-phenyl-3-butene-2-ketone:

Fusing point: 41-42 ℃;

MS(m/Z)：146.19(M ⁺)、169.19(M ⁺+23)；

IR(KBr，cm ^-1)：3000(C-H)，1670(C＝O)，1610(C＝C)，960(C-H)；

¹³CNMR(δ，ppm)：27.4(-CH ₃)，127.2(C＝C)，143.1(-C＝)，197.6(C＝O).

Reaction equation is as follows:

The synthesis technique step of described 4-phenyl-3-butene-2-ketone is:

The first step, in being housed, the round-bottomed flask of return duct adds the benzaldehyde newly distill out successively, acetone and ZD composite catalyst, and water-bath slowly is heated to 80 ℃, and magnetic agitation refluxed 6 hours.

After second step, reaction finish, reactant mixture is reduced to room temperature, vacuum filtration gets pale yellow solution.

The 3rd goes on foot, the gained pale yellow solution is added in the flask, and low-boiling point material is removed in decompression distillation, obtains the light yellow solid product, and yield reaches 95%.

The 4th step, will obtain light yellow solid product acetone recrystallization, must light yellow acicular crystals.

The selection of optimum reaction condition:

By orthogonal table L ₁₆(4 ⁵) experiment and the processing of quadrature experimental data obtained influencing the data area of reaction yield principal element, and investigated of the influence of factors such as reactant ratio, reaction temperature and reaction time to productive rate, obtained optimum reaction condition.

Table 1 orthogonal experiment data

As can be seen, the size order of influence factor is the reaction time from orthogonal table, the ratio of temperature and reactant, and their data area.

Reaction temperature is to the influence of reaction yield

Other condition is constant, experimentizes under different temperatures, and the experimental result of gained is as shown in table 2.

Experimental result under the table 2 differential responses temperature

As shown in Table 2, along with the rising productive rate of temperature increases gradually, but when temperature reached more than 80 ℃, productive rate obviously descended.Mainly be the rising along with temperature, reaction rate increases, so productive rate increases; Yet, when temperature is increased to after 80 ℃, because reflux ratio increases, cause the amounts of acetone deficiency in the reaction system on the one hand, thereby generate dibenzalacetone; Temperature raises on the other hand, and the condensation reaction rate between the acetone strengthens, and influences the generation of BENZYLIDENE ACETONE, so productive rate reduces.

Reaction time is to the influence of reaction yield

Other condition is constant.Experimentize in different time sections, the experimental result of gained is as shown in table 3.

Experimental result in table 3 different time

As can be seen from Table 3, along with the prolongation in reaction time, productive rate increases gradually, and after 6h, though productive rate increases to some extent, but what increase is not clearly, is 6h so choose the reaction time.

Reactant ratio is to the influence of reaction yield

Constant at other reaction conditions, only change under the situation of reactant ratio, the experimental result that obtains is as shown in table 4.

Experimental result (benzaldehyde: acetone) during table 4 reactant different proportion

Table 4 shows, along with the increase productive rate of reactant ratio reduces gradually, this mainly is because the increase of amounts of acetone causes the amount of two acetone alkene to increase, and influences the raising of productive rate.

Optimum process condition by the synthetic 4-phenyl-3-butene-2-ketone of orthogonal experiment gained is:

Synthesize 4-phenyl-3-butene-2-ketone by aldol reaction, (1) selecting the ZD composite catalyst is catalyst, (2) n (benzaldehyde): n (acetone): n (catalyst)=1: 1.2: 0.001-0.005, and (3) reaction time is 6h, (4) reaction temperature is 80 ℃, and productive rate is up to 95%.

Claims

1. aldol condensation catalyst, it is the percentage by weight preparation by following raw material:

5-15％ CaO

3-5％ MgO

1-2％ La ₂O ₃

0.01-0.02％ Pt

0.01-0.02％ Pd

Surplus is Al ₂O ₃

After getting each raw material by the percentage of above-mentioned raw materials weight, stir, add an amount of carboxymethylcellulose sodium solution and make adhesive, homogeneous granules is made in stirring, and oven dry was 200-300 ℃ of activation 2 hours, naturally after being cooled to room temperature, be put in the drier standby.

2. the application of aldol condensation catalyst as claimed in claim 1 in organic synthesis 4-phenyl-3-butene-2-ketone is synthetic.