CN1100611C - Catalyst for olefine cyclopropaning reaction - Google Patents

Abstract

A catalyst for the cyclopropanation reaction of 1,1-dichloro-4-methyl-1,3-pentadiene and methyl diazoacetate, containing copper oxide as an active component, adding manganese oxide, cobalt oxide or One or several kinds of iron oxides form a multi-metal oxide catalyst, and the weight ratio of each oxide in the catalyst is copper: manganese: iron: cobalt = 1-50:0-2:0-2:0-2. The catalyst has high catalytic activity for the above reaction, the yield of the product methyl permethrin can reach more than 67%, and the catalyst has a long service life and has industrial application value.

Description

Catalyst for olefin cyclopropanation reaction

technical field

The present invention relates to a catalyst, in particular to provide a catalyst for the cyclopropanation of 1,1-dichloro-4-methyl-1,3-pentadiene and methyl diazoacetate to prepare permethrin Catalysts for methyl esters and the catalytic reaction.

Background technique

Cyclopropanation of 1,1-dichloro-4-methyl-1,3-pentadiene with methyl diazoacetate is an important method for the synthesis of the pesticide intermediate methyl permethrin. Its related technology, as reported in Japanese Patent Laid-Open No. 51-19747, uses copper oxide as a catalyst to make 1,1-dichloro-4-methyl-1,3-pentadiene and ethyl diazoacetate cyclopropane Ethyl permethrin was prepared by chemical reaction, and the chemical yield was 35% based on ethyl diazoacetate under homogeneous reaction conditions. For another example, in the above-mentioned reaction reported by British Patent GB 1,533,381, copper sulfate is used as a catalyst to prepare permethrin ethyl ester, and the chemical yield of permethrin ethyl ester calculated with glycine ethyl ester hydrochloride is 40～50% after the reaction. %. The main problem of the known technology is the low activity of the catalyst and thus the low yield of the product.

Contents of the invention

The purpose of this invention is to provide a kind of catalyzer for the cyclopropanation reaction of 1,1-dichloro-4-methyl-1,3-pentadiene and methyl diazoacetate, because this catalyzer has very high to above-mentioned reaction High catalytic activity, so that the yield of the product methyl permethrin can reach more than 67%.

The catalyst for olefin cyclopropanation of the present invention refers to a catalyst containing copper oxide as an active group for the cyclopropanation of 1,1-dichloro-4-methyl-1,3-pentadiene and methyl diazoacetate. The catalyst of part is characterized in that adding one or more metal oxide catalysts of multiple components in manganese oxide, cobalt oxide or iron oxide, and the weight ratio of each oxide in the catalyst is copper: manganese: iron: cobalt= 1～50: 0～2: 0～2: 0～2, but manganese, iron or cobalt are not zero at the same time.

When the catalyst is a two-component metal oxide catalyst composed of copper and manganese, iron or cobalt, its preferred weight ratio of each oxide is copper: manganese (or iron or cobalt)=1～10 : 1~2.

When the catalyst is a three-component metal oxide catalyst composed of two kinds of copper and manganese, iron or cobalt, its preferred weight ratio of each oxide is copper=1～10, manganese, iron or cobalt Each of the two kinds is selected in a ratio of 1 to 2 parts by weight.

When the catalyst is a four-component metal oxide catalyst composed of copper, manganese, iron and cobalt, the preferred weight ratio of each oxide is 1～10:1～2:1～2:1～ 2.

The preparation method of the catalyst of the present invention can be carried out with reference to known techniques, for example, various metal oxides are mixed or co-mixed and pulverized by a mechanical mixing method to obtain a micropowder with a particle size less than 150 μm; In the soluble salt solution of Fe, two or more kinds of solutions are added with alkali to make hydroxides containing the above metal elements, and then dried and roasted to obtain co-precipitated oxides.

Detailed ways

The technology of the present invention will be further described below by way of examples.

The preparation of embodiment 1 catalyst I

Mix two or more powders of copper oxide, cobalt oxide, manganese trioxide or iron oxide (oxide particle size < 150 μm) in proportion, and then pass through a 100-mesh sieve to prepare the catalyst. Alternatively, after mixing the above-mentioned oxide powders, continue pulverizing to make the average particle size less than 150 μm, and then pass through a 100-mesh sieve to obtain a catalyst. The preparation method I is to obtain the catalyst by means of mechanical mixing, and the weight ratio of the prepared catalyst components (calculated as oxides) is listed in Table 1.

The preparation II of embodiment 2 catalyst

Mix two or more nitrates of copper, cobalt, manganese or iron in proportion, add 10% NaOH until the pH is 10, stir well, filter, wash with water until neutral, dry at 80-100°C for 1 hour, and then Calcined at 500°C for 4 hours to decompose it into oxides, the catalyst of the present invention can be obtained. The preparation method II is to obtain the catalyst by the co-precipitation method, and the weight ratio of the prepared catalyst components (calculated as oxides) is listed in Table 1.

The performance of embodiment 3 catalyst

In a 100ml three-necked flask, add 0.20g of the catalyst prepared by Preparation Method I or II, then add 20ml of 1,1-dichloro-4-methyl-1,3-pentadiene, and raise the temperature to 146 ℃, dropwise add 11.4g (weight concentration: 14.6%) of dichloroethane solution of methyl diazoacetate, dropwise in 1 hour, continue to stir for 1 hour and cool down to room temperature, filter, and separate the catalyst for reuse. After the filtrate was weighed, the content of methyl permethrin was determined by gas chromatography internal standard method, and the yield was calculated based on the amount of methyl diazoacetate. The above reactions were repeated with different catalysts, and the yield results of the products are listed in Table 1.

Comparative example 1

Get copper oxide differential, cross 100 mesh sieves to obtain catalyst, carry out the evaluation of catalytic performance by the method described in above-mentioned embodiment 3, its result is also listed in table 1 with.

The performance of embodiment 4 catalyst

The composition of utilization is the catalyst of Cu: Co: Fe=4: 1: 2, reacts by the method described in embodiment 3, adds in the there-necked flask again after the catalyst separation after reaction, repeats the reaction of embodiment 3, through 5 For each reaction, the activity of the catalyst hardly changes, and the specific results are listed in Table 2.

Table 1 Catalyst performance Catalyst preparation method Catalyst composition The yield of permethrin methyl ester

(The weight meter with the oxide of the element) ( %) ( %) I CU: Fe = 1: 1 56.7i CU: Fe = 10: 1 52.1II CU: Fe = 3: 1 57.2II CU: Mn = 2: 1 59.1II CU : CO = 4: 1 59.3i CU: CO: FE = 4: 1: 2 67.5i CO: F: FE = 2: 1 63.5II CO: F: 1: 1: 2 65.3II CU: CU: CU: CU : FE = 8: 2: 1 64.5I CO: Mn = 8: 1: 2 57.3i CO: Mn = 2: 1: 1 58.2II CU: Mn = 4: 1: 1 60.3II CU : FE: Mn = 2: 1: 1 59.2II CU: FE: Mn = 8: 1: 2 61.2II CU: Mn: CO = 4: 1: 1: 1 62.1i Cu 36.0

Table 2 Catalyst performance experiment 1 2 3 4 5 Permethrin methyl yield (%) 67.5 66.8 67.6 67.1 67.2

Can see by the result of above-mentioned embodiment and comparative example, the catalyst that the present invention prepares contains multiple metal oxide Methyl ester is subjected to cyclopropanation reaction, the reaction is easy to operate, the conditions are mild, the life of the catalyst is long and the yield of the product methyl permethrin is high. Therefore, the catalyst of the present invention has industrial application value.

Claims (4)

1. A catalyst for olefin cyclopropanation, namely 1,1-dichloro-4-methyl-1,3-pentadiene and methyl diazoacetate used for the cyclopropanation reaction containing copper oxide as The catalyst of the active component is characterized in that one or more metal oxide catalysts composed of multiple components are added in manganese oxide, cobalt oxide or iron oxide, and the weight ratio of each oxide in the catalyst is copper: manganese: iron: Cobalt=1～50:0～2:0～2:0～2, but manganese, iron or cobalt are not zero at the same time. 2. according to the described catalyzer of claim 1, it is characterized in that being the two-component metal oxide catalyst of a kind of composition in copper and manganese, iron or cobalt, the weight ratio of each oxide is copper: manganese (or iron or cobalt)=1～10:1～2. 3. according to the described catalyzer of claim 1, it is characterized in that being the three-component metal oxide catalyst that is made up of two kinds in copper and manganese, iron or cobalt, and the weight ratio that each oxide share is copper=1～ 10. Two kinds of manganese, iron or cobalt are selected in a weight ratio of 1 to 2 each. 4. according to the described catalyst of claim 1, it is characterized in that being the four-component metal oxide catalyst that is made up of copper, manganese, iron and cobalt, and the weight ratio that every kind of oxide accounts for is 1～10: 1～2 : 1～2: 1～2.