CN112250561B - Preparation method of 3-chlorotetrapentanoic acid - Google Patents

Preparation method of 3-chlorotetrapentanoic acid Download PDF

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CN112250561B
CN112250561B CN202011174714.6A CN202011174714A CN112250561B CN 112250561 B CN112250561 B CN 112250561B CN 202011174714 A CN202011174714 A CN 202011174714A CN 112250561 B CN112250561 B CN 112250561B
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acid
carbon monoxide
methylpropene
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CN112250561A (en
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米鹏
朱军伟
陈琦
张烨
魏凤
邢文国
冯维春
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Shandong Xingqiang Chemical Industry Technology Research Institute Co ltd
Qingdao University of Science and Technology
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Qingdao University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
    • C07C51/14—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on a carbon-to-carbon unsaturated bond in organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
    • C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
    • C07C51/445—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation by steam distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

The invention relates to a preparation method of 3-chlorotetrapentanoic acid, in particular to a method for preparing 3-chlorotetrapentanoic acid by taking 3-chloro-2-methylpropene and carbon monoxide as raw materials. The method takes 3-chloro-2-methyl propylene and carbon monoxide as raw materials, the raw materials are subjected to copolymerization reaction in the presence of a hydrated strong acid catalyst to obtain the 3-chloro-pivalic acid refined product with the purity of more than 99 percent, and the method is high in conversion rate, high in yield, less in by-product, simple in product post-treatment and in line with the concept of green economic cycle.

Description

Preparation method of 3-chlorotetrapentanoic acid
Technical Field
The invention relates to a preparation method of 3-chlorotetrapentanoic acid, in particular to a method for preparing 3-chlorotetrapentanoic acid by taking 3-chloro-2-methylpropene and carbon monoxide as raw materials.
Technical Field
The herbicide clomazone is a novel high-efficiency pesticide in China, and has the advantages of wide weed control spectrum, good weeding effect, long application time, good mixability, safety to environment and the like. At present, the application of the composite material is more and more extensive.
The 3-chloro-pivalic acid is used as an intermediate of herbicide clomazone, the preparation of the intermediate is particularly critical, most of the currently reported synthetic processes of the 3-chloro-pivalic acid are chlorine chlorination processes, the preparation method is that pivalic acid is chlorinated by chlorine at a certain temperature, but the traditional process relates to chlorine chlorination reaction, the conversion rate of the chlorination reaction is relatively low, and the quality of the product is low because of more side reaction impurities, the refining is difficult and the quality of the product is low, thereby influencing the quality of the final clomazone product.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method for producing 3-chloro-pivalic acid, the technological process of the invention has high conversion rate and yield, the occurrence of side reaction is greatly reduced, the product is easy to refine, and the final product quality is greatly improved.
The invention takes 3-chloro-2-methyl propylene and carbon monoxide as raw materials and is prepared by copolymerization reaction in the presence of a hydrated strong acid catalyst. The specific reaction route is as follows:
Figure BDA0002748378060000011
the hydrated strong acid catalyst is BF3·(H2O)xOr H2SO4·(H2O)xOr H3PO4·(H2O)xOr mixtures thereof. The using amount of the hydrated strong acid catalyst is 3-5% of the molar weight of 3-chloro-2-methylpropene.
BF3·(H2O)xSelecting BF3·(H2O)2；H2SO4·(H2O)xChoose H2SO4·H2O or H2SO4·(H2O)2Or H2SO4·(H2O)4；H3PO4·(H2O)xPhosphoric acid hemihydrate is selected.
3-chloro-2-methylpropene: carbon monoxide is 1:1.5 to 2.0.
The copolymerization reaction pressure is maintained at 10 to 100MPa, and further, the reaction pressure is preferably 30 to 60 MPa.
The copolymerization reaction temperature is 120-150 ℃, and preferably 130-135 ℃.
The copolymerization reaction time is 3-5 hours.
After the copolymerization reaction is finished, cooling to 75-80 ℃ to obtain a 3-chlorotetradecanoic acid reaction liquid, and then carrying out steam distillation and ether extraction on the obtained 3-chlorotetradecanoic acid reaction liquid to obtain a refined 3-chlorotetradecanoic acid product with the content of about 98%.
The more specific operation is as follows:
adding a hydrated strong acid catalyst into a reactor, injecting a carbon monoxide gas source, heating to 120-150 ℃ under the high pressure of 10-100 MPa, adding 3-chloro-2-methylpropene, carrying out vaporization copolymerization reaction on the 3-chloro-2-methylpropene and the carbon monoxide gas in a reaction kettle, carrying out heat preservation reaction for 3-5 hours to obtain a 3-chlorotetradecanoic acid reaction liquid, stopping the carbon monoxide gas source after the reaction is finished, and cooling to 75-80 ℃ to obtain the 3-chlorotetradecanoic acid reaction liquid. And distilling the 3-chlorotetrapentanoic acid reaction liquid by using steam, and extracting and refining by using diethyl ether to obtain the 3-chlorotetrapentanoic acid with the content of about 98%.
Compared with the prior art, the method has the advantages of high conversion rate, high yield, less byproducts and simple product post-treatment, and accords with the concept of green economic cycle.
The specific implementation mode is as follows:
in order to better understand the technical scheme of the present invention, the following detailed description of the present invention is provided by way of examples, but the present invention should not be construed as limited to the above description.
The percentages mentioned in the following examples are given by mass.
Example 1
A preparation method of 3-chloro pivalic acid comprises the following specific steps:
adding a hydrated strong acid catalyst into a reactor, injecting a carbon monoxide gas source, heating to 150 ℃ under the high pressure of 100MPa, adding 90.5g of 3-chloro-2-methyl propylene in batches, carrying out vaporization copolymerization reaction on the 3-chloro-2-methyl propylene and the carbon monoxide gas in the reaction kettle, keeping the temperature for 5 hours to obtain a 3-chlorotetraacetic acid reaction solution, stopping the carbon monoxide gas source after the reaction is finished, and cooling to 80 ℃. Distilling the reaction liquid of the 3-chloro pivalic acid by steam, extracting and refining 150g of diethyl ether to obtain 133.9g of 3-chloro pivalic acid with the content of about 99.5 percent;
the hydrated strong acid catalyst is BF3·(H2O)2The using amount is 5 percent of the mol amount of the 3-chloro-2-methyl propylene;
3-chloro-2-methylpropene: carbon monoxide 1: 1.5.
Example 2
A preparation method of 3-chloro pivalic acid comprises the following specific steps:
adding a quantitative hydrated strong acid catalyst into a reactor, injecting a carbon monoxide gas source, heating to 150 ℃ under the high pressure of 100MPa, adding 90.5g of 3-chloro-2-methylpropene in batches, carrying out vaporization copolymerization reaction on the 2-methylpropene and the carbon monoxide gas in the reactor, keeping the temperature for 5 hours to obtain a 3-chlorotetraacetic acid reaction solution, stopping the carbon monoxide gas source after the reaction is finished, and cooling to 80 ℃. The reaction solution of 3-chlorotetradecanoic acid was distilled with steam, and 150g of diethyl ether was extracted and purified to obtain 135.7g of 3-chlorotetradecanoic acid having a content of about 99.2%.
The hydrated strong acid catalyst is phosphoric acid hemihydrate, and the using amount of the hydrated strong acid catalyst is 3 percent of the molar weight of 3-chloro-2-methyl propylene;
3-chloro-2-methylpropene: carbon monoxide 1: 2.0.
Example 3
A preparation method of 3-chloro pivalic acid comprises the following specific steps:
adding a quantitative hydrated strong acid catalyst into a reactor, injecting a carbon monoxide gas source, heating to 150 ℃ under the high pressure of 10MPa, adding 90.5g of 3-chloro-2-methyl propylene in batches, carrying out vaporization copolymerization reaction on the 2-methyl propylene and the carbon monoxide gas in the reactor, keeping the temperature for 5 hours to obtain a 3-chloro-pivalic acid reaction solution, stopping the carbon monoxide gas source after the reaction is finished, and cooling to 75 ℃. The 3-chlorotetradecanoic acid reaction solution was subjected to steam distillation and 150g of diethyl ether was extracted and purified to obtain 102.8g of 3-chlorotetradecanoic acid having a content of about 99.2%.
The hydrated strong acid catalyst is BF3·(H2O)2The using amount is 5 percent of the mol amount of the 3-chloro-2-methyl propylene;
3-chloro-2-methylpropene: carbon monoxide 1: 1.5.
Example 4
A preparation method of 3-chloro pivalic acid comprises the following specific steps:
adding a quantitative hydrated strong acid catalyst into a reactor, injecting a carbon monoxide gas source, heating to 135 ℃ under the high pressure of 10MPa, adding 90.5g of 3-chloro-2-methylpropene in batches, carrying out vaporization copolymerization reaction on the 2-methylpropene and the carbon monoxide gas in the reactor, keeping the temperature for 3 hours to obtain a 3-chlorotetraacetic acid reaction solution, stopping the carbon monoxide gas source after the reaction is finished, and cooling to 80 ℃. The 3-chlorotetradecanoic acid reaction solution was subjected to steam distillation and extracted and purified with 100g of diethyl ether to give 116.4g of 3-chlorotetradecanoic acid having a content of about 99.3%.
The hydrated strong acid catalyst is phosphoric acid hemihydrate, and the using amount of the hydrated strong acid catalyst is 3 percent of the molar weight of 3-chloro-2-methyl propylene;
3-chloro-2-methylpropene: carbon monoxide 1: 2.0.
Example 5
A preparation method of 3-chloro pivalic acid comprises the following specific steps:
adding a quantitative hydrated strong acid catalyst into a reactor, injecting a carbon monoxide gas source, heating to 120 ℃ under the high pressure of 50MPa, adding 90.5g of 3-chloro-2-methylpropene in batches, carrying out vaporization copolymerization reaction on the 2-methylpropene and the carbon monoxide gas in the reactor, keeping the temperature for 5 hours to obtain a 3-chlorotetraacetic acid reaction solution, stopping the carbon monoxide gas source after the reaction is finished, and cooling to 80 ℃. The 3-chlorotetradecanoic acid reaction solution was subjected to steam distillation and extracted and purified with 100g of diethyl ether to give 126.5g of 3-chlorotetradecanoic acid having a content of about 99.2%.
The hydrated strong acid catalyst is H2SO4·H2O, the using amount is 4 percent of the mol amount of the 3-chloro-2-methyl propylene;
3-chloro-2-methylpropene: carbon monoxide 1: 2.0.
Example 6
A preparation method of 3-chloro pivalic acid comprises the following specific steps:
adding a quantitative hydrated strong acid catalyst into a reactor, injecting a carbon monoxide gas source, heating to 130 ℃ under the high pressure of 30MPa, adding 90.5g of 3-chloro-2-methylpropene in batches, carrying out vaporization copolymerization reaction on the 2-methylpropene and the carbon monoxide gas in the reactor, keeping the temperature for 4 hours to obtain a 3-chlorotetraacetic acid reaction solution, stopping the carbon monoxide gas source after the reaction is finished, and cooling to 75 ℃. The 3-chlorotetrapentanoic acid reaction solution was subjected to steam distillation and extracted and purified with 100g of diethyl ether to obtain 122.7g of 3-chlorotetrapentanoic acid having a content of about 99.5%.
The hydrated strong acid catalyst is H2SO4·(H2O)2The using amount is 3 percent of the mol amount of the 3-chloro-2-methyl propylene;
3-chloro-2-methylpropene: carbon monoxide 1: 1.8.
Example 7
A preparation method of 3-chloro pivalic acid comprises the following specific steps:
adding a quantitative hydrated strong acid catalyst into a reactor, injecting a carbon monoxide gas source, heating to 150 ℃ under the high pressure of 80MPa, adding 90.5g of 3-chloro-2-methylpropene in batches, carrying out vaporization copolymerization reaction on the 2-methylpropene and the carbon monoxide gas in the reactor, keeping the temperature for 3 hours to obtain a 3-chlorotetraacetic acid reaction solution, stopping the carbon monoxide gas source after the reaction is finished, and cooling to 80 ℃. The 3-chlorotetradecanoic acid reaction solution was subjected to steam distillation and extracted and purified with 100g of diethyl ether to give 132.5g of 3-chlorotetradecanoic acid having a content of about 99.3%.
The hydrated strong acid catalyst is H2SO4·(H2O)4The using amount is 5 percent of the mol amount of the 3-chloro-2-methyl propylene;
3-chloro-2-methylpropene: carbon monoxide 1: 2.0.

Claims (3)

1. A preparation method of 3-chloro pivalic acid is characterized in that 3-chloro-2-methyl propylene and carbon monoxide are used as raw materials, and the raw materials are subjected to copolymerization reaction in the presence of a hydrated strong acid catalyst to obtain the 3-chloro pivalic acid;
the hydrated strong acid catalyst is BF3·(H2O)xOr H2SO4·(H2O)xOr H3PO4·(H2O)xOr mixtures thereof;
the using amount of the hydrated strong acid catalyst is 3-5% of the molar weight of 3-chloro-2-methylpropene;
after the copolymerization reaction is finished, cooling to 75-80 ℃, distilling with water vapor, and extracting with diethyl ether to obtain a refined product of 3-chlorotetradecanoic acid;
the copolymerization reaction pressure is maintained at 10-100 MPa;
the method is characterized in that the copolymerization reaction temperature is 120-150 ℃.
2. The method according to claim 1, wherein the copolymerization reaction time is 3 to 5 hours.
3. The method according to claim 1, wherein the ratio of 3-chloro-2-methylpropene: carbon monoxide is 1:1.5 to 2.0.
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