Synthesis method of alpha,gamma,gamma,gamma-tetrachlorobutyrate

A technology of tetrachlorobutyrate and synthesis method, which is applied in the field of synthesis of -α,γ,γ,γ-tetrachlorobutyrate, and can solve problems such as complex preparation methods, complex components of reaction by-products, and difficult post-processing

Inactive Publication Date: 2021-03-30
HUNAN NORMAL UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the yield of synthesizing α, γ, γ, γ-methyl tetrachlorobutyrate with methyl acrylate as the basic raw material is only 47%; the synthesis of α-methyl-α, γ , The yield of γ, γ-tetrachlorobutyric acid methyl ester is only 66%, and the preparation method of the catalyst tris (2-pyridylmethyl

Method used

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  • Synthesis method of alpha,gamma,gamma,gamma-tetrachlorobutyrate
  • Synthesis method of alpha,gamma,gamma,gamma-tetrachlorobutyrate
  • Synthesis method of alpha,gamma,gamma,gamma-tetrachlorobutyrate

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0054] 13.0g (84.5mmol) carbon tetrachloride and 6.54g (76.0mmol) methyl acrylate, with 0.13g (0.76mmol) CuCl 2 • 2H 2 O main catalyst, 0.088g (0.76mmol) N,N,N',N'-tetramethylethylenediamine cocatalyst and 10mL of acetonitrile were placed in a stainless steel reactor with a polytetrafluoroethylene liner and stirred at room temperature After mixing for 20 minutes, close the reaction kettle, raise the temperature to 110°C, carry out the addition reaction for 12 hours, then cool to room temperature, filter, and distill the filtrate at 70°C for 2 hours under normal pressure to recover carbon tetrachloride. Under reduced pressure, rectify under reduced pressure for 2 hours to obtain 14.87 g of α, γ, γ, γ-tetrachlorobutyric acid methyl ester.

[0055] Through GC analysis, the purity of α, γ, γ, γ-methyl tetrachlorobutyrate obtained in the examples of the present invention is 95.6%, and the single-pass reaction yield calculated with methyl acrylate as the reference raw material is: ...

Embodiment 2

[0059] 23.4g (152.1mmol) of carbon tetrachloride and 6.54g (76.0mmol) of methyl acrylate were mixed with 0.95g (3.8mmol) of CuSO 4 • 5H 2 O main catalyst, 0.93g (15.2mmol) ethanolamine co-catalyst and 100mL propionitrile were placed in a stainless steel reaction kettle with a polytetrafluoroethylene liner, first stirred at room temperature for 40min after mixing, the reaction kettle was sealed, and the temperature was raised to 100°C. Addition reaction for 10 hours, then cooled to room temperature, filtered, the filtrate was distilled at 80°C for 2 hours at atmospheric pressure to recover carbon tetrachloride, and then rectified under reduced pressure at 90°C and 15kPa for 3 hours to obtain α, γ, γ , 15.49 g of methyl γ-tetrachlorobutyrate.

[0060]Through GC analysis, the purity of α, γ, γ, γ-methyl tetrachlorobutyrate obtained in the examples of the present invention is 96.5%, and the single-pass reaction yield calculated with methyl acrylate as the reference raw material i...

Embodiment 3

[0063] 2.59g (15.20mmol) CuCl 2 • 2H 2 O main catalyst and 2.50g (30.40mmol) N-methylimidazole cocatalyst in 100mL of methanol, at 70°C, reflux reaction for 2h, at 50°C, 10kPa, after vacuum distillation for 1.5h, wash with ether Disperse, filter, and vacuum-dry at 50°C and 10kPa for 8 hours to obtain 4.08g of catalyst complex 1.

[0064] Such as Figure 4 Shown, analyze the XRD spectrogram of the obtained catalyst complex cupric chloride of the embodiment of the present invention and N-methylimidazole, in 2 θ =14.25°, 15.81°, 17.58°, 20.90°, 24.22°, 26.47° and 26.67° all produce strong absorption peaks, which can be seen from the XRD spectrum of this series of absorption peaks and its standard card (PDF#32-1608), The catalyst complex obtained in the embodiment of the present invention is a single crystal formed by copper chloride and N-methylimidazole in a molar ratio of 1:2.

[0065] 46.8g (304.2mmol) carbon tetrachloride and 6.54g (76.0mmol) methyl acrylate, and 0.23g c...

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Abstract

The invention relates to a synthesis method of alpha,gamma,gamma,gamma-tetrachlorobutyrate. The synthesis method comprises the following steps: stirring and mixing carbon tetrachloride and acrylate with a copper salt and/or cuprous salt main catalyst, an organic amine or imidazole cocatalyst and a polar inert organic solvent at room temperature, sealing a reaction kettle, conducting heating for anaddition reaction, preforming cooling to room temperature, carrying out filtering, distilling a filtrate under normal pressure to recover carbon tetrachloride, and performing rectifying under reducedpressure to obtain alpha,gamma,gamma,gamma-tetrachlorobutyrate. The purity of the alpha,gamma,gamma,gamma-tetrachlorobutyrate obtained by using the method is up to 99.5%, one-way reaction yield is upto 96.1%, a product is easy to separate, reaction byproducts are few, the catalytic effect of the catalysts and the ligand is excellent, the raw materials and the catalysts are cheap and easy to obtain, and the solvent and the catalysts are easy to recycle; and the method is mild in reaction condition, simple in technological operation, low in production cost, good in economic benefit and suitable for industrial production.

Description

technical field [0001] The invention relates to a synthesis method of α, γ, γ, γ-tetrachlorobutyrate, in particular to a synthesis method of (α-methyl)-α, γ, γ, γ-tetrachlorobutyrate. Background technique [0002] (α-Methyl)-α,γ,γ,γ-Tetrachlorobutyrate is an important class of raw materials for organic synthesis and an important initiator in the synthesis of acrylic resins. It is used in the synthesis of fine chemicals It also has more important uses; it has broad application prospects in the field of pesticide synthesis, especially in the synthesis of chlorinated pyrethroid compounds. As we all know, chlorine is one of the commonly used highly active non-metallic elements. Based on its nuclear structure characteristics, it has strong reaction advantages in terms of electronegativity and bond energy. Many properties such as anti-corrosion and anti-corrosion have been strengthened. Therefore, (α-methyl)-α,γ,γ,γ-tetrachlorobutyrate has great development potential in the new ...

Claims

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Application Information

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IPC IPC(8): C07C69/63C07C67/30
CPCC07C67/30C07C69/63Y02P20/584
Inventor 肖自胜尹笃林兰支利蔡果张超钟文周毛丽秋
Owner HUNAN NORMAL UNIVERSITY
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