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Preparation method of 3-methylene cyclobutyl derivative

A technology of methylenecyclobutyl derivatives, which is applied in the field of preparation of 3-methylenecyclobutyl derivatives, can solve problems such as difficulty in equipment cleaning, easy polymerization of propylene derivatives, safety risks, etc. The product conversion rate and the effect of safe and controllable reaction process

Pending Publication Date: 2021-10-12
PHARMABLOCK SCIENCES (NANJING) INC
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] Existing 3-methylenecyclobutyl derivatives, such as the preparation of 3-methylenecyclobutylcarbonitrile, are usually reacted for a long time (more than 30 hours) at high temperature (200°C) and high pressure (3-4MPa), Need to use an autoclave, which has high requirements on equipment; and propylene derivatives are very easy to polymerize, resulting in out-of-control reactions. Long-term high-temperature reactions have great safety risks. difficulty

Method used

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  • Preparation method of 3-methylene cyclobutyl derivative
  • Preparation method of 3-methylene cyclobutyl derivative
  • Preparation method of 3-methylene cyclobutyl derivative

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0016] The preparation of embodiment 1 3-methylene cyclobutylcarbonitrile

[0017] Dissolve acrylonitrile (3.71kg, 69.9mol, 3.5eq.), 4-methoxyphenol (24.8g, 0.20mol, 0.01eq.) in N-methylpyrrolidone (8800g), and cool down to 10-15°C , feed propadiene (800g, 20.0mol, 1.0eq.), and keep warm at about 10°C.

[0018] The continuous reactor (stainless steel tubular reactor with an inner diameter of 6mm and effective volume of 380mL) is set at a temperature of 250°C for the heat-conducting oil, and the configured solution enters the continuous reactor at a rate of 5.43mL / min with a plunger pump, and the system pressure 5.5MPa, the residence time is 70 minutes, and the material is discharged after being cooled by water. The reaction solution was distilled with a thorn column (20cm), the fractions were combined, water (1600mL) and MTBE (8000mL) were added, the liquid was stirred and separated, the organic phase was washed twice with water (1600mL), and 1414g of a colorless liquid was o...

Embodiment 2

[0019] Example 2 Preparation of 3-methylenecyclobutane-1-carboxylic acid methyl ester

[0020] Dissolve methyl acrylate (6.02kg, 70.0mol, 3.5eq.), 4-methoxyphenol (124g, 1.0mol, 0.05eq.) in N-methylpyrrolidone (8800g), and cool down to 10-15°C , feed propadiene (800g, 20.0mol, 1.0eq.), and keep warm at about 10°C.

[0021] The continuous reactor (stainless steel tubular reactor with an inner diameter of 6mm, effective volume of 300mL) is set at 250°C for the heat transfer oil, and the prepared solution enters the continuous reactor at a rate of 4.29mL / min with a plunger pump, and the system pressure 5.5MPa, the residence time is 70 minutes, and the material is discharged after being cooled by water. The reaction solution was distilled with a thorn column (20cm), the fractions were combined, water (1600mL) and MTBE (8000mL) were added, the liquid was stirred and separated, the organic phase was washed twice with water (1600mL), and 1765g of light yellow oil was precipitated. ...

Embodiment 3

[0022] Example 3 Preparation of ethyl 3-methylenecyclobutane-1-carboxylate

[0023] Dissolve ethyl acrylate (3.0kg, 30.0mol, 1.5eq.), 4-methoxyphenol (124g, 1.0mol, 0.05eq.) in N-methylpyrrolidone (8800g), and cool down to 10-15°C , feed propadiene (800g, 20.0mol, 1.0eq.), and keep warm at about 10°C.

[0024] The continuous reactor (stainless steel tubular reactor with an inner diameter of 6mm and an effective volume of 300mL) is set at a temperature of 250°C for the heat-conducting oil, and the configured solution enters the continuous reactor at a speed of 5mL / min with a plunger pump, and the system pressure is 5.5 MPa, the residence time is 60 minutes, and the material is discharged after being cooled by water. The reaction solution was distilled with a thorn column (20cm), the fractions were combined, water (1600mL) and MTBE (8000mL) were added, the liquid was stirred and separated, the organic phase was washed twice with water (1600mL), and 1820g of light yellow oil was...

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Abstract

The invention provides a preparation method of a 3-methylene cyclobutyl derivative, which takes a propylene derivative and propadiene as initial raw materials, adopts a continuous flow chemical technology, and solves the problem that a reaction channel is blocked by propylene derivative polymerization while ensuring the product conversion rate by screening process conditions such as a polymerization inhibitor and a reaction solvent. Reaction is safe and controllable, equipment cost is low, and the method is suitable for industrial production.

Description

technical field [0001] The invention relates to the field of organic chemical synthesis, in particular to a preparation method of 3-methylenecyclobutyl derivatives. Background technique [0002] 3-Methylenecyclobutyl derivatives, as a versatile pharmaceutical intermediate, have been widely used in the synthesis of various drug molecules. [0003] Existing 3-methylenecyclobutyl derivatives, such as the preparation of 3-methylenecyclobutylcarbonitrile, are usually reacted for a long time (more than 30 hours) at high temperature (200°C) and high pressure (3-4MPa), Need to use an autoclave, which has high requirements on equipment; and propylene derivatives are very easy to polymerize, resulting in out-of-control reactions. Long-term high-temperature reactions have great safety risks. difficulty. Contents of the invention [0004] In order to solve the problems of safety, controllability and high equipment requirements in the industrial production of existing 3-methylenecycl...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C253/30C07C255/46C07C67/347C07C69/608
CPCC07C253/30C07C67/347C07C2601/04C07C255/46C07C69/608
Inventor 项宗涛张峰陈志华朱经伟
Owner PHARMABLOCK SCIENCES (NANJING) INC
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