Unlock instant, AI-driven research and patent intelligence for your innovation.

A kind of synthetic method of 3-hydroxymethyl tetrahydrofuran

A technology of hydroxymethyltetrahydrofuran and synthetic methods, applied in the direction of organic chemistry, etc., can solve the problems of long synthetic route, complicated production operation, high risk, etc., and achieve the effect of mild reaction conditions, simple process operation and short synthetic route

Active Publication Date: 2020-11-27
LANZHOU INST OF CHEM PHYSICS CHINESE ACAD OF SCI
View PDF7 Cites 0 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] However, the above-mentioned synthetic method has problems such as long synthetic route, complex production operation, low total yield of reaction or high production cost and process energy consumption, high risk, etc., which is not conducive to industrial production

Method used

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0018] Synthesis of tetrahydrofuran-3-carbaldehyde:

[0019] Add 2,5-dihydrofuran (84.11 g, 1.2 mol), rhodium dicarbonyl acetylacetonate (1.05 g, 4 mmol) and triphenylphosphine (3.15 g, 12 mmol) in the reaction kettle, and use N 2 After replacing deoxygenation, 2 MPa H is introduced 2 and 2 MPa CO at 60 o C was stirred and reacted for 6 h, cooled to room temperature, slowly vented, and filtered to obtain 119.42 g of tetrahydrofuran-3-carbaldehyde with a yield of 99.4%. 1 H NMR (400 MHz, CDCl 3 ) δ 9.64 (1H), 4.09-4.06 (q, J = 4.0 Hz, 1H),3.90-3.93 (m, 2H), 3.77-3.71 (q, J = 8.0 Hz, 1H), 3.07-3.01 (m, 1H), 2.22-2.06 (m, 2H); 13 C NMR (101 MHz, CDCl 3 ) δ 200.96, 68.00, 67.36, 51.15, 26.59.

[0020] Synthesis of 3-hydroxymethyltetrahydrofuran:

[0021] Dissolve tetrahydrofuran-3-carbaldehyde (50.06 g, 0.5 mol) in ethanol (400 mL), then cool to 0 o C. Add sodium borohydride (18.92 g, 0.5 mol) to the above solution in batches, after the addition is complete, stir the re...

Embodiment 2

[0023] Synthesis of tetrahydrofuran-3-carbaldehyde:

[0024] Add 2,5-dihydrofuran (84.11 g, 1.2 mol), rhodium dicarbonyl acetylacetonate (0.31 g, 1.2 mmol) and triphenylphosphine (1.26 g, 4.8 mmol) in the reaction kettle, and use N 2 After replacing deoxygenation, 2 MPa H is introduced 2 and 2 MPa CO at 60 o C was stirred and reacted for 8 h, cooled to room temperature, slowly vented, and filtered to obtain 118.58 g of tetrahydrofuran-3-carbaldehyde with a yield of 98.7%.

[0025] Synthesis of 3-hydroxymethyltetrahydrofuran:

[0026] Dissolve tetrahydrofuran-3-carbaldehyde (50.06 g, 0.5 mol) in methanol (400 mL), then cool to 0 o C. Add sodium borohydride (22.69 g, 0.6 mol) to the above solution in batches, after the addition is complete, stir the reaction at room temperature for 2 h until the raw material disappears, then slowly add concentrated hydrochloric acid (51 mL) dropwise to adjust the pH value to neutral , a large amount of white solid precipitated, filtered, and...

Embodiment 3

[0028] Synthesis of tetrahydrofuran-3-carbaldehyde:

[0029] Add 2,5-dihydrofuran (84.11 g, 1.2 mol), rhodium dicarbonyl acetylacetonate (0.06 g, 0.24 mmol) and triphenylphosphine (0.25 g, 0.96 mmol) into the reaction kettle, and use N 2 After replacement deoxygenation, 2 MPa H is introduced 2 and 2 MPaCO at 80 o C was stirred and reacted for 24 h, cooled to room temperature, slowly vented, and filtered to obtain 116.66 g of tetrahydrofuran-3-carbaldehyde with a yield of 97.1%.

[0030] Synthesis of 3-hydroxymethyltetrahydrofuran:

[0031] Dissolve tetrahydrofuran-3-carbaldehyde (50.06 g, 0.5 mol) in methanol (400 mL), then cool to 0 oC. Add sodium borohydride (22.69 g, 0.6 mol) to the above solution in batches. After the addition is complete, stir the reaction at room temperature for 5 h until the raw material disappears, then slowly add concentrated hydrochloric acid (51 mL) to adjust the pH value to neutral , a large amount of white solid precipitated, filtered, and the...

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

PUM

No PUM Login to View More

Abstract

The invention relates to a synthesis method of tetrahydrofuran-3-methanol. According to the method, 2,5-dihydrofuran is taken as an initial raw material and subjected to two-step reactions including Rh-catalyzed hydroformylation and hydroboration reduction, and tetrahydrofuran-3-methanol is synthesized. The synthesis method is high in reaction selectivity, the product yield is high, a process is simple to operate, the reaction conditions are mild and the method is suitable for industrial production.

Description

technical field [0001] The invention relates to a method for synthesizing a third-generation neonicotinoid insecticide intermediate, in particular to a method for synthesizing 3-hydroxymethyltetrahydrofuran. Background technique [0002] 3-Hydroxytetrahydrofuran is an important intermediate in the synthesis of the third-generation nicotinic insecticide dinotefuran (JPH 07173157 A). Dinotefuran was developed by Mitsui Corporation of Japan, and was first registered and marketed in Japan in 2002, and has now obtained pesticide registration in many countries. Due to its special structure, compared with traditional neonicotinoid insecticides, dinotefuran has better performance, has excellent systemic penetration, and shows high insecticidal activity at a very low dose. Therefore, dinotefuran is safe to animals and plants, has a long residual effect, and has a broad spectrum of insecticidal properties, so it has a wide range of applications, and is suitable for rice, vegetables, ...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

Application Information

Patent Timeline
no application Login to View More
Patent Type & Authority Patents(China)
IPC IPC(8): C07D307/12
CPCC07D307/12
Inventor 王来来李海峰马鸿儒
Owner LANZHOU INST OF CHEM PHYSICS CHINESE ACAD OF SCI