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Synthesis method of 3-tetrahydro-furanmethanamine

A technology of aminomethyltetrahydrofuran and nitromethyltetrahydrofuran, which is applied in the field of synthesizing 3-aminomethyltetrahydrofuran, can solve the problems of unsuitability for industrial production, long synthesis route, improper operation, etc., and achieves low cost of raw materials and short synthesis route. , The effect of low production cost

Active Publication Date: 2017-12-01
LANZHOU INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Therefore, the synthesis route of this method is longer, the total yield is lower, and if use NaN in synthesis 3 , there is a risk of explosion due to improper operation, so it is not suitable for industrial production

Method used

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  • Synthesis method of 3-tetrahydro-furanmethanamine
  • Synthesis method of 3-tetrahydro-furanmethanamine
  • Synthesis method of 3-tetrahydro-furanmethanamine

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0037] Synthesis of 2-nitromethyl-1,4-diethyl succinate:

[0038] Add potassium carbonate (10.4 g, 0.075 mol) to nitromethane (100 mL), then add diethyl maleate (43.0 g, 0.25 mol), after the addition is complete, stir the reaction at room temperature for 12 h, filter off potassium carbonate , concentrated to recover nitromethane, and the residue was distilled under reduced pressure to obtain 54.0 g of diethyl 2-nitromethyl-1,4-butanedioate with a yield of 92.6%. 1 H NMR (400MHz, CDCl 3 ) δ 4.82-4.77 (dd, J = 8.0, 4.0 Hz, 1H), 4.71-4.66 (dd, J = 8.0,4.0 Hz, 1H), 4.21-4.17 (q, J = 4.0 Hz, 2H), 4.16-4.12 (q, J = 4.0 Hz, 2H),3.55-3.49 (m, 1H), 2.84-2.79 (dd, J = 4.0, 4.0 Hz, 1H), 2.71-2.65 (dd, J =8.0, 8.0 Hz, 1H), 1.26-1.22 (t, J = 8.0 Hz, 3H); 13 C NMR (101 MHz, CDCl 3 ) δ170.49, 170.23, 74.41, 61.84, 61.16, 39.05, 32.87, 14.02, 13.88.

[0039] Synthesis of 2-nitromethyl-1,4-butanediol:

[0040]A solution of 2-nitromethyl-1,4-butanedioic acid diethyl ester (46....

Embodiment 2

[0046] Synthesis of 2-nitromethyl-1,4-diethyl succinate:

[0047] Add potassium carbonate (6.9 g, 0.05 mol) to nitromethane (75 mL), then add diethyl maleate (43.0 g, 0.25 mol), after the addition is complete, stir the reaction at room temperature for 14 h, filter off potassium carbonate , concentrated to recover nitromethane, and the residue was distilled under reduced pressure to obtain 52.9 g of diethyl 2-nitromethyl-1,4-butanedioate with a yield of 90.7%.

[0048] Synthesis of 2-nitromethyl-1,4-butanediol:

[0049] A solution of 2-nitromethyl-1,4-butanedioic acid diethyl ester (46.6 g, 0.20 mol) in MeOH (42 mL) was slowly added dropwise to sodium borohydride (13.6 g, 0.36 mol) in tetrahydrofuran (180 mL) suspension, keep the reaction temperature at 20~30°C during the dropwise addition o Between C. The dropwise addition was complete, and the reaction was maintained at this temperature with stirring for 4 h, and then the temperature was raised to 60 o C was refluxed and ...

Embodiment 3

[0055] Synthesis of 2-nitromethyl-1,4-dibutyl succinate:

[0056] Potassium fluoride (3.5 g, 0.06 mol) was added to nitromethane (100 mL), and then dibutyl maleate (45.7 g, 0.2 mol) was added. After the addition was complete, the reaction was stirred at room temperature for 13 h, concentrated to recover nitrate Dichloromethane, the residue was dissolved in dichloromethane (100 mL), then washed with water, the organic phase was dried over anhydrous sodium sulfate, filtered, concentrated, and distilled under reduced pressure to obtain 2-nitromethyl-1,4-butane 49.5 g of dibutyl diacid, the yield is 85.5%.

[0057] Synthesis of 2-nitromethyl-1,4-butanediol:

[0058] A solution of 2-nitromethyl-1,4-butanedioic acid dibutyl (57.9 g, 0.2 mol) in MeOH (42 mL) was slowly added dropwise to potassium borohydride (21.6 g, 0.4 mol) in tetrahydrofuran (180 mL) suspension, keep the reaction temperature at 15~30°C during the dropwise addition o Between C. The dropwise addition was complet...

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Abstract

The invention discloses a synthesis method of 3-tetrahydro-furanmethanamine. According to the method, maleic acid diester is used as a starting material to synthesize 3-tetrahydro-furanmethanamine via four steps of reaction of Michael addition, metal borohydride reduction, dehydration cyclization and catalytic hydrogenation reduction. The synthesis method provided by the invention has the advantages of mild reaction conditions, high product yield, less pollution discharge, simple process operation and suitability for industrialized production.

Description

technical field [0001] The invention discloses a method for synthesizing a third-generation nicotinic insecticide intermediate, in particular to a method for synthesizing 3-aminomethyltetrahydrofuran. Background technique [0002] 3-Aminomethyltetrahydrofuran is an important intermediate in the synthesis of the third-generation nicotinic insecticide dinotefuran (JPH 07173157 A) and other novel drugs (WO 2015123365 A1 and WO 2015162456 A1). Dinotefuran was developed by Mitsui Corporation of Japan. It 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. It is suitable for r...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D307/14
CPCC07D307/14
Inventor 李海峰王来来
Owner LANZHOU INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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