CN107501213B - Synthetic method of 3-aminomethyl tetrahydrofuran - Google Patents

Synthetic method of 3-aminomethyl tetrahydrofuran Download PDF

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CN107501213B
CN107501213B CN201710730682.5A CN201710730682A CN107501213B CN 107501213 B CN107501213 B CN 107501213B CN 201710730682 A CN201710730682 A CN 201710730682A CN 107501213 B CN107501213 B CN 107501213B
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tetrahydrofuran
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李海峰
王来来
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Lanzhou Institute of Chemical Physics LICP of CAS
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    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
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Abstract

The invention relates to a synthetic method of 3-aminomethyl tetrahydrofuran. The method takes 2, 5-dihydrofuran as a starting material, and synthesizes the 3-aminomethyl tetrahydrofuran through two steps of reactions of hydroformylation catalyzed by Rh and catalytic reduction ammoniation. The synthesis method has the advantages of high reaction selectivity, simple process operation, short synthesis route, high yield of the two-step reaction up to more than 95 percent, and suitability for industrial production.

Description

Synthetic method of 3-aminomethyl tetrahydrofuran
Technical Field
The invention relates to a method for synthesizing a third generation nicotine pesticide intermediate, in particular to a method for synthesizing 3-aminomethyl tetrahydrofuran.
Background
3-aminomethyl tetrahydrofuran is an important intermediate for synthesizing third-generation nicotinoid insecticide dinotefuran (JPH 07173157A) and other novel medicines (WO 2015123365A 1 and WO 2015162456A 1). Dinotefuran was developed by mitsui, japan and first registered in japan in 2002, and has now been registered for agricultural chemicals in many countries. Due to the special structure, compared with the traditional nicotine pesticide, the dinotefuran has more excellent performance, excellent systemic osmosis effect and high insecticidal activity at a very low dosage. Therefore, the dinotefuran is safe to animals and plants, long in residual effect and wide in insecticidal spectrum, and is suitable for preventing and controlling pests such as orthoptera, hymenoptera, diptera, beetle, hemiptera, lepidoptera and the like of rice, vegetables, fruit trees and flowers.
Dinotefuran is obtained by further reacting a key intermediate 3-hydroxymethyl tetrahydrofuran or 3-aminomethyl tetrahydrofuran. Currently, there are several methods for the synthesis of 3-aminomethyltetrahydrofuran:
1) 3-hydroxymethyl tetrahydrofuran is used as a raw material, reacts with methanesulfonyl chloride to generate 3-methanesulfonyloxymethyl tetrahydrofuran, then reacts with potassium phthalimide through Gabriel to generate N- (3-tetrahydrofurylmethyl) phthalimide, and then is hydrolyzed to obtain 3-aminomethyl tetrahydrofuran (EP 0649845;J Pestic Sci2004, 29 (4), 356-363) or reacting with sodium azide to generate 3-azidomethyltetrahydrofuran, and then obtaining the 3-aminomethyl tetrahydrofuran through catalytic reduction (WO 2005066126).
Figure 64739DEST_PATH_IMAGE001
The method firstly needs to synthesize 3-hydroxymethyl tetrahydrofuran through three-step or four-step reaction, and then 3-aminomethyl tetrahydrofuran is synthesized by taking the 3-hydroxymethyl tetrahydrofuran as a raw material. Therefore, the method has long synthesis route of the 3-aminomethyl tetrahydrofuran and low total yield. In addition, if NaN is used in the synthesis3Improper operation can result in explosion risks, which is detrimental to industrial production.
2) The method comprises the steps of taking malic acid as a raw material, obtaining 1, 2, 4-butanetriol through Ru/C catalytic hydrogenation, cyclizing under the catalytic action of p-toluenesulfonic acid to obtain 3-hydroxytetrahydrofuran, chlorinating with thionyl chloride to obtain 3-chlorotetrahydrofuran, carrying out nucleophilic substitution reaction with sodium cyanide to obtain 3-nitrile-based tetrahydrofuran, and finally carrying out Raney Ni catalytic hydrogenation to obtain 3-aminomethyl tetrahydrofuran (JP 7173157).
Figure 255943DEST_PATH_IMAGE002
The catalytic hydrogenation reduction conditions of the malic acid in the method are harsh, and the virulent sodium cyanide is required to be used in the nucleophilic substitution reaction, so that the method has great harm to human bodies and can cause serious environmental pollution, and is not suitable for industrial production.
3) Acrylonitrile is used as a raw material, and is firstly subjected to addition reaction with 2-halogenated ethanol to obtain 2-halogenated ethyl-2-nitrile ethyl ether, then the 2-halogenated ethyl-2-nitrile ethyl ether is subjected to condensation cyclization to obtain an intermediate 3-nitrile tetrahydrofuran, and then the intermediate 3-nitrile tetrahydrofuran is subjected to catalytic hydrogenation reduction to obtain 3-aminomethyl tetrahydrofuran (CN 106366056A).
Figure 891455DEST_PATH_IMAGE003
Although the method has the advantages of cheap and easily obtained starting materials, short synthetic route and simple process operation, the method has the yield of only 19 percent and is not beneficial to industrial production.
Disclosure of Invention
The invention aims to solve the problems and provides a synthesis method of 3-aminomethyl tetrahydrofuran, which has the advantages of good reaction selectivity, short synthesis route, lower production cost, high reaction yield, safety, environmental protection and suitability for industrial production.
A method for synthesizing 3-aminomethyl tetrahydrofuran is characterized by comprising the following steps in sequence:
1) hydroformylation reaction: 2, 5-dihydrofuran is used as a raw material, and tetrahydrofuran-3-formaldehyde is generated through hydroformylation reaction catalyzed by Rh;
2) catalytic reduction ammoniation reaction: the tetrahydrofuran-3-formaldehyde obtained in the step 1) is catalyzed, reduced and aminated to synthesize the 3-aminomethyl tetrahydrofuran.
The hydroformylation reaction method in the step 1) comprises the following steps: adding 2, 5-dihydrofuran, Rh catalyst precursor and organic phosphine ligand into a reaction kettle, and adding N2Introducing 1-2 MPa of H after displacement deoxidation2And 1-2 MPa of CO at 60-80%oC, reacting for 6-24 h, cooling to room temperature, slowly emptying, and filtering to obtain tetrahydrofuran-3-formaldehyde.
The method for the catalytic reduction ammoniation reaction in the step 2) comprises the following steps: adding tetrahydrofuran-3-formaldehyde, reductive ammoniation catalyst and ammonia methanol solution into a reaction kettle, and adding N2Introducing 2-4 MPa of H after displacement deoxidation2In the range of 60 to 80oC, reacting for 6-12 h, cooling to room temperature, slowly emptying, filtering out the catalyst, and concentrating the filtrate in vacuum to obtain the 3-aminomethyl tetrahydrofuran.
The mass ratio of the 2, 5-dihydrofuran to the Rh catalyst precursor and the organic phosphine ligand in the step 1) is 300-5000: 1: 3 to 4, said H2And CO at a pressure ratio of 1: 1.
the mass ratio of the tetrahydrofuran-3-formaldehyde to ammonia in the step 2) is 1: 2-3, wherein the dosage of the reductive amination catalyst is 10-20% of the mass of the tetrahydrofuran-3-formaldehyde.
In the step 1), the Rh catalyst precursor is one of bis (1, 5-cyclooctadiene rhodium chloride), dicarbonyl rhodium acetylacetonate or monochlorodicarbonylrhodium dimer, and the organic phosphine ligand is one of triphenylphosphine, tri-o-tolylphosphine or tris (2, 4, 6-trimethylphenyl) phosphine.
The reductive amination catalyst in the step 2) is Raney Ni or Pd/C.
The method for synthesizing the 3-aminomethyl tetrahydrofuran has the advantages of high reaction selectivity, simple process operation, short synthetic route and high yield of the two-step reaction which can reach more than 95 percent, thereby being suitable for industrial production.
Detailed Description
The invention is illustrated by the following examples, which are not intended to limit the invention.
Example 1
And (3) synthesizing tetrahydrofuran-3-formaldehyde:
2, 5-dihydrofuran (84.11 g, 1.2 mol), rhodium dicarbonylacetylacetonate (1.05 g, 4 mmol) and triphenylphosphine (3.15 g, 12 mmol) were charged into the reactor using N2Introducing 2 MPa H after displacement deoxidation2And 2 MPa CO at 60oC, stirring and reacting for 6 hours, cooling to room temperature, slowly emptying, and filtering to obtain 119.42 g of tetrahydrofuran-3-formaldehyde with the yield of 99.4%.1H NMR (400 MHz, CDCl3) 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)；13C NMR (101 MHz, CDCl3) 200.96, 68.00, 67.36, 51.15, 26.59。
Synthesis of 3-aminomethyl tetrahydrofuran:
tetrahydrofuran-3-carbaldehyde (100.12 g, 1.0 mol), Raney Ni (20.02 g) and a 15% ammonia methanol solution (340.0 g, 3.0 mol) were charged in a reaction vessel, followed by introduction of 2 MPa of H2At 60oC, stirring and reacting for 12 hours, cooling to room temperature, slowly emptying, filtering out the catalyst, and concentrating the filtrate in vacuum to obtain 100.03 g of 3-aminomethyl tetrahydrofuran with the yield of 98.9%.1H NMR (400 MHz, CD3OD) 3.87-3.82 (q, J = 8.0, 8.0 Hz, 2H), 3.75-3.70 (q, J = 4.0, 8.0 Hz, 1H), 3.51-3.48 (t, J = 8.0 Hz, 1H), 2.73-2.72 (d, J = 4.0, 2H), 2.40-2.34 (m, 1H), 2.09-2.06 (m, 1H), 1.66-1.58 (m, 1H); 13C NMR (101 MHz, CD3OD) 72.24, 68.71, 44.92, 42.02, 31.05。
Example 2
And (3) synthesizing tetrahydrofuran-3-formaldehyde:
2, 5-dihydrofuran (84.11 g, 1.2 mol), rhodium dicarbonylacetylacetonate (0.31 g, 1.2 mmol) and triphenylphosphine (1.26 g, 4.8 mmol) were charged into the autoclave with N2Introducing 2 MPa H after displacement deoxidation2And 2 MPa CO at 60oC, stirring and reacting for 8 hours, cooling to room temperature, slowly emptying,the mixture was filtered to obtain 118.58 g of tetrahydrofuran-3-carbaldehyde with a yield of 98.7%.
Synthesis of 3-aminomethyl tetrahydrofuran:
tetrahydrofuran-3-carbaldehyde (100.12 g, 1.0 mol), Raney Ni (20.02 g) and a 15% ammonia methanol solution (340 g, 3.0 mol) were charged in a reaction vessel, followed by introduction of 3 MPa of H2At 60oC, stirring and reacting for 12 h, cooling to room temperature, slowly emptying, filtering out the catalyst, and concentrating the filtrate in vacuum to obtain 100.34 g of 3-aminomethyl tetrahydrofuran with the yield of 99.2%.
Example 3
And (3) synthesizing tetrahydrofuran-3-formaldehyde:
2, 5-dihydrofuran (84.11 g, 1.2 mol), rhodium dicarbonylacetylacetonate (0.06 g, 0.24 mmol) and triphenylphosphine (0.25 g, 0.96 mmol) were charged into the autoclave with N2Introducing 2 MPa H after displacement deoxidation2And 2 MPa CO at 80oC, stirring and reacting for 24 hours, cooling to room temperature, slowly emptying, and filtering to obtain 116.66 g of tetrahydrofuran-3-formaldehyde with the yield of 97.1%.
Synthesis of 3-aminomethyl tetrahydrofuran:
tetrahydrofuran-3-carbaldehyde (100.12 g, 1.0 mol), Raney Ni (20.02 g) and a 15% ammonia methanol solution (340 g, 3.0 mol) were charged in a reaction vessel, followed by introduction of 4 MPa of H2At 60oC, stirring and reacting for 12 h, cooling to room temperature, slowly emptying, filtering out the catalyst, and concentrating the filtrate in vacuum to obtain 100.64 g of 3-aminomethyl tetrahydrofuran with the yield of 99.5%.
Example 4
And (3) synthesizing tetrahydrofuran-3-formaldehyde:
2, 5-dihydrofuran (84.11 g, 1.2 mol), rhodium dicarbonylacetylacetonate (1.05 g, 4 mmol) and triphenylphosphine (3.15 g, 12 mmol) were charged into the reactor using N2Introducing 1 MPa H after displacement deoxidation2And 1 MPa CO at 70oC, stirring and reacting for 9 hours, cooling to room temperature, slowly emptying, and filtering to obtain 118.46 g of tetrahydrofuran-3-formaldehyde with the yield of 98.6 percent.
Synthesis of 3-aminomethyl tetrahydrofuran:
tetrahydrofuran-3-carbaldehyde (100.12 g, 1.0 mol), 10% Pd/C (10.01 g) and 15% methanolic ammonia solution (340 g, 3.0 mol) were charged into a reaction vessel, followed by introduction of 2 MPa of H2At 60oC, stirring and reacting for 12 hours, cooling to room temperature, slowly emptying, filtering out the catalyst, and concentrating the filtrate in vacuum to obtain 99.13 g of 3-aminomethyl tetrahydrofuran with the yield of 98.0%.
Example 5
And (3) synthesizing tetrahydrofuran-3-formaldehyde:
2, 5-dihydrofuran (84.11 g, 1.2 mol), chlorodicarbonylrhodium dimer (1.56 g, 4 mmol) and triphenylphosphine (3.15 g, 12 mmol) were charged to the reaction kettle using N2Introducing 2 MPa H after displacement deoxidation2And 2 MPa CO at 70oC, stirring and reacting for 20 hours, cooling to room temperature, slowly emptying, and filtering to obtain 115.70 g of tetrahydrofuran-3-formaldehyde with the yield of 96.3%.
Synthesis of 3-aminomethyl tetrahydrofuran:
tetrahydrofuran-3-carbaldehyde (100.12 g, 1.0 mol), 10% Pd/C (10.01 g) and 15% methanolic ammonia (340 g, 3.0 mol) were charged into a reaction vessel, followed by introduction of 4 MPa of H2At 80oC, stirring and reacting for 10 hours, cooling to room temperature, slowly emptying, filtering out the catalyst, and concentrating the filtrate in vacuum to obtain 99.73 g of 3-aminomethyl tetrahydrofuran with the yield of 98.6%.
Example 6
And (3) synthesizing tetrahydrofuran-3-formaldehyde:
2, 5-dihydrofuran (84.11 g, 1.2 mol), bis (1, 5-cyclooctadienerhodium chloride) (1.97 g, 4 mmol) and triphenylphosphine (3.15 g, 12 mmol) were added to the reaction vessel, and N was added to the reaction vessel2Introducing 2 MPa H after displacement deoxidation2And 2 MPa CO at 70oC, stirring and reacting for 20 hours, cooling to room temperature, slowly emptying, and filtering to obtain 116.63 g of tetrahydrofuran-3-formaldehyde with the yield of 97.1%.
Synthesis of 3-aminomethyl tetrahydrofuran:
tetrahydrofuran-3-carbaldehyde (100.12 g, 1.0 mol), Raney Ni (10.01 g) and a 15% ammonia methanol solution (227 g, 2.0 mol) were charged in a reaction vessel, followed by introduction of 4 MPa of H2In a80 oC, stirring and reacting for 6 hours, cooling to room temperature, slowly emptying, filtering out the catalyst, and concentrating the filtrate in vacuum to obtain 99.13 g of 3-aminomethyl tetrahydrofuran with the yield of 98.0%.
Example 7
And (3) synthesizing tetrahydrofuran-3-formaldehyde:
2, 5-dihydrofuran (84.11 g, 1.2 mol), rhodium dicarbonylacetylacetonate (1.05 g, 4 mmol) and tri-o-tolylphosphine (3.65 g, 12 mmol) were charged to the reaction kettle using N2Introducing 2 MPa H after displacement deoxidation2And 2 MPa CO at 60oC, stirring and reacting for 24 hours, cooling to room temperature, slowly emptying, and filtering to obtain 116.39 g of tetrahydrofuran-3-formaldehyde with the yield of 96.9%.
Synthesis of 3-aminomethyl tetrahydrofuran:
tetrahydrofuran-3-carbaldehyde (100.12 g, 1.0 mol), Raney Ni (10.01 g) and a 15% ammonia methanol solution (227 g, 2.0 mol) were charged in a reaction vessel, followed by introduction of 3 MPa of H2At 80oC, stirring and reacting for 12 h, cooling to room temperature, slowly emptying, filtering out the catalyst, and concentrating the filtrate in vacuum to obtain 99.33 g of 3-aminomethyl tetrahydrofuran with the yield of 98.2%.
Example 8
And (3) synthesizing tetrahydrofuran-3-formaldehyde:
2, 5-dihydrofuran (84.11 g, 1.2 mol), rhodium dicarbonylacetylacetonate (1.05 g, 4 mmol) and tris (2, 4, 6-trimethylphenyl) phosphine (6.39 g, 12 mmol) were charged to the reaction vessel and the reaction vessel was purged with N2Introducing 2 MPa H after displacement deoxidation2And 2 MPa CO at 60oC, stirring and reacting for 24 hours, cooling to room temperature, slowly emptying, and filtering to obtain 116.18 g of tetrahydrofuran-3-formaldehyde with the yield of 96.7%.
Synthesis of 3-aminomethyl tetrahydrofuran:
tetrahydrofuran-3-carbaldehyde (100.12 g, 1.0 mol), Raney Ni (10.01 g) and a 15% ammonia methanol solution (227 g, 2.0 mol) were charged in a reaction vessel, followed by introduction of 4 MPa of H2At 70oC, stirring and reacting for 12 hours, cooling to room temperature, slowly emptying, filtering out the catalyst, carrying out vacuum concentration on the filtrate to obtain 99.43g of 3-aminomethyl tetrahydrofuran,the yield thereof was found to be 98.3%.

Claims (3)

1. A method for synthesizing 3-aminomethyl tetrahydrofuran is characterized by comprising the following steps in sequence:
1) hydroformylation reaction: adding 2, 5-dihydrofuran, Rh catalyst precursor and organic phosphine ligand into a reaction kettle, and adding N2Introducing 1-2 MPa of H after displacement deoxidation2Reacting with 1-2 MPa CO at 60-80 ℃ for 6-24 h, cooling to room temperature, slowly emptying, and filtering to obtain tetrahydrofuran-3-formaldehyde; the mass ratio of the 2, 5-dihydrofuran to the Rh catalyst precursor and the organic phosphine ligand is 300-5000: 1: 3-4; the Rh catalyst precursor is one of bis (1, 5-cyclooctadiene rhodium chloride), dicarbonyl acetylacetone rhodium or monochlorodicarbonylrhodium dimer, and the organic phosphine ligand is one of triphenylphosphine, tri-o-tolylphosphine or tris (2, 4, 6-trimethylphenyl) phosphine;
2) catalytic reduction ammoniation reaction: synthesizing 3-aminomethyl tetrahydrofuran from tetrahydrofuran-3-formaldehyde obtained in the step 1) through catalytic reduction and ammoniation; the method for catalytic reduction ammoniation reaction comprises the following steps: adding tetrahydrofuran-3-formaldehyde, reductive ammoniation catalyst and ammonia methanol solution into a reaction kettle, and adding N2Introducing 2-4 MPa of H after displacement deoxidation2Reacting at 60-80 ℃ for 6-12 h, cooling to room temperature, slowly emptying, filtering out a catalyst, and concentrating the filtrate in vacuum to obtain 3-aminomethyl tetrahydrofuran; the reductive amination catalyst is Raney Ni or Pd/C.
2. The method of claim 1, wherein said H in step 1) is2And CO at a pressure ratio of 1: 1.
3. the synthesis process according to claim 2, characterized in that the ratio of the quantities of the substances of tetrahydrofuran-3-carbaldehyde and methanolic ammonia solution in step 2) is 1: 2-3, wherein the dosage of the reductive amination catalyst is 10-20% of the mass of the tetrahydrofuran-3-formaldehyde.
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CN109438396B (en) * 2018-10-31 2020-11-13 山东新和成药业有限公司 Preparation method of tetrahydrofuran-3-methylamine
CN112375050A (en) * 2020-12-04 2021-02-19 大连九信精细化工有限公司 Synthesis method of tetrahydrofuran-3-formaldehyde
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US5945549A (en) * 1999-01-22 1999-08-31 Eastman Chemical Company Production of aqueous solutions of mixtures of formyltertrahydrofuran and hydrates thereof
JP2000290273A (en) * 1999-04-01 2000-10-17 Kuraray Co Ltd Production of 3-formyltetrahydrofuran
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CN106866588A (en) * 2017-02-23 2017-06-20 西安凯立新材料股份有限公司 A kind of synthetic method of 3 aminomethyl tetrahydrofuran

Patent Citations (5)

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Publication number Priority date Publication date Assignee Title
EP0795552A1 (en) * 1996-03-12 1997-09-17 Mitsui Toatsu Chemicals, Incorporated A method for production of 3-formyl-tetrahydrofuran
US5945549A (en) * 1999-01-22 1999-08-31 Eastman Chemical Company Production of aqueous solutions of mixtures of formyltertrahydrofuran and hydrates thereof
JP2000290273A (en) * 1999-04-01 2000-10-17 Kuraray Co Ltd Production of 3-formyltetrahydrofuran
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CN106866588A (en) * 2017-02-23 2017-06-20 西安凯立新材料股份有限公司 A kind of synthetic method of 3 aminomethyl tetrahydrofuran

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