CN107501212B - Synthetic method of 3-hydroxymethyl tetrahydrofuran - Google Patents

Synthetic method of 3-hydroxymethyl tetrahydrofuran Download PDF

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CN107501212B
CN107501212B CN201710729641.4A CN201710729641A CN107501212B CN 107501212 B CN107501212 B CN 107501212B CN 201710729641 A CN201710729641 A CN 201710729641A CN 107501212 B CN107501212 B CN 107501212B
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tetrahydrofuran
reaction
formaldehyde
hydroxymethyl
borohydride
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CN107501212A (en
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王来来
李海峰
马鸿儒
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Lanzhou Institute of Chemical Physics LICP of CAS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • 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
    • C07D307/10—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 with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/12—Radicals substituted by oxygen atoms

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Abstract

The invention relates to a synthesis method of tetrahydrofuran-3-methanol. The method takes 2, 5-dihydrofuran as a starting material, and tetrahydrofuran-3-methanol is synthesized through two-step reactions of hydroformylation and hydroboration reduction catalyzed by Rh. The synthesis method disclosed by the invention is good in reaction selectivity, high in product yield, simple in process operation, mild in reaction conditions and suitable for industrial production.

Description

Synthetic method of 3-hydroxymethyl 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-hydroxymethyl tetrahydrofuran.
Background
3-hydroxytetrahydrofuran is an important intermediate for synthesizing third-generation nicotinoidic insecticide dinotefuran (JPH 07173157A). 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, so that the dinotefuran is wide in application range and is suitable for preventing and controlling pests such as orthoptera, hymenoptera, diptera, beetle, hemiptera, lepidoptera and the like in rice, vegetables, fruit trees and flowers.
European patent WO 2005065689 discloses that diethyl malonate reacts with ethyl chloroacetate under the action of alkali to generate 1, 1, 2-ethane-triethyl tricarboxylate, the triethyl 1, 1-ethane-tricarboxylate is reduced by sodium borohydride to obtain 2-hydroxymethyl-1, 4-butanediol, and the 2-hydroxymethyl-tetrahydrofuran is obtained by catalytic dehydration and cyclization of p-toluenesulfonic acid. Chinese patent CN 105254598 discloses that diethyl malonate reacts with bromoethanol under alkaline conditions to generate 2-hydroxyethyl-diethyl malonate, then the 2-hydroxyethyl-malonic acid is obtained by strong acid or strong base hydrolysis, then the 2-hydroxymethyl-1, 4-butanediol is obtained by high pressure catalytic hydrogenation reduction, and finally the 3-hydroxymethyl tetrahydrofuran is obtained by acid-catalyzed dehydration cyclization. U.S. Pat. No. 4, 6355814, 1 discloses a process for the synthesis of 3-hydroxymethyltetrahydrofuran from cyclohexanone. In the method, cyclohexanone firstly reacts with 1, 4-dihydroxy-2-butene under the action of p-toluenesulfonic acid to prepare 7, 12-dioxyspiro [5, 6] -9-dodecene, the compound is subjected to hydroformylation reaction under the catalysis of tris (triphenylphosphine) rhodium chloride to generate 9-formyl-7, 12-dioxyspiro [5, 6] dodecane, the formyl is further reduced by sodium borohydride to generate 9-hydroxymethyl-7, 12-dioxyspiro [5, 6] dodecane, and the 9-hydroxymethyl tetrahydrofuran is hydrolyzed by Amberlyst-15 strong acid cation resin to obtain the 3-hydroxymethyl tetrahydrofuran. Sunlega (Guangzhou chemical, 2010, 38(1), 104-105) reported a method for obtaining 3-hydroxymethyl tetrahydrofuran by reducing alpha-ethoxycarbonyl-gamma-butyrolactone generated by the reaction of diethyl malonate and ethylene oxide under the action of sodium metal by potassium borohydride. Tsunami et al (north-river science and technology, 2014, 31(5), 417-.
However, the above synthesis method has the problems of long synthesis route, complex production operation, low total yield of reaction, high production cost and energy consumption of the process, high risk and the like, and is not favorable for industrial production.
Disclosure of Invention
The invention aims to solve the problems and provides a synthesis method of 3-hydroxymethyl tetrahydrofuran, which has the advantages of short reaction route, simple process flow, high reaction yield, safety, environmental protection and suitability for industrial production.
A method for synthesizing 3-hydroxymethyl 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 of Rh catalyst precursor and organic phosphine ligand complex catalysis;
2) carrying out hydroboration reduction reaction: reducing the tetrahydrofuran-3-formaldehyde obtained in the step 1) by using metal borohydride to generate 3-hydroxymethyl 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 hydroboration reduction reaction method in the step 2) comprises the following steps: dissolving tetrahydrofuran-3-formaldehyde in an organic solvent, and then cooling to 0-10 DEGoC, adding metal borohydride in batches, stirring and reacting for 2-5 h at room temperature, and using concentrated hydrochloric acidAdjusting pH to neutral, filtering, vacuum concentrating the filtrate, and vacuum distilling to obtain 3-hydroxymethyl 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 the metal borohydride in the step 2) is 1: 1 to 1.2.
In the step 1), the Rh catalyst precursor is one of dicarbonyl acetylacetone rhodium, chlorodicarbonyl rhodium dimer, bis (norbornadiene) rhodium tetrafluoroborate or bis (1, 5-cyclooctadiene rhodium chloride), and the organic phosphine ligand is one of tris (2, 4, 6-trimethylphenyl) phosphine, tri-o-tolylphosphine or triphenylphosphine.
In the step 2), the metal borohydride is one of sodium borohydride and potassium borohydride, and the organic solvent is one of tetrahydrofuran, methanol or ethanol.
The synthesis method has the advantages of good reaction selectivity, high product yield, short synthesis route, mild reaction conditions and simple process operation, 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-hydroxymethyltetrahydrofuran:
tetrahydrofuran-3-carbaldehyde (50.06 g, 0.5 mol) was dissolved in ethanol (400 mL) and then cooled to 0oAnd C, adding sodium borohydride (18.92 g and 0.5 mol) into the solution in batches, stirring at room temperature for 5 hours after the addition is finished, reacting until the raw materials disappear, then slowly dropwise adding concentrated hydrochloric acid (42 mL) to adjust the pH value to be neutral, separating out a large amount of white solids, filtering, and washing a filter cake with ethanol. The filtrate was concentrated in vacuo and then distilled under reduced pressure to give 44.59 g of 3-hydroxymethyltetrahydrofuran in 87.3% yield.1H NMR (400 MHz, CD3OD) 3.85-3.78 (m, 2H), 3.73-3.68 (q, J = 4.0, 8.0 Hz, 1H), 3.62-3.49 (m, 3H), 2.48-2.38 (m, 1H), 2.02-1.96 (m, 1H), 1.64-1.56 (m, 1H)；13C NMR (101 MHz, CDCl3) 70.52, 67.74, 64.57, 41.33, 28.59。
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, and filtering to obtain 118.58 g of tetrahydrofuran-3-formaldehyde with the yield of 98.7%.
Synthesis of 3-hydroxymethyltetrahydrofuran:
tetrahydrofuran-3-carbaldehyde (50.06 g, 0.5 mol) was dissolved in methanol (400 mL) and then cooled to 0oAnd C, adding sodium borohydride (22.69 g and 0.6 mol) into the solution in batches, stirring at room temperature for reaction for 2 hours after the addition is finished until the raw materials disappear, then slowly dropwise adding concentrated hydrochloric acid (51 mL) to adjust the pH value to be neutral, separating out a large amount of white solid, filtering, and washing a filter cake with methanol. The filtrate was concentrated in vacuo and then distilled under reduced pressure to give 49.02 g of 3-hydroxymethyltetrahydrofuran in a yield of 96.0%.
Example 3
And (3) synthesizing tetrahydrofuran-3-formaldehyde:
in the reaction2, 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 added to the kettle using 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-hydroxymethyltetrahydrofuran:
tetrahydrofuran-3-carbaldehyde (50.06 g, 0.5 mol) was dissolved in methanol (400 mL) and then cooled to 0oAnd C, adding sodium borohydride (22.69 g and 0.6 mol) into the solution in batches, stirring at room temperature for 5 hours after the addition is finished, reacting until the raw materials disappear, then slowly dropwise adding concentrated hydrochloric acid (51 mL) to adjust the pH value to be neutral, separating out a large amount of white solid, filtering, and washing a filter cake with methanol. The filtrate was concentrated in vacuo and then distilled under reduced pressure to give 48.46 g of 3-hydroxymethyltetrahydrofuran in a yield of 94.9%.
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-hydroxymethyltetrahydrofuran:
tetrahydrofuran-3-carbaldehyde (50.06 g, 0.5 mol) was dissolved in tetrahydrofuran (400 mL) and then cooled to 0oAnd C, adding sodium borohydride (22.69 g and 0.6 mol) into the solution in batches, stirring at room temperature for reacting for 4 hours after the addition is finished until the raw materials disappear, then slowly dropwise adding concentrated hydrochloric acid (51 mL) to adjust the pH value to be neutral, separating out a large amount of white solid, filtering, and washing a filter cake with tetrahydrofuran. The filtrate was concentrated in vacuo and then distilled under reduced pressure to give 46.78 g of 3-hydroxymethyltetrahydrofuran in a yield of 91.6%.
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-hydroxymethyltetrahydrofuran:
tetrahydrofuran-3-carbaldehyde (50.06 g, 0.5 mol) was dissolved in methanol (400 mL) and then cooled to 0oAnd C, adding potassium borohydride (32.36 g, 0.6 mol) into the solution in batches, stirring at room temperature for reaction for 3 hours after adding, then slowly dropwise adding concentrated hydrochloric acid (51 mL) to adjust the pH value to be neutral, separating out a large amount of white solid, filtering, and washing a filter cake with tetrahydrofuran. The filtrate was concentrated in vacuo and then distilled under reduced pressure to give 48.1 g of 3-hydroxymethyltetrahydrofuran in a yield of 94.2%.
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-hydroxymethyltetrahydrofuran:
tetrahydrofuran-3-carbaldehyde (50.06 g, 0.5 mol) was dissolved in tetrahydrofuran (400 mL) and then cooled to 0oAnd C, adding potassium borohydride (32.36 g, 0.6 mol) into the solution in batches, stirring at room temperature for reaction for 3 hours after adding until the raw materials disappear, then slowly dropwise adding concentrated hydrochloric acid (51 mL) to adjust the pH value to be neutral, separating out a large amount of white solids, filtering, and washing a filter cake with methanol. The filtrate was concentrated in vacuo and then distilled under reduced pressure to give 47.85 g of 3-hydroxymethyltetrahydrofuran in 93.7% yield.

Claims (4)

1. A method for synthesizing 3-hydroxymethyl 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 Rh catalyst precursor is one of rhodium monochlorodicarbonyl dimer or bis (1, 5-cyclooctadiene rhodium chloride), and the organic phosphine ligand is one of tris (2, 4, 6-trimethylphenyl) phosphine and tri-o-tolylphosphine; the mass ratio of the 2, 5-dihydrofuran to the Rh catalyst precursor and the organic phosphine ligand is 300-5000: 1: 3-4;
2) carrying out hydroboration reduction reaction: reducing the tetrahydrofuran-3-formaldehyde obtained in the step 1) by using metal borohydride to generate 3-hydroxymethyl tetrahydrofuran; the hydroboration reduction reaction method comprises the following steps: dissolving tetrahydrofuran-3-formaldehyde in an organic solvent, cooling to 0-10 ℃, adding metal borohydride in batches, stirring at room temperature for reaction for 2-5 hours, adjusting the pH to be neutral by using concentrated hydrochloric acid, filtering, concentrating the filtrate in vacuum, and finally distilling under reduced pressure to obtain 3-hydroxymethyl tetrahydrofuran; the organic solvent is one of tetrahydrofuran, methanol or ethanol.
2. The method of claim 1, wherein said H in step 1) is2And CO at a pressure ratio of 1: 1.
3. the synthesis method according to claim 1, wherein the ratio of the amounts of the tetrahydrofuran-3-carbaldehyde and the metal borohydride in step 2) is 1: 1 to 1.2.
4. The method of claim 1, wherein the metal borohydride in step 2) is one of sodium borohydride and potassium borohydride.
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CN107793383A (en) * 2017-12-06 2018-03-13 成都化润药业有限公司 A kind of preparation method of 3 hydroxymethyl tetrahydrofuran
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Citations (4)

* Cited by examiner, † Cited by third party
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
CN106957286A (en) * 2017-05-17 2017-07-18 成都化润药业有限公司 A kind of synthetic method of 3 hydroxymethyl tetrahydrofuran

Patent Citations (4)

* Cited by examiner, † Cited by third party
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
CN106957286A (en) * 2017-05-17 2017-07-18 成都化润药业有限公司 A kind of synthetic method of 3 hydroxymethyl tetrahydrofuran

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