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CN111303083A - Synthetic method of 3-aminomethyl tetrahydrofuran - Google Patents

Synthetic method of 3-aminomethyl tetrahydrofuran Download PDF

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CN111303083A
CN111303083A CN202010240670.6A CN202010240670A CN111303083A CN 111303083 A CN111303083 A CN 111303083A CN 202010240670 A CN202010240670 A CN 202010240670A CN 111303083 A CN111303083 A CN 111303083A
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tetrahydrofuran
reaction
palladium
catalyst
aminomethyl
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刘显伟
马青松
马心旺
孙东艳
魏力璟
苏建
刘娇
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Anhui Zhongcarbonyl Carbon 1 Industrial Technology Co ltd
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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
    • C07D307/14—Radicals substituted by nitrogen atoms not forming part of a nitro radical
    • 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
    • C07D307/18—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/24—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen

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Abstract

The invention provides a synthesis method of 3-aminomethyl tetrahydrofuran, which is characterized in that 2, 5-dihydrofuran is used as an initial raw material to prepare a target product of 3-aminomethyl tetrahydrofuran, and the raw material used in the whole synthesis process is green and environment-friendly, the reaction condition is mild and is beneficial to control, the production is safe, the risk is lower, the process is simple, the yield is high, and the synthesis method is more suitable for industrial production.

Description

Synthetic method of 3-aminomethyl tetrahydrofuran
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a synthetic method of 3-aminomethyl tetrahydrofuran.
Background
Dinotefuran is the latest generation of nicotine pesticide, and has the following chemical structural formula:
Figure BDA0002432442220000011
compared with the traditional nicotine pesticide, the structure of the pesticide replaces the prior chloropyridyl and chlorothiazide with tetrahydrofuranyl, so that the pesticide has better water solubility, wider insecticidal range on performance and longer pesticide effect period, thereby having wide market prospect.
3-aminomethyl tetrahydrofuran is an important intermediate for industrial production of dinotefuran, and a plurality of methods for synthesizing 3-aminomethyl tetrahydrofuran are reported in the prior literature.
For example, in the method for synthesizing 3-aminomethyl tetrahydrofuran generally used in actual production in factories at present, reference is made to a method for preparing 3-hydroxymethyl tetrahydrofuran by using diethyl malonate and ethyl chloroacetate as raw materials proposed in Liuanchang et al in 2009, and reference can also be made to patent CN104961710A, wherein the produced 3-hydroxymethyl tetrahydrofuran is reacted with methanesulfonyl chloride to prepare 3-methylsulfonate tetrahydrofuran, and finally the 3-aminomethyl tetrahydrofuran is obtained by reacting Schiff base with hydrazine hydrate. The specific route is as follows:
Figure BDA0002432442220000012
however, in the above method, the operation process is complicated, a large amount of three wastes exist, and the amount of the auxiliary raw materials used in the reaction, such as sodium borohydride and the like, is large and the price rises all the time, so that the production cost is higher and higher.
The methods proposed in recent years are simpler than the reaction routes in the past, but have drawbacks. For example, chinese patent CN106316993A reports a method for synthesizing 3-aminomethyl tetrahydrofuran from 2, 3-dihydrofuran or 2, 5-dihydrofuran:
Figure BDA0002432442220000021
although the method has fewer steps, the reaction conditions are harsh, the used inorganic acyl chloride is toxic, strong acid can be generated to cause great corrosivity to reaction equipment, and the industrialization difficulty is great.
Chinese patents CN106866588A and CN108424406A both use 1, 4-butylene glycol as a raw material to produce 2, 5-dihydrofuran, so that the 2, 5-dihydrofuran, carbon monoxide and hydrogen undergo a hydroformylation reaction under the action of a Rh homogeneous catalyst to produce 3-formyltetrahydrofuran, and then prepare 3-aminomethyl tetrahydrofuran, the methods are respectively:
Figure BDA0002432442220000022
both methods have high requirements on the catalyst, and the selectable catalysts have few types and high price, so the industrial cost is too high.
Chinese patent CN106995422A discloses a method for synthesizing 3-cyanotetrahydrofuran by using acrylonitrile and ethylene oxide as raw materials and using organic base and the like as catalysts at low temperature, and then obtaining 3-aminomethyl tetrahydrofuran by catalytic hydrogenation:
Figure BDA0002432442220000031
although the starting raw materials are simple and easy to obtain, the reaction needs to be controlled under low-temperature and dry conditions, the conditions are harsh, the amount of the used organic strong base catalyst is large, the production cost is increased, and the method is not beneficial to industrialization.
Therefore, the defects of poor process safety, high technical condition requirement, high cost, low yield and the like in the existing synthesis production of the 3-aminomethyl tetrahydrofuran are overcome.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a synthesis method of 3-aminomethyl tetrahydrofuran, which is characterized in that 2, 5-dihydrofuran is used as an initial raw material to prepare a target product of 3-aminomethyl tetrahydrofuran, the raw materials used in the whole synthesis process are green and environment-friendly, the reaction conditions are mild and are beneficial to control, the production is safe, the risk is low, the process is simple, the yield is high, and the method is more suitable for industrial production.
The invention provides a synthetic method of 3-aminomethyl tetrahydrofuran, which comprises the following steps:
(1) performing hydro-aminocarbonylation reaction on 2, 5-dihydrofuran to obtain 3-formamide tetrahydrofuran;
(2) performing dehydration cyanation reaction on 3-formamide tetrahydrofuran to obtain 3-cyano tetrahydrofuran;
(3) and carrying out catalytic hydrogenation reaction on the 3-cyano tetrahydrofuran to obtain the 3-aminomethyl tetrahydrofuran.
Preferably, the structural formula of the 3-carboxamide tetrahydrofuran is:
Figure BDA0002432442220000032
in the step (1), the hydroaminocarbonylation reaction of olefin specifically comprises: under the action of a catalyst, 2, 5-dihydrofuran reacts with carbon monoxide and ammonium salt in a solvent to obtain 3-formamide tetrahydrofuran.
Preferably, the catalyst is one or a combination of more of palladium dichloride, palladium dibromide, palladium diiodide, palladium acetate, palladium trifluoroacetate, allyl palladium chloride, sodium chloropalladate, potassium chloropalladate, palladium trifluoromethanesulfonate, tetrakis (acetonitrile) palladium (II) bis (trifluoromethanesulfonate), tris (dibenzylideneacetone) dipalladium, diacetonitrile palladium dichloride and dibenzonitrile palladium dichloride;
the ammonium salt is one or a combination of ammonium chloride and ammonium bromide;
the solvent is one or more of toluene, xylene, trifluorotoluene, acetonitrile, propionitrile, dichloromethane, chloroform, carbon tetrachloride, methyl tert-butyl ether, tetrahydrofuran, N-dimethylformamide, N-methylpyrrolidone, methanol, ethanol and tert-amyl alcohol.
Preferably, the dosage of the catalyst is 0.1-10% of the molar amount of 2, 5-dihydrofuran, the dosage of the ammonium salt is 1-10 times of the molar amount of 2, 5-dihydrofuran, and the pressure of carbon monoxide is 0.1-10 MPa; preferably, the reaction temperature is 50-200 ℃.
In the step (1), the reaction raw materials and the catalyst of the 2, 5-dihydrofuran and the ammonium salt are cheap and easy to obtain, are clean and nontoxic and have little pollution to the environment; the integral synthesis process is simple, and the cost is greatly reduced; meanwhile, the reaction condition is mild, the reaction selectivity is good, and the yield is high.
Preferably, the structural formula of the 3-cyanotetrahydrofuran is:
Figure BDA0002432442220000041
in the step (2), the dehydrocyanation reaction specifically comprises: under the action of a dehydrating agent and/or a catalyst, 3-formamide tetrahydrofuran reacts in an organic solvent to obtain 3-cyano tetrahydrofuran.
Preferably, the dehydrating agent is one or a combination of more of phosphorus oxychloride, phosphorus pentachloride, thionyl chloride, trifluoroacetic anhydride, methanesulfonyl chloride and titanium tetrachloride;
the catalyst is one or a combination of more of dibutyl tin oxide, aluminum oxide, sulfamic acid, p-toluenesulfonic acid, zinc chloride and boric acid;
the organic solvent is one or a combination of more of toluene, xylene, methyl benzoate, diphenyl ether, diethyl ether, tetrahydrofuran, chloroform, carbon tetrachloride, dimethyl sulfoxide and acetonitrile.
Preferably, the dosage of the dehydrating agent is 1 to 3 times of the molar weight of the 3-formamide tetrahydrofuran, and the dosage of the catalyst is 0.1 to 10 percent of the molar weight of the 3-formamide tetrahydrofuran; preferably, the reaction temperature is 50-200 ℃.
In the step (2), the 3-formamide tetrahydrofuran generated in the previous step is subjected to dehydration cyanation reaction. The reaction process is simple, the product is single, and the yield is high.
Preferably, the structural formula of the 3-aminomethyl tetrahydrofuran is:
Figure BDA0002432442220000051
in the step (3), the catalytic hydrogenation reaction specifically comprises: under the action of a hydrogenation catalyst, 3-cyano tetrahydrofuran and hydrogen react in a reaction solvent to obtain 3-aminomethyl tetrahydrofuran.
Preferably, the hydrogenation catalyst is a raney-type catalyst and/or a transition metal supported catalyst;
the Raney type catalyst is preferably one or the combination of more of Raney nickel, Raney cobalt, Raney palladium and Raney copper; the transition metal supported catalyst is preferably one or a combination of more of palladium/carbon, platinum/carbon, palladium/barium sulfate, nickel/alumina, platinum/alumina, palladium/ferroferric oxide, nickel-copper/alumina, rhodium/silica and platinum-rhodium/alumina;
the reaction solvent is one or the combination of more of methanol, ethanol and isopropanol.
Preferably, the dosage of the hydrogenation catalyst is 1-10% of the mass of the 3-cyano tetrahydrofuran, and the pressure of hydrogen is 0.1-10 MPa; preferably, the reaction temperature is 50-150 ℃.
In the step (3), the 3-cyano tetrahydrofuran generated in the previous step is subjected to catalytic hydrogenation reaction to obtain the target product 3-aminomethyl tetrahydrofuran. The catalytic hydrogenation reaction conditions (temperature range of 50-150 ℃, hydrogen pressure of 0.1-10 MPa) of nitrile groups are relatively mild, the product yield is high, the product separation is easy, the process is simple, and the method is environment-friendly, so that the method has strong industrial application significance.
The invention provides a synthetic method of 3-aminomethyl tetrahydrofuran, which comprises the following synthetic route:
Figure BDA0002432442220000061
the method is green and environment-friendly, has simple process, is a breakthrough of germplasm in the conventional synthesis method and process, avoids the defects of the conventional method, and is expected to realize industrialization.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of 3-aminomethyl tetrahydrofuran;
FIG. 2 is a gas chromatogram of 3-aminomethyltetrahydrofuran.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
A synthetic method of 3-aminomethyl tetrahydrofuran specifically comprises the following steps:
(1) adding ammonium chloride (5.35g, 0.1mol), 2, 5-dihydrofuran (7.01g, 0.1mol) and palladium dichloride (0.0177g, 0.0001mol) into 20mL of N-methylpyrrolidone, placing the mixture into a high-pressure reaction kettle, replacing air in the reaction kettle with carbon monoxide for three times, filling carbon monoxide (0.1MPa) into the reaction kettle, reacting in an oil bath at 200 ℃ for 24 hours, stopping the reaction, evaporating the solvent to dryness, and recrystallizing with ethanol to obtain a white-like solid 7.63g, namely 3-formamide tetrahydrofuran, wherein the purity is 95% and the yield is 63%;
(2) dissolving the off-white solid (6.06g, 0.05mol of 3-formamide tetrahydrofuran) obtained in the step (1) in toluene (50mL), adding phosphorus pentachloride (10.41g, 0.05mol), stirring at room temperature for 20min, heating to 50 ℃, stirring for 30min, washing with 10mL of water for three times after the reaction is finished, separating an organic phase, and distilling under reduced pressure to obtain light yellow oily liquid 4.78g, namely 3-cyano tetrahydrofuran with the purity of 91% and the yield of 89.6%;
(3) putting the light yellow oily liquid (5.33g, 0.05mol of 3-cyanotetrahydrofuran) obtained in the step (2), absolute ethyl alcohol (20mL) and raney nickel (0.055g) into a high-pressure reaction kettle, closing a kettle cover, introducing nitrogen for leak detection, introducing nitrogen into the high-pressure reaction kettle for three times and then introducing hydrogen for three times if no gas is leaked, wherein the replacement pressure is 1MPa, then introducing hydrogen (0.1MPa), heating to 150 ℃ under stirring, carrying out heat preservation reaction for 3 hours, filtering the reaction liquid after the reaction is finished, washing filter residues with a small amount of ethanol twice, combining the filtrate and the washing liquid, and concentrating to obtain 4.84g of colorless oily liquid, namely 3-aminomethyl tetrahydrofuran, the purity (gas chromatography internal standard method) is 96%, and the yield is 92%;
wherein, the hydrogen spectrum of the 3-aminomethyl tetrahydrofuran is shown in figure 1,1HNMR(400MHz，Chloroform-d)3.64-3.52(m，2H)，3.46(dt，J＝8.4，7.3Hz，1H)，3.23(dd，J＝8.6，5.9Hz，1H)，2.49-2.36(m，2H)，2.07-1.95(m，1H)，1.83-1.70(m，1H)，1.31(dtd，J＝12.2，7.7，6.5Hz，1H)，1.14(s，2H)。
gas chromatography of 3-aminomethyl tetrahydrofuran as shown in fig. 2, the purity was as high as 99% or more as determined by Gas Chromatography (GC), wherein the retention time (min) of the peak of 3-aminomethyl tetrahydrofuran in the gas chromatogram shown in fig. 2: 4.059, type: BB, peak width (min): 0.0702, peak area: 24317.8887, peak height: 4363.3940, area (%): 99.4053.
example 2
A synthetic method of 3-aminomethyl tetrahydrofuran specifically comprises the following steps:
(1) adding ammonium chloride (107g, 2mol), 2, 5-dihydrofuran (14.02g, 0.2mol) and palladium acetate (4.49g, 0.02mol) into 40mL tetrahydrofuran, then placing the tetrahydrofuran into a high-pressure reaction kettle, replacing air in the reaction kettle with carbon monoxide for three times, filling carbon monoxide (10MPa), reacting in an oil bath at 50 ℃ for 24 hours, stopping the reaction, evaporating the solvent from the reaction solution, and recrystallizing with ethanol to obtain 15.73g of a white-like solid, namely 3-formamide tetrahydrofuran, wherein the purity is 95% and the yield is 65%;
(2) dissolving the off-white solid (6.06g, 0.05mol of 3-formamide tetrahydrofuran) obtained in the step (1) in diphenyl ether (50mL), adding dibutyltin oxide (1.245g, 0.005mol), heating to 200 ℃, reacting for 1.5h until no water is distilled off, filtering to remove dibutyltin oxide while hot, concentrating to remove diphenyl ether, carrying out reduced pressure distillation, and collecting light yellow oily liquid 4.75g, namely 3-cyano tetrahydrofuran, wherein the purity is 92% and the yield is 90%;
(3) putting the light yellow oily liquid (5.28g, 0.05mol of 3-cyanotetrahydrofuran) obtained in the step (2), anhydrous methanol (20mL) and a Pd/C catalyst (0.51g) into a high-pressure reaction kettle, closing a kettle cover, introducing nitrogen for leak detection, introducing nitrogen into the reaction kettle for three times for replacement if no gas is leaked, introducing hydrogen into the reaction kettle for three times for replacement, introducing hydrogen (10MPa), heating to 50 ℃ under stirring, carrying out heat preservation reaction for 5 hours, filtering the reaction liquid after the reaction is finished, washing filter residues with a small amount of methanol twice, combining the filtrate and a washing liquid, carrying out reduced pressure distillation, and collecting 4.8g of colorless oily liquid of the fraction, namely the 3-aminomethyl tetrahydrofuran, wherein the purity (gas chromatography internal standard method) is 96%, and the yield is 91%.
Example 3
A synthetic method of 3-aminomethyl tetrahydrofuran specifically comprises the following steps:
(1) adding ammonium bromide (48.98g, 0.5mol), 2, 5-dihydrofuran (14.02g, 0.2mol) and sodium chloropalladate (2.942g, 0.01mol) into 40mL of N, N-dimethylformamide, then placing into a high-pressure reaction kettle, replacing air in the reaction kettle with carbon monoxide for three times, filling carbon monoxide (3MPa), reacting in an oil bath at 100 ℃ for 24 hours, stopping the reaction, distilling under reduced pressure, collecting required fractions, cooling, recrystallizing with ethanol to obtain 15.75g of white-like solid, namely 3-formamide tetrahydrofuran, with the purity of 95% and the yield of 65%;
(2) dissolving the off-white solid (4.24g, 0.035mol of 3-formamide tetrahydrofuran) obtained in the step (1) in toluene (50mL), adding phosphorus oxychloride (9.79mL, 0.105mol) and aluminum oxide (0.036g, 0.00035mol), heating until reflux reaction lasts for 2 hours until no water is distilled off, carrying out heat filtration after the reaction is finished, washing with 10mL water for three times, separating out an organic phase, and carrying out reduced pressure distillation to obtain 3.31g of light yellow oily liquid, namely 3-cyano tetrahydrofuran, wherein the purity is 90%, and the yield is 87.6%;
(3) the pale yellow oily liquid obtained in step (2) (4.85g, 0.045mol of 3-cyanotetrahydrofuran) and absolute ethanol (20mL), Pt/Al2O3Putting a catalyst (0.1g) into a high-pressure reaction kettle, closing a kettle cover, introducing nitrogen for leak detection, introducing nitrogen into the reaction kettle for three times of replacement and then introducing hydrogen for three times of replacement if no gas is leaked, wherein the replacement pressure is 1MPa, then introducing hydrogen (4MPa), heating to 75 ℃ under the stirring condition, carrying out heat preservation reaction for 2 hours, carrying out suction filtration on reaction liquid after the reaction is finished, washing filter residues twice by using a small amount of ethanol, combining filtrate and washing liquid, carrying out reduced pressure distillation, cooling and crystallizing to obtain colorless oily liquid4.36g of the product is 3-aminomethyl tetrahydrofuran, the purity (gas chromatography internal standard method) is 96 percent, and the yield is 92 percent.
Example 4
A synthetic method of 3-aminomethyl tetrahydrofuran specifically comprises the following steps:
(1) adding ammonium bromide (48.98g, 0.5mol), 2, 5-dihydrofuran (14.02g, 0.2mol) and diacetonitrile palladium dichloride (0.104g, 0.0004mol) into 40mL of chloroform, then placing the chloroform into a high-pressure reaction kettle, replacing air in the reaction kettle with carbon monoxide for three times, filling carbon monoxide (3MPa), reacting in an oil bath at 60 ℃ for 24 hours, stopping the reaction, distilling under reduced pressure, collecting required fractions, cooling and crystallizing, and recrystallizing with ethanol to obtain a white-like solid 16.17g, namely 3-formamide tetrahydrofuran, wherein the purity is 95%, and the yield is 67%;
(2) dissolving the off-white solid (4.24g, 0.035mol of 3-formamide tetrahydrofuran) obtained in the step (1) in dimethylbenzene (50mL), dropwise adding titanium tetrachloride (7.7mL, 0.07mol) under the condition of ice-water bath, stirring at room temperature for 10min after dropwise adding is finished, then stirring for 60min after heating to 50 ℃, finishing the reaction, washing with 20mL of water for three times, separating an organic phase, and then carrying out reduced pressure distillation to collect 3.22g of light yellow oily liquid, namely 3-cyano tetrahydrofuran, wherein the purity is 89%, and the yield is 84%;
(3) putting the light yellow oily liquid (5.45g, 0.05mol of 3-cyanotetrahydrofuran) obtained in the step (2), isopropanol (20mL) and a Pt/C catalyst (0.1g) into a high-pressure reaction kettle, closing a kettle cover, introducing nitrogen for leak detection, introducing nitrogen into the reaction kettle for three times for replacement if no gas is leaked, introducing hydrogen for three times for replacement, introducing hydrogen (4MPa), heating to 70 ℃ under the stirring condition, keeping the temperature for reaction for 5 hours, performing suction filtration on reaction liquid after the reaction is finished, washing filter residues with a small amount of isopropanol for two times, combining the filtrate and washing liquid for reduced pressure distillation, and cooling and crystallizing to obtain 4.85g of colorless oily liquid, namely 3-aminomethyl tetrahydrofuran, with the purity (gas chromatography internal standard method) of 96% and the yield of 92%.
Example 5
A synthetic method of 3-aminomethyl tetrahydrofuran specifically comprises the following steps:
(1) adding ammonium bromide (97.95g, 1mol), 2, 5-dihydrofuran (35.05g, 0.5mol) and sodium chloropalladate (2.942g, 0.01mol) into 100mL of ethanol, then placing the mixture into a high-pressure reaction kettle, replacing air in the reaction kettle with carbon monoxide for three times, filling carbon monoxide (3MPa), reacting in an oil bath at 100 ℃ for 24 hours, stopping the reaction, distilling under reduced pressure, collecting required fractions, cooling for crystallization, and recrystallizing with ethanol to obtain a white-like solid 41.81g, namely 3-formamide tetrahydrofuran, wherein the purity is 95% and the yield is 69%;
(2) dissolving the off-white solid (36.36g, 0.3mol of 3-formamide tetrahydrofuran) obtained in the step (1) in methyl benzoate (200mL), adding phosphorus pentachloride (62.47g, 0.3mol) in batches under the condition of stirring in an ice-water bath, slowly dropwise adding p-toluenesulfonic acid (0.52g, 0.003mol) after the addition is finished, removing the ice-water bath after the dropwise adding is finished, stirring for 1 hour at room temperature, gradually heating to reflux reaction for 1 hour, carrying out thermal filtration after the reaction is finished, washing the filtrate for three times by 50mL of water, and carrying out reduced pressure distillation or rectification on the layered collected organic phase to obtain 29.13g of light yellow oily liquid, namely 3-cyano tetrahydrofuran, wherein the purity is 90% and the yield is 90%;
(3) the pale yellow oily liquid obtained in step (2) (37.72g, 0.35mol of 3-cyanotetrahydrofuran) and anhydrous ethanol (200mL), Pd/Fe3O4Putting a catalyst (1g) into a high-pressure reaction kettle, closing a kettle cover, introducing nitrogen for leak detection, introducing nitrogen into the reaction kettle for three times of replacement and then introducing hydrogen for three times of replacement if no gas is leaked, wherein the replacement pressure is 1MPa, then introducing hydrogen (6MPa), heating to 80 ℃ under the stirring condition, carrying out heat preservation reaction for 3 hours, carrying out suction filtration on reaction liquid after the reaction is finished, washing filter residues twice by using a small amount of ethanol, combining filtrate and washing liquid, carrying out reduced pressure distillation, cooling and crystallizing to obtain 33.02g of colorless oily liquid, namely 3-aminomethyl tetrahydrofuran, wherein the purity (gas chromatography internal standard method) is 96.5%, and the yield is 90%.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered as the technical scope of the present invention, and equivalents and modifications thereof should be included in the technical scope of the present invention.

Claims (10)

1. A method for synthesizing 3-aminomethyl tetrahydrofuran is characterized by comprising the following steps:
(1) performing hydro-aminocarbonylation reaction on 2, 5-dihydrofuran to obtain 3-formamide tetrahydrofuran;
(2) performing dehydration cyanation reaction on 3-formamide tetrahydrofuran to obtain 3-cyano tetrahydrofuran;
(3) and carrying out catalytic hydrogenation reaction on the 3-cyano tetrahydrofuran to obtain the 3-aminomethyl tetrahydrofuran.
2. The method of claim 1, wherein the structural formula of the 3-carboxamide tetrahydrofuran is:
Figure FDA0002432442210000011
in the step (1), the hydroaminocarbonylation reaction of olefin specifically comprises: under the action of a catalyst, 2, 5-dihydrofuran reacts with carbon monoxide and ammonium salt in a solvent to obtain 3-formamide tetrahydrofuran.
3. The method of claim 2, wherein the catalyst is a combination of one or more of palladium dichloride, palladium dibromide, palladium diiodide, palladium acetate, palladium trifluoroacetate, allylpalladium chloride, sodium chloropalladate, potassium chloropalladate, palladium trifluoromethanesulfonate, tetrakis (acetonitrile) palladium (II) bis (trifluoromethanesulfonate), tris (dibenzylideneacetone) dipalladium, bis-acetonitrile palladium dichloride, and dibenzonitrile palladium dichloride;
the ammonium salt is one or a combination of ammonium chloride and ammonium bromide;
the solvent is one or more of toluene, xylene, trifluorotoluene, acetonitrile, propionitrile, dichloromethane, chloroform, carbon tetrachloride, methyl tert-butyl ether, tetrahydrofuran, N-dimethylformamide, N-methylpyrrolidone, methanol, ethanol and tert-amyl alcohol.
4. The method for synthesizing 3-aminomethyl tetrahydrofuran according to claim 2 or 3, wherein the amount of said catalyst is 0.1 to 10% by mole of 2, 5-dihydrofuran, the amount of said ammonium salt is 1 to 10 times by mole of 2, 5-dihydrofuran, and the pressure of carbon monoxide is 0.1 to 10 MPa; preferably, the reaction temperature is 50-200 ℃.
5. The method for synthesizing 3-aminomethyl tetrahydrofuran according to any one of claims 1 to 4, wherein the structural formula of 3-cyanotetrahydrofuran is:
Figure FDA0002432442210000021
in the step (2), the dehydrocyanation reaction specifically comprises: under the action of a dehydrating agent and/or a catalyst, 3-formamide tetrahydrofuran reacts in an organic solvent to obtain 3-cyano tetrahydrofuran.
6. The method for synthesizing 3-aminomethyl tetrahydrofuran according to claim 5, wherein the dehydrating agent is one or more of phosphine oxychloride, phosphorus pentachloride, thionyl chloride, trifluoroacetic anhydride, methanesulfonyl chloride, and titanium tetrachloride;
the catalyst is one or a combination of more of dibutyl tin oxide, aluminum oxide, sulfamic acid, p-toluenesulfonic acid, zinc chloride and boric acid;
the organic solvent is one or a combination of more of toluene, xylene, methyl benzoate, diphenyl ether, diethyl ether, tetrahydrofuran, chloroform, carbon tetrachloride, dimethyl sulfoxide and acetonitrile.
7. The method for synthesizing 3-aminomethyl tetrahydrofuran according to claim 5 or 6, wherein the amount of the dehydrating agent is 1 to 3 times of the molar amount of 3-formamide tetrahydrofuran, and the amount of the catalyst is 0.1 to 10% of the molar amount of 3-formamide tetrahydrofuran; preferably, the reaction temperature is 50-200 ℃.
8. The method for synthesizing 3-aminomethyl tetrahydrofuran according to any one of claims 1 to 7, wherein the structural formula of 3-aminomethyl tetrahydrofuran is:
Figure FDA0002432442210000022
in the step (3), the catalytic hydrogenation reaction specifically comprises: under the action of a hydrogenation catalyst, 3-cyano tetrahydrofuran and hydrogen react in a reaction solvent to obtain 3-aminomethyl tetrahydrofuran.
9. The method according to claim 8, wherein the hydrogenation catalyst is a raney-type catalyst and/or a transition metal-supported catalyst;
the Raney type catalyst is preferably one or the combination of more of Raney nickel, Raney cobalt, Raney palladium and Raney copper; the transition metal supported catalyst is preferably one or a combination of more of palladium/carbon, platinum/carbon, palladium/barium sulfate, nickel/alumina, platinum/alumina, palladium/ferroferric oxide, nickel-copper/alumina, rhodium/silica and platinum-rhodium/alumina;
the reaction solvent is one or the combination of more of methanol, ethanol and isopropanol.
10. The method for synthesizing 3-aminomethyl tetrahydrofuran according to claim 8 or 9, wherein the amount of the hydrogenation catalyst is 1 to 10% by mass of the 3-cyanotetrahydrofuran, and the pressure of hydrogen is 0.1 to 10 MPa; preferably, the reaction temperature is 50-150 ℃.
CN202010240670.6A 2020-03-31 2020-03-31 Synthetic method of 3-aminomethyl tetrahydrofuran Pending CN111303083A (en)

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