CN108424406B - Production process of 3-aminomethyl tetrahydrofuran - Google Patents

Production process of 3-aminomethyl tetrahydrofuran Download PDF

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CN108424406B
CN108424406B CN201810422658.XA CN201810422658A CN108424406B CN 108424406 B CN108424406 B CN 108424406B CN 201810422658 A CN201810422658 A CN 201810422658A CN 108424406 B CN108424406 B CN 108424406B
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tetrahydrofuran
dihydrofuran
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杨辉
崔军霞
刘镇
吴志强
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Hubei Jinghong Chemical Co ltd
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    • 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
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Abstract

The invention discloses a production process of 3-aminomethyl tetrahydrofuran, belonging to the field of pesticide intermediate synthesis processes. The process takes 2-butylene-1, 4-diol as an initial raw material, and synthesizes the 3-aminomethyl tetrahydrofuran through three steps of reactions of dehydration cyclization, hydroformylation and reductive amination. The production process has mild reaction conditions, low cost and less three wastes, and is suitable for industrial production.

Description

Production process of 3-aminomethyl tetrahydrofuran
Technical Field
The invention relates to the technical field of synthesis of pesticide intermediates, and particularly relates to a production process of 3-aminomethyl tetrahydrofuran.
Background
Dinotefuran is a novel nicotine pesticide developed by mitsui chemical corporation of japan, and has the following structure:
Figure BDA0001651154470000011
the dinotefuran does not contain chlorine atoms and aromatic rings, has the characteristic structure of 3-tetrahydrofuran methyl and is high in water solubility. It can kill insects by contact and stomach toxicity, and has the advantages of convenient use, strong systemic property, long lasting period, etc.; can be used on various crops such as rice, wheat and the like. Dinotefuran was marketed in japan in 2002; in 2003, it was marketed in korea; in 2004, first registered in the united states; in 2013, it was registered in China. Since the time of sale of dinotefuran, its sales continued to increase, reaching us $ 0.95 billion worldwide in 2014. Its compound patent CN1046508C in China and its key intermediate 3-aminomethyl tetrahydrofuran have expired in 10 months in 2014 in Chinese patent CN 1099418C. With the expiration of its patent and the expansion of the range of registered crops, its market prospect is much broader. The market demand for 3-aminomethyl tetrahydrofuran, a key intermediate, is also rapidly increasing.
At present, the literature reports that the synthesis of 3-aminomethyl tetrahydrofuran mainly comprises the following processes: the first synthetic route is as follows: (from patent CN1099418C)
Figure BDA0001651154470000021
Firstly, 3-hydroxymethyl tetrahydrofuran reacts with p-toluenesulfonyl chloride under the catalysis of triethylamine to generate sulfonic ester, then reacts with phthalimide potassium salt to obtain N- { (tetrahydro-3-furyl) -methyl) } phthalimide, and finally is hydrolyzed by sodium hydroxide to obtain 3-aminomethyl tetrahydrofuran.
Although the yield of the first route is high, the first route has many byproducts, high cost and poor atom economy.
The second synthetic route is as follows: (from patent CN1968941A)
Figure BDA0001651154470000022
Firstly, the malic acid is hydrogenated and reduced into 1, 2, 4-butanetriol by Ru/C catalysis, then the ring is closed under the catalysis of TsOH to obtain 3-hydroxytetrahydrofuran, and the 3-hydroxytetrahydrofuran is further reacted with SOCl2Obtaining 3-chloro tetrahydrofuran through reaction, then reacting with NaCN to generate 3-cyano tetrahydrofuran, and finally obtaining 3-aminomethyl tetrahydrofuran through Raney Ni catalytic hydrogenation.
The route two has five steps, the steps are longer, and expensive Ru/C and virulent NaCN are used, so that the cost is increased and the operation risk is increased.
The third synthetic route is as follows: (from patent WO2005066126)
Figure BDA0001651154470000023
Firstly, 3-tetrahydrofuran methanol reacts with methanesulfonic anhydride to generate sulfonic ester, and then reacts with NaN3The reaction is carried out to obtain 3- (azidomethyl) tetrahydrofuran, and finally the 3- (azidomethyl) tetrahydrofuran is reduced by catalytic hydrogenation.
Route three, NaN used3And the resulting azide are explosive, increasing the operational risk.
The synthesis route is four: (from patent CN106866588A)
Figure BDA0001651154470000031
Wherein X is H, F, Cl, OCH3、CF3Or SO3Na and the like.
Firstly, 1, 4-butylene glycol is dehydrated and cyclized under the action of a fixed acid catalyst (heteropoly acid, acidic resin or molecular sieve) to generate 2, 5-dihydrofuran, and then the 2, 5-dihydrofuran is added into HRhCO [ P (PhX)3]3Carrying out hydroformylation reaction under the catalysis of the catalyst to obtain 3-formyl tetrahydrofuran, then reacting with hydroxylamine to generate oxime compounds, and finally carrying out hydrogenation reaction under the action of Pd/C or Raney Ni to obtain the 3-aminomethyl tetrahydrofuran.
And the route IV has longer steps, the reaction temperature of the first step is too high (200 ℃ C. and 250 ℃ C.), the requirement on equipment is high, and the operation risk is increased.
The fifth synthetic route is as follows: (from patent CN106316993A)
Figure BDA0001651154470000041
And the fifth route is that dihydrofuran is firstly used as a raw material, dihydrofuran-3-formaldehyde is obtained through Vilsmeier formylation reaction, and finally, 3-aminomethyl tetrahydrofuran is obtained through reduction ammoniation under the catalysis of Pd/C or Raney Ni.
Route five although the procedure is short, POCl used in the first Vilsmeier formylation reaction3Has strong corrosion to equipment and has troublesome post-treatment.
The synthesis route is six: (from patent CN107417648A)
Figure BDA0001651154470000042
The sixth route is that diethyl maleate and nitromethane are subjected to Michael addition reaction to generate 2-nitromethyl-1, 4-diethyl succinate, and then the obtained product is subjected to NaBH4Reducing to obtain 2-nitromethyl-1, 4-butanediol, dehydrating and cyclizing under the catalysis of TsOH to generate 3-nitromethyl tetrahydrofuran, and finally obtaining the 3-aminomethyl tetrahydrofuran through catalytic hydrogenation.
The six steps of the route are longer, and NaBH4It is expensive and the post-treatment is complicated.
Disclosure of Invention
The invention aims to provide a production process of 3-aminomethyl tetrahydrofuran, which has the advantages of short synthetic route, low production cost, less three wastes and suitability for industrial production. The process is carried out by reacting 2-butene-1, 4-diol in B (C)6F5)3Heating to react under catalysis to generate 2, 5-dihydrofuran, and then reacting in Rh catalyst and NaBAr4(wherein Ar is aryl containing substituent trifluoromethyl) to produce hydroformylation reaction to obtain 3-formyl tetrahydrofuran, and finally to produce 3-aminomethyl tetrahydrofuran by Raney Ni catalytic hydrogenation reaction, wherein the process route is as follows:
Figure BDA0001651154470000051
the specific process steps of the process route of the invention are as follows:
first, 2-butene-1, 4-diol, at B (C)6F5)3Heating to react under catalysis to generate 2, 5-dihydrofuran; secondly, dissolving 2, 5-dihydrofuran in toluene, and introducing CO and H2In the presence of Rh catalyst and NaBAr4(wherein Ar is aryl containing substituent trifluoromethyl) at 80-100 ℃ to obtain 3-formyl tetrahydrofuran; in the third step, 3-formyltetrahydrofuran in NH3Heating to 50-80 deg.C, and carrying out Raney Ni catalytic hydrogenation reaction to obtain 3-aminomethyl tetrahydrofuran.
In the first step, the reaction temperature is 120-150 ℃.
In the first step, 2-butene-1, 4-diol, B (C)6F5)3In a molar ratio of 100: 1-5.
In the second step, the Rh catalyst is RhCl (CO) (DPPB).
In the second step, Ar is 3, 5-bis (trifluoromethyl) phenyl.
In the second step, the 2, 5-dihydrofuran, Rh catalyst and NaBAr4The molar ratio of (A) to (B) is 10000:1-1.5: 1-1.5.
In the second step, the reaction temperature is 90-95 ℃.
In the third step, the NH3The methanol solution of (2) was 7.0M.
The invention has the beneficial effects that:
1. the method has the advantages of short steps, high total yield, low cost and easy realization of industrial production.
2. The invention has mild reaction condition, no strong corrosive and explosive reagent, less three wastes and stronger production safety and operability.
Detailed Description
Example 1
The embodiment comprises the following steps:
step one, adding 8.81kg (100mol) of 1, 4-butylene glycol and 0.615kg (1.2mol) of tris (pentafluorophenyl) borane into a reaction kettle, reacting for 4.5h at 135 ℃, and carrying out reduced pressure distillation to obtain 6.71kg (95.7mol) of 2, 5-dihydrofuran, wherein the yield is 95.7%; h NMR (400MHz, CDCl)3):5.80(s,2H),4.55(s,4H)；
In a second step, 6.71kg (95.7mol) of 2, 5-dihydrofuran was dissolved in 9.5L of toluene in an autoclave, and 8.5g (14.4mmol) of RhCl (CO) (DPPB), NaB [3,5- (CF) were added3)2C6H3]412.7g (14.4mmol) of hydrogen was introduced into the autoclave after the atmosphere in the autoclave was replaced with nitrogen three times2Mixing with CO (volume ratio 1:1) until the total pressure is 4MPa, heating to 100 ℃, reacting for 2.5h, cooling to room temperature, slowly emptying, filtering, and distilling under reduced pressure to obtain 9.03kg (90.15mol) of 3-formyl tetrahydrofuran with the yield of 94.2%; h NMR (400MHz, CDCl)3):9.60(d,1H),3.92(m,2H),3.87(m,2H),3.05(m,1H),2.16(m,2H)；
Third, 9.03kg (90.15mol) of 3-formyltetrahydrofuran, 0.45kg of Raney Ni and 7.0M methanol solution (270.45mol,38.6L) were charged into an autoclave, and after the atmosphere in the autoclave was replaced with nitrogen gas three times, H was introduced thereinto2The reaction was stirred at 60 ℃ for 8h to a total pressure of 3.5MPa, cooled to room temperature, filtered to remove Raney Ni, concentrated to remove methanol, and distilled under reduced pressure to give 8.88kg (87.8mol) of 3-aminomethyltetrahydrofuran in a yield of 97.4%. H NMR (400MHz, CDCl)3):4.82(s,2H),3.82-3.91(m,1H),3.72-3.78(m,1H),3.49-3.51(m,1H),2.70-2.73(d,2H),2.23-2.35(m,2H),1.99-2.10(m,1H),1.53-1.63(m,1H).
Example 2
The embodiment comprises the following steps:
in the first step, 8.81kg of 1, 4-butylene glycol (1, 4-butylene glycol) is added into a reaction kettle100mol) and 1.024kg (2mol) of tris (pentafluorophenyl) borane, reacting for 5h at 125 ℃, and distilling under reduced pressure to obtain 6.48kg (92.5mol) of 2, 5-dihydrofuran, wherein the yield is 92.5%; h NMR (400MHz, CDCl)3):5.80(s,2H),4.55(s,4H)；
In a second step, 6.48kg (92.5mol) of 2, 5-dihydrofuran was dissolved in 9L of toluene in an autoclave, and 6.5g (11.1mmol) of RhCl (CO) (DPPB), NaB (3,5- (CF)3)2C6H3)49.8g (11.1mmol) of the reaction solution was purged with nitrogen three times, and then H was introduced thereinto2Mixing with CO (volume ratio 1:1) until the total pressure is 4MPa, heating to 90 ℃, reacting for 4h, cooling to room temperature, slowly emptying, filtering, and distilling under reduced pressure to obtain 8.87kg (88.6mol) of 3-formyl tetrahydrofuran with the yield of 95.8%; h NMR (400MHz, CDCl)3):9.60(d,1H),3.92(m,2H),3.87(m,2H),3.05(m,1H),2.16(m,2H)；
Third, 8.87kg (88.6mol) of 3-formyltetrahydrofuran, 0.44kg of Raney Ni, and 7.0M methanol solution (265.8mol,38L) were charged into an autoclave, and after the atmosphere in the autoclave was replaced with nitrogen three times, H was introduced thereinto2The reaction was stirred at 60 ℃ for 8h to a total pressure of 3.5MPa, cooled to room temperature, filtered to remove Raney Ni, concentrated to remove methanol, and distilled under reduced pressure to give 8.76kg (86.65mol) of 3-aminomethyltetrahydrofuran in a yield of 97.8%. H NMR (400MHz, CDCl)3):4.82(s,2H),3.82-3.91(m,1H),3.72-3.78(m,1H),3.49-3.51(m,1H),2.70-2.73(d,2H),2.23-2.35(m,2H),1.99-2.10(m,1H),1.53-1.63(m,1H).
Example 3
The embodiment comprises the following steps:
step one, adding 8.81kg (100mol) of 1, 4-butylene glycol and 0.512kg (1mol) of tris (pentafluorophenyl) borane into a reaction kettle, reacting for 6h at 125 ℃, and carrying out reduced pressure distillation to obtain 6.81kg (97.1mol) of 2, 5-dihydrofuran, wherein the yield is 97.1%; h NMR (400MHz, CDCl)3):5.80(s,2H),4.55(s,4H)；
In a second step, 6.81kg (97.1mol) of 2, 5-dihydrofuran was dissolved in 10L of toluene in an autoclave, and 5.7g (9.71mmol) of RhCl (CO) (DPPB), NaB (3,5- (CF)3)2C6H3)48.5g (9.71mmol), and the atmosphere in the autoclave was replaced with nitrogen three timesThereafter, H is introduced2Mixing with CO (volume ratio 1:1) until the total pressure is 4MPa, heating to 95 ℃, reacting for 3h, cooling to room temperature, slowly emptying, filtering, and distilling under reduced pressure to obtain 9.39kg (93.8mol) of 3-formyl tetrahydrofuran with the yield of 96.6%; h NMR (400MHz, CDCl)3):9.60(d,1H),3.92(m,2H),3.87(m,2H),3.05(m,1H),2.16(m,2H)；
Third, 9.39kg (93.8mol) of 3-formyltetrahydrofuran, 0.47kg of Raney Ni, and 7.0M methanol solution (281.4mol,40.2L) were charged into an autoclave, and after the atmosphere in the autoclave was replaced with nitrogen three times, H was introduced thereinto2The reaction was stirred at 60 ℃ for 8.5h to a total pressure of 3.5MPa, cooled to room temperature, filtered to remove Raney Ni, concentrated to remove methanol, and distilled under reduced pressure to give 9.32kg (92.11mol) of 3-aminomethyltetrahydrofuran in a yield of 98.2%. H NMR (400MHz, CDCl)3):4.82(s,2H),3.82-3.91(m,1H),3.72-3.78(m,1H),3.49-3.51(m,1H),2.70-2.73(d,2H),2.23-2.35(m,2H),1.99-2.10(m,1H),1.53-1.63(m,1H).
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.

Claims (6)

1. The production process of the 3-aminomethyl tetrahydrofuran is obtained by three steps of reactions and is characterized in that the reaction route is as follows:
Figure FDA0002942990800000011
the method comprises the following steps:
the first step is as follows: 2-butene-1, 4-diol in B (C)6F5)3Heating to react under catalysis to generate 2, 5-dihydrofuran;
the second step is that: dissolving 2, 5-dihydrofuran in toluene, and introducing CO and H in a volume ratio of 1:12In the presence of Rh catalyst and NaBAr4In the presence of the solvent, reacting at 80-100 ℃ to obtain 3-formyl tetrahydrofuran; the Rh catalyzesThe reagent is RhCl (CO) (DPPB), Ar is 3, 5-bis (trifluoromethyl) phenyl;
the third step: 3-formyl tetrahydrofuran, heating to 50-80 ℃ in an ammonia methanol solution, and carrying out Raney Ni catalytic hydrogenation reaction to obtain the 3-aminomethyl tetrahydrofuran.
2. The process according to claim 1, wherein the reaction is carried out in the presence of a catalyst selected from the group consisting of: in the first step, the reaction temperature is 120-150 ℃.
3. The process according to claim 1, wherein the reaction is carried out in the presence of a catalyst selected from the group consisting of: in the first step, 2-butene-1, 4-diol, B (C)6F5)3In a molar ratio of 100: 1-5.
4. The process according to claim 1, wherein the reaction is carried out in the presence of a catalyst selected from the group consisting of: in the second step, 2, 5-dihydrofuran, Rh catalyst and NaBAr4The molar ratio is 10000:1-1.5: 1-1.5.
5. The process according to claim 1, wherein the reaction is carried out in the presence of a catalyst selected from the group consisting of: in the second step, the reaction temperature is 90-95 ℃.
6. The process according to claim 1, wherein the reaction is carried out in the presence of a catalyst selected from the group consisting of: in the third step, the ammonia methanol solution was 7.0M.
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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
CN116063256A (en) * 2022-12-24 2023-05-05 宁波科诺华化工有限公司 Preparation method of 3-aminomethyltetrahydrofuran based on palladium-catalyzed cyano exchange

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