CN116063256B - Preparation method of 3-aminomethyltetrahydrofuran based on palladium-catalyzed cyano exchange - Google Patents

Preparation method of 3-aminomethyltetrahydrofuran based on palladium-catalyzed cyano exchange Download PDF

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CN116063256B
CN116063256B CN202211669240.1A CN202211669240A CN116063256B CN 116063256 B CN116063256 B CN 116063256B CN 202211669240 A CN202211669240 A CN 202211669240A CN 116063256 B CN116063256 B CN 116063256B
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cyano
catalyst
dihydrofuran
tetrahydrofuran
cyclohexadiene
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CN116063256A (en
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葛主阁
王都广
曾小军
冯高峰
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Ningbo Kenova Chemical Co ltd
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    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
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    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2419—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising P as ring member
    • B01J31/2428—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising P as ring member with more than one complexing phosphine-P atom
    • B01J31/2433—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising P as ring member with more than one complexing phosphine-P atom comprising aliphatic or saturated rings
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    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
    • B01J31/2447—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring
    • B01J31/2452—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom
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    • B01J2531/824—Palladium
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Abstract

The invention discloses a preparation method of 3-aminomethyltetrahydrofuran based on palladium-catalyzed cyano exchange, which belongs to the technical field of chemical synthesis and is characterized in that: under the catalysis of Pd, phosphorus ligand and Lewis acid, 2, 5-dihydrofuran and 2, 5-cyclohexadiene cyanide are heated in an organic solvent for a certain time at a certain temperature; concentrating the reaction solution, and performing column chromatography to obtain 3-cyano tetrahydrofuran; then in an organic solvent, under the catalysis of transition metal, 3-cyano tetrahydrofuran is subjected to catalytic hydrogenation to obtain a key intermediate 3-aminomethyl tetrahydrofuran for synthesizing dinotefuran, the invention takes 2, 5-dihydrofuran as a raw material, the 3-aminomethyl tetrahydrofuran is obtained through two steps of reactions of palladium catalytic cyanogen transfer and catalytic hydrogenation, and has the advantages of green and safe, simple operation, recoverable and reusable metal catalyst, low cost and the like.

Description

Preparation method of 3-aminomethyltetrahydrofuran based on palladium-catalyzed cyano exchange
Technical Field
The invention belongs to the technical field of fine chemical synthesis, and particularly relates to synthesis of 3-aminomethyl tetrahydrofuran, which is a key intermediate for dinotefuran synthesis.
Technical Field
Dinotefuran is 1-methyl-2-nitro-3- (tetrahydro-3-furanmethyl) guanidine, and is a third generation novel nicotinic pesticide. The nicotine pesticide is the only nicotine pesticide without halogen and aromatic ring, the molecular skeleton of the nicotine pesticide replaces the original heterocyclic structures such as pyridine, thiazole and the like with tetrahydrofuranmethyl, and the nicotine pesticide has great improvement on various performances.
3-Aminomethyl tetrahydrofuran is a key intermediate for the synthesis of dinotefuran at present, and at present, the synthesis of 3-aminomethyl tetrahydrofuran has two methods of metal catalysis and nonmetal catalysis, as shown in formula 2: according to the nonmetal-catalyzed synthesis method, acrylonitrile and halogenated ethanol are used as raw materials, michael addition is carried out on the raw materials to obtain an ether compound, and then intramolecular nucleophilic substitution reaction is carried out under the action of alkali to obtain the 3-cyano tetrahydrofuran. The 3-cyano tetrahydrofuran is subjected to catalytic hydrogenation to obtain 3-aminomethyl tetrahydrofuran.
As shown in formula 3: the synthesis of metal-catalyzed 3-aminomethyl tetrahydrofuran is generally carried out by taking 2, 5-dihydrofuran as raw material, subjecting 2, 5-dihydrofuran to hydroformylation reaction to obtain 3-formyltetrahydrofuran, reacting the obtained 3-formyltetrahydrofuran with ammonia water or hydroxylamine to generate imine or oxime in situ, and carrying out catalytic hydrogenation to obtain 3-aminomethyl tetrahydrofuran (ZL 201610819639.1; ZL201510447636.5; ZL201710100969. X). 3-formyl tetrahydrofuran is a key intermediate for the synthesis of 3-aminomethyl. However, in the catalytic hydroformylation process, 2-formyltetrahydrofuran byproducts are generally generated, so that the yield of the reaction is reduced, and the difficulty of product purification is increased.
The formula 3 is based on metal catalyzed 'catalytic hydroformylation-catalytic hydrogenation' to synthesize 3-aminomethyltetrahydrofuran.
Disclosure of Invention
The invention provides a novel method for synthesizing 3-aminomethyltetrahydrofuran based on palladium-catalyzed cyano transfer, which aims to solve the defects of low product yield, difficult separation, complex operation and the like of the existing method.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
A preparation method of 3-aminomethyl tetrahydrofuran based on palladium-catalyzed cyano exchange is characterized by comprising the following steps: under the catalysis of palladium catalyst, phosphorus ligand and Lewis acid, 2, 5-dihydrofuran and cyclohexadiene cyanide are reacted in an organic solvent to obtain a product 3-cyano tetrahydrofuran; in an organic solvent, under the catalysis of transition metal, 3-cyano tetrahydrofuran is subjected to catalytic hydrogenation to obtain a key intermediate 3-aminomethyl tetrahydrofuran for synthesizing dinotefuran.
The reaction equation involved in the invention is as follows:
Further:
A method for preparing 3-aminomethyl tetrahydrofuran based on palladium-catalyzed cyano exchange, which is characterized by comprising the following steps:
(1) Catalytic cyanogen exchange
2, 5-Dihydrofuran and cyclohexadiene cyanide are taken as raw materials, a reaction mixture is heated for a certain time at a certain temperature under the catalysis of Pd catalyst, phosphorus ligand and Lewis acid in an organic solvent, after the reaction is finished, the reaction solution is concentrated, and column chromatography is carried out to obtain a product 3-cyano tetrahydrofuran;
(2) Catalytic hydrogenation
The preparation method comprises the steps of taking transition metal as a catalyst, dissolving the obtained 3-cyano tetrahydrofuran product in an organic solvent, introducing hydrogen with certain pressure, reacting for a certain time at a certain temperature, concentrating under reduced pressure after the reaction is finished, and obtaining the 3-aminomethyltetrahydrofuran by column chromatography.
Still further, in step (1):
The cyclohexadiene cyanide is any one of 1-methyl-1-cyano-2, 5-cyclohexadiene, 1-ethyl-1-cyano-2, 5-cyclohexadiene, 1-isopropyl-1-cyano-2, 5-cyclohexadiene, 1,3, 5-trimethyl-1-cyano-2, 5-cyclohexadiene and the like.
The Pd catalyst is any one of Pd (PPh) 3、Pd2(dba)3、Pd(OAc)2、PdCl2 and the like, and the molar dosage of the Pd catalyst is 1-5% of that of 2, 5-dihydrofuran. Pd (PPh 3)2, molar amount of 5% of 2, 5-dihydrofuran) is particularly preferred.
The phosphorus ligand is any one or more of PPh 3, xantphos, DPEphos, (+ -.) BINAP, dppf and the like, and the molar dosage of the phosphorus ligand is 2-10% of that of 2, 5-dihydrofuran. DPEphos is particularly preferred in a molar amount of 10% relative to the 2, 5-dihydrofuran.
The Lewis acid is a boron reagent, preferably any one of BF 3.EtOEt、BF3.THF、B(C6F5)3、BPh3 and the like, and the molar amount of the Lewis acid is 10-20% of that of the 2, 5-dihydrofuran. BPh 3 is particularly preferred in a molar amount of 20% of 2, 5-dihydrofuran.
The reaction temperature is 80-120 ℃ and the reaction time is 20-30 hours. Preferably at 110 c for 20 hours.
Still further, in step (2):
the transition metal catalyst is any one of Pd-C, raney Ni, pt and the like, and the mass dosage of the transition metal catalyst is 5-10% of that of 3-cyano tetrahydrofuran.
The solvent is any one of methanol, ethyl acetate, isopropanol and the like.
The hydrogen pressure is 5-10MPa, the reaction temperature is 100-120 ℃, and the reaction time is 15-20 hours. Preferably, the hydrogen pressure is 10MPa, and the reaction temperature is 100 ℃ for 15 hours.
Preferably, the catalyst in the step (2) is Raney Ni, and after the catalytic hydrogenation reaction is finished, the Raney Ni catalyst is recovered by a filtering method and reused in the catalytic hydrogenation reaction, and the number of times of repeated recovery and utilization of the catalyst is 6-7.
The beneficial effects of the invention are as follows:
(1) Organic nitrile compound is used as raw material, and catalytic cyanogen transfer reaction is carried out under metal catalysis to synthesize 3-cyano tetrahydrofuran. The method uses the organic nitrile as a cyanide source, is green and safe, does not need high pressure, is simple to operate, and can recycle the metal catalyst, thereby reducing the cost.
(2) The 3-aminomethyl tetrahydrofuran can be obtained by the catalytic hydrogenation of the 3-cyano tetrahydrofuran, and the operation is simple.
(3) The 3-aminomethyl tetrahydrofuran is obtained by taking 2, 5-dihydrofuran as a raw material and carrying out 'palladium-catalyzed cyano transfer-catalytic hydrogenation' is a novel synthetic route and strategy.
The invention is further described below in conjunction with the detailed description.
Detailed Description
Example 1: catalytic cyanogen exchange
In a reaction tube, a magneton, a boron reagent (20 mol%), pd (PPh 3)2 mol%), DPEphos (10 mol%) and 1,4-dioxane (5 mL) were sequentially added under nitrogen protection, and after the mixture was stirred for 10 minutes, 2, 5-dihydrofuran (1 mmol) and 1-methyl-1-cyano-2, 5-cyclohexadiene (1.5 mmol) were added, and the reaction mixture was heated at 110℃for 20 hours.
According to the above synthesis method, different boron reagents as shown in table 1 were selected to test the effect of different boron reagents on reaction yield:
Table 1.
Examples 1-1 1-2 1-3 1-4
Boron reagent BPh3 BF3.EtOEt BF3.THF、 B(C6F5)3
Yield rate 83 25 31 53
。
As shown in Table 1, the selection of different boron reagents has a large influence on the yield of the reaction, and the yield is highest when the boron reagent BPh 3 is selected.
Example 2: catalytic cyanogen exchange
Under the protection of nitrogen, a magnet, BPh 3(20mol％)、Pd(PPh3)2 (5 mol%), a phosphorus ligand (10 mol%), and 1,4-dioxane (5 mL) were added in this order to the reaction tube. After stirring the mixture for 10 minutes, 2, 5-dihydrofuran (1 mmol) and 1-methyl-1-cyano-2, 5-cyclohexadiene (1.5 mmol) were added and the reaction mixture was heated at 110℃for 20 hours. After the reaction, the temperature was lowered, n-dodecane was added as an internal standard, and the yield was calculated by GC.
According to the above synthesis method, different phosphorus ligands as shown in table 2 were selected to test the effect of different phosphorus ligands on reaction yield:
Table 2.
Examples 2-1 2-2 2-3 2-4 2-5 2-6 2-7 2-8
Phosphorus ligands DPEphos Xantphos dppf (±)BINAP PCy3 L6 L7 L8
Yield rate 83 79 53 7 5 43 5 5
The phosphorus ligand in Table 2 has the structural formula:
As shown in table 2:
The choice of different phosphorus ligands has a large influence on the yield of the reaction, which is highest when the phosphorus ligand DPEphos is chosen.
Example 3: catalytic hydrogenation
In a catalytic hydrogenation reaction kettle, stirring magneton, methanol (5 mL), 3-cyano tetrahydrofuran (1.0 mmol), raney Ni (10 wt%) and hydrogen are sequentially added, the pressure of the introduced hydrogen is 10MPa, the reaction is carried out for 15 hours at 100 ℃, the concentration is reduced after the reaction is finished, and the 3-aminomethyltetrahydrofuran is obtained by column chromatography, wherein the yield is 75%.
Example 4: catalytic hydrogenation metal catalyst recovery and reuse
After the reaction of example 3 was completed, raney Ni catalyst was recovered by filtration, the raw materials and the solvent were added again, and repeated experiments were conducted under the same conditions to examine the reusability of the catalyst, and the statistical results are shown in Table 3.
TABLE 3 Table 3
Number of times/times of reuse 1 2 3 4 5 6 7
Yield (%) 75 73 75 75 72 72 68
。
As can be seen from table 3: the catalyst of the invention shows higher activity after 7 times of repeated use.

Claims (4)

1. A method for preparing 3-aminomethyl tetrahydrofuran based on palladium-catalyzed cyano exchange, which is characterized by comprising the following steps:
(1) Catalytic cyanogen exchange
2, 5-Dihydrofuran and cyclohexadiene cyanide are taken as raw materials, a reaction mixture is reacted for 20-30 hours at 80-120 ℃ in an organic solvent under the catalysis of Pd catalyst, phosphorus ligand and Lewis acid, and after the reaction is finished, the reaction solution is concentrated and column chromatography is carried out to obtain the product 3-cyano tetrahydrofuran;
In step (1): the cyclohexadiene cyanide is any one of 1-methyl-1-cyano-2, 5-cyclohexadiene, 1-ethyl-1-cyano-2, 5-cyclohexadiene, 1-isopropyl-1-cyano-2, 5-cyclohexadiene and 1,3, 5-trimethyl-1-cyano-2, 5-cyclohexadiene;
in step (1): the Lewis acid is BPh 3, and the molar dosage of the Lewis acid is 10-20% of that of 2, 5-dihydrofuran;
in step (1): the molar amount of the phosphorus ligand is DPEphos, and is 2-10% of that of 2, 5-dihydrofuran;
In step (1): the Pd catalyst is Pd 2(dba)3, and the molar dosage of the Pd catalyst is 1-5% of that of 2, 5-dihydrofuran;
(2) Catalytic hydrogenation
Dissolving the obtained 3-cyano tetrahydrofuran product in an organic solvent by using transition metal as a catalyst, introducing hydrogen with the pressure of 5-10MPa, reacting for 15-20 hours at the temperature of 100-120 ℃, concentrating under reduced pressure after the reaction is finished, and performing column chromatography to obtain 3-aminomethyltetrahydrofuran;
In the step (2): the catalyst is any one of Pd-C, raney Ni and Pt, and the mass dosage of the catalyst is 5-10% of that of 2, 5-dihydrofuran.
2. The method for preparing 3-aminomethyltetrahydrofuran based on palladium-catalyzed cyano exchange as claimed in claim 1, wherein in step (1): the phosphorus ligand is DPEpho, and the molar dosage of the phosphorus ligand is 10 percent of that of 2, 5-dihydrofuran.
3. The method for preparing 3-aminomethyltetrahydrofuran based on palladium-catalyzed cyano exchange as claimed in claim 1, wherein in step (1): the Lewis acid is BPh 3, and the molar dosage of the Lewis acid is 20% of that of 2, 5-dihydrofuran.
4. The method for preparing 3-aminomethyltetrahydrofuran based on palladium-catalyzed cyano exchange as claimed in claim 1, wherein in step (2): the catalyst is Raney Ni, the mass consumption of the catalyst is 10% of that of 3-cyano tetrahydrofuran, and after the catalytic hydrogenation reaction is finished, the Raney Ni catalyst is recovered by a filtering method and reused in the catalytic hydrogenation reaction, and the repeated recovery and utilization times of the catalyst are 6-7 times.
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CN111303083A (en) * 2020-03-31 2020-06-19 安徽中羰碳一工业技术有限责任公司 Synthetic method of 3-aminomethyl tetrahydrofuran

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Anup Bhunia et al..Cooperative Palladium/Lewis Acid-Catalyzed Transfer Hydrocyanation of Alkenes and Alkynes Using 1-Methylcyclohexa-2,5-diene-1-carbonitrile.《J. Am. Chem. Soc.》.2018,第140卷(第47期),第16353-16359、S1-S110页. *

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