Patent ID: 12187693

DETAILED DESCRIPTION

The technical solution of the present invention is further described below with reference to examples, but the present invention is not limited by the examples.

Example 1

(1) Microwave-Assisted Catalytic Synthesis of N-Furylmethyl Formamide

2 mmol of furfural, 12 mmol of formamide, and 6 mmol of formic acid were put into a 10 mL pressure-resistant microwave reaction tube, and after the pressure-resistant microwave reaction tube was closed, nitrogen at 2 MPa was introduced. The pressure-resistant microwave reaction tube was placed in a microwave reactor (Shikoku Keisoku Corporation, Japan, model number: SMW-087, microwave frequency: 2.45 GHz, and maximum power: 700 W), the microwave reactor was turned on, a reaction temperature was set to 180° C., a reaction system absorbed microwaves and was rapidly heated up to 180° C., the reaction temperature of the reaction system was controlled by using a thermocouple, microwave-assisted heating and stirring were conducted at this temperature for 3 min, after the reaction was finished, 2 mL of tetrahydrofuran was added, and a furfural conversion rate and an N-furylmethyl formamide yield were measured by using gas chromatography (GC).

(2) Alcoholysis of N-Furylmethyl Formamide

1 mmol of N-furylmethyl formamide was solved into 2 mL of methanol, then 2 mmol of cesium carbonate was added for a reaction at 60° C. for 6 h, and a 2-furfurylamine yield was measured by using GC.

Naphthalene was used as an internal standard for making a standard curve, and the N-furylmethyl formamide yield in the reaction solution was detected to be 98% by using GC. A mass spectrum of the purified N-furylmethyl formamide was shown inFIG.1, where a molecular ion peak was m/z: 125.0. A hydrogen spectrum and a carbon spectrum were respectively shownFIG.2andFIG.3, where a furfural conversion rate was 100%; and measured based on N-furylmethyl formamide, a 2-furfurylamine yield was 94% (m/z: 97.1).

Comparative Example 1

(1) Catalytic Synthesis of N-Furylmethyl Formamide Through Oil Bath Heating

2 mmol of furfural, 12 mmol of formamide, and 6 mmol of formic acid were put into a 10 mL pressure-resistant reaction tube, and after the pressure-resistant reaction tube was closed, nitrogen at 2 MPa was introduced. Stirring was carried out through oil bath heating under the condition of 180° C. for 60 min, after the reaction was finished, 2 mL of tetrahydrofuran was added to dilute a reaction system, and a furfural conversion rate and an N-furylmethyl formamide yield were measured by using gas chromatography (GC).

Naphthalene was used as an internal standard for making a standard curve, and by using GC, the N-furylmethyl formamide yield in the reaction solution was detected to be 72%, and the furfural conversion rate was detected to be 87%.

Example 2

(1) Microwave-Assisted Catalytic Synthesis of N-Benzylformamide

2 mmol of benzaldehyde, 15 mmol of formamide, and 15 mmol of formic acid were put into a 10 mL pressure-resistant microwave reaction tube, and after the pressure-resistant microwave reaction tube was closed, nitrogen at 1 MPa was introduced; the pressure-resistant microwave reaction tube was placed in a microwave reactor, the microwave reactor was turned on, a reaction temperature was set to 180° C., a reaction system absorbed microwaves and was rapidly heated up to 180° C., the reaction temperature of the reaction system was controlled by using a thermocouple, the reaction system was heated and stirred by using microwaves at 180° C. for 5 min; and after the reaction was finished, 2 mL of tetrahydrofuran was added, and a benzaldehyde conversion rate and an N-benzylformamide yield were measured by using GC.

(2) Alcoholysis of N-Benzylformamide

1 mmol of N-benzylformamide was solved into 2 mL of methanol, then 1 mmol of sodium ethoxide was added for a reaction at 80° C. for 2 h, and a benzylamine yield was measured by using GC.

Naphthalene was used as an internal standard for making a standard curve, and by using GC, the N-benzylformamide yield (m/z: 135.1) in the reaction mixture was detected to be 99%, and the benzaldehyde conversion rate was detected to be 100%; and measured based on N-benzylformamide, the benzylamine yield (m/z: 107.0) was 99%.

Example 3

(1) Microwave-Assisted Catalytic Synthesis of N-Phenylacrylformamide

2 mmol of cinnamaldehyde, 10 mmol of formamide, and 10 mmol of formic acid were put into a 10 mL pressure-resistant microwave reaction tube, and after the pressure-resistant microwave reaction tube was closed, nitrogen at 2 MPa was introduced. The pressure-resistant microwave reaction tube was placed in a microwave reactor, the microwave reactor was turned on, a reaction temperature was set to 200° C., a reaction system absorbed microwaves and was rapidly heated up to 200° C., the reaction temperature of the reaction system was controlled by using a thermocouple, the reaction system was heated and stirred by using microwaves at 200° C. for 2 min, after the reaction was finished, 2 mL, of tetrahydrofuran was added, and a cinnamaldehyde conversion rate and an N-phenylacrylformamide yield were measured by using GC.

(2) Alcoholysis of N-Phenylacrylformamide

1 mmol of N-phenylacrylformamide was solved into 2 mL of methanol, then 1 mmol of sodium hydroxide was added for a reaction at 100° C. for 4 h, and a cinnamamide yield was measured by using GC.

Naphthalene was used as an internal standard for making a standard curve, and by using GC, the N-phenylacrylformamide yield (m/z: 161.0) in the reaction mixture was detected to be 95%, and the cinnamaldehyde conversion rate was detected to be 100%; and measured based on N-phenylacrylformamide, the cinnamamide yield (m/z: 133.1) was 96%.

Example 4

(1) Microwave-Assisted Catalytic Synthesis of N-2-Hydroxyethyl Formamide

2 mmol of 2-glycolaldehyde, 6 mmol of formamide, and 6 mmol of formic acid were put into a 10 mL pressure-resistant microwave reaction tube, and after the pressure-resistant microwave reaction tube was closed, nitrogen at 3 MPa was introduced. The pressure-resistant microwave reaction tube was placed in a microwave reactor, the microwave reactor was turned on, a reaction temperature was set to 160° C., a reaction system absorbed microwaves and was rapidly heated up to 160° C., the reaction temperature of the reaction system was controlled by using a thermocouple, the reaction system was heated and stirred by using microwaves at 160° C. for 15 min, after the reaction was finished, 2 mL of dichloromethane was added, and a 2-glycolaldehyde conversion rate and an N-2-hydroxyethyl formamide yield were measured by using GC.

(2) Alcoholysis of N-2-Hydroxyethyl Formamide

1 mmol of N-2-hydroxyethyl formamide was solved into 1 mL of methanol, then 2 mmol of cesium carbonate was added for a reaction at 60° C. for 8 h, and a yield of obtained 2-aminoethanol was measured by using GC.

Naphthalene was used as an internal standard for making a standard curve, and by using GC, the N-2-hydroxyethyl formamide yield (m/z: 89.1) in the reaction mixture was detected to be 85%, and the 2-glycolaldehyde conversion rate was detected to be 99%; and measured based on N-2-hydroxyethyl formamide, the 2-aminoethanol yield (m/z: 61.0) was 92%.

Example 5

(1) Microwave-Assisted Catalytic Synthesis of N-Methyl Isobutyl Formamide

2 mmol of methyl isobutyl ketone, 15 mmol of formamide, and 10 mmol of formic acid were put into a 10 mL pressure-resistant microwave reaction tube, and after the pressure-resistant microwave reaction tube was closed, nitrogen at 2 MPa was introduced. The pressure-resistant microwave reaction tube was placed in a microwave reactor, the microwave reactor was turned on, a reaction temperature was set to 190° C., a reaction system absorbed microwaves and was rapidly heated up to 190° C., the reaction temperature of the reaction system was controlled by using a thermocouple, the reaction system was heated and stirred by using microwaves at 190° C. for 3 min, after the reaction was finished, 2 mL, of tetrahydrofuran was added, and a methyl isobutyl ketone conversion rate and an N-methyl isobutyl formamide yield were measured by using GC.

(2) Alcoholysis of N-Methyl Isobutyl Formamide

1 mmol of N-methyl isobutyl formamide was solved into 2 mL of methanol, then 1 mmol of cesium carbonate was added for a reaction at 80° C. for 5 h, and a yield of obtained methylisobutylamine was measured by using GC.

Naphthalene was used as an internal standard for making a standard curve, and by using GC, the N-methyl isobutyl formamide yield (m/z: 129.0) in the reaction mixture was detected to be 87%, and the methyl isobutyl ketone conversion rate was detected to be 96%; and the methylisobutylamine yield (m/z: 101.1) was 98%.

Example 6

(1) Microwave-Assisted Catalytic Synthesis of N-Cyclopentylformamide

2 mmol of cyclopentanone, 10 mmol of formamide, and 6 mmol of formic acid were put into a 10 mL pressure-resistant microwave reaction tube, and after the pressure-resistant microwave reaction tube was closed, nitrogen at 2 MPa was introduced. The pressure-resistant microwave reaction tube was placed in a microwave reactor, the microwave reactor was turned on, a reaction temperature was set to 200° C., a reaction system absorbed microwaves and was rapidly heated up to 200° C., the reaction temperature of the reaction system was controlled by using a thermocouple, the reaction system was heated and stirred by using microwaves at 200° C. for 2 min, after the reaction was finished, 2 mL of dichloromethane was added, and a cyclopentanone conversion rate and an N-cyclopentylformamide yield were measured by using GC.

(2) Alcoholysis of N-Cyclopentylformamide

1 mmol of N-cyclopentylformamide was solved into 3 mL of methanol, then 2 mmol of cesium carbonate was added for a reaction at 60° C. for 8 h, and a yield of obtained cyclopentylamine was measured by using GC.

Naphthalene was used as an internal standard for making a standard curve, and by using GC, the N-cyclopentylformamide yield (m/z: 113.1) in the reaction mixture was detected to be 98%, and the cyclopentanone conversion rate was detected to be 100%; and the cyclopentylamine yield (m/z: 85.1) was 99%.

Example 7

(1) Microwave-Assisted Catalytic Synthesis of N-Benzyl Methyl Formamide

2 mmol of acetophenone, 6 mmol of formamide, and 12 mmol of formic acid were put into a 10 mL pressure-resistant microwave reaction tube, and after the pressure-resistant microwave reaction tube was closed, nitrogen at 2 MPa was introduced. The pressure-resistant microwave reaction tube was placed in a microwave reactor, the microwave reactor was turned on, a reaction temperature was set to 180° C., a reaction system absorbed microwaves and was rapidly heated up to 180° C., the reaction temperature of the reaction system was controlled by using a thermocouple, the reaction system was heated and stirred by using microwaves at 180° C. for 5 min, after the reaction was finished, 2 mL of tetrahydrofuran was added, and a acetophenone conversion rate and an N-benzyl methyl formamide yield were measured by using GC.

(2) Alcoholysis of N-Benzyl Methyl Formamide

1 mmol of N-benzyl methyl formamide was solved into 2 mL of methanol, then 1 mmol of cesium carbonate was added for a reaction at 80° C. for 3 h, and a yield of obtained 1-phenylethylamine was measured by using GC.

Naphthalene was used as an internal standard for making a standard curve, and by using GC, the N-benzyl methyl formamide yield (m/z: 149.0) in the reaction mixture was detected to be 92%, and the acetophenone conversion rate was detected to be 99%; and the 1-phenylethylamine yield (m/z: 121.1) was 97%.