(4) embodiment
The invention will be further described below in conjunction with embodiment, but protection scope of the present invention is not limited to this.
Embodiment 1
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 1: 1: 0.02 (mol ratio), amine is aniline, and the original carboxylic acid ester is a triethyl orthoformate, and the hydrazoic acid metal-salt is a sodiumazide, chloroform is as organic solvent, and its consumption is 10 times of aniline.
Thermometer is being housed, in reflux condensing tube and the churned mechanically 150ml four-hole boiling flask, at room temperature add aniline 4.56ml (50mmol), sodiumazide 3.25g (50mmol), triethyl orthoformate 8.34ml (50mmol), Ytterbiumtriflate 0.62g (1mmol) is with chloroform 46g dissolving, finish, be warming up to 60 ℃, and, use HPLC tracking monitor (flow velocity: 1.5ml/min simultaneously 60~65 ℃ of reactions 3 hours, acetonitrile: water: acetic acid=20: 80: 0.05), reaction finishes, and boils off solvent, and the ice bath cooling down, slowly add the 20ml frozen water, constantly stir 10min, ethyl acetate extraction 3 times, each 30ml.
The water concentrating under reduced pressure, washing, 190 ℃ of thermal dehydrations are 4 hours under vacuum, white Ytterbiumtriflate crystal 0.95mmol, the rate of recovery 95.1%.
Merge organic phase, behind the concentrating under reduced pressure, ethyl alcohol recrystallization, obtaining white crystal is 1-phenyl tetrazole, 5.95g, fusing point 64.8-65.1 ℃, yield 81.4%, purity 99.6%.
Embodiment 2
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 1: 1: 0.02 (mol ratio), amine is aniline, and the original carboxylic acid ester is a triethyl orthoformate, and the hydrazoic acid metal-salt is a sodiumazide, chloroform is as organic solvent, and its consumption is 8 times of aniline.
Other are operated with embodiment 1, product yield 81.1%, purity 99.6%, fusing point 64.7-65.1 ℃, the Ytterbiumtriflate rate of recovery 94.2%.
Embodiment 3
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 1: 1: 0.02 (mol ratio), amine is aniline, and the original carboxylic acid ester is a triethyl orthoformate, and the hydrazoic acid metal-salt is a sodiumazide, chloroform is as organic solvent, and its consumption is 5 times of aniline.
Other are operated with embodiment 1, product yield 80.5%, purity 99.7%, fusing point 64.5-65.0 ℃, the Ytterbiumtriflate rate of recovery 95.1%.
Embodiment 4
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 1: 1: 0.02 (mol ratio), amine is aniline, and the original carboxylic acid ester is a triethyl orthoformate, and the hydrazoic acid metal-salt is a sodiumazide, chloroform is as organic solvent, and its consumption is 15 times of aniline.
Other are operated with embodiment 1, product yield 82.1%, purity 99.6%, fusing point 64.8-65.2 ℃, the Ytterbiumtriflate rate of recovery 96.7%.
Embodiment 5
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 1: 1: 0.02 (mol ratio), amine is aniline, and the original carboxylic acid ester is a triethyl orthoformate, and the hydrazoic acid metal-salt is a sodiumazide, chloroform is as organic solvent, and its consumption is 20 times of aniline.
Other are operated with embodiment 1, product yield 83.5%, purity 99.7%, fusing point 64.7-65.3 ℃, the Ytterbiumtriflate rate of recovery 95.5%.
Embodiment 6
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 1.5: 1: 0.02 (mol ratio), amine is aniline, and the original carboxylic acid ester is a triethyl orthoformate, and the hydrazoic acid metal-salt is a sodiumazide, chloroform is as organic solvent, and its consumption is 10 times of aniline.
Other are operated with embodiment 1, product yield 84.1%, purity 99.6%, fusing point 64.7-65.1 ℃, the Ytterbiumtriflate rate of recovery 95.3%.
Embodiment 7
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 1.5: 1: 0.02 (mol ratio), amine is aniline, and the original carboxylic acid ester is a triethyl orthoformate, and the hydrazoic acid metal-salt is a sodiumazide, chloroform is as organic solvent, and its consumption is 10 times of aniline.
Other are operated with embodiment 1, product yield 84.1%, purity 99.6%, fusing point 64.7-65.1 ℃, the Ytterbiumtriflate rate of recovery 95.4%.
Embodiment 8
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 2: 1: 0.02 (mol ratio), amine is aniline, and the original carboxylic acid ester is a triethyl orthoformate, and the hydrazoic acid metal-salt is a sodiumazide, chloroform is as organic solvent, and its consumption is 10 times of aniline.
Other are operated with embodiment 1, product yield 84.5%, purity 99.6%, fusing point 64.8-65.2 ℃, the Ytterbiumtriflate rate of recovery 95.6%.
Embodiment 9
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 2.5: 1: 0.02 (mol ratio), amine is aniline, and the original carboxylic acid ester is a triethyl orthoformate, and the hydrazoic acid metal-salt is a sodiumazide, chloroform is as organic solvent, and its consumption is 10 times of aniline.
Other are operated with embodiment 1, product yield 85.2%, purity 99.5%, fusing point 64.9-65.2 ℃, the Ytterbiumtriflate rate of recovery 96.1%.
Embodiment 10
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 3: 1: 0.02 (mol ratio), amine is aniline, and the original carboxylic acid ester is a triethyl orthoformate, and the hydrazoic acid metal-salt is a sodiumazide, chloroform is as organic solvent, and its consumption is 10 times of aniline.
Other are operated with embodiment 1, product yield 85.4%, purity 99.6%, fusing point 64.9-65.1 ℃, the Ytterbiumtriflate rate of recovery 96.1%.
Embodiment 11
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 4: 1: 0.02 (mol ratio), amine is aniline, and the original carboxylic acid ester is a triethyl orthoformate, and the hydrazoic acid metal-salt is a sodiumazide, chloroform is as organic solvent, and its consumption is 10 times of aniline.
Other are operated with embodiment 1, product yield 85.8%, purity 99.6%, fusing point 64.8-65.0 ℃, the Ytterbiumtriflate rate of recovery 96.5%.
Embodiment 12
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 5: 1: 0.02 (mol ratio), amine is aniline, and the original carboxylic acid ester is a triethyl orthoformate, and the hydrazoic acid metal-salt is a sodiumazide, chloroform is as organic solvent, and its consumption is 10 times of aniline.
Other are operated with embodiment 1, product yield 85.7%, purity 99.5%, fusing point 64.5-64.9 ℃, the Ytterbiumtriflate rate of recovery 95.8%.
Embodiment 13
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 1.5: 1.5: 0.02 (mol ratio), amine is aniline, and the original carboxylic acid ester is a triethyl orthoformate, and the hydrazoic acid metal-salt is a sodiumazide, chloroform is as organic solvent, and its consumption is 10 times of aniline.
Other are operated with embodiment 1, product yield 85.9%, purity 99.6%, fusing point 64.5-65.0 ℃, the Ytterbiumtriflate rate of recovery 94.7%.
Embodiment 14
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 1.5: 2.0: 0.02 (mol ratio), amine is aniline, and the original carboxylic acid ester is a triethyl orthoformate, and the hydrazoic acid metal-salt is a sodiumazide, chloroform is as organic solvent, and its consumption is 10 times of aniline.
Other are operated with embodiment 1, product yield 85.5%, purity 99.4%, fusing point 64.7-65.1 ℃, the Ytterbiumtriflate rate of recovery 94.6%.
Embodiment 15
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 1.5: 3: 0.02 (mol ratio), amine is aniline, and the original carboxylic acid ester is a triethyl orthoformate, and the hydrazoic acid metal-salt is a sodiumazide, chloroform is as organic solvent, and its consumption is 10 times of aniline.
Other are operated with embodiment 1, product yield 85.1%, purity 99.5%, fusing point 64.8-65.1 ℃, the Ytterbiumtriflate rate of recovery 93.9%.
Embodiment 16
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 1.5: 1.5: 0.05 (mol ratio), amine is aniline, and the original carboxylic acid ester is a triethyl orthoformate, and the hydrazoic acid metal-salt is a sodiumazide, chloroform is as organic solvent, and its consumption is 10 times of aniline.
Other are operated with embodiment 1, product yield 85.4%, purity 99.6%, fusing point 64.8-65.0 ℃, the Ytterbiumtriflate rate of recovery 96.2%.
Embodiment 17
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 1.5: 1.5: 0.1 (mol ratio), amine is aniline, and the original carboxylic acid ester is a triethyl orthoformate, and the hydrazoic acid metal-salt is a sodiumazide, chloroform is as organic solvent, and its consumption is 10 times of aniline.
Other are operated with embodiment 1, product yield 85.9%, purity 99.5%, fusing point 64.7-65.2 ℃, the Ytterbiumtriflate rate of recovery 96.6%.
Embodiment 18
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 1.5: 1.5: 0.5 (mol ratio), amine is aniline, and the original carboxylic acid ester is a triethyl orthoformate, and the hydrazoic acid metal-salt is a sodiumazide, chloroform is as organic solvent, and its consumption is 10 times of aniline.
Other are operated with embodiment 1, product yield 85.7%, purity 99.4%, fusing point 64.7-65.4 ℃, the Ytterbiumtriflate rate of recovery 96.1%.
Embodiment 19
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 1.5: 1.5: 1.0 (mol ratios), amine is aniline, and the original carboxylic acid ester is a triethyl orthoformate, and the hydrazoic acid metal-salt is a sodiumazide, chloroform is as organic solvent, and its consumption is 10 times of aniline.
Other are operated with embodiment 1, product yield 85.6%, purity 99.5%, fusing point 64.7-65.3 ℃, the Ytterbiumtriflate rate of recovery 97.2%.
Embodiment 20
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 1.5: 1.5: 0.05 (mol ratio), amine is aniline, and the original carboxylic acid ester is a triethyl orthoformate, and the hydrazoic acid metal-salt is a potassium azide, chloroform is as organic solvent, and its consumption is 10 times of aniline.
Other are operated with embodiment 1, product yield 85.8%, purity 99.3%, fusing point 64.8-65.0 ℃, the Ytterbiumtriflate rate of recovery 96.2%.
Embodiment 21
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 1.5: 1.5: 0.05 (mol ratio), amine is aniline, and the original carboxylic acid ester is a triethyl orthoformate, and the hydrazoic acid metal-salt is an azide calcium, chloroform is as organic solvent, and its consumption is 10 times of aniline.
Other are operated with embodiment 1, product yield 84.1%, purity 99.2%, fusing point 64.8-65.1 ℃, the Ytterbiumtriflate rate of recovery 95.7%.
Embodiment 22
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 1.5: 1.5: 0.05 (mol ratio), amine is aniline, and the original carboxylic acid ester is a triethyl orthoformate, and the hydrazoic acid metal-salt is an azide magnesium, chloroform is as organic solvent, and its consumption is 10 times of aniline.
Other are operated with embodiment 1, product yield 84.1%, purity 99.2%, fusing point 64.8-65.1 ℃, the Ytterbiumtriflate rate of recovery 95.4%.
Embodiment 23
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 1.5: 1.5: 0.05 (mol ratio), amine is aniline, and the original carboxylic acid ester is a triethyl orthoformate, and the hydrazoic acid metal-salt is an azide zinc, chloroform is as organic solvent, and its consumption is 10 times of aniline.
Other are operated with embodiment 1, product yield 83.2%, purity 99.4%, fusing point 64.7-65.1 ℃, the Ytterbiumtriflate rate of recovery 96.1%.
Embodiment 24
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 1.5: 1.5: 0.05 (mol ratio), amine is aniline, and the original carboxylic acid ester is a triethyl orthoformate, and the hydrazoic acid metal-salt is a copper azide, chloroform is as organic solvent, and its consumption is 10 times of aniline.
Other are operated with embodiment 1, product yield 81.9%, purity 99.5%, fusing point 64.6-65.0 ℃, the Ytterbiumtriflate rate of recovery 96.3%.
Embodiment 25
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 1.5: 1.5: 0.05 (mol ratio), amine is aniline, and the original carboxylic acid ester is a triethyl orthoformate, and the hydrazoic acid metal-salt is a Lithium Azide, chloroform is as organic solvent, and its consumption is 10 times of aniline.
Other are operated with embodiment 1, product yield 84.9%, purity 99.5%, fusing point 64.7-65.2 ℃, the Ytterbiumtriflate rate of recovery 96.1%.
Embodiment 26
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 1.5: 1.5: 0.05 (mol ratio), amine is aniline, and the original carboxylic acid ester is a triethyl orthoformate, and the hydrazoic acid metal-salt is a sodiumazide, chloroform is as organic solvent, and its consumption is 10 times of aniline.
Other are operated with embodiment 1, product yield 84.9%, purity 99.5%, fusing point 64.7-65.2 ℃, the Ytterbiumtriflate rate of recovery 96.2%.
Embodiment 27
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 1.5: 1.5: 0.05 (mol ratio), amine is aniline, the original carboxylic acid ester is a triethyl orthoformate, the hydrazoic acid metal-salt is a sodiumazide, ethanol is as organic solvent, its consumption is 10 times of aniline, and temperature of reaction is 70~75 ℃.
Other are operated with embodiment 1, product yield 84.4%, purity 99.4%, fusing point 64.7-65.1 ℃, the Ytterbiumtriflate rate of recovery 96.5%.
Embodiment 28
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 1.5: 1.5: 0.05 (mol ratio), amine is aniline, the original carboxylic acid ester is a triethyl orthoformate, the hydrazoic acid metal-salt is a sodiumazide, Virahol is as organic solvent, its consumption is 10 times of aniline, and temperature of reaction is 78~82 ℃.
Other are operated with embodiment 1, product yield 84.1%, purity 99.5%, fusing point 64.7-65.0 ℃, the Ytterbiumtriflate rate of recovery 95.3%.
Embodiment 29
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 1.5: 1.5: 0.05 (mol ratio), amine is aniline, the original carboxylic acid ester is a triethyl orthoformate, the hydrazoic acid metal-salt is a sodiumazide, butanols is as organic solvent, its consumption is 10 times of aniline, and temperature of reaction is 115~117 ℃.
Other are operated with embodiment 1, product yield 84.1%, purity 99.5%, fusing point 64.7-65.0 ℃, the Ytterbiumtriflate rate of recovery 95.7%.
Embodiment 30
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 1.5: 1.5: 0.05 (mol ratio), amine is aniline, the original carboxylic acid ester is a triethyl orthoformate, the hydrazoic acid metal-salt is a sodiumazide, n-propyl alcohol is as organic solvent, its consumption is 10 times of aniline, and temperature of reaction is 95~97 ℃.
Other are operated with embodiment 1, product yield 82.1%, purity 99.4%, fusing point 64.6-65.2 ℃, the Ytterbiumtriflate rate of recovery 96.2%.
Embodiment 31
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 1.5: 1.5: 0.05 (mol ratio), amine is aniline, the original carboxylic acid ester is a triethyl orthoformate, the hydrazoic acid metal-salt is a sodiumazide, Pentyl alcohol is as organic solvent, its consumption is 10 times of aniline, and temperature of reaction is 135~138 ℃.
Other are operated with embodiment 1, product yield 81.5%, purity 99.5%, fusing point 64.6-65.1 ℃, the Ytterbiumtriflate rate of recovery 96.7%.
Embodiment 32
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 1.5: 1.5: 0.05 (mol ratio), amine is aniline, the original carboxylic acid ester is a triethyl orthoformate, the hydrazoic acid metal-salt is a sodiumazide, methylene dichloride is as organic solvent, its consumption is 10 times of aniline, and temperature of reaction is 35~40 ℃.
Other are operated with embodiment 1, product yield 78.4%, purity 99.6%, fusing point 64.7-65.0 ℃, the Ytterbiumtriflate rate of recovery 95.8%.
Embodiment 33
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 1.5: 1.5: 0.05 (mol ratio), amine is aniline, the original carboxylic acid ester is a triethyl orthoformate, the hydrazoic acid metal-salt is a sodiumazide, 1, the 1-ethylene dichloride is as organic solvent, and its consumption is 10 times of aniline, and temperature of reaction is 55~60 ℃.
Other are operated with embodiment 1, product yield 76.8%, purity 99.5%, fusing point 64.4-64.9 ℃, the Ytterbiumtriflate rate of recovery 95.7%.
Embodiment 34
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 1.5: 1.5: 0.05 (mol ratio), amine is aniline, the original carboxylic acid ester is a triethyl orthoformate, the hydrazoic acid metal-salt is a sodiumazide, 1, the 2-ethylene dichloride is as organic solvent, and its consumption is 10 times of aniline, and temperature of reaction is 80~84 ℃.
Other are operated with embodiment 1, product yield 75.9%, purity 99.5%, fusing point 64.5-64.9 ℃, the Ytterbiumtriflate rate of recovery 96.0%.
Embodiment 35
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 1.5: 1.5: 0.05 (mol ratio), amine is aniline, the original carboxylic acid ester is a triethyl orthoformate, the hydrazoic acid metal-salt is a sodiumazide, tetracol phenixin is as organic solvent, its consumption is 10 times of aniline, and temperature of reaction is 70~75 ℃.
Other are operated with embodiment 1, product yield 73.4%, purity 99.4%, fusing point 64.7-65.1 ℃, the Ytterbiumtriflate rate of recovery 96.1%.
Embodiment 36
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 1.5: 1.5: 0.05 (mol ratio), amine is aniline, the original carboxylic acid ester is a triethyl orthoformate, the hydrazoic acid metal-salt is a sodiumazide, 1,1,2, the 2-tetrachloroethane is as organic solvent, and its consumption is 10 times of aniline, and temperature of reaction is 55~57 ℃.
Other are operated with embodiment 1, product yield 74.7%, purity 99.6%, fusing point 64.8-65.1 ℃, the Ytterbiumtriflate rate of recovery 96.2%.
Embodiment 37
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 1.5: 1.5: 0.05 (mol ratio), amine is aniline, the original carboxylic acid ester is a triethyl orthoformate, the hydrazoic acid metal-salt is a sodiumazide, methyl acetate is as organic solvent, its consumption is 10 times of aniline, and temperature of reaction is 54~56 ℃.
Other are operated with embodiment 1, product yield 76.3%, purity 99.6%, fusing point 64.7-65.0 ℃, the Ytterbiumtriflate rate of recovery 96.6%.
Embodiment 38
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 1.5: 1.5: 0.05 (mol ratio), amine is aniline, the original carboxylic acid ester is a triethyl orthoformate, the hydrazoic acid metal-salt is a sodiumazide, ethyl acetate is as organic solvent, its consumption is 10 times of aniline, and temperature of reaction is 75~77 ℃.
Other are operated with embodiment 1, product yield 76.8%, purity 99.6%, fusing point 64.7-65.1 ℃, the Ytterbiumtriflate rate of recovery 96.0%.
Embodiment 39
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 1.5: 1.5: 0.05 (mol ratio), amine is aniline, the original carboxylic acid ester is a triethyl orthoformate, the hydrazoic acid metal-salt is a sodiumazide, propyl acetate is as organic solvent, its consumption is 10 times of aniline, and temperature of reaction is 80~85 ℃.
Other are operated with embodiment 1, product yield 76.1%, purity 99.6%, fusing point 64.5-65.0 ℃, the Ytterbiumtriflate rate of recovery 96.4%.
Embodiment 40
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 1.5: 1.5: 0.05 (mol ratio), amine is aniline, the original carboxylic acid ester is a triethyl orthoformate, the hydrazoic acid metal-salt is a sodiumazide, ether is as organic solvent, its consumption is 10 times of aniline, and temperature of reaction is 30~34 ℃.
Other are operated with embodiment 1, product yield 72.1%, purity 99.5%, fusing point 64.6-65.2 ℃, the Ytterbiumtriflate rate of recovery 96.7%.
Embodiment 41
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 1.5: 1.5: 0.05 (mol ratio), amine is aniline, the original carboxylic acid ester is a triethyl orthoformate, the hydrazoic acid metal-salt is a sodiumazide, propyl ether is as organic solvent, its consumption is 10 times of aniline, and temperature of reaction is 85~90 ℃.
Other are operated with embodiment 1, product yield 71.5%, purity 99.5%, fusing point 64.6-65.1 ℃, the Ytterbiumtriflate rate of recovery 96.3%.
Embodiment 42
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 1.5: 1.5: 0.05 (mol ratio), amine is aniline, the original carboxylic acid ester is a triethyl orthoformate, the hydrazoic acid metal-salt is a sodiumazide, dithiocarbonic anhydride is as organic solvent, its consumption is 10 times of aniline, and temperature of reaction is 41~46 ℃.
Other are operated with embodiment 1, product yield 68.7%, purity 99.4%, fusing point 64.5-65.1 ℃, the Ytterbiumtriflate rate of recovery 96.5%.
Embodiment 43
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 1.5: 1.5: 0.05 (mol ratio), amine is aniline, the original carboxylic acid ester is a triethyl orthoformate, the hydrazoic acid metal-salt is a sodiumazide, Nitromethane 99Min. is as organic solvent, its consumption is 10 times of aniline, and temperature of reaction is 80~85 ℃.
Other are operated with embodiment 1, product yield 75.8%, purity 99.5%, fusing point 64.8-65.3 ℃, the Ytterbiumtriflate rate of recovery 96.6%.
Embodiment 44
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 1.5: 1.5: 0.05 (mol ratio), amine is aniline, the original carboxylic acid ester is a triethyl orthoformate, the hydrazoic acid metal-salt is a sodiumazide, oil of mirbane is as organic solvent, its consumption is 10 times of aniline, and temperature of reaction is 80~85 ℃.
Other are operated with embodiment 1, product yield 70.3%, purity 99.6%, fusing point 64.8-65.1 ℃, the Ytterbiumtriflate rate of recovery 96.8%.
Embodiment 45
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 1.5: 1.5: 0.05 (mol ratio), amine is aniline, the original carboxylic acid ester is a triethyl orthoformate, the hydrazoic acid metal-salt is a sodiumazide, N, dinethylformamide is as organic solvent, and its consumption is 10 times of aniline, and temperature of reaction is 80~85 ℃.
Other are operated with embodiment 1, product yield 79.8%, purity 99.6%, fusing point 64.8-65.2 ℃, the Ytterbiumtriflate rate of recovery 96.9%.
Embodiment 46
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 1.5: 1.5: 0.05 (mol ratio), amine is aniline, the original carboxylic acid ester is a triethyl orthoformate, the hydrazoic acid metal-salt is a sodiumazide, dimethyl sulfoxide (DMSO) is as organic solvent, its consumption is 10 times of aniline, and temperature of reaction is 80~85 ℃.
Other are operated with embodiment 1, product yield 80.1%, purity 99.6%, fusing point 64.8-65.1 ℃, the Ytterbiumtriflate rate of recovery 96.1%.
Embodiment 47
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 1.5: 1.5: 0.05 (mol ratio), amine is aniline, the original carboxylic acid ester is a triethyl orthoformate, the hydrazoic acid metal-salt is a sodiumazide, tetrahydrofuran (THF) is as organic solvent, its consumption is 10 times of aniline, and temperature of reaction is 60~65 ℃.
Other are operated with embodiment 1, product yield 77.4%, purity 99.6%, fusing point 64.7-65.1 ℃, the Ytterbiumtriflate rate of recovery 96.5%.
Embodiment 48
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 1.5: 1.5: 0.05 (mol ratio), amine is aniline, the original carboxylic acid ester is a triethyl orthoformate, the hydrazoic acid metal-salt is a sodiumazide, toluene is as organic solvent, its consumption is 10 times of aniline, and temperature of reaction is 80~85 ℃.
Other are operated with embodiment 1, product yield 72.2%, purity 99.5%, fusing point 64.5-65.0 ℃, the Ytterbiumtriflate rate of recovery 96.5%.
Embodiment 49
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 1.5: 1.5: 0.05 (mol ratio), amine is aniline, the original carboxylic acid ester is a triethyl orthoformate, the hydrazoic acid metal-salt is a sodiumazide, 1, the 4-dioxane is as organic solvent, and its consumption is 10 times of aniline, and temperature of reaction is 80~85 ℃.
Other are operated with embodiment 1, product yield 80.6%, purity 99.6%, fusing point 64.7-65.1 ℃, the Ytterbiumtriflate rate of recovery 96.2%.
Embodiment 50~97
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 1.5: 1.5: 0.05 (mol ratio), the amine charging capacity is 50mmol, original carboxylic acid ester's charging capacity is 75mmol, the hydrazoic acid metal-salt is a sodiumazide, charging capacity is 75mmol, chloroform is as organic solvent, and its consumption is 10 times of aniline, and temperature of reaction is 50-60 ℃.Its operation is with embodiment 1.Wherein embodiment 50~97 described amine and original carboxylic acid ester's compound molecule formula is as shown in table 1.Experimental result sees Table 1, and reaction formula is as follows:
Table 1
Sequence number | R
1 | R
2 | R
3 | The product fusing point (℃) the or boiling point (℃ | Product yield (%) | Product purity (%) | Yb(OTf)
3The rate of recovery (%)
|
| | | | /mmHg) | | | |
50 | H | H | C
2H
5 | 155-156 | 75.4 | 99.6 | 96.3 |
51 | CH
3 | H | C
2H
5 | 36-37 | 75.6 | 99.4 | 96.1 |
52 | CH
3 | H | CH
3 | 36-37 | 75.8 | 99.5 | 96.2 |
53 | CH
3 | CH
3 | C
2H
5 | 70-71 | 76.8 | 99.4 | 96.3 |
54 | C
2H
5 | H | C
2H
5 | 162-164/30 | 78.2 | 99.2 | 96.4 |
55 | n-C
4H
9 | H | C
2H
5 | 143-144/2 | 80.1 | 99.3 | 96.4 |
56 | iso-C
4H
9 | H | C
2H
5 | 121-123/1 | 81.2 | 99.4 | 96.4 |
57 | n-C
5H
11 | H | C
2H
5 | 138-139/1 | 82.4 | 99.5 | 96.1 |
58 | iso-C
5H
11 | H | C
2H
5 | 143-145/1 | 81.7 | 99.4 | 96.1 |
59 | n-C
6H
13 | H | C
2H
5 | 144-146/1 | 82.3 | 99.3 | 96.5 |
60 | n-C
7H
15 | H | C
2H
5 | 150-152/1 | 83.2 | 99.5 | 96.5 |
61 | n-C
7H
15 | H | CH
3 | 150-152/1 | 83.7 | 99.2 | 96.4 |
62 | CH
2COOH
| H | C
2H
5 | 125-127 | 72.5 | 99.2 | 95.8 |
63 | CH
2COOH
| CH
3 | CH
3 | 191-192 | 76.2 | 99.3 | 95.9 |
64 | CH
2COOC
2H
5 | H | C
2H
5 | 32-34 | 78.4 | 99.2 | 95.7 |
65 | C
6H
5 | H | C
2H
5 | 64-65 | 83.8 | 99.7 | 96.9 |
66 | C
6H
5 | CH
3 | C
2H
5 | 98-99 | 84.2 | 99.6 | 96.5 |
67 | 2-NO
2C
6H
4 | H | CH
3 | 85-86 | 80.1 | 99.5 | 96.3 |
68 | 3-NO
2C
6H
4 | H | CH
3 | 109-110 | 79.2 | 99.4 | 96.0 |
69 | 3-NO
2C
6H
4 | CH
3 | CH
3 | 150-151 | 78.9 | 99.2 | 96.0 |
70 | 4-NO
2C
6H
4 | H | CH
3 | 201-203 | 80.4 | 99.3 | 96.4 |
71 | 4-NO
2C
6H
4 | CH
3 | CH
3 | 129 | 81.0 | 99.2 | 96.1 |
72 | 3-CH
3C
6H
4 | H | C
2H
5 | 53-54 | 93.6 | 99.5 | 96.7 |
73 | 4-CH
3C
6H
4 | H | C
2H
5 | 96 | 95.2 | 99.5 | 96.8 |
74 | 4-CH
3C
6H
4 | CH
3 | C
2H
5 | 106 | 96.2 | 99.4 | 96.7 |
75 | 3-FC
6H
4 | H | C
2H
5 | 65-66 | 90.2 | 99.3 | 96.4 |
76 | 4-FC
6H
4 | H | C
2H
5 | 92-93 | 91.2 | 99.5 | 96.5 |
77 | 2-ClC
6H
4 | H | CH
3 | 86-87 | 92.5 | 99.6 | 96.1 |
78 | 3-C1C
6H
4 | H | C
2H
5 | 101-102 | 93.1 | 99.5 | 96.8 |
79 | 4-ClC
6H
4 | H | C
2H
5 | 155-156 | 95.4 | 99.4 | 96.1 |
80 | 2-OHC
6H
4 | H | C
2H
5 | 56-57 | 84.7 | 99.3 | 96.3 |
81 | 4-OHC
6H
4 | H | C
2H
5 | 85-86 | 88.9 | 99.4 | 96.1 |
82 | 2-CH
3OC
6H
4 | H | C
2H
5 | 48-49 | 95.1 | 99.2 | 96.3 |
83 | 4-CH
3OC
6H
4 | H | CH
3 | 116-117 | 95.2 | 99.5 | 96.3 |
84 | 3-NO
2-2-CH
3OC
6H
3 | CH
3 | CH
3 | 174-175 | 75.4 | 99.4 | 95.9 |
85 | 3-NO
2-4-CH
3OC
6H
3 | CH
3 | CH
3 | 149-150 | 78.3 | 99.2 | 96.4 |
86 | 4-NO
2-2-CH
3OC
6H
3 | CH
3 | CH
3 | 140-141 | 76.5 | 99.3 | 96.4 |
87 | 3-NO
2-2-C
2H
5OC
6H
3 | CH
3 | CH
3 | 146-147 | 74.8 | 99.2 | 96.4 |
88 | 2,4-2Cl-C
6H
3 | H | C
2H
5 | 146 | 86.2 | 99.4 | 96.7 |
89 | 3,5-2Cl-C
6H
3 | H | C
2H
5 | 128 | 87.6 | 99.2 | 96.1 |
90 | C
6H
5CH
2 | H | C
2H
5 | 58-59 | 84.3 | 99.3 | 96.5 |
91 | 4-CH
3OC
6H
4CH
2 | H | C
2H
5 | 67-68 | 87.2 | 99.3 | 96.4 |
92 | 2-C
4H
3O
| H | C
2H
5 | 56-57 | 82.3 | 99.4 | 96.2 |
93 | 2-C
4H
3S
| H | C
2H
5 | 68-69 | 84.5 | 99.4 | 96.2 |
94 | 2-C
4H
4N
| H | C
2H
5 | 75-76 | 81.7 | 99.3 | 96.1 |
95 | 2-C
5H
4N
| H | C
2H
5 | 125-126 | 90.8 | 99.4 | 96.8 |
96 | 2-(4-CH
3C
5H
3N)
| H | C
2H
5 | 130 | 91.5 | 99.3 | 96.4 |
97 | 2-C
4H
3OCH
2 | H | C
2H
5 | 85 | 82.6 | 99.5 | 96.4 |
Embodiment 98
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 1.5: 1.5: 0.05 (mol ratio), amine is aniline, the original carboxylic acid ester is a triethyl orthoformate, the hydrazoic acid metal-salt is a potassium azide, Virahol is as organic solvent, its consumption is 15 times of aniline, and temperature of reaction is 80~85 ℃.
Other are operated with embodiment 1, product yield 84.1%, purity 99.6%, fusing point 64.8-65.1 ℃, the Ytterbiumtriflate rate of recovery 96.1%.
Embodiment 99
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 2.0: 1.5: 0.05 (mol ratio), amine is aniline, the original carboxylic acid ester is a triethyl orthoformate, the hydrazoic acid metal-salt is a potassium azide, Virahol is as organic solvent, its consumption is 20 times of aniline, and temperature of reaction is 80~85 ℃.
Other are operated with embodiment 1, product yield 84.5%, purity 99.3%, fusing point 64.6-65.0 ℃, the Ytterbiumtriflate rate of recovery 95.8%.
Embodiment 100
Feed ratio is an amine: the original carboxylic acid ester: the hydrazoic acid metal-salt: Ytterbiumtriflate=1: 1.5: 2.0: 0.05 (mol ratio), amine is aniline, the original carboxylic acid ester is a triethyl orthoformate, the hydrazoic acid metal-salt is a potassium azide, ethanol is as organic solvent, its consumption is 20 times of aniline, and temperature of reaction is 80~85 ℃.
Other are operated with embodiment 1, product yield 83.5%, purity 99.1%, fusing point 64.7-65.1 ℃, the Ytterbiumtriflate rate of recovery 96.2%.