CN1775764A - A kind of chemical synthesis method of tetrazole compound - Google Patents
A kind of chemical synthesis method of tetrazole compound Download PDFInfo
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- CN1775764A CN1775764A CN 200510061754 CN200510061754A CN1775764A CN 1775764 A CN1775764 A CN 1775764A CN 200510061754 CN200510061754 CN 200510061754 CN 200510061754 A CN200510061754 A CN 200510061754A CN 1775764 A CN1775764 A CN 1775764A
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Abstract
The invention relates to a chemical method for synthesizing tetrazole compound, including the steps as follows: making amine and crude carboxylic ester reacts with nitrine metallic salt in organic solvent at 20 deg.C-150 deg.C under the action of a catalyst ytterbium trifluoro methyl sulfonate, and afterprocessing to obtain the target product. The synthesizing method has the advantages of reasonable technique, high reaction yield, less catalyst dosage, low production cost, no three wastes, and being able to conveniently recover and use indiscriminately.
Description
(1) technical field
The present invention relates to a kind of chemical synthesis process of tetrazole compound.
(2) background technology
Before the present invention made, the chemical synthesis process of prior art tetrazole compound mainly was to prepare as catalyzer with traditional Bo Langside acid such as acetate, trifluoroacetic acids.As US3,767,667 reacting under the effect of 10ml acetic acid catalysis with 2.6g anilinechloride and 1.5g sodiumazide, 5ml triethyl orthoformate of proposition make.
Three component reaction routes of amine hydrochlorate, sodiumazide and triethyl orthoformate have the reaction conditions gentleness, productive rate is than advantages such as height, and the hydrazoic acid of using the isonitrile compounds that is more difficult to get and severe toxicity before comparing reacts and prepares tetrazole compound and have greatly improved.But this reaction scheme still has big shortcoming: at first be amine will be made hydrochloride to react, operation is trouble comparatively; Next is to have strongly-acid medium such as hydrochloric acid, acetate in the reaction system and the sodiumazide effect still has severe toxicity, explosive hydrazoic acid gas is emitted, and makes reaction have bigger potential safety hazard; Be that excessive difficult the recovery by distillation of acetate purified once more, easily cause environmental pollution.Therefore, the many problems that exist in this reaction scheme wait to improve.
(3) summary of the invention
Task of the present invention is the shortcoming that overcomes prior art, provides that a kind of technology is reasonable, reaction yield is high, catalyst levels can make things convenient for again less that recovery set is low with, production cost, the chemical synthesis process of the tetrazole compound of environmental protection.
Described tetrazole compound is suc as formula shown in (I), and described chemical synthesis process comprises the steps:
Suc as formula the amine of (II), suc as formula the original carboxylic acid ester of (III), with hydrazoic acid metal-salt (IV) under the effect of catalyzer Ytterbiumtriflate in organic solvent in 20～150 ℃ of reactions, aftertreatment and target product;
R
1-NH
2(II) R
2C(OR
3)
3(III) M
m+(N
3)
m(IV)
Its Chinese style (I) and (II) in, R
1Represent hydrogen, or C
1～C
6Alkyl or carboxyl or ester group, or as the substituting group of formula V:
R in the formula V wherein
4Represent hydrogen, C
1～C
4Alkyl or alkoxyl group, halogen, hydroxyl or nitro, A represents phenyl ring or one of following heterocycle: furans, thiophene, pyrroles, pyridine, n are 0 or 1;
R in the formula (III)
2Be hydrogen or C
1～C
6Alkyl, R
3Be C
1～C
6Alkyl;
M is metal Li, Na, K, Ca, Mg, Zn or Cu in the formula IV, and m is 1 or 2.
R
1Be preferably hydrogen, C
1～C
6Alkyl, phenyl, benzyl or A be heterocyclic formula V substituting group; R
2Be preferably hydrogen or methyl, R
3Be preferably methyl or ethyl; M is preferably metal Na.
Reaction formula is as follows:
Described organic solvent can be one of following or more than one arbitrary combination: 1. carbonatoms is 1～4 halohydrocarbon, 2. carbonatoms is 1～7 ester, 3. carbonatoms is 1～4 alcohol, 4. carbonatoms is 2～6 ether, concrete as: methylene dichloride, trichloromethane, tetracol phenixin, 1, the 1-ethylene dichloride, 1, the 2-ethylene dichloride, 1,1, the 1-trichloroethane, 1,1, the 2-trichloroethane, methyl acetate, ethyl acetate, propyl acetate, butylacetate, isopropyl acetate, isobutyl acetate, pentyl acetate, Isoamyl Acetate FCC, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, amyl propionate, methyl alcohol, ethanol, Virahol, butanols, ether, propyl ether, isopropyl ether, butyl ether, dithiocarbonic anhydride, Nitromethane 99Min., oil of mirbane, N, dinethylformamide, dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), toluene, 1, the 4-dioxane; Organic solvent is preferably one of following or more than one arbitrary combination: 1. chloroform, 2. methylene dichloride, 3. ethanol, 4. Virahol, 5. N, dinethylformamide, 6. ethyl acetate, 7. dimethyl sulfoxide (DMSO).
Described amine: original carboxylic acid ester: hydrazoic acid metal-salt: the molar ratio of Ytterbiumtriflate is generally 1: 1.0～5.0: 1.0～3.0: 0.02～1.0, be preferably 1: 1.5～3.0: 1.0～2.0: 0.02～and 0.05.
Described consumption of organic solvent is generally 2～20 times of amine quality, is preferably 10～15 times of amine quality.
Described temperature of reaction is preferably 50～80 ℃, and the reaction times was generally 2～10 hours.
Further, the chemical synthesis process of tetrazole compound is to carry out as follows:
A. be amine with molar ratio under the room temperature: original carboxylic acid ester: hydrazoic acid metal-salt: Ytterbiumtriflate is 1: 1.5～3.0: 1.0～2.0: 0.02～0.05 to add in the organic solvent chloroform and dissolve;
B. be warmed up to 50～60 ℃ of temperature of reaction, reacted 2-10 hour, use simultaneously the HPLC tracking monitor (flow velocity: 1.5ml/min, acetonitrile: water: acetic acid=20: 80: 0.05), reaction finishes;
C. boil off solvent, ice bath cooling slowly adds the 20ml frozen water down, constantly stirs 10min, ethyl acetate extraction three times, organic phase concentrates, ethyl alcohol recrystallization, filter drain finished product.
Recyclable the applying mechanically of catalyzer that the present invention is used, recovery method are that reaction is finished gained water concentrating under reduced pressure, washing, 190 ℃ of thermal dehydrations are 4 hours under vacuum, white Ytterbiumtriflate crystal, the rate of recovery can reach more than 95%.
The present invention replaces acetate, trifluoroacetic acid as catalyzer compared with prior art with Ytterbiumtriflate, and beneficial effect is embodied in:
1. reaction yield height (generally more than 80%), production cost are low;
2. have operational path advanced person, reaction conditions gentleness;
3. catalyst levels is few and recyclablely apply mechanically, do not have substantially the three wastes.
(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-ClC 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%.
Claims (10)
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102906075A (en) * | 2010-03-12 | 2013-01-30 | 拜耳知识产权有限责任公司 | Process for the preparation of 5-substituted 1-alkyltetrazoles |
| CN103724288A (en) * | 2013-12-16 | 2014-04-16 | 山东艾孚特科技有限公司 | Post-processing method for preparing 1H-tetrazole-1-acetic acid through triethyl orthoformate method |
| CN106831628A (en) * | 2017-03-07 | 2017-06-13 | 山东省化工研究院 | A kind of new technique for synthesizing of tetrazoleacetic acid |
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| DE2147023C3 (en) * | 1971-09-21 | 1982-04-29 | Fujisawa Pharmaceutical Co., Ltd., Osaka | Process for the preparation of 1H-tetrazole compounds |
| US4036849A (en) * | 1974-05-15 | 1977-07-19 | American Cyanamid Company | 1-(Para-substituted-phenyl)-1H-tetrazoles |
| CS259379B1 (en) * | 1986-04-25 | 1988-10-14 | Lubomir Janda | A method for preparing β-1-tetrazolylacetic acid |
| CN1071918A (en) * | 1992-11-17 | 1993-05-12 | 蒋飞龙 | The preparation technology of tetrazolium and amine salt thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102906075A (en) * | 2010-03-12 | 2013-01-30 | 拜耳知识产权有限责任公司 | Process for the preparation of 5-substituted 1-alkyltetrazoles |
| CN102906075B (en) * | 2010-03-12 | 2016-01-13 | 拜耳知识产权有限责任公司 | The preparation method of the 1-alkyl tetrazolium that 5-replaces |
| CN103724288A (en) * | 2013-12-16 | 2014-04-16 | 山东艾孚特科技有限公司 | Post-processing method for preparing 1H-tetrazole-1-acetic acid through triethyl orthoformate method |
| CN103724288B (en) * | 2013-12-16 | 2015-11-04 | 山东艾孚特科技有限公司 | Triethyl orthoformate legal system is for the post-treating method of 1H-tetrazole-1-acetic acid |
| CN106831628A (en) * | 2017-03-07 | 2017-06-13 | 山东省化工研究院 | A kind of new technique for synthesizing of tetrazoleacetic acid |
| CN106831628B (en) * | 2017-03-07 | 2019-04-23 | 山东省化工研究院 | A kind of new technique for synthesizing of tetrazoleacetic acid |
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