CN1304381C - Chemical synthesis method of 1,2,3,4-tetra nitroazole kind compound - Google Patents

Chemical synthesis method of 1,2,3,4-tetra nitroazole kind compound Download PDF

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CN1304381C
CN1304381C CNB200410052775XA CN200410052775A CN1304381C CN 1304381 C CN1304381 C CN 1304381C CN B200410052775X A CNB200410052775X A CN B200410052775XA CN 200410052775 A CN200410052775 A CN 200410052775A CN 1304381 C CN1304381 C CN 1304381C
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nitrile
chemical synthesis
sodiumazide
solution
reaction
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CN1718574A (en
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苏为科
金灿
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Zhejiang University of Technology ZJUT
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Zhejiang University of Technology ZJUT
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Abstract

The present invention relates to a chemical synthesis method of a 1, 2, 3, 4-tetra nitroazole compound. The chemical synthesis method orderly comprises the following steps: step 1, zinc trifluoro methylsulfonate is dissolved in water to form solution A, the solution A is supplied, nitrile and sodium azide react in the solution A at the temperature of 50 to 100 DEG C, and reaction liquid is obtained; step 2, acid is added to the reaction liquid obtained in step 1, the reaction liquid is neutralized, the neutralized reaction liquid is filtered, a filter cake as a product is obtained, and filtered liquid is solution B. The chemical synthesis method of the present invention has the advantages that the reaction yield is high (which can reach more than 80% in general), the preparation cost is low, the technical line is advanced, the reaction condition is moderate, the dosage of a catalyst is little, the catalyst can be recovered and reused, almost no waste water, or waste gas, or waste slag is generated, water is used as solvent, and therefore, the use and the pollution of organic solvent can be avoided up to the hilt.

Description

1,2,3, the chemical synthesis process of 4-tetrazole compound
(1) technical field
The present invention relates to a kind of 1,2,3, the chemical synthesis process of 4-tetrazole compound.
(2) background technology
1,2,3, the 4-tetrazole compound is widely used in the synthetic of agricultural chemicals, medicine and dyestuff, has very high practical value.
In the prior art, 1,2,3, the chemosynthesis of 4-tetrazole compound is to prepare in organic solvent with amine or amine salt catalyzer.As US4,097,479 reacting under the katalysis of 1mol amine salt with 1mol nitrile and 1mol sodiumazide of proposition makes.This method needs equimolar amine salt as catalyzer, and temperature of reaction is higher, and yield is generally lower.
(3) summary of the invention
The objective of the invention is to overcome the shortcoming of prior art, provide 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, environmental protection 1,2,3, the chemical synthesis process of 4-tetrazole compound.
Of the present invention 1,2,3, the 4-tetrazole compound is the tautomerism compound shown in the formula (I),
R wherein 1Be C 1~C 18Saturated alkyl or the substituting group shown in general formula (II)~(VII),
R wherein 2For one of following: hydrogen, methyl, ethyl, propyl group, butyl, chlorine, bromine, iodine, amido, hydroxyl;
Chemical synthesis process of the present invention comprises following sequential steps:
(1) provide trifluoromethanesulfonic acid zinc water-soluble solution A, will suc as formula the sodiumazide shown in nitrile shown in (VIII) and the formula (IX) in above-mentioned solution A, under 50~100 ℃, react reaction solution;
(2) step (1) gained reaction solution is added the acid neutralization, filter to such an extent that filter cake is a product, filtrate is solution B;
(VIII) R 1-CN (IX) NaN 3
Formula (VIII) R 1Define the same
The reaction formula of described reaction is as follows:
The molar ratio of described nitrile, sodiumazide, trifluoromethanesulfonic acid zinc is 1: 1.0~4.0: 0.02~1.0, be preferably 1: 1.0~2.0: 0.1~and 1.0; The weight ratio of described water and nitrile is 2~50: 1, is preferably 10~30: 1.
The reaction times is preferably 1-24 hour in the above-mentioned synthetic method, more preferably 4~24 hours.
When described reactant nitrile is solid, then when adding acid neutralizing filter, unreacted completely nitrile can to remain in filter cake be in the middle of the product, to influence degree of purity of production.As of the present invention preferred, in step (1), also described reaction solution is filtered to remove unreacted reactant completely.
Above-mentioned 1,2,3, the chemical synthesis process of 4-tetrazole compound, preferably carry out as follows: molar ratio is that 1: 1.0~2.0: 0.1~1.0 nitrile, sodiumazide, trifluoromethanesulfonic acid zinc join in the water of 10~30 times of nitrile quality, is warmed up to 50~100 ℃ of reactions 4~24 hours, filters, filtrate is neutralized to pH=5~6 with hydrochloric acid, filters to such an extent that filter cake is a product.
Recyclable the applying mechanically of catalyzer that the present invention is used, recoverying and utilizing method is: the solution B described in the step (2) directly is used as the solution A described in the step (1).
Chemical synthesis process of the present invention compared with prior art, beneficial effect is embodied in:
1. reaction yield height (generally more than 80%), production cost are low;
2. operational path advanced person, reaction conditions gentleness;
3. catalyst levels is few and recyclablely apply mechanically, do not have substantially the three wastes.
4. water can be avoided using of organic solvent to greatest extent as solvent and pollute.
(4) embodiment
The invention will be further described below in conjunction with specific embodiment, but protection scope of the present invention is not limited to this.
Embodiment 1
The molar ratio of nitrile, sodiumazide, trifluoromethanesulfonic acid zinc is 1: 1: 0.1, and nitrile is a benzonitrile, and water consumption is 10 times of nitrile quality.
In thermometer, reflux condensing tube and churned mechanically 150ml four-hole boiling flask are housed, add entry 100g, benzonitrile 10.3g (0.1mol), sodiumazide 6.5g (0.1mol), trifluoromethanesulfonic acid zinc 3.63g (10mmol) is heated to backflow (100 ℃), refluxes 4 hours.Reaction finishes, and is cooled to room temperature, is neutralized to pH=5 with concentrated hydrochloric acid.Filter, collect the white solid of being separated out, get 5-phenyl-1H-tetrazole 13.4g, yield 90%, purity 98.2%, 215 ℃ of fusing points.
Embodiment 2
The molar ratio of nitrile, sodiumazide, trifluoromethanesulfonic acid zinc is 1: 1: 1, and nitrile is a benzonitrile, and water consumption is 10 times of nitrile quality.Benzonitrile 10.3g (0.1mol), sodiumazide 6.5g (0.1mol), trifluoromethanesulfonic acid zinc 36.3g (0.1mol), temperature of reaction is 90 ℃.
Other gets 5-phenyl-1H-tetrazole 14.1g, yield 95%, purity 98.3%, 215 ℃ of fusing points with embodiment 1.
Embodiment 3
The molar ratio of nitrile, sodiumazide, trifluoromethanesulfonic acid zinc is 1: 1: 0.5, and nitrile is a benzonitrile, and water consumption is 30 times of nitrile quality.Benzonitrile 10.3g (0.1mol), sodiumazide 6.5g (0.1mol), trifluoromethanesulfonic acid zinc 18.2g (50mmol), the reaction times is 6 hours.
Other gets 5-phenyl-1H-tetrazole 13.8g, yield 93%, purity 98.5%, 215 ℃ of fusing points with embodiment 1.
Embodiment 4
The molar ratio of nitrile, sodiumazide, trifluoromethanesulfonic acid zinc is 1: 2: 0.1, and nitrile is a benzonitrile, and water consumption is 20 times of nitrile quality.Benzonitrile 10.3g (0.1mol), sodiumazide 13g (0.2mmol), trifluoromethanesulfonic acid zinc 3.63g (10mmol).Reaction times is 8 hours.
Other gets 5-phenyl-1H-tetrazole 12.7g, yield 85%, purity 97.8%, 215 ℃ of fusing points with embodiment 1.
Embodiment 5
The molar ratio of nitrile, sodiumazide, trifluoromethanesulfonic acid zinc is 1: 4: 0.02, and nitrile is a benzonitrile, and water consumption is 50 times of nitrile quality.Benzonitrile 10.3g (0.1mol), sodiumazide 26g (0.4mol), trifluoromethanesulfonic acid zinc 3.63g (10mmol).
Other gets 5-phenyl-1H-tetrazole 13.2g, yield 89%, purity 98.2%, 215 ℃ of fusing points with embodiment 1
Embodiment 6
The molar ratio of nitrile, sodiumazide, trifluoromethanesulfonic acid zinc is 1: 1: 0.6; Nitrile is a p-Nitrobenzyl Cyanide, and consumption is 14.8g (0.1mol); Water consumption is 20 times of nitrile quality.Reaction times is 15 hours.
Other gets 5-(4-nitrophenyl)-1H-tetrazole 18.1g, yield 80%, purity 84.5%, 220 ℃ of fusing points with embodiment 1.
Embodiment 7
The molar ratio of nitrile, sodiumazide, trifluoromethanesulfonic acid zinc is 1: 2: 0.3; Nitrile is the beta-cyano naphthalene, and consumption is 15.3g (0.1mol); Water consumption is 10 times of nitrile quality.
Other gets 5-(2-naphthyl)-1H-tetrazole 18.6g, yield 81%, purity 85.5%, 204 ℃ of fusing points with embodiment 1.
Embodiment 8
The molar ratio of nitrile, sodiumazide, trifluoromethanesulfonic acid zinc is 1: 1: 0.1; Nitrile is a p-Nitrobenzyl Cyanide, and consumption is 14.8g (0.1mol); Water consumption is 30 times of nitrile quality.
Other gets 5-(4-nitrophenyl)-1H-tetrazole 17.9g, yield 81%, purity 86.4%, 220 ℃ of fusing points with embodiment 1.
Embodiment 9
The molar ratio of nitrile, sodiumazide, trifluoromethanesulfonic acid zinc is 1: 3: 0.4; Nitrile is an acetonitrile, and consumption is 4.1g (0.1mol); Water consumption is 40 times of nitrile quality.
Other gets 5-methyl isophthalic acid H-tetrazole 6.6g, yield 78%, purity 99.0%, 146 ℃ of fusing points with embodiment 1.
Embodiment 10
The molar ratio of nitrile, sodiumazide, trifluoromethanesulfonic acid zinc is 1: 1: 0.1; Nitrile is the 2-cyanopyridine, and consumption is 10.4g (0.1mol); Water consumption is 20 times of nitrile quality.
Other gets 5-(2-pyridyl)-1H-tetrazole 12.3g, yield 82%, purity 98.3%, 211 ℃ of fusing points with embodiment 1.
Embodiment 11
The molar ratio of nitrile, sodiumazide, trifluoromethanesulfonic acid zinc is 1: 1: 0.5; Nitrile is a lauronitrile, and consumption is 18.1 (0.1mol); Water consumption is 20 times of nitrile quality, and temperature of reaction is 70 ℃.
Other gets 5-undecyl-1H-tetrazole 17.1g, yield 75%, purity 98.1%, 206 ℃ of fusing points with embodiment 1.
Embodiment 12
The molar ratio of nitrile, sodiumazide, trifluoromethanesulfonic acid zinc is 1: 1: 0.1, and nitrile is a benzonitrile, and water consumption is 10 times of nitrile quality.
In thermometer, reflux condensing tube and churned mechanically 150ml four-hole boiling flask are housed, add entry 100g, benzonitrile 10.3g (0.1mol), sodiumazide 6.5g (0.1mol), trifluoromethanesulfonic acid zinc 3.63g (10mmol) is heated to backflow (100 ℃), refluxes 4 hours.Reaction finishes, and is cooled to room temperature, filters, and removes unreacted raw material nitrile, and the filtrate water layer is neutralized to pH=5 with concentrated hydrochloric acid.Filter, collect the white solid of being separated out, get 5-phenyl-1H-tetrazole 13.14g, yield 90%, purity 99.6%, 215 ℃ of fusing points.
Embodiment 13
The molar ratio of nitrile, sodiumazide, trifluoromethanesulfonic acid zinc is 1: 1: 1, and nitrile is a benzonitrile, and water consumption is 10 times of nitrile quality.Benzonitrile 10.3g (0.1mol), sodiumazide 6.5g (0.1mol), trifluoromethanesulfonic acid zinc 36.3g (0.1mol).
Other gets 5-phenyl-1H-tetrazole 13.9g, yield 95%, purity 99.7%, 215 ℃ of fusing points with embodiment 12.
Embodiment 14
The molar ratio of nitrile, sodiumazide, trifluoromethanesulfonic acid zinc is 1: 1: 0.5, and nitrile is a benzonitrile, and water consumption is 10 times of nitrile quality.Benzonitrile 10.3g (0.1mol), sodiumazide 6.5g (0.1mol), trifluoromethanesulfonic acid zinc 18.2g (50mmol).
Other gets 5-phenyl-1H-tetrazole 13.6g, yield 93%, purity 99.5%, 215 ℃ of fusing points with embodiment 12.
Embodiment 15
The molar ratio of nitrile, sodiumazide, trifluoromethanesulfonic acid zinc is 1: 2: 0.1, and nitrile is a benzonitrile, and water consumption is 10 times of nitrile quality.Benzonitrile 10.3g (0.1mol), sodiumazide 13g (0.2mmol), trifluoromethanesulfonic acid zinc 3.63g (10mmol).
Other gets 5-phenyl-1H-tetrazole 14.2g, yield 97%, purity 99.8%, 215 ℃ of fusing points with embodiment 12.
Embodiment 16
The molar ratio of nitrile, sodiumazide, trifluoromethanesulfonic acid zinc is 1: 4: 0.1, and nitrile is a benzonitrile, and water consumption is 10 times of nitrile quality.Benzonitrile 10.3g (0.1mol), sodiumazide 26g (0.4mol), trifluoromethanesulfonic acid zinc 3.63g (10mmol).
Other gets 5-phenyl-1H-tetrazole 14.3g, yield 98%, purity 99.7%, 215 ℃ of fusing points with embodiment 12
Embodiment 17
The molar ratio of nitrile, sodiumazide, trifluoromethanesulfonic acid zinc is 1: 1: 0.1; Nitrile is a p-Nitrobenzyl Cyanide, and consumption is 14.8g (0.1mol); Water consumption is 10 times of nitrile quality.Reaction times is 2 hours.
Other gets 5-(4-nitrophenyl)-1H-tetrazole 17.6g, yield 92%, purity 99.7%, 220 ℃ of fusing points with embodiment 12.
Embodiment 18
The molar ratio of nitrile, sodiumazide, trifluoromethanesulfonic acid zinc is 1: 2: 0.1; Nitrile is the beta-cyano naphthalene, and consumption is 15.3g (0.1mol); Water consumption is 10 times of nitrile quality.
Other gets 5-(2-naphthyl)-1H-tetrazole 17.8g, yield 91%, purity 99.7%, 204 ℃ of fusing points with embodiment 12.
Embodiment 19
The molar ratio of nitrile, sodiumazide, trifluoromethanesulfonic acid zinc is 1: 3: 0.1; Nitrile is an acetonitrile, and consumption is 4.1g (0.1mol); Water consumption is 10 times of nitrile quality.Reaction times is 1 hour.
Other gets 5-methyl isophthalic acid H-tetrazole 6.72g, yield 80%, purity 99.1%, 146 ℃ of fusing points with embodiment 12.
Embodiment 20
The molar ratio of nitrile, sodiumazide, trifluoromethanesulfonic acid zinc is 1: 2: 0.1; Nitrile is positive caprylic nitrile, and consumption is 12.5 (10mmol); Water consumption is 10 times of nitrile quality.Reaction times is 24 hours.
Other gets 5-heptyl-1H-tetrazole 13.3g, yield 78%, purity 99.2%, 36 ℃ of fusing points with embodiment 12.
Embodiment 21
The molar ratio of nitrile, sodiumazide, trifluoromethanesulfonic acid zinc is 1: 1: 0..02; Nitrile is the 2-cyanopyridine, and consumption is 10.4g (0.1mol); Water consumption is 10 times of nitrile quality.
Other gets 5-(2-pyridyl)-1H-tetrazole 13.5g, yield 92%, purity 99.0%, 211 ℃ of fusing points with embodiment 12.
Embodiment 22
The molar ratio of nitrile, sodiumazide, trifluoromethanesulfonic acid zinc is 1: 1: 0.1; Nitrile is a 2-cyano group furans, and consumption is 9.3g (0.1mol); Water consumption is 10 times of nitrile quality.Reaction times is 10 hours.
Other gets 5-(2-furyl)-1H-tetrazole 13.4g, yield 88%, purity 99.6%, 166 ℃ of fusing points with embodiment 12.
Embodiment 23
Water consumption is 20 times of nitrile quality.
Other gets 5-phenyl-1H-tetrazole 13g, yield 89%, purity 99.5%, 215 ℃ of fusing points with embodiment 12.
Embodiment 24
Water consumption is 40 times of nitrile quality.
Other gets 5-phenyl-1H-tetrazole 12.8g, yield 88%, purity 99.8%, 215 ℃ of fusing points with embodiment 12.
Embodiment 25
Temperature of reaction is 50 ℃.
Other gets 5-phenyl-1H-tetrazole 11.7g, yield 80%, purity 99.5%, 215 ℃ of fusing points with embodiment 12.
Embodiment 26
Temperature of reaction is 70 ℃.
Other gets 5-phenyl-1H-tetrazole 12.3g, yield 84%, purity 99.1%, 215 ℃ of fusing points with embodiment 12.
Embodiment 27
Temperature of reaction is 90 ℃.
Other gets 5-phenyl-1H-tetrazole 12.7g, yield 87%, purity 99.3%, 215 ℃ of fusing points with embodiment 12.
Embodiment 28
Reaction times is 12 hours.
Other gets 5-phenyl-1H-tetrazole 13.4g, yield 92%, purity 99.4%, 215 ℃ of fusing points with embodiment 12.
Embodiment 29
Reaction times is 24 hours.
Other gets 5-phenyl-1H-tetrazole 13.7g, yield 94%, purity 99.6%, 215 ℃ of fusing points with embodiment 12.
Embodiment 30
The molar ratio of nitrile, sodiumazide, trifluoromethanesulfonic acid zinc is 1: 1: 0.1; Nitrile is a lauronitrile, and consumption is 18.1 (0.1mol); Water consumption is 20 times of nitrile quality, and temperature of reaction is 70 ℃.
Other gets 5-undecyl-1H-tetrazole 16.8g, yield 75%, purity 99.5%, 206 ℃ of fusing points with embodiment 12.
Embodiment 31
The molar ratio of nitrile, sodiumazide, trifluoromethanesulfonic acid zinc is 1: 1: 0.5; Nitrile is to the benzyl chloride nitrile, and consumption is 13.8g (0.1mol); Water consumption is 15 times of nitrile quality.
Other gets 5-(4-chloro-phenyl-)-1H-tetrazole 15.0g, yield 83%, purity 99.1%, fusing point 247-248 ℃ with embodiment 1.
Embodiment 32
The molar ratio of nitrile, sodiumazide, trifluoromethanesulfonic acid zinc is 1: 1: 0.1; Nitrile is a 2-chloro-3-cyanopyridine, and consumption is 13.8g (0.1mol); Water consumption is 20 times of nitrile quality.
Other gets 5-[3-(2-chlorine)-pyridyl with embodiment 12]-1H-tetrazole 12.7g, yield 70%, purity 99.4%, fusing point 219-221 ℃.
Embodiment 33
The molar ratio of nitrile, sodiumazide, trifluoromethanesulfonic acid zinc is 1: 2: 0.2, and nitrile is a 2 thiophene acetonitrile, and consumption is 12.4g (0.1mol); Water consumption is 20 times of nitrile quality.
Other gets 5-(2-thenyl)-1H-tetrazole 13.5g, yield 81%, purity 99.6%, fusing point 204-207 ℃ with embodiment 12.

Claims (10)

1, a kind of suc as formula 1,2,3 shown in (I), the chemical synthesis process of 4-tetrazole compound,
R wherein 1Be C 1~C 18Saturated alkyl or the substituting group shown in general formula (II)~(VII),
R wherein 2For one of following: hydrogen, methyl, ethyl, propyl group, butyl, chlorine, bromine, iodine, amido, hydroxyl;
It is characterized in that comprising following sequential steps:
(1) provide trifluoromethanesulfonic acid zinc water-soluble solution A, will suc as formula the sodiumazide shown in nitrile shown in (VIII) and the formula (IX) in above-mentioned solution A, under 50~100 ℃, react reaction solution;
(2) step (1) gained reaction solution is added the acid neutralization, filter to such an extent that filter cake is a product, filtrate is solution B;
(VIII) R 1-CN (IX) NaN 3
Formula (VIII) R 1Define the same.
2, by the described chemical synthesis process of claim 1, the mol ratio that it is characterized in that described nitrile, sodiumazide, trifluoromethanesulfonic acid zinc is 1: 1.0~4.0: 0.02~1.0.
3, by the described chemical synthesis process of claim 2, the weight ratio that it is characterized in that described water and nitrile is 2~50: 1.
4,, it is characterized in that described step (1) also filters described reaction solution by the described chemical synthesis process of claim 3.
5, by one of claim 2~4 described chemical synthesis process, the mol ratio that it is characterized in that described nitrile, sodiumazide, trifluoromethanesulfonic acid zinc is 1: 1.0~2.0: 0.1~1.0.
6, by the described chemical synthesis process of claim 5, the weight ratio that it is characterized in that described water and nitrile is 10~30: 1.
7, by one of claim 1~4 described chemical synthesis process, it is characterized in that the reaction times is 1~24 hour.
8, by the described chemical synthesis process of claim 7, it is characterized in that the reaction times is 4~24 hours.
9, by one of claim 1~4 described chemical synthesis process, the solution B that it is characterized in that step (2) filtration gained is as the solution A described in the step (1).
10. by the described chemical synthesis process of claim 8, it is characterized in that: mol ratio is that 1: 1.0~2.0: 0.1~1.0 nitrile, sodiumazide, trifluoromethanesulfonic acid zinc join in the water that quality is 10~30 times of nitriles, be warmed up to 50~100 ℃ of reactions 4~24 hours, filter, filtrate is neutralized to pH=5~6 with hydrochloric acid, filters to such an extent that filter cake is a product.
CNB200410052775XA 2004-07-09 2004-07-09 Chemical synthesis method of 1,2,3,4-tetra nitroazole kind compound Expired - Fee Related CN1304381C (en)

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CN1189158A (en) * 1995-05-26 1998-07-29 中国化药株式会社 Novel reagent for tetrazole synthesis and process for producing tetrazoles therewith
JPH10114772A (en) * 1996-03-21 1998-05-06 Toyo Kasei Kogyo Co Ltd Production of 1-(tetrazolylbiphenylmethyl) midazole derivative

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