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 PDFInfo
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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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- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title abstract description 6
- FGYTYYKNCOBFCF-UHFFFAOYSA-N 1,2,3,4-tetranitropyrrole Chemical compound [N+](=O)([O-])N1C(=C(C(=C1)[N+](=O)[O-])[N+](=O)[O-])[N+](=O)[O-] FGYTYYKNCOBFCF-UHFFFAOYSA-N 0.000 title 1
- 150000001875 compounds Chemical class 0.000 title 1
- 150000002825 nitriles Chemical class 0.000 claims abstract description 97
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 claims abstract description 90
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000012065 filter cake Substances 0.000 claims abstract description 6
- 239000000047 product Substances 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 4
- NGOCMUBXJDDBLB-UHFFFAOYSA-N trifluoromethanesulfonic acid;zinc Chemical compound [Zn].OS(=O)(=O)C(F)(F)F NGOCMUBXJDDBLB-UHFFFAOYSA-N 0.000 claims description 43
- 230000035484 reaction time Effects 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims 1
- -1 1, 2, 3, 4-tetra nitroazole compound Chemical class 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-M Methanesulfonate Chemical compound CS([O-])(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-M 0.000 abstract 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 239000002893 slag Substances 0.000 abstract 1
- 239000002912 waste gas Substances 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 abstract 1
- 239000011701 zinc Substances 0.000 abstract 1
- 229910052725 zinc Inorganic materials 0.000 abstract 1
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 60
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 17
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 4
- PXNJGLAVKOXITN-UHFFFAOYSA-N 2-(4-nitrophenyl)acetonitrile Chemical compound [O-][N+](=O)C1=CC=C(CC#N)C=C1 PXNJGLAVKOXITN-UHFFFAOYSA-N 0.000 description 3
- MIUOBAHGBPSRKY-UHFFFAOYSA-N 5-(4-nitrophenyl)-2h-tetrazole Chemical compound C1=CC([N+](=O)[O-])=CC=C1C1=NNN=N1 MIUOBAHGBPSRKY-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- LQWXEEDCMLEVHU-UHFFFAOYSA-N 2-(2h-tetrazol-5-yl)pyridine Chemical compound N1=CC=CC=C1C1=NNN=N1 LQWXEEDCMLEVHU-UHFFFAOYSA-N 0.000 description 2
- FFNVQNRYTPFDDP-UHFFFAOYSA-N 2-cyanopyridine Chemical compound N#CC1=CC=CC=N1 FFNVQNRYTPFDDP-UHFFFAOYSA-N 0.000 description 2
- PMZBHPUNQNKBOA-UHFFFAOYSA-N 5-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=CC(C(O)=O)=CC(C(O)=O)=C1 PMZBHPUNQNKBOA-UHFFFAOYSA-N 0.000 description 2
- CEKHHZHWADUZJK-UHFFFAOYSA-N 5-naphthalen-2-yl-2h-tetrazole Chemical compound C1=CC2=CC=CC=C2C=C1C1=NN=NN1 CEKHHZHWADUZJK-UHFFFAOYSA-N 0.000 description 2
- DAPQABYVGNGQLN-UHFFFAOYSA-N 5-undecyl-2h-tetrazole Chemical compound CCCCCCCCCCCC1=NN=NN1 DAPQABYVGNGQLN-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- AZKDTTQQTKDXLH-UHFFFAOYSA-N naphthalene-2-carbonitrile Chemical compound C1=CC=CC2=CC(C#N)=CC=C21 AZKDTTQQTKDXLH-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Substances C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 description 1
- JAUPUQRPBNDMDT-UHFFFAOYSA-N 2-chloropyridine-3-carbonitrile Chemical compound ClC1=NC=CC=C1C#N JAUPUQRPBNDMDT-UHFFFAOYSA-N 0.000 description 1
- CLSHQIDDCJTHAJ-UHFFFAOYSA-N 2-thienylacetonitrile Chemical compound N#CCC1=CC=CS1 CLSHQIDDCJTHAJ-UHFFFAOYSA-N 0.000 description 1
- BGKOVWIBDZMJPN-UHFFFAOYSA-N 5-(4-chlorophenyl)-2h-tetrazole Chemical compound C1=CC(Cl)=CC=C1C1=NNN=N1 BGKOVWIBDZMJPN-UHFFFAOYSA-N 0.000 description 1
- OEBGMJBGNZGVJV-UHFFFAOYSA-N 5-(furan-2-yl)-2h-tetrazole Chemical compound C1=COC(C2=NNN=N2)=C1 OEBGMJBGNZGVJV-UHFFFAOYSA-N 0.000 description 1
- BFCXMQOUSDALQE-UHFFFAOYSA-N 5-(thiophen-2-ylmethyl)-2h-tetrazole Chemical compound C=1C=CSC=1CC=1N=NNN=1 BFCXMQOUSDALQE-UHFFFAOYSA-N 0.000 description 1
- YQMOOZYBLZGKRU-UHFFFAOYSA-N 5-heptyl-2h-tetrazole Chemical compound CCCCCCCC1=NN=NN1 YQMOOZYBLZGKRU-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000003419 tautomerization reaction Methods 0.000 description 1
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- Plural Heterocyclic Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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) 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.
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| CN100591674C (en) * | 2008-02-21 | 2010-02-24 | 南京大学 | Method for catalytic synthesis of 5-substituted tetrazole by tungstate |
| CN101857577B (en) * | 2010-04-27 | 2012-07-04 | 盐城市康乐化工有限公司 | Method for preparing tetrazole compound by taking core-shell magnetic nanoparticles as catalyst |
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| CN103351353A (en) * | 2013-07-25 | 2013-10-16 | 浙江海蓝化工有限公司 | Aqueous phase synthesis method of 5-methyl tetrazole |
| CN105237490A (en) * | 2015-11-16 | 2016-01-13 | 江苏恒祥化工有限责任公司 | Synthesis method of 5-methyl tetrazole |
| CN106905254B (en) * | 2017-02-20 | 2019-04-16 | 衢州学院 | A kind of preparation method of 5- phenyl -1H- tetrazole |
| CN107602495B (en) * | 2017-10-13 | 2018-07-24 | 盐城工学院 | A method of preparing chiral amino acid tetrazole compound |
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| CN108358863A (en) * | 2018-03-08 | 2018-08-03 | 湖北佰智昂生物化工有限公司 | A kind of method that zinc lewis acid Surfactant-Catalyzed prepares 5 '-substituted tetrazole compounds |
| CN108864157A (en) * | 2018-08-14 | 2018-11-23 | 江苏科技大学 | A kind of fluorescent probe molecule and the preparation method and application thereof for metal ion detection |
| CN109503505B (en) * | 2019-01-09 | 2020-07-21 | 浙江工业大学 | Synthesis method of 5-substituted tetrazole compound |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4097479A (en) * | 1977-03-11 | 1978-06-27 | Miles Laboratories, Inc. | Synthesis of 5-substituted tetrazoles |
| US5502191A (en) * | 1993-07-01 | 1996-03-26 | American Cyanamid Company | Method of synthesizing sterically hindered 5-substituted-1H-tetrazoles from nitriles using a lewis acid and an azide |
| JPH10114772A (en) * | 1996-03-21 | 1998-05-06 | Toyo Kasei Kogyo Co Ltd | Production of 1-(tetrazolylbiphenylmethyl) midazole derivative |
| 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 |
-
2004
- 2004-07-09 CN CNB200410052775XA patent/CN1304381C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4097479A (en) * | 1977-03-11 | 1978-06-27 | Miles Laboratories, Inc. | Synthesis of 5-substituted tetrazoles |
| US5502191A (en) * | 1993-07-01 | 1996-03-26 | American Cyanamid Company | Method of synthesizing sterically hindered 5-substituted-1H-tetrazoles from nitriles using a lewis acid and an azide |
| 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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