CN104557745A - Method for synthesizing 4,5-diphenyl-1,4,5-trihydro-1,2,3-triazole - Google Patents
Method for synthesizing 4,5-diphenyl-1,4,5-trihydro-1,2,3-triazole Download PDFInfo
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- CN104557745A CN104557745A CN201510028653.5A CN201510028653A CN104557745A CN 104557745 A CN104557745 A CN 104557745A CN 201510028653 A CN201510028653 A CN 201510028653A CN 104557745 A CN104557745 A CN 104557745A
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- phenylbenzene
- triazole
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- VFOKYTYWXOYPOX-PTNGSMBKSA-N N#C/C(/c1ccccc1)=C/c1ccccc1 Chemical compound N#C/C(/c1ccccc1)=C/c1ccccc1 VFOKYTYWXOYPOX-PTNGSMBKSA-N 0.000 description 1
- UZSNTAMDYBDDHH-UHFFFAOYSA-N c1ccc(C2NN=NC2c2ccccc2)cc1 Chemical compound c1ccc(C2NN=NC2c2ccccc2)cc1 UZSNTAMDYBDDHH-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/04—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles
- C07D249/06—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles with aryl radicals directly attached to ring atoms
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- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention discloses a method for synthesizing 4,5-diphenyl-1,4,5-trihydro-1,2,3-triazole. The method comprises the following steps of firstly mixing 1,2-diphenyl-acrylonitrile, potassium carbonate, sodium azide, cuprous iodide and dimethyl sulfoxide DMSO, stirring and heating to 95-105 DEG C, reacting for 3-3.5 hours, after the reaction is completed, adding water to obtain a mixture, extracting the mixture, distilling to remove the solvent, purifying the residue by column chromatography to obtain 4,5-diphenyl-1,4,5-trihydro-1,2,3-triazole, wherein the feeding molar ratio of 1,2-diphenyl-acrylonitrile, potassium carbonate, sodium azide and cuprous iodide is 1:2:2:0.2. The reaction time and the reaction temperature adopted in the invention are more suitable reaction time and temperature, too high temperature, the ratio of reaction byproducts too high, if the temperature is too low, the reaction cannot be carried out; if the reaction time is shortened, the incomplete reaction can be caused and the reaction time is prolonged, the yield of the byproducts is high.
Description
Technical field
The present invention relates to the field of chemical synthesis, be specifically related to a kind of 4,5-phenylbenzene-Isosorbide-5-Nitrae, the synthetic method of 5-tri-hydrogen-1,2,3-triazole.
Background technology
1,2,3-triazoles ring is very important five member ring heterocyclic compound, because its pharmacologically active better receives much concern.Its synthetic method of bibliographical information is a lot, and as the NH-1 synthesized under suitable pressure and heating condition by cycloaddition tri-n-butyl tin trinitride and monosubstituted or dibasic alkynes, 2,3-triazole, its productive rate only has (30-67%).And tri-n-butyl tin trinitride costly.We used comparatively safe sodiumazide and 1,2-phenylbenzene acrylonitrile reactor generates 4,5-phenylbenzene-Isosorbide-5-Nitrae, 5-tri-hydrogen-1,2,3-triazole, compared with additive method, our method have reaction temperature and, reaction conditions is easy, uses the features such as cheaper starting materials.In prior art, adopt 1,2-phenylbenzene acrylonitrile reactor to generate 4,5-phenylbenzene-Isosorbide-5-Nitrae, the method for 5-tri-hydrogen-1,2,3-triazole there is not yet bibliographical information.
At present, lack 4,5-phenylbenzene-Isosorbide-5-Nitrae that a kind of technique is simple, product purity is high, the synthetic method of 5-tri-hydrogen-1,2,3-triazole.
Summary of the invention
The object of the present invention is to provide 4,5-phenylbenzene-Isosorbide-5-Nitrae that a kind of technique is simple, product purity is high, the synthetic method of 5-tri-hydrogen-1,2,3-triazole.
Technical scheme of the present invention is as follows: the invention provides a kind of 4,5-phenylbenzene-Isosorbide-5-Nitrae, the synthetic method of 5-tri-hydrogen-1,2,3-triazole, first react being warming up to 95-105 DEG C after 1,2-phenylbenzene vinyl cyanide, salt of wormwood, sodiumazide, cuprous iodide and dimethyl sulfoxide (DMSO) DMSO mix and blend, the reaction times is 3-3.5h, add water after reaction terminates, mixture steams and desolventizes after extraction, and residue obtains 4 after column chromatography, 5-phenylbenzene-Isosorbide-5-Nitrae, 5-tri-hydrogen-1,2,3-triazole.
Further, described 1,2-phenylbenzene vinyl cyanide, salt of wormwood, sodiumazide and cuprous iodide molar ratio are 1 ︰ 2 ︰ 2 ︰ 0.2.
Further, described dimethyl sulfoxide (DMSO) DMSO is reaction solvent, and its consumption is that to add dimethyl sulfoxide (DMSO) DMSO be 10ml to every mole of 1,2-phenylbenzene vinyl cyanide raw material.
Further, the water added described in and the mass ratio of dimethyl sulfoxide (DMSO) DMSO are 1 ︰ 10.
Further, the solvent for extracting is ethyl acetate.
Further, column chromatography adopts silica gel solid phase, and eluent is the mixture of ethyl acetate and hexanaphthene, and the mixed volume ratio of described ethyl acetate and hexanaphthene is 1 ︰ 4.
Beneficial effect: reaction times of the present invention and temperature are all this reaction comparatively suitable reaction times and temperature, the ratio of the too high byproduct of reaction of temperature is too high, temperature is too low, and reaction can not be carried out, and time shorten can cause reaction not exclusively, and time lengthening then causes by-product rate too much.Under this ratio, the productive rate of product is the highest, and by product is minimum.The present invention is compared with similar multistep processes, and the reagent inexpensive safety obviously used, present invention process process operation is simple simultaneously, and the product purity that the present invention makes is higher, and by product is less.Ethyl acetate and hexanaphthene polarity moderate and to environmental facies to close friend, can separating-purifying product preferably under this proportioning.
Embodiment
Further specific descriptions will be done by specific embodiment to the present invention below, but can not be interpreted as it is limiting the scope of the present invention.
Embodiment 1
Reaction expression of the present invention is:
The invention provides a kind of 4, 5-phenylbenzene-1, 4, 5-tri-hydrogen-1, 2, the synthetic method of 3-triazole, 1mmol 1 is added successively in 50ml round-bottomed flask, 2-phenylbenzene vinyl cyanide, 2mmol salt of wormwood, 2mmol sodiumazide, 0.2mmol cuprous iodide and 10ml DMSO, be heated to 100 DEG C of reactions, after having reacted after 3h, cooling, system is poured in 100ml water, mixture is extracted with ethyl acetate 2-3 time, steam after merging organic layer and desolventize, resistates thin layer is analysed, column chromatography adopts silica gel solid phase, eluent is the mixture of ethyl acetate and hexanaphthene, the mixed volume ratio of described ethyl acetate and hexanaphthene is 1 ︰ 4.Separation obtains 4,5-phenylbenzene-Isosorbide-5-Nitrae, 5-tri-hydrogen-1,2,3-triazole.
Described 1,2-phenylbenzene vinyl cyanide, salt of wormwood, sodiumazide and cuprous iodide molar ratio are 1 ︰ 2 ︰ 2 ︰ 0.2, and under this ratio, the productive rate of product is the highest, and by product is minimum.
The mass ratio of the described water that adds and dimethyl sulfoxide (DMSO) DMSO is 1 ︰ 10, waste of solvent when hypervolia then extracts, and when the water yield crosses extraction at least, percentage extraction is lower and cause waste.
The solvent of described extraction is ethyl acetate, and the while that this solvent price being lower, effect of extracting is best.
Ethyl acetate and hexanaphthene polarity moderate and to environmental facies to close friend, can separating-purifying product preferably under this proportioning.
Reaction times of the present invention and temperature are all this reaction comparatively suitable reaction times and temperature, the ratio of the too high byproduct of reaction of temperature is too high, temperature is too low, and reaction can not be carried out, and time shorten can cause reaction not exclusively, and time lengthening then causes by-product rate too much.The present invention is compared with similar multistep processes, and the reagent inexpensive safety obviously used, present invention process process operation is simple simultaneously, and the product purity that the present invention makes is higher, and by product is less.
Test 1
Product Identification 4,5-phenylbenzene-Isosorbide-5-Nitrae, 5-tri-hydrogen-1,2,3-triazole, white solid, fusing point: 139-140 DEG C, productive rate: 93%.
1H NMR(400MHz,CDCl3)δ(ppm):7.638-7.686(m,4H,ArH),7.548(d,J＝7.2Hz,1H,ArH),7.528(d,J＝7.2Hz,1H,ArH),7.430-7.475(m,4H,ArH)；13C NMR(100MHz,CDCl3)δ(ppm):133.00,132.12,132.02,131.92,131.89,128.53,128.41,127.41；
Wherein 7.548 and 7.528 is the hydrogen of carbon in triazole ring, is 7.2 can find out it is trans position by constant.7.430-7.475 be substituted benzene ring hydrogen, displacement is close, display multiplet.In carbon spectrum, because this molecule is symmetrical molecule, the signal of part carbon there occurs overlap.These data are obviously different with raw material, prove the exactness of the compound that we synthesize.
More than show and describe ultimate principle of the present invention, principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and application claims protection domain is defined by appending claims, specification sheets and equivalent thereof.
Claims (6)
1.4,5-phenylbenzene-Isosorbide-5-Nitrae, the synthetic method of 5-tri-hydrogen-1,2,3-triazole, it is characterized in that: first react being warming up to 95-105 DEG C after 1,2-phenylbenzene vinyl cyanide, salt of wormwood, sodiumazide, cuprous iodide and dimethyl sulfoxide (DMSO) DMSO mix and blend, the reaction times is 3-3.5h, add water after reaction terminates, mixture steams and desolventizes after extraction, and residue obtains 4 after column chromatography, 5-phenylbenzene-Isosorbide-5-Nitrae, 5-tri-hydrogen-1,2,3-triazole.
2. 4,5-phenylbenzene according to claim 1-Isosorbide-5-Nitrae, the synthetic method of 5-tri-hydrogen-1,2,3-triazole, is characterized in that: described 1,2-phenylbenzene vinyl cyanide, salt of wormwood, sodiumazide and cuprous iodide molar ratio are 1 ︰ 2 ︰ 2 ︰ 0.2.
3. 4,5-phenylbenzene according to claim 1-Isosorbide-5-Nitrae, the synthetic method of 5-tri-hydrogen-1,2,3-triazole, it is characterized in that: described dimethyl sulfoxide (DMSO) DMSO is reaction solvent, its consumption is that to add dimethyl sulfoxide (DMSO) DMSO be 10ml to every mole of 1,2-phenylbenzene vinyl cyanide raw material.
4. 4,5-phenylbenzene according to claim 3-Isosorbide-5-Nitrae, the synthetic method of 5-tri-hydrogen-1,2,3-triazole, is characterized in that: described in the mass ratio of the water that adds and dimethyl sulfoxide (DMSO) DMSO be 1 ︰ 10.
5. 4,5-phenylbenzene according to claim 1-Isosorbide-5-Nitrae, the synthetic method of 5-tri-hydrogen-1,2,3-triazole, is characterized in that: the solvent for extracting is ethyl acetate.
6. 4,5-phenylbenzene according to claim 1-Isosorbide-5-Nitrae, the synthetic method of 5-tri-hydrogen-1,2,3-triazole, it is characterized in that: column chromatography adopts silica gel solid phase, and eluent is the mixture of ethyl acetate and hexanaphthene, and the mixed volume ratio of described ethyl acetate and hexanaphthene is 1 ︰ 4.
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| CN201510028653.5A CN104557745A (en) | 2015-01-20 | 2015-01-20 | Method for synthesizing 4,5-diphenyl-1,4,5-trihydro-1,2,3-triazole |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106986836A (en) * | 2017-04-26 | 2017-07-28 | 毛阿龙 | The preparation method of novel techykinin antagonist with antibacterial activity |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106986836A (en) * | 2017-04-26 | 2017-07-28 | 毛阿龙 | The preparation method of novel techykinin antagonist with antibacterial activity |
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Application publication date: 20150429 |