CN103058940B - 1-replaces the bromo-2H-1 of-4-, 2,3-triazole derivatives and preparation method thereof - Google Patents
1-replaces the bromo-2H-1 of-4-, 2,3-triazole derivatives and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of 1-and replace the bromo-2H-1 of-4-, 2,3-triazole derivatives and preparation method thereof.1-disclosed by the invention replaces the bromo-2H-1 of-4-, and 2,3-triazole derivatives has the structure shown in following formula I:
Description
Technical field
The present invention relates to a kind of 1-and replace the bromo-2H-1 of-4-, 2,3-triazole derivatives and preparation method thereof.
Background technology
1-replaces-4-bromo-2H-1, and 2,3-triazole derivatives is the novel compound with huge Development volue of a class.Be that the compound of parent nucleus has potential using value widely with triazole, being the important intermediate of current many medicines, weedicide and agrochemical compound, is also pharmacophoric group main in a lot of drug molecule.
Summary of the invention
A kind of novel 1-is the object of the present invention is to provide to replace the bromo-2H-1 of-4-, 2,3-triazole derivatives and preparation method thereof.
In order to realize foregoing invention object, the technical solution used in the present invention is as follows:
A kind of 1-replaces the bromo-2H-1 of-4-, and 2,3-triazole derivatives, has the structure shown in following formula I:
Wherein, R represents alkyl, aryl, aralkyl, cycloalkyl, cycloalkylalkyl, heteroaryl, heteroarylalkyl or Heterocyclylalkyl; X represents chlorine or iodine.
When X is chlorine, described 1-replaces the bromo-2H-1 of-4-, and 2,3-triazole derivatives is the chloro-1H-1 of the 1-replacement bromo-5-of-4-shown in formula III, 2,3-triazole; When X is iodine, described 1-replaces the bromo-2H-1 of-4-, and 2,3-triazole derivatives is the iodo-1H-1 of the 1-replacement bromo-5-of-4-shown in formula IV, 2,3-triazole.
1-disclosed by the invention replaces the bromo-2H-1 of-4-, and 2,3-triazole derivatives is obtained by following steps:
1) compound shown in Formula Il is dissolved in the first organic solvent, is cooled to-78 ~ 0 DEG C, adds Grignard reagent, stir 0.5 ~ 2 hour,
Wherein, R represents alkyl, aryl, aralkyl, cycloalkyl, cycloalkylalkyl, heteroaryl, heteroarylalkyl or Heterocyclylalkyl;
2) pass into chlorine or add chlorizating agent, or adding iodine, stirring 5 ~ 30 minutes, be warming up to room temperature, after saturated aqueous ammonium chloride or hydrochloric acid soln cancellation, use the second organic solvent extraction;
3) step 2) gained extraction liquid is evaporated to dry after drying, and the enriched material obtained obtains described 1-through recrystallization and replaces the bromo-2H-1 of-4-, 2,3-triazole derivatives.
In the step 1) of embodiments of the invention, the mass volume ratio of compound and the first organic solvent shown in described formula II is 1: 2 ~ 20; The mol ratio of compound and Grignard reagent shown in described formula II is 1: 0.8 ~ 1.5, is preferably 1: 0.8 ~ 1.2; Described first organic solvent is ether, tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane or methyltetrahydrofuran; Described Grignard reagent is isopropylmagnesium chloride or isopropylmagnesium chloride-lithium chloride mixture.
Isopropylmagnesium chloride of the present invention or isopropylmagnesium chloride-lithium chloride mixture are the tetrahydrofuran solution of its different volumetric molar concentration, 2-methyltetrahydrofuran solution or diethyl ether solution, and commercially available concentration is generally 1.0 ~ 2.0 mol/L.
Step 2 at embodiments of the invention) in, the mol ratio of compound and chlorine, chlorizating agent or iodine shown in described formula II is 1: 1 ~ 10, is preferably 1: 2 ~ 5; Described chlorizating agent comprises N-chlorosuccinimide and chloro-5, the 5-dimethyl hydantion of 1,3-bis-; Described second organic solvent is the mixing of one or more arbitrary proportions in fatty acid ester or ethers, wherein, fatty acid ester comprises ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, butylacetate, isopropyl acetate, isobutyl acetate, pentyl acetate, Isoamyl Acetate FCC, methyl propionate, ethyl propionate, propyl propionate, butyl propionate and amyl propionate, and ethers comprises ether, propyl ether, isopropyl ether and methyl tertiary butyl ether.
In the step 3) of embodiments of the invention, by anhydrous sodium sulphate or anhydrous magnesium sulfate drying step 2) gained extraction liquid, described recrystallization comprises the following steps: add in solvent by mass volume ratio 1: 1 ~ 100 by enriched material, stir 0.5 ~ 24 hour at-20 ~ 50 DEG C, obtain described 1-after filtration, vacuum-drying and replace the bromo-2H-1 of-4-, 2,3-triazole derivatives, described solvent is water, alcohols, fatty acid ester, ketone, the mixing of one or more arbitrary proportions in ethers and hydro carbons, wherein, alcohols comprises methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol and the trimethyl carbinol, fatty acid ester comprises ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, butylacetate, isopropyl acetate, isobutyl acetate, pentyl acetate, Isoamyl Acetate FCC, methyl propionate, ethyl propionate, propyl propionate, butyl propionate and amyl propionate, ketone comprises acetone, 2-butanone, cyclopentanone and pimelinketone, ethers comprises ether, propyl ether, isopropyl ether, methyl tertiary butyl ether and tetrahydrofuran (THF), 1, 4-dioxane and sherwood oil, hydro carbons comprises normal hexane, hexanaphthene, methylcyclohexane and normal heptane.
In No. 201110166067.9 of applicant and No. 201210051904.8 patent application, describe 1-in detail replace-4,5-bis-bromo-1H-1, the preparation method of 2,3-triazole (formula II).
1-disclosed by the invention replaces the bromo-2H-1 of-4-, and the reaction formula of the preparation method of 2,3-triazole derivatives is as follows:
1-of the present invention replaces the bromo-2H-1 of-4-, and the preparation method of 2,3-triazole derivatives is simple, and the compound yield of acquisition is high.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but and unrestricted range of application of the present invention.
embodiment 1
By 3.0g(12.45mmol) the bromo-2H-1 of 1-methyl-4,5-bis-, 2,3-triazole is dissolved in 25ml tetrahydrofuran (THF), is cooled to-15 ~ 0 DEG C, in 30 minutes, slowly drip 7.47ml(14.95mmol) 2.0M isopropylmagnesium chloride tetrahydrofuran solution.Dropwise, continue stirring 30 ~ 60 minutes.Slowly pass into chlorine, until reaction solution no longer heats up.Reaction solution adds 20ml saturated aqueous ammonium chloride, extract with 80ml methyl tertiary butyl ether, the extraction liquid anhydrous sodium sulfate drying obtained, be evaporated to dry, residual solid adds 30ml methyl tertiary butyl ether/normal hexane (1/3), is heated to backflow 1 hour, be cooled to 0 ~ 10 DEG C, continue stirring 1 hour, filter, <40 DEG C of vacuum-drying.Obtain the chloro-2H-1 of the bromo-5-of 1-methyl-4-, 2,3-triazole solid 2.01g, yield 82%.
1HNMR(CDCl
3,400MHz)：δ4.02(s,3H)；
13CNMR(CDCl
3,400MHz)：δ125.9,119.0,35.9。
embodiment 2
Working method is with embodiment 1, and by the bromo-2H-1 of 1-methyl-4,5-bis-, 2,3-triazole replaces with the bromo-2H-1 of 3.17g (12.45mmol) 1-ethyl-4,5-bis-, 2,3-triazole.Obtain the chloro-2H-1 of the bromo-5-of 1-ethyl-4-, 2,3-triazole solid 2.33g, yield 89%.
1HNMR(CDCl
3,400MHz)：δ4.38(q,J=7.2Hz,2H),1.51(t,J=7.2Hz,3H)；
13CNMR(CDCl
3,400MHz)δ124.9,119.2,44.9,14.5。
embodiment 3
Working method is with embodiment 1, and by the bromo-2H-1 of 1-methyl-4,5-bis-, 2,3-triazole replaces with the bromo-2H-1 of 3.35g (12.45mmol) 1-n-propyl-4,5-bis-, 2,3-triazole.Obtain the chloro-2H-1 of the bromo-5-of 1-n-propyl-4-, 2,3-triazole oily matter 2.58g, yield 92%.
1HNMR(CDCl
3,400MHz)：δ4.31(t,J=7.2Hz,2H),1.97-1.90(m,2H),0.97(t,J=7.2Hz,3H)；
13CNMR(CDCl
3,400MHz)：δ125.2,119.1,51.1,22.7,10.9。
embodiment 4
Working method is with embodiment 1, and by the bromo-2H-1 of 1-methyl-4,5-bis-, 2,3-triazole replaces with the bromo-2H-1 of 3.50g (12.45mmol) 1-Cvclopropvlmethvl-4,5-bis-, 2,3-triazole.Obtain the chloro-2H-1 of the bromo-5-of 1-Cvclopropvlmethvl-4-, 2,3-triazole oily matter 2.71g, yield 92%.
1HNMR(CDCl
3,400MHz)：δ4.22(d,J=7.2Hz,2H),1.40-1.32(m,1H),0.67(m,2H),0.53(m,2H)；
13CNMR(CDCl
3,400MHz)：δ124.9,119.2,54.3,10.7,4.3。
embodiment 5
Working method is with embodiment 1, and by the bromo-2H-1 of 1-methyl-4,5-bis-, 2,3-triazole replaces with the bromo-2H-1 of 3.67g (12.45mmol) 1-cyclobutylmethyl-4,5-bis-, 2,3-triazole.Obtain the chloro-2H-1 of the bromo-5-of 1-cyclobutylmethyl-4-, 2,3-triazole oily matter 2.84g, yield 91%.
1HNMR(CDCl
3,400MHz)：δ4.36(d,J=7.2Hz,2H),2.93-2.85(m,1H),2.12-2.06(m,2H),1.96-1.82(m,4H)；
13CNMR(CDCl
3,400MHz)：δ124.0,117.9,53.0,33.7,24.6,16.9。
embodiment 6
Working method is with embodiment 1, and by the bromo-2H-1 of 1-methyl-4,5-bis-, 2,3-triazole replaces with the bromo-2H-1 of 3.67g (12.45mmol) 1-cyclopentyl-4,5-bis-, 2,3-triazole.Obtain the chloro-2H-1 of the bromo-5-of 1-cyclopentyl-4-, 2,3-triazole oily matter 2.87g, yield 92%.
1HNMR(CDCl
3,400MHz)：δ4.86-4.80(m,1H),2.21-2.16(m,4H),1.99-1.95(m,2H),1.79-1.74(m,2H)；
13CNMR(CDCl
3,400MHz)：δ124.8,119.3,61.3,32.3,24.4。
embodiment 7
Working method with embodiment 1, by the bromo-2H-1 of 1-methyl-4,5-bis-, 2,3-triazole replaces with 3.87g (12.45mmol) 1-(tetrahydrofuran (THF)-3-methyl)-4,5-bis-bromo-2H-1,2,3-triazole, saturated aqueous ammonium chloride replaces with hydrochloric acid soln.Obtain 1-(tetrahydrofuran (THF)-3-methyl) the chloro-2H-1 of the bromo-5-of-4-, 2,3-triazole oily matter 3.05g, yield 92%.
1HNMR(CDCl
3,400MHz)：δ4.33(d,J=7.6Hz,2H),3.66(dd,J=4.8,9.2Hz,1H),2.94-2.87(m,1H),2.12-2.03(m,1H),1.76-1.68(m,1H)；
13CNMR(CDCl
3,400MHz)：δ125.4,119.3,70.6,67.5,51.7,39.0,29.5。
embodiment 8
Working method is with embodiment 1, and by the bromo-2H-1 of 1-methyl-4,5-bis-, 2,3-triazole replaces with the bromo-2H-1 of 3.87g (12.45mmol) 1-(4-tetrahydropyrans)-4,5-bis-, 2,3-triazole.Obtain the chloro-2H-1 of 1-(4-tetrahydropyrans) the bromo-5-of-4-, 2,3-triazole solid 3.15g, yield 95%.
1HNMR(CDCl
3,400MHz)：δ4.60-4.53(m,1H),4.15(dt,J=2.0,10.0Hz,2H),3.56(dt,J=2.0,12.0Hz,2H),2.36(dq,J=4.4,12.0Hz,2H),2.02(dd,J=2.0,12.8Hz,2H)；
13CNMR(CDCl
3,400MHz)：δ124.5,119.5,66.6,57.0,31.8.。
embodiment 9
Working method is with embodiment 1, and by the bromo-2H-1 of 1-methyl-4,5-bis-, 2,3-triazole replaces with the bromo-2H-1 of 3.32g (12.45mmol) 1-allyl group-4,5-bis-, 2,3-triazole.Obtain the chloro-2H-1 of the bromo-5-of 1-allyl group-4-, 2,3-triazole oily matter 2.49g, yield 90%.
1HNMR(CDCl
3,400MHz)：δ6.00-5.90(m,1H),5.36(dd,J=0.4,10.0Hz,1H),5.25(dd,J=0.4,17.2Hz,1H),4.97(dd,J=1.6,6.0Hz,2H)；
13CNMR(CDCl
3,400MHz)：δ129.5,125.5,120.5,119.4,51.9。
embodiment 10
Working method is with embodiment 1, and by the bromo-2H-1 of 1-methyl-4,5-bis-, 2,3-triazole replaces with the bromo-2H-1 of 4.12g (12.45mmol) 1-styroyl-4,5-bis-, 2,3-triazole.Obtain the chloro-2H-1 of the bromo-5-of 1-styroyl-4-, 2,3-triazole oily matter 3.10g, yield 87%.
1HNMR(CDCl
3,400MHz)：δ7.32-7.24(m,3H),7.13(d,J=7.2Hz,2H),4.56(t,J=7.6Hz,2H),3.21(t,J=7.6Hz,2H)；
13CNMR(CDCl
3,400MHz)：δ136.1,128.9,128.7,127.4,125.5,119.1,50.7,35.8。
embodiment 11
Working method is with embodiment 1, and by the bromo-2H-1 of 1-methyl-4,5-bis-, 2,3-triazole replaces with 4.17g (12.45mmol) 1-to the bromo-2H-1 of benzyl-4,5-bis-, 2,3-triazole.Obtain 1-to the chloro-2H-1 of the bromo-5-of benzyl-4-, 2,3-triazole solid 3.18g, yield 88%.
1HNMR(CDCl
3,400MHz)：δ7.33-7.26(m,2H),7.06(dd,J=8.4,8.8Hz,2H),5.50(s,2H)；
13CNMR(CDCl
3,400MHz)：δ163.0(d,J=248.0Hz),130.0(d,J=9.0Hz),128.9(d,J=3.0Hz),125.3,119.7,116.2(d,J=21.0Hz),52.5。
embodiment 12
Working method is with embodiment 1, and by the bromo-2H-1 of 1-methyl-4,5-bis-, 2,3-triazole replaces with the bromo-2H-1 of benzyl-4,5-bis-between 4.17g (12.45mmol) 1-, 2,3-triazole.Obtain the chloro-2H-1 of the bromo-5-of benzyl-4-between 1-, 2,3-triazole solid 2.98g, yield 83%.
1HNMR(CDCl
3,400MHz)：δ7.37-7.32(m,1H),7.08(d,J=0.8Hz,1H),7.06-7.03(m,1H),6.99(d,J=8.6Hz,1H),5.52(s,2H)；
13CNMR(CDCl
3,400MHz)：δ163.0(d,J=247.0Hz),135.3(d,J=8.0Hz),130.9(d,J=8.0Hz),125.5,123.5(d,J=3.0Hz),119.7,116.1(d,J=20.0Hz),115.0(d,J=22.0Hz),52.5(d,J=1.0Hz)。
embodiment 13
Working method is with embodiment 1, and by the bromo-2H-1 of 1-methyl-4,5-bis-, 2,3-triazole replaces with 4.38g (12.45mmol) 1-to the bromo-2H-1 of chlorophenylmethyl-4,5-bis-, 2,3-triazole.Obtain 1-to the chloro-2H-1 of the bromo-5-of chlorophenylmethyl-4-, 2,3-triazole solid 3.25g, yield 85%.
1HNMR(CDCl
3,400MHz)：δ7.35(ABq,J=8.0Hz,2H),7.25(ABq,J=8.0Hz,2H),5.50(s,2H)；
13CNMR(CDCl
3,400MHz)：δ135.1,131.5,129.4,129.3,125.4,119.7,52.5。
embodiment 14
Working method is with embodiment 1, and by the bromo-2H-1 of 1-methyl-4,5-bis-, 2,3-triazole replaces with the bromo-2H-1 of chlorophenylmethyl-4,5-bis-between 4.38g (12.45mmol) 1-, 2,3-triazole.Obtain the chloro-2H-1 of the bromo-5-of chlorophenylmethyl-4-between 1-, 2,3-triazole solid 3.17g, yield 83%.
1HNMR(CD
3COCD
3,400MHz)：δ7.4-7.41(m,3H),7.31(d,J=6.8Hz,1H),5.74(s,2H)；
13CNMR(CD
3COCD
3,400MHz)：δ137.4,135.1,131.6,129.6,128.8,127.4,125.8,119.7,52.9。
embodiment 15
Working method is with embodiment 1, and by the bromo-2H-1 of 1-methyl-4,5-bis-, 2,3-triazole replaces with 4.93g (12.45mmol) 1-to the bromo-2H-1 of Brombenzyl-4,5-bis-, 2,3-triazole.Obtain 1-to the chloro-2H-1 of the bromo-5-of Brombenzyl-4-, 2,3-triazole solid 3.90g, yield 89%.
1HNMR(CD
3COCD
3,400MHz)：δ7.60(ABq,J=8.4Hz,2H),7.33(ABq,J=8.4Hz,2H),5.71(s,2H)；
13CNMR(CD
3COCD
3,400MHz)：δ134.4,132.9,131.1,130.9,125.7,119.7,53.0。
embodiment 16
Working method is with embodiment 1, and by the bromo-2H-1 of 1-methyl-4,5-bis-, 2,3-triazole replaces with 4.90g (12.45mmol) 1-to the bromo-2H-1 of trifluoromethoxy phenmethyl-4,5-bis-, 2,3-triazole.Obtain 1-to the chloro-2H-1 of the bromo-5-of trifluoromethoxy phenmethyl-4-, 2,3-triazole solid 3.53g, yield 83%.
1HNMR(CDCl
3,500MHz)：δ7.35(ABq,J=8.5Hz,2H),7.22(ABq,J=8.5Hz,2H),5.53(s,2H)；
13CNMR(CDCl
3,500MHz)：δ149.6(d,J=2.0Hz),131.7,129.7,125.5,121.5(d,J=1.0Hz),120.3(q,J=256.0Hz),119.7,112.6,52.3。
embodiment 17
Working method is with embodiment 1, and by the bromo-2H-1 of 1-methyl-4,5-bis-, 2,3-triazole replaces with the bromo-2H-1 of 3.95g (12.45mmol) 1-benzyl-4,5-bis-, 2,3-triazole.Obtain the chloro-2H-1 of the bromo-5-of 1-benzyl-4-, 2,3-triazole oily matter 2.88g, yield 85%.
1HNMR(CDCl
3,500MHz)：δ7.40-7.35(m,3H),7.31-7.29(m,2H),5.53(s,2H)；
13CNMR(CDCl
3,500MHz)：δ133.1,129.1,129.0,128.0,125.4,119.6,53.3。
embodiment 18
Working method is with embodiment 1, and by the bromo-2H-1 of 1-methyl-4,5-bis-, 2,3-triazole replaces with 4.80g (12.45mmol) 1-to the bromo-2H-1 of trifluoromethylbenzel-4,5-bis-, 2,3-triazole.Obtain 1-to the chloro-2H-1 of the bromo-5-of trifluoromethylbenzel-4-, 2,3-triazole solid 3.18g, yield 75%.
1HNMR(CDCl
3,500MHz)：δ7.64(ABq,J=8.0Hz,2H),7.41(ABq,J=8.0Hz,2H),5.59(s,2H)；
13CNMR(CDCl
3,500MHz)：δ136.9(d,J=1.3Hz),131.3(q,J=32.6Hz),128.3,126.2(q,J=3.9Hz),125.6,123.7(q,J=270.6Hz),119.8,52.5。
embodiment 19
Working method is with embodiment 1, and by the bromo-2H-1 of 1-methyl-4,5-bis-, 2,3-triazole replaces with 4.32g (12.45mmol) 1-to the bromo-2H-1 of mehtoxybenzyl-4,5-bis-, 2,3-triazole.Obtain 1-to the chloro-2H-1 of the bromo-5-of mehtoxybenzyl-4-, 2,3-triazole solid 3.37g, yield 90%.
1HNMR(CDCl
3,400MHz)：δ7.31(ABq,J=8.8Hz,2H),6.89(ABq,J=8.8Hz,2H),5.41(s,2H),3.80(s,3H)；
13CNMR(CDCl
3,400MHz)：δ160.1,137.3,130.0,125.9,121.1,114.3,59.8,55.3。
embodiment 20
Working method is with embodiment 1, and by the bromo-2H-1 of 1-methyl-4,5-bis-, 2,3-triazole replaces with 4.30g (12.45mmol) 1-to the bromo-2H-1 of methylbenzyl-4,5-bis-, 2,3-triazole.Obtain 1-to the chloro-2H-1 of the bromo-5-of mehtoxybenzyl-4-, 2,3-triazole solid 3.30g, yield 88%.
1HNMR(CDCl
3,400MHz)：δ7.20(ABq,J=8.0Hz,2H),7.16(ABq,J=8.0Hz,2H),5.48(s,2H),2.34(s,3H)；
13CNMR(CDCl
3,400MHz)：δ139.0,130.1,129.8,128.0,125.3,119.6,53.1,21.2。
embodiment 21
Chlorine, with embodiment 1, is replaced with 1.66g (12.45mmol) N-chlorosuccinimide by working method.Obtain the chloro-2H-1 of the bromo-5-of 1-methyl-4-, 2,3-triazole solid 1.67g, yield 68%.1HNMR(CDCl
3,400MHz)：δ4.15(s,3H)；
13CNMR(CDCl
3,400MHz)：δ137.0,120.8,43.1。
embodiment 22
By 1.20g(5.0mmol) the bromo-2H-1 of 1-methyl-4,5-bis-, 2,3-triazole is dissolved in 10ml tetrahydrofuran (THF), is cooled to-20 ~ 0 DEG C, in 30 minutes, slowly drip 2.74ml(5.18mmol) 2.0M isopropylmagnesium chloride tetrahydrofuran solution.Dropwise, continue stirring 30 ~ 60 minutes.Add solid iodine 1.26g(5.0mmol), continue reaction 30 minutes.Reaction solution adds 20ml saturated aqueous ammonium chloride, use 30ml extraction into ethyl acetate, anhydrous sodium sulfate drying, is evaporated to dry, and residual solid adds 10ml isopropanol/water (5/1), be heated to backflow 1 hour, be cooled to 0 ~ 10 DEG C, continue stirring 1 hour, filter, <40 DEG C of vacuum-drying.Obtain the iodo-2H-1 of the bromo-5-of 1-methyl-4-, 2,3-triazole solid 1.22g, yield 85%.
1HNMR(CDCl
3,400MHz)：δ4.10(s,3H)；
13CNMR(CDCl
3,400MHz)：δ131.6,95.3,43.7。
The foregoing is only preferred embodiment of the present invention, be not used for limiting practical range of the present invention; If do not depart from the spirit and scope of the present invention, the present invention is modified or equivalent to replace, in the middle of the protection domain that all should be encompassed in the claims in the present invention.
Claims (18)
1. 1-replaces the bromo-2H-1 of-4-, the preparation method of 2,3-triazole derivatives, and this 1-replaces the bromo-2H-1 of-4-, and 2,3-triazole derivatives has the structure shown in following formula I:
Wherein, R represents alkyl, aryl, aralkyl, cycloalkyl, cycloalkylalkyl, heteroaryl, heteroarylalkyl or Heterocyclylalkyl; X represents chlorine;
It is characterized in that, described preparation method comprises following steps:
1) compound shown in Formula Il is dissolved in the first organic solvent, is cooled to-78 ~ 0 DEG C, adds Grignard reagent, stir 0.5 ~ 2 hour,
Wherein, R represents alkyl, aryl, aralkyl, cycloalkyl, cycloalkylalkyl, heteroaryl, heteroarylalkyl or Heterocyclylalkyl; The mass volume ratio of compound and the first organic solvent shown in described formula II is 1: 8.33; The mol ratio of compound and Grignard reagent shown in described formula II is 1: 1.2;
2) pass into chlorine or add chlorizating agent, stirring 5 ~ 30 minutes, be warming up to room temperature, after saturated aqueous ammonium chloride or hydrochloric acid soln cancellation, use the second organic solvent extraction; The mol ratio of compound and chlorine or chlorizating agent shown in wherein said formula II is 1: 1 ~ 10;
3) step 2) gained extraction liquid is evaporated to dry after drying, and the enriched material obtained obtains described 1-through recrystallization and replaces the bromo-2H-1 of-4-, 2,3-triazole derivatives.
2. 1-replaces the bromo-2H-1 of-4-, the preparation method of 2,3-triazole derivatives, and this 1-replaces the bromo-2H-1 of-4-, and 2,3-triazole derivatives has the structure shown in following formula I:
Wherein, R represents alkyl, aryl, aralkyl, cycloalkyl, cycloalkylalkyl, heteroaryl, heteroarylalkyl or Heterocyclylalkyl; X represents chlorine;
It is characterized in that, described preparation method comprises following steps:
1) compound shown in Formula Il is dissolved in the first organic solvent, is cooled to-78 ~ 0 DEG C, adds Grignard reagent, stir 0.5 ~ 2 hour,
Wherein, R represents alkyl, aryl, aralkyl, cycloalkyl, cycloalkylalkyl, heteroaryl, heteroarylalkyl or Heterocyclylalkyl; The mass volume ratio of compound and the first organic solvent shown in described formula II is 1: 7.89; The mol ratio of compound and Grignard reagent shown in described formula II is 1: 1.2;
2) pass into chlorine or add chlorizating agent, stirring 5 ~ 30 minutes, be warming up to room temperature, after saturated aqueous ammonium chloride or hydrochloric acid soln cancellation, use the second organic solvent extraction; The mol ratio of compound and chlorine or chlorizating agent shown in wherein said formula II is 1: 1 ~ 10;
3) step 2) gained extraction liquid is evaporated to dry after drying, and the enriched material obtained obtains described 1-through recrystallization and replaces the bromo-2H-1 of-4-, 2,3-triazole derivatives.
3. 1-replaces the bromo-2H-1 of-4-, the preparation method of 2,3-triazole derivatives, and this 1-replaces the bromo-2H-1 of-4-, and 2,3-triazole derivatives has the structure shown in following formula I:
Wherein, R represents alkyl, aryl, aralkyl, cycloalkyl, cycloalkylalkyl, heteroaryl, heteroarylalkyl or Heterocyclylalkyl; X represents chlorine;
It is characterized in that, described preparation method comprises following steps:
1) compound shown in Formula Il is dissolved in the first organic solvent, is cooled to-78 ~ 0 DEG C, adds Grignard reagent, stir 0.5 ~ 2 hour,
Wherein, R represents alkyl, aryl, aralkyl, cycloalkyl, cycloalkylalkyl, heteroaryl, heteroarylalkyl or Heterocyclylalkyl; The mass volume ratio of compound and the first organic solvent shown in described formula II is 1: 7.46; The mol ratio of compound and Grignard reagent shown in described formula II is 1: 1.2;
2) pass into chlorine or add chlorizating agent, stirring 5 ~ 30 minutes, be warming up to room temperature, after saturated aqueous ammonium chloride or hydrochloric acid soln cancellation, use the second organic solvent extraction; The mol ratio of compound and chlorine or chlorizating agent shown in wherein said formula II is 1: 1 ~ 10;
3) step 2) gained extraction liquid is evaporated to dry after drying, and the enriched material obtained obtains described 1-through recrystallization and replaces the bromo-2H-1 of-4-, 2,3-triazole derivatives.
4. 1-replaces the bromo-2H-1 of-4-, the preparation method of 2,3-triazole derivatives, and this 1-replaces the bromo-2H-1 of-4-, and 2,3-triazole derivatives has the structure shown in following formula I:
Wherein, R represents alkyl, aryl, aralkyl, cycloalkyl, cycloalkylalkyl, heteroaryl, heteroarylalkyl or Heterocyclylalkyl; X represents chlorine;
It is characterized in that, described preparation method comprises following steps:
1) compound shown in Formula Il is dissolved in the first organic solvent, is cooled to-78 ~ 0 DEG C, adds Grignard reagent, stir 0.5 ~ 2 hour,
Wherein, R represents alkyl, aryl, aralkyl, cycloalkyl, cycloalkylalkyl, heteroaryl, heteroarylalkyl or Heterocyclylalkyl; The mass volume ratio of compound and the first organic solvent shown in described formula II is 1: 7.14; The mol ratio of compound and Grignard reagent shown in described formula II is 1: 1.2;
2) pass into chlorine or add chlorizating agent, stirring 5 ~ 30 minutes, be warming up to room temperature, after saturated aqueous ammonium chloride or hydrochloric acid soln cancellation, use the second organic solvent extraction; The mol ratio of compound and chlorine or chlorizating agent shown in wherein said formula II is 1: 1 ~ 10;
3) step 2) gained extraction liquid is evaporated to dry after drying, and the enriched material obtained obtains described 1-through recrystallization and replaces the bromo-2H-1 of-4-, 2,3-triazole derivatives.
5. 1-replaces the bromo-2H-1 of-4-, the preparation method of 2,3-triazole derivatives, and this 1-replaces the bromo-2H-1 of-4-, and 2,3-triazole derivatives has the structure shown in following formula I:
Wherein, R represents alkyl, aryl, aralkyl, cycloalkyl, cycloalkylalkyl, heteroaryl, heteroarylalkyl or Heterocyclylalkyl; X represents chlorine;
It is characterized in that, described preparation method comprises following steps:
1) compound shown in Formula Il is dissolved in the first organic solvent, is cooled to-78 ~ 0 DEG C, adds Grignard reagent, stir 0.5 ~ 2 hour,
Wherein, R represents alkyl, aryl, aralkyl, cycloalkyl, cycloalkylalkyl, heteroaryl, heteroarylalkyl or Heterocyclylalkyl; The mass volume ratio of compound and the first organic solvent shown in described formula II is 1: 6.81; The mol ratio of compound and Grignard reagent shown in described formula II is 1: 1.2;
2) pass into chlorine or add chlorizating agent, stirring 5 ~ 30 minutes, be warming up to room temperature, after saturated aqueous ammonium chloride or hydrochloric acid soln cancellation, use the second organic solvent extraction; The mol ratio of compound and chlorine or chlorizating agent shown in wherein said formula II is 1: 1 ~ 10;
3) step 2) gained extraction liquid is evaporated to dry after drying, and the enriched material obtained obtains described 1-through recrystallization and replaces the bromo-2H-1 of-4-, 2,3-triazole derivatives.
6. 1-replaces the bromo-2H-1 of-4-, the preparation method of 2,3-triazole derivatives, and this 1-replaces the bromo-2H-1 of-4-, and 2,3-triazole derivatives has the structure shown in following formula I:
Wherein, R represents alkyl, aryl, aralkyl, cycloalkyl, cycloalkylalkyl, heteroaryl, heteroarylalkyl or Heterocyclylalkyl; X represents chlorine;
It is characterized in that, described preparation method comprises following steps:
1) compound shown in Formula Il is dissolved in the first organic solvent, is cooled to-78 ~ 0 DEG C, adds Grignard reagent, stir 0.5 ~ 2 hour,
Wherein, R represents alkyl, aryl, aralkyl, cycloalkyl, cycloalkylalkyl, heteroaryl, heteroarylalkyl or Heterocyclylalkyl; The mass volume ratio of compound and the first organic solvent shown in described formula II is 1: 6.46; The mol ratio of compound and Grignard reagent shown in described formula II is 1: 1.2;
2) pass into chlorine or add chlorizating agent, stirring 5 ~ 30 minutes, be warming up to room temperature, after saturated aqueous ammonium chloride or hydrochloric acid soln cancellation, use the second organic solvent extraction; The mol ratio of compound and chlorine or chlorizating agent shown in wherein said formula II is 1: 1 ~ 10;
3) step 2) gained extraction liquid is evaporated to dry after drying, and the enriched material obtained obtains described 1-through recrystallization and replaces the bromo-2H-1 of-4-, 2,3-triazole derivatives.
7. 1-replaces the bromo-2H-1 of-4-, the preparation method of 2,3-triazole derivatives, and this 1-replaces the bromo-2H-1 of-4-, and 2,3-triazole derivatives has the structure shown in following formula I:
Wherein, R represents alkyl, aryl, aralkyl, cycloalkyl, cycloalkylalkyl, heteroaryl, heteroarylalkyl or Heterocyclylalkyl; X represents chlorine;
It is characterized in that, described preparation method comprises following steps:
1) compound shown in Formula Il is dissolved in the first organic solvent, is cooled to-78 ~ 0 DEG C, adds Grignard reagent, stir 0.5 ~ 2 hour,
Wherein, R represents alkyl, aryl, aralkyl, cycloalkyl, cycloalkylalkyl, heteroaryl, heteroarylalkyl or Heterocyclylalkyl; The mass volume ratio of compound and the first organic solvent shown in described formula II is 1: 7.53; The mol ratio of compound and Grignard reagent shown in described formula II is 1: 1.2;
2) pass into chlorine or add chlorizating agent, stirring 5 ~ 30 minutes, be warming up to room temperature, after saturated aqueous ammonium chloride or hydrochloric acid soln cancellation, use the second organic solvent extraction; The mol ratio of compound and chlorine or chlorizating agent shown in wherein said formula II is 1: 1 ~ 10;
3) step 2) gained extraction liquid is evaporated to dry after drying, and the enriched material obtained obtains described 1-through recrystallization and replaces the bromo-2H-1 of-4-, 2,3-triazole derivatives.
8. 1-replaces the bromo-2H-1 of-4-, the preparation method of 2,3-triazole derivatives, and this 1-replaces the bromo-2H-1 of-4-, and 2,3-triazole derivatives has the structure shown in following formula I:
Wherein, R represents alkyl, aryl, aralkyl, cycloalkyl, cycloalkylalkyl, heteroaryl, heteroarylalkyl or Heterocyclylalkyl; X represents chlorine;
It is characterized in that, described preparation method comprises following steps:
1) compound shown in Formula Il is dissolved in the first organic solvent, is cooled to-78 ~ 0 DEG C, adds Grignard reagent, stir 0.5 ~ 2 hour,
Wherein, R represents alkyl, aryl, aralkyl, cycloalkyl, cycloalkylalkyl, heteroaryl, heteroarylalkyl or Heterocyclylalkyl; The mass volume ratio of compound and the first organic solvent shown in described formula II is 1: 6.07; The mol ratio of compound and Grignard reagent shown in described formula II is 1: 1.2;
2) pass into chlorine or add chlorizating agent, stirring 5 ~ 30 minutes, be warming up to room temperature, after saturated aqueous ammonium chloride or hydrochloric acid soln cancellation, use the second organic solvent extraction; The mol ratio of compound and chlorine or chlorizating agent shown in wherein said formula II is 1: 1 ~ 10;
3) step 2) gained extraction liquid is evaporated to dry after drying, and the enriched material obtained obtains described 1-through recrystallization and replaces the bromo-2H-1 of-4-, 2,3-triazole derivatives.
9. 1-replaces the bromo-2H-1 of-4-, the preparation method of 2,3-triazole derivatives, and this 1-replaces the bromo-2H-1 of-4-, and 2,3-triazole derivatives has the structure shown in following formula I:
Wherein, R represents alkyl, aryl, aralkyl, cycloalkyl, cycloalkylalkyl, heteroaryl, heteroarylalkyl or Heterocyclylalkyl; X represents chlorine;
It is characterized in that, described preparation method comprises following steps:
1) compound shown in Formula Il is dissolved in the first organic solvent, is cooled to-78 ~ 0 DEG C, adds Grignard reagent, stir 0.5 ~ 2 hour,
Wherein, R represents alkyl, aryl, aralkyl, cycloalkyl, cycloalkylalkyl, heteroaryl, heteroarylalkyl or Heterocyclylalkyl; The mass volume ratio of compound and the first organic solvent shown in described formula II is 1: 5.7; The mol ratio of compound and Grignard reagent shown in described formula II is 1: 1.2;
2) pass into chlorine or add chlorizating agent, stirring 5 ~ 30 minutes, be warming up to room temperature, after saturated aqueous ammonium chloride or hydrochloric acid soln cancellation, use the second organic solvent extraction; The mol ratio of compound and chlorine or chlorizating agent shown in wherein said formula II is 1: 1 ~ 10;
3) step 2) gained extraction liquid is evaporated to dry after drying, and the enriched material obtained obtains described 1-through recrystallization and replaces the bromo-2H-1 of-4-, 2,3-triazole derivatives.
10. 1-replaces the bromo-2H-1 of-4-, the preparation method of 2,3-triazole derivatives, and this 1-replaces the bromo-2H-1 of-4-, and 2,3-triazole derivatives has the structure shown in following formula I:
Wherein, R represents alkyl, aryl, aralkyl, cycloalkyl, cycloalkylalkyl, heteroaryl, heteroarylalkyl or Heterocyclylalkyl; X represents chlorine;
It is characterized in that, described preparation method comprises following steps:
1) compound shown in Formula Il is dissolved in the first organic solvent, is cooled to-78 ~ 0 DEG C, adds Grignard reagent, stir 0.5 ~ 2 hour,
Wherein, R represents alkyl, aryl, aralkyl, cycloalkyl, cycloalkylalkyl, heteroaryl, heteroarylalkyl or Heterocyclylalkyl; The mass volume ratio of compound and the first organic solvent shown in described formula II is 1: 5.1; The mol ratio of compound and Grignard reagent shown in described formula II is 1: 1.2;
2) pass into chlorine or add chlorizating agent, stirring 5 ~ 30 minutes, be warming up to room temperature, after saturated aqueous ammonium chloride or hydrochloric acid soln cancellation, use the second organic solvent extraction; The mol ratio of compound and chlorine or chlorizating agent shown in wherein said formula II is 1: 1 ~ 10;
3) step 2) gained extraction liquid is evaporated to dry after drying, and the enriched material obtained obtains described 1-through recrystallization and replaces the bromo-2H-1 of-4-, 2,3-triazole derivatives.
11. 1 kinds of 1-replace the bromo-2H-1 of-4-, the preparation method of 2,3-triazole derivatives, and this 1-replaces the bromo-2H-1 of-4-, and 2,3-triazole derivatives has the structure shown in following formula I:
Wherein, R represents alkyl, aryl, aralkyl, cycloalkyl, cycloalkylalkyl, heteroaryl, heteroarylalkyl or Heterocyclylalkyl; X represents chlorine;
It is characterized in that, described preparation method comprises following steps:
1) compound shown in Formula Il is dissolved in the first organic solvent, is cooled to-78 ~ 0 DEG C, adds Grignard reagent, stir 0.5 ~ 2 hour,
Wherein, R represents alkyl, aryl, aralkyl, cycloalkyl, cycloalkylalkyl, heteroaryl, heteroarylalkyl or Heterocyclylalkyl; The mass volume ratio of compound and the first organic solvent shown in described formula II is 1: 6.33; The mol ratio of compound and Grignard reagent shown in described formula II is 1: 1.2;
2) pass into chlorine or add chlorizating agent, stirring 5 ~ 30 minutes, be warming up to room temperature, after saturated aqueous ammonium chloride or hydrochloric acid soln cancellation, use the second organic solvent extraction; The mol ratio of compound and chlorine or chlorizating agent shown in wherein said formula II is 1: 1 ~ 10;
3) step 2) gained extraction liquid is evaporated to dry after drying, and the enriched material obtained obtains described 1-through recrystallization and replaces the bromo-2H-1 of-4-, 2,3-triazole derivatives.
12. 1 kinds of 1-replace the bromo-2H-1 of-4-, the preparation method of 2,3-triazole derivatives, and this 1-replaces the bromo-2H-1 of-4-, and 2,3-triazole derivatives has the structure shown in following formula I:
Wherein, R represents alkyl, aryl, aralkyl, cycloalkyl, cycloalkylalkyl, heteroaryl, heteroarylalkyl or Heterocyclylalkyl; X represents chlorine;
It is characterized in that, described preparation method comprises following steps:
1) compound shown in Formula Il is dissolved in the first organic solvent, is cooled to-78 ~ 0 DEG C, adds Grignard reagent, stir 0.5 ~ 2 hour,
Wherein, R represents alkyl, aryl, aralkyl, cycloalkyl, cycloalkylalkyl, heteroaryl, heteroarylalkyl or Heterocyclylalkyl; The mass volume ratio of compound and the first organic solvent shown in described formula II is 1: 5.21; The mol ratio of compound and Grignard reagent shown in described formula II is 1: 1.2;
2) pass into chlorine or add chlorizating agent, stirring 5 ~ 30 minutes, be warming up to room temperature, after saturated aqueous ammonium chloride or hydrochloric acid soln cancellation, use the second organic solvent extraction; The mol ratio of compound and chlorine or chlorizating agent shown in wherein said formula II is 1: 1 ~ 10;
3) step 2) gained extraction liquid is evaporated to dry after drying, and the enriched material obtained obtains described 1-through recrystallization and replaces the bromo-2H-1 of-4-, 2,3-triazole derivatives.
13. 1 kinds of 1-replace the bromo-2H-1 of-4-, the preparation method of 2,3-triazole derivatives, and this 1-replaces the bromo-2H-1 of-4-, and 2,3-triazole derivatives has the structure shown in following formula I:
Wherein, R represents alkyl, aryl, aralkyl, cycloalkyl, cycloalkylalkyl, heteroaryl, heteroarylalkyl or Heterocyclylalkyl; X represents chlorine;
It is characterized in that, described preparation method comprises following steps:
1) compound shown in Formula Il is dissolved in the first organic solvent, is cooled to-78 ~ 0 DEG C, adds Grignard reagent, stir 0.5 ~ 2 hour,
Wherein, R represents alkyl, aryl, aralkyl, cycloalkyl, cycloalkylalkyl, heteroaryl, heteroarylalkyl or Heterocyclylalkyl; The mass volume ratio of compound and the first organic solvent shown in described formula II is 1: 5.81; The mol ratio of compound and Grignard reagent shown in described formula II is 1: 1.2;
2) pass into chlorine or add chlorizating agent, stirring 5 ~ 30 minutes, be warming up to room temperature, after saturated aqueous ammonium chloride or hydrochloric acid soln cancellation, use the second organic solvent extraction; The mol ratio of compound and chlorine or chlorizating agent shown in wherein said formula II is 1: 1 ~ 10;
3) step 2) gained extraction liquid is evaporated to dry after drying, and the enriched material obtained obtains described 1-through recrystallization and replaces the bromo-2H-1 of-4-, 2,3-triazole derivatives.
14. 1-according to any one of claim 1-13 replace the bromo-2H-1 of-4-, and 2,3-triazole derivatives, is characterized in that, step 1) in, described first organic solvent is ether, tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane or methyltetrahydrofuran; Described Grignard reagent is isopropylmagnesium chloride or isopropylmagnesium chloride-lithium chloride mixture.
15. 1-according to any one of claim 1-13 replace the bromo-2H-1 of-4-, and 2,3-triazole derivatives, is characterized in that, described chlorizating agent comprises N-chlorosuccinimide and chloro-5, the 5-dimethyl hydantion of 1,3-bis-.
16. 1-according to claim 15 replace the bromo-2H-1 of-4-, 2, 3-triazole derivatives, it is characterized in that, step 2) in, described second organic solvent is the mixing of one or more arbitrary proportions in fatty acid ester or ethers, wherein fatty acid ester comprises ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, butylacetate, isopropyl acetate, isobutyl acetate, pentyl acetate, Isoamyl Acetate FCC, methyl propionate, ethyl propionate, propyl propionate, butyl propionate and amyl propionate, ethers comprises ether, propyl ether, isopropyl ether and methyl tertiary butyl ether.
17. 1-according to claim 16 replace the bromo-2H-1 of-4-, 2,3-triazole derivatives, it is characterized in that, step 3) in, described recrystallization comprises the following steps: add in solvent by mass volume ratio 1: 1 ~ 100 by enriched material, stir 0.5 ~ 24 hour at-20 ~ 50 DEG C, obtain described 1-after filtration, vacuum-drying and replace the bromo-2H-1 of-4-, 2,3-triazole derivatives.
18. 1-according to claim 17 replace the bromo-2H-1 of-4-, 2, 3-triazole derivatives, it is characterized in that, described solvent is water, alcohols, fatty acid ester, ketone, the mixing of one or more arbitrary proportions in ethers and hydro carbons, wherein, alcohols comprises methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol and the trimethyl carbinol, fatty acid ester comprises ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, butylacetate, isopropyl acetate, isobutyl acetate, pentyl acetate, Isoamyl Acetate FCC, methyl propionate, ethyl propionate, propyl propionate, butyl propionate and amyl propionate, ketone comprises acetone, 2-butanone, cyclopentanone and pimelinketone, ethers comprises ether, propyl ether, isopropyl ether, methyl tertiary butyl ether, tetrahydrofuran (THF), 1, 4-dioxane and sherwood oil, hydro carbons comprises normal hexane, hexanaphthene, methylcyclohexane and normal heptane.
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| CN102603659A (en) * | 2012-03-01 | 2012-07-25 | 苏州雅本化学股份有限公司 | Preparation method of 1-substituted-4-bromo-1H-1,2,3-triazole-5-carboxylic acid |
| CN102786485A (en) * | 2012-08-24 | 2012-11-21 | 苏州雅本化学股份有限公司 | 2-substituted-2H-1,2,3-triazole derivative and preparation method thereof |
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| CN102603659A (en) * | 2012-03-01 | 2012-07-25 | 苏州雅本化学股份有限公司 | Preparation method of 1-substituted-4-bromo-1H-1,2,3-triazole-5-carboxylic acid |
| CN102786485A (en) * | 2012-08-24 | 2012-11-21 | 苏州雅本化学股份有限公司 | 2-substituted-2H-1,2,3-triazole derivative and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Highly Regioselective N-2 Arylation of 4,5-Dibromo-1,2,3-triazole: Efficient Synthesis of 2-Aryltriazoles;Xiao-jun Wang 等;《ORGANIC LETTERS》;20091008;第11卷(第21期);第5026-5028页 * |
| Regioselective Synthesis of Polysubstituted N2-Alkyl/Aryl-1,2,3-Triazoles via 4-Bromo-5-iodo-1,2,3-triazole;Li Zhang 等;《Synlett.》;20120504;第23卷(第7期);第1053页Table 1 * |
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