CN103450100A - Carfentrazone-ethyl synthesis method - Google Patents
Carfentrazone-ethyl synthesis method Download PDFInfo
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- CN103450100A CN103450100A CN2013104000970A CN201310400097A CN103450100A CN 103450100 A CN103450100 A CN 103450100A CN 2013104000970 A CN2013104000970 A CN 2013104000970A CN 201310400097 A CN201310400097 A CN 201310400097A CN 103450100 A CN103450100 A CN 103450100A
- Authority
- CN
- China
- Prior art keywords
- add
- cuprous chloride
- drip
- ethyl propenoate
- triazoline
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000005492 Carfentrazone-ethyl Substances 0.000 title abstract description 4
- MLKCGVHIFJBRCD-UHFFFAOYSA-N ethyl 2-chloro-3-{2-chloro-5-[4-(difluoromethyl)-3-methyl-5-oxo-4,5-dihydro-1H-1,2,4-triazol-1-yl]-4-fluorophenyl}propanoate Chemical group C1=C(Cl)C(CC(Cl)C(=O)OCC)=CC(N2C(N(C(F)F)C(C)=N2)=O)=C1F MLKCGVHIFJBRCD-UHFFFAOYSA-N 0.000 title abstract description 3
- 238000001308 synthesis method Methods 0.000 title 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims abstract description 43
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims abstract description 43
- 229940045803 cuprous chloride Drugs 0.000 claims abstract description 43
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 54
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 42
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 39
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 38
- 238000003756 stirring Methods 0.000 claims description 34
- RMFGNMMNUZWCRZ-UHFFFAOYSA-N Humulone Natural products CC(C)CC(=O)C1=C(O)C(O)(CC=C(C)C)C(O)=C(CC=C(C)C)C1=O RMFGNMMNUZWCRZ-UHFFFAOYSA-N 0.000 claims description 30
- 150000003851 azoles Chemical class 0.000 claims description 30
- VMSLCPKYRPDHLN-NRFANRHFSA-N humulone Chemical compound CC(C)CC(=O)C1=C(O)C(CC=C(C)C)=C(O)[C@@](O)(CC=C(C)C)C1=O VMSLCPKYRPDHLN-NRFANRHFSA-N 0.000 claims description 30
- 238000004821 distillation Methods 0.000 claims description 18
- 239000012535 impurity Substances 0.000 claims description 18
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims 2
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000002363 herbicidal effect Effects 0.000 abstract description 3
- 239000004009 herbicide Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 238000006193 diazotization reaction Methods 0.000 abstract 2
- 238000005580 one pot reaction Methods 0.000 abstract 2
- 238000007192 Meerwein reaction reaction Methods 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- IZBNNCFOBMGTQX-UHFFFAOYSA-N etoperidone Chemical compound O=C1N(CC)C(CC)=NN1CCCN1CCN(C=2C=C(Cl)C=CC=2)CC1 IZBNNCFOBMGTQX-UHFFFAOYSA-N 0.000 abstract 1
- 229960005437 etoperidone Drugs 0.000 abstract 1
- 239000000575 pesticide Substances 0.000 abstract 1
- 230000035484 reaction time Effects 0.000 abstract 1
- IOGXOCVLYRDXLW-UHFFFAOYSA-N tert-butyl nitrite Chemical compound CC(C)(C)ON=O IOGXOCVLYRDXLW-UHFFFAOYSA-N 0.000 abstract 1
- 239000012414 tert-butyl nitrite Substances 0.000 abstract 1
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 235000010288 sodium nitrite Nutrition 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 5
- 240000006122 Chenopodium album Species 0.000 description 3
- 235000009344 Chenopodium album Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 240000006995 Abutilon theophrasti Species 0.000 description 2
- 235000001808 Ceanothus spinosus Nutrition 0.000 description 2
- 241001264786 Ceanothus spinosus Species 0.000 description 2
- 240000005702 Galium aparine Species 0.000 description 2
- 235000014820 Galium aparine Nutrition 0.000 description 2
- 244000292697 Polygonum aviculare Species 0.000 description 2
- 235000006386 Polygonum aviculare Nutrition 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NPZTUJOABDZTLV-UHFFFAOYSA-N 1,2-dihydrobenzotriazol-4-one Chemical compound O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 description 1
- 244000237956 Amaranthus retroflexus Species 0.000 description 1
- 235000013479 Amaranthus retroflexus Nutrition 0.000 description 1
- 235000007319 Avena orientalis Nutrition 0.000 description 1
- 241000209763 Avena sativa Species 0.000 description 1
- 235000007558 Avena sp Nutrition 0.000 description 1
- 241001645380 Bassia scoparia Species 0.000 description 1
- 244000178993 Brassica juncea Species 0.000 description 1
- 235000005855 Brassica juncea var. subintegrifolia Nutrition 0.000 description 1
- 241000207199 Citrus Species 0.000 description 1
- 240000007154 Coffea arabica Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 235000002848 Cyperus flabelliformis Nutrition 0.000 description 1
- 240000001505 Cyperus odoratus Species 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 241000219146 Gossypium Species 0.000 description 1
- 238000007341 Heck reaction Methods 0.000 description 1
- 240000005979 Hordeum vulgare Species 0.000 description 1
- 235000007340 Hordeum vulgare Nutrition 0.000 description 1
- 241000110847 Kochia Species 0.000 description 1
- 240000006240 Linum usitatissimum Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- 241001504654 Mustela nivalis Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229940087098 Oxidase inhibitor Drugs 0.000 description 1
- 102000004316 Oxidoreductases Human genes 0.000 description 1
- 108090000854 Oxidoreductases Proteins 0.000 description 1
- 240000006928 Persicaria lapathifolia Species 0.000 description 1
- 241000124033 Salix Species 0.000 description 1
- 244000058416 Scirpus paludosus Species 0.000 description 1
- 235000005010 Scirpus paludosus Nutrition 0.000 description 1
- 235000002594 Solanum nigrum Nutrition 0.000 description 1
- 240000002307 Solanum ptychanthum Species 0.000 description 1
- 244000046109 Sorghum vulgare var. nervosum Species 0.000 description 1
- 229940100389 Sulfonylurea Drugs 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 244000098338 Triticum aestivum Species 0.000 description 1
- 241000159750 Urtica cannabina Species 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000020971 citrus fruits Nutrition 0.000 description 1
- 235000016213 coffee Nutrition 0.000 description 1
- 235000013353 coffee beverage Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- -1 hydroxyethyl ethyl Chemical group 0.000 description 1
- VYQNWZOUAUKGHI-UHFFFAOYSA-N monobenzone Chemical compound C1=CC(O)=CC=C1OCC1=CC=CC=C1 VYQNWZOUAUKGHI-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- YROXIXLRRCOBKF-UHFFFAOYSA-N sulfonylurea Chemical class OC(=N)N=S(=O)=O YROXIXLRRCOBKF-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009333 weeding Methods 0.000 description 1
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
The invention belongs to the technical field of pesticide herbicide, and particularly relates to a preparation method of a triazolinone herbicide carfentrazone-ethyl. The method is implemented mainly by a one-pot process, wherein 1-(5-amino-2-fluoro-4-chlorphenyl)-3-methyl-4-difluoromethyl-1H-1,2,4-triazoline-5-ketone is used as a raw material, acetonitrile or butanone is used as a solvent, tert-butyl nitrite is used as a diazotization reagent, and the compound carfentrazone-ethyl is synthesized by a one-pot process through diazotization and Meerwein reaction under the catalysis of cuprous chloride. The method provided by the invention has the advantages of high selectivity, mild reaction conditions, short reaction time, high product yield, environmental friendliness, easy implementation of industrialization and the like.
Description
Technical field
The invention belongs to the synthetic of organic compound in chemical field.Be specifically related to a kind of preparation method of azoles humulone.
Technical background
Weedicide azoles humulone (claiming again carfentrazoneethyl, good fortune agriculture, the spirit of going out soon), molecular formula: C
15h
14o
3n
3f
3c1
2, its structural formula is as follows:
People's reported first such as the nineteen ninety Kathleen of FMC Corp. M.Poss by nitrite tert-butyl, be diazo reagent, cupric chloride is catalyzer, acetonitrile is that solvent has synthesized the benz triazolinone weedicide that comprises the azoles humulone, and its activity is tested, applied for the U.S., China and world patent (WO1990002120, CN1041154, US5125958), structure to this series compound is protected, and determined that weedicide azoles humulone has higher weeding activity, it belongs to proporphyrinogen oxidase inhibitor, cause that by suppressing proporphyrinogen oxidase in the chlcrophyll biosynthesis process cytolemma destroys, make blade withered rapidly, dead.Be mainly used in preventing and kill off broadleaf weeds and nutgrass flatsedge as Tender Catchweed Bedstraw Herb, Herba lamii barbati, veronica, piemarker, hold, the weeds such as lamb's-quarters, red heart lamb's-quarters, blank pipe are led a cow, weasel hemp nettle, pale persicaria, willow leaf thorn knotweed, volume stem knotweed, Amaranthus retroflexus, Herba Acalyphae, precious leaf mustard, Herba Sonchi Arvensis, Herba lamii barbati, fruitlet flax, summer cypress, black nightshade, sinapsis alba.Tender Catchweed Bedstraw Herb, piemarker, red heart lamb's-quarters, the blank pipe weeds such as lead a cow are had to excellent preventive effect.The weeds that sulfonylurea herbicide produced to resistance have good activity as Kochia scoperiade etc.Be applicable to wheat, barley, oat, paddy rice, corn, soybean, citrus, coffee, cotton, Chinese sorghum, vineyard, lawn etc., transformation period because of it in soil is only several hours, therefore to also safety of second stubble crop, but to the invalid (Hu Naidong of the weeds that grow after dispenser, Liu Changling. meticulous and specialty chemicals, 2003,14:21-24).
Subsequently, it is diazo reagent that the people such as John W.Ager use Sodium Nitrite instead, and cuprous chloride is catalyzer, and acetone is the synthetic azoles humulone (US5621112, WO1997007107, CN1193969) of solvent, and product yield is only 75-80%, and purity is 91%.
After this, the human hairs such as Gerard understand patent (WO1999019308), with 1-(the fluoro-4-chloro-phenyl-of 2-)-3-methyl-4-difluoromethyl-1H-1,2,4-triazoline-5-ketone is raw material, by iodide reaction, Heck reaction and the synthetic target product of replacement elimination reaction three steps, wherein the different hydroxyethyl ethyl propenoate of a kind of raw material 2-is difficult for obtaining.
Within 2011, the people such as Qunzhen Guo have invented again patent (CN102174026C, WO2012122863), with 1-(the fluoro-4-chloro-phenyl-of 5-amino-2-)-3-methyl-4-difluoromethyl-1H-1,2,4-triazoline-5-ketone is raw material, by diazonium alkylation and the synthetic target product of esterification two steps, complicated operation.
For this reason the present invention on the people's such as Kathleen M.Poss and John W.Ager basis in line with improving quality, the purposes such as environmental friendliness, further the technique of " one kettle way " synthetic target product azoles humulone has been optimized in research, be about to solvent acetone and change acetonitrile or butanone into, the diazo reagent Sodium Nitrite changes nitrite tert-butyl into, by changing 1-(the fluoro-4-chloro-phenyl-of 5-amino-2-)-3-methyl-4-difluoromethyl-1H-1, 2, the ratio of 4-triazoline-5-ketone and cuprous chloride, the time for adding of concentrated hydrochloric acid and nitrite tert-butyl and post-treating method, make product yield be increased to 105% by 75-80%, content is 91-92% (document: 91%), and the diazo reagent nitrite tert-butyl used due to reaction is organism, aftertreatment does not make water yet, thereby reduced the processing of trade effluent, in aftertreatment, filter the cuprous chloride that obtains can direct reuse simultaneously, repeat still there is catalytic activity 6 times, reduced the catalyzer use cost, therefore possesses industrial prospect preferably.
Summary of the invention
Purpose of the present invention: a kind of method that synthetic azoles humulone is provided.
Reaction equation of the present invention is as follows.
Specifically in reactor, add solvent acetonitrile or butanone, logical N
2, be cooled to-10-0 ℃, add while stirring 1-(the fluoro-4-chloro-phenyl-of 5-amino-2-)-3-methyl-4-difluoromethyl-1H-1, 2, 4-triazoline-5-ketone and cuprous chloride, drip concentrated hydrochloric acid in 20-50min, add again ethyl propenoate, then control temperature at 0-5 ℃, drip the diazo reagent nitrite tert-butyl in 0-4.0h, reaction 20-100min, solvent and unreacted ethyl propenoate are reclaimed in air distillation, by ethyl acetate, dilute again, the filtered and recycled cuprous chloride, in temperature, be finally 110-125 ℃, boil off impurity under the condition that pressure is 15-20mmHg, obtain product azoles humulone, wherein the consumption of reaction solvent acetonitrile or butanone is the 15-20 equivalent, its consumption all is expressed as corresponding to 1 molar equivalent 1-(the fluoro-4-chloro-phenyl-of 5-amino-2-)-3-methyl-4-difluoromethyl-1H-1, 2, the molar equivalent of 4-triazoline-5-ketone, lower same, the consumption of concentrated hydrochloric acid is the 2.0-4.0 equivalent, the consumption of ethyl propenoate is the 1-15 equivalent, the consumption of nitrite tert-butyl is the 1.0-1.5 equivalent, the cuprous chloride that filtration obtains can direct reuse, reuse still has catalytic activity 6 times.
Embodiment
Below by specific examples, the present invention is elaborated.
Embodiment 1:
Add acetonitrile (32.4g, 790mmol) in the 250mL there-necked flask, logical N
2, be cooled to-5-0 ℃, add 1-(the fluoro-4-chloro-phenyl-of 5-amino-2-)-3-methyl-4-difluoromethyl-1H-1, 2, 4-triazoline-5-ketone (10.5g, 35.9mmol) and cuprous chloride (2.50g, 25.1mmol), drip while stirring concentrated hydrochloric acid (11.8g, 120mmol), 20min dropwises, add again ethyl propenoate (49.4g, 494mmol), then control temperature at 0-5 ℃, drip nitrite tert-butyl (5.6g, 53.9mmol), 2.5h add, stirring reaction 1h, solvent and unreacted ethyl propenoate are reclaimed in air distillation, by ethyl acetate, dilute again, the filtered and recycled cuprous chloride, in temperature, be finally 110-125 ℃, boil off impurity under the condition that pressure is 15-20mmHg, obtain product azoles humulone 15.2g, productive rate 103%, content 91.8%.
Embodiment 2:
Add acetonitrile (32.4g, 790mmol) in the 250mL there-necked flask, logical N
2, be cooled to-5-0 ℃, add 1-(the fluoro-4-chloro-phenyl-of 5-amino-2-)-3-methyl-4-difluoromethyl-1H-1, 2, 4-triazoline-5-ketone (10.5g, 35.9mmol) and cuprous chloride (2.50g, 25.1mmol), drip while stirring concentrated hydrochloric acid (11.8g, 120mmol), 20min dropwises, add again ethyl propenoate (49.4g, 494mmol), then control temperature at 0-5 ℃, drip nitrite tert-butyl (5.6g, 53.9mmol), 2h adds, stirring reaction 1h, solvent and unreacted ethyl propenoate are reclaimed in air distillation, by ethyl acetate, dilute again, the filtered and recycled cuprous chloride, in temperature, be finally 110-125 ℃, boil off impurity under the condition that pressure is 15-20mmHg, obtain product azoles humulone 14.7g, productive rate 99.3%, content 92.0%.
Embodiment 3:
Add acetonitrile (32.4g, 790mmol) in the 250mL there-necked flask, logical N
2, be cooled to-5-0 ℃, add 1-(the fluoro-4-chloro-phenyl-of 5-amino-2-)-3-methyl-4-difluoromethyl-1H-1, 2, 4-triazoline-5-ketone (10.5g, 35.9mmol) and cuprous chloride (2.50g, 25.1mmol), drip while stirring concentrated hydrochloric acid (11.8g, 120mmol), 20min dropwises, add again ethyl propenoate (49.4g, 494mmol), then control temperature at 0-5 ℃, drip nitrite tert-butyl (5.6g, 53.9mmol), 3.5h add, stirring reaction 1h, solvent and unreacted ethyl propenoate are reclaimed in air distillation, by ethyl acetate, dilute again, the filtered and recycled cuprous chloride, in temperature, be finally 110-125 ℃, boil off impurity under the condition that pressure is 15-20mmHg, obtain product azoles humulone 15.5g, productive rate 105%, content 91.8%.
Embodiment 4:
Add acetonitrile (32.4g, 790mmol) in the 250mL there-necked flask, logical N
2, be cooled to-5-0 ℃, add 1-(the fluoro-4-chloro-phenyl-of 5-amino-2-)-3-methyl-4-difluoromethyl-1H-1, 2, 4-triazoline-5-ketone (10.5g, 35.9mmol) and cuprous chloride (1.07g, 10.8mmol), drip while stirring concentrated hydrochloric acid (11.8g, 120mmol), 20min dropwises, add again ethyl propenoate (49.4g, 494mmol), then control temperature at 0-5 ℃, drip nitrite tert-butyl (5.6g, 53.9mmol), 2h adds, stirring reaction 1h, solvent and unreacted ethyl propenoate are reclaimed in air distillation, by ethyl acetate, dilute again, the filtered and recycled cuprous chloride, in temperature, be finally 110-125 ℃, boil off impurity under the condition that pressure is 15-20mmHg, obtain product azoles humulone 14.5g, productive rate 97.9%, content 92.2%.
Embodiment 5:
Add acetonitrile (32.4g, 790mmol) in the 250mL there-necked flask, logical N
2, be cooled to-5-0 ℃, add 1-(the fluoro-4-chloro-phenyl-of 5-amino-2-)-3-methyl-4-difluoromethyl-1H-1, 2, 4-triazoline-5-ketone (10.5g, 35.9mmol) and cuprous chloride (1.79g, 18.0mmol), drip while stirring concentrated hydrochloric acid (11.8g, 120mmol), 20min dropwises, add again ethyl propenoate (49.4g, 494mmol), then control temperature at 0-5 ℃, drip nitrite tert-butyl (5.6g, 53.9mmol), 2h adds, stirring reaction 1h, solvent and unreacted ethyl propenoate are reclaimed in air distillation, by ethyl acetate, dilute again, the filtered and recycled cuprous chloride, in temperature, be finally 110-125 ℃, boil off impurity under the condition that pressure is 15-20mmHg, obtain product azoles humulone 14.1g, productive rate 95.3%, content 92.1%.
Embodiment 6:
Add acetonitrile (32.4g, 790mmol) in the 250mL there-necked flask, logical N
2, be cooled to-5-0 ℃, add 1-(the fluoro-4-chloro-phenyl-of 5-amino-2-)-3-methyl-4-difluoromethyl-1H-1, 2, 4-triazoline-5-ketone (10.5g, 35.9mmol) and cuprous chloride (0.46g, 4.67mmol), drip while stirring concentrated hydrochloric acid (11.8g, 120mmol), 20min dropwises, add again ethyl propenoate (49.4g, 494mmol), then control temperature at 0-5 ℃, drip nitrite tert-butyl (5.6g, 53.9mmol), 2h adds, stirring reaction 1h, solvent and unreacted ethyl propenoate are reclaimed in air distillation, by ethyl acetate, dilute again, the filtered and recycled cuprous chloride, in temperature, be finally 110-125 ℃, boil off impurity under the condition that pressure is 15-20mmHg, obtain product azoles humulone 13.7g, productive rate 92.5%, content 91.3%.
Embodiment 7:
Add acetonitrile (32.4g, 790mmol) in the 250mL there-necked flask, logical N
2, be cooled to-5-0 ℃, add 1-(the fluoro-4-chloro-phenyl-of 5-amino-2-)-3-methyl-4-difluoromethyl-1H-1, 2, 4-triazoline-5-ketone (10.5g, 35.9mmol) and cuprous chloride (2.50g, 25.1mmol), drip while stirring concentrated hydrochloric acid (11.8g, 120mmol), 20min dropwises, add again ethyl propenoate (49.4g, 494mmol), then control temperature at 0-5 ℃, drip nitrite tert-butyl (5.6g, 53.9mmol), 3h adds, stirring reaction 1h, solvent and unreacted ethyl propenoate are reclaimed in air distillation, by ethyl acetate, dilute again, the filtered and recycled cuprous chloride, in temperature, be finally 110-125 ℃, boil off impurity under the condition that pressure is 15-20mmHg, obtain product azoles humulone 15.1g, productive rate 102%, content 91.4%.
Embodiment 8:
Add acetonitrile (32.4g, 790mmol) in the 250mL there-necked flask, logical N
2, be cooled to-5-0 ℃, add 1-(the fluoro-4-chloro-phenyl-of 5-amino-2-)-3-methyl-4-difluoromethyl-1H-1, 2, 4-triazoline-5-ketone (10.5g, 35.9mmol) and cuprous chloride (2.50g, 25.1mmol), drip while stirring concentrated hydrochloric acid (11.8g, 120mmol), 30min dropwises, add again ethyl propenoate (49.4g, 494mmol), then control temperature at 0-5 ℃, drip nitrite tert-butyl (5.6g, 53.9mmol), 2h adds, stirring reaction 1h, solvent and unreacted ethyl propenoate are reclaimed in air distillation, by ethyl acetate, dilute again, the filtered and recycled cuprous chloride, in temperature, be finally 110-125 ℃, boil off impurity under the condition that pressure is 15-20mmHg, obtain product azoles humulone 14.3g, productive rate 96.6%, content 91.8%.
Embodiment 9:
Add acetonitrile (32.4g, 790mmol) in the 250mL there-necked flask, logical N
2, be cooled to-5-0 ℃, add 1-(the fluoro-4-chloro-phenyl-of 5-amino-2-)-3-methyl-4-difluoromethyl-1H-1, 2, 4-triazoline-5-ketone (10.5g, 35.9mmol) and cuprous chloride (2.50g, 25.1mmol), drip while stirring concentrated hydrochloric acid (11.8g, 120mmol), 50min dropwises, add again ethyl propenoate (49.4g, 494mmol), then control temperature at 0-5 ℃, drip nitrite tert-butyl (5.6g, 53.9mmol), 2h adds, stirring reaction 1h, solvent and unreacted ethyl propenoate are reclaimed in air distillation, by ethyl acetate, dilute again, the filtered and recycled cuprous chloride, in temperature, be finally 110-125 ℃, boil off impurity under the condition that pressure is 15-20mmHg, obtain product azoles humulone 13.9g, productive rate 93.9%, content 92.1%.
Embodiment 10:
Add acetonitrile (32.4g, 790mmol) in the 250mL there-necked flask, logical N
2, be cooled to-5-0 ℃, add 1-(the fluoro-4-chloro-phenyl-of 5-amino-2-)-3-methyl-4-difluoromethyl-1H-1, 2, 4-triazoline-5-ketone (10.5g, 35.9mmol) and cuprous chloride (2.50g, 25.1mmol), drip while stirring concentrated hydrochloric acid (11.8g, 120mmol), 20min dropwises, add again ethyl propenoate (49.4g, 494mmol), then control temperature at 0-5 ℃, drip nitrite tert-butyl (5.6g, 53.9mmol), 4h adds, stirring reaction 1h, solvent and unreacted ethyl propenoate are reclaimed in air distillation, by ethyl acetate, dilute again, the filtered and recycled cuprous chloride, in temperature, be finally 110-125 ℃, boil off impurity under the condition that pressure is 15-20mmHg, obtain product azoles humulone 14.9g, productive rate 101%, content 92.2%.
Embodiment 11:
Add acetonitrile (32.4g, 790mmol) in the 250mL there-necked flask, logical N
2, be cooled to-5-0 ℃, inject 1-(the fluoro-4-chloro-phenyl-of 5-amino-2-)-3-methyl-4-difluoromethyl-1H-1, 2, 4-triazoline-5-ketone (10.5g, 35.9mmol) and cuprous chloride (2.50g, 25.1mmol), drip while stirring concentrated hydrochloric acid (11.8g, 120mmol), 40min dropwises, add again ethyl propenoate (49.4g, 494mmol), then control temperature at 0-5 ℃, drip nitrite tert-butyl (5.6g, 53.9mmol), 2h adds, stirring reaction 1h, solvent and unreacted ethyl propenoate are reclaimed in air distillation, by ethyl acetate, dilute again, the filtered and recycled cuprous chloride, in temperature, be finally 110-125 ℃, boil off impurity under the condition that pressure is 15-20mmHg, obtain product azoles humulone 14.0g, productive rate 94.6%, content 91.6%.
Embodiment 12:
Add butanone (56.9g, 790mmol) in the 250mL there-necked flask, logical N
2, be cooled to-5-0 ℃, add 1-(the fluoro-4-chloro-phenyl-of 5-amino-2-)-3-methyl-4-difluoromethyl-1H-1, 2, 4-triazoline-5-ketone (10.5g, 35.9mmol) and cuprous chloride (1.07g, 10.8mmol), drip while stirring concentrated hydrochloric acid (11.8g, 120mmol), 20min dropwises, add again ethyl propenoate (49.4g, 494mmol), then control temperature at 0-5 ℃, drip nitrite tert-butyl (5.6g, 53.9mmol), 2.5h add, stirring reaction 1h, solvent and unreacted ethyl propenoate are reclaimed in air distillation, by ethyl acetate, dilute again, the filtered and recycled cuprous chloride, in temperature, be finally 110-125 ℃, boil off impurity under the condition that pressure is 15-20mmHg, obtain product azoles humulone 14.5g, productive rate 98.0%, content 92.3%.
Embodiment 13:
Add butanone (64.9g, 902mmol) in the 250mL there-necked flask, logical N
2, be cooled to-5-0 ℃, add 1-(the fluoro-4-chloro-phenyl-of 5-amino-2-)-3-methyl-4-difluoromethyl-1H-1, 2, 4-triazoline-5-ketone (12.0g, 41.0mmol) and cuprous chloride (28.6g, 28.7mmol), drip while stirring concentrated hydrochloric acid (13.5g, 137mmol), 20min dropwises, add again ethyl propenoate (56.4g, 564mmol), then control temperature at 0-5 ℃, drip nitrite tert-butyl (6.33g, 61.5mmol), 2h adds, stirring reaction 1h, solvent and unreacted ethyl propenoate are reclaimed in air distillation, by ethyl acetate, dilute again, the filtered and recycled cuprous chloride, in temperature, be finally 110-125 ℃, boil off impurity under the condition that pressure is 15-20mmHg, obtain product azoles humulone 16.6g, productive rate 98.2%, content 92.4%.
Embodiment 14: the cuprous chloride of recovery is as the synthetic azoles humulone of catalyzer
Add acetonitrile (32.4g, 790mmol) in the 250mL there-necked flask, logical N
2, be cooled to-5-0 ℃, inject 1-(the fluoro-4-chloro-phenyl-of 5-amino-2-)-3-methyl-4-difluoromethyl-1H-1, 2, 4-triazoline-5-ketone (10.5g, 35.9mmol) and cuprous chloride (2.50g, 25.1mmol), drip while stirring concentrated hydrochloric acid (11.8g, 120mmol), 20min dropwises, add again ethyl propenoate (49.4g, 494mmol), then control temperature at 0-5 ℃, drip nitrite tert-butyl (5.6g, 53.9mmol), 2h adds, stirring reaction 1h, solvent and unreacted ethyl propenoate are reclaimed in air distillation, by ethyl acetate, dilute again, the filtered and recycled cuprous chloride, in temperature, be finally 110-125 ℃, boil off impurity under the condition that pressure is 15-20mmHg, obtain product azoles humulone 15.1g, productive rate 102%, content 91.6%.
Case of comparative examples 1: Sodium Nitrite is as the synthetic azoles humulone of diazo reagent
Add acetone (52.3g, 902mmol) in the 250mL there-necked flask, logical N
2, be cooled to-5-0 ℃, add 1-(the fluoro-4-chloro-phenyl-of 5-amino-2-)-3-methyl-4-difluoromethyl-1H-1, 2, 4-triazoline-5-ketone (12.0g, 41.0mmol) and cuprous chloride (28.6g, 28.7mmol), drip while stirring concentrated hydrochloric acid (13.5g, 137mmol), 20min dropwises, add again ethyl propenoate (56.4g, 564mmol), then control temperature at 0-5 ℃, drip Sodium Nitrite (42.4g, 6.15mmol), 2h adds, stirring reaction 1h, solvent and unreacted ethyl propenoate are reclaimed in air distillation, by ethyl acetate, dilute again, the filtered and recycled cuprous chloride, in temperature, be finally 110-125 ℃, boil off impurity under the condition that pressure is 15-20mmHg, obtain product azoles humulone 14.9g, productive rate 88.2%, content 90.8%.
Case of comparative examples 2: Sodium Nitrite is as the synthetic azoles humulone of diazo reagent
Add acetone (52.3g, 902mmol) in the 250mL there-necked flask, logical N
2, be cooled to-5-0 ℃, add 1-(the fluoro-4-chloro-phenyl-of 5-amino-2-)-3-methyl-4-difluoromethyl-1H-1, 2, 4-triazoline-5-ketone (12.0g, 41.0mmol) and cuprous chloride (12.2g, 12.3mmol), drip while stirring concentrated hydrochloric acid (13.5g, 137mmol), 20min dropwises, add again ethyl propenoate (56.4g, 564mmol), then control temperature at 0-5 ℃, drip Sodium Nitrite (42.4g, 6.15mmol), 2h adds, stirring reaction 1h, solvent and unreacted ethyl propenoate are reclaimed in air distillation, by ethyl acetate, dilute again, the filtered and recycled cuprous chloride, in temperature, be finally 110-125 ℃, boil off impurity under the condition that pressure is 15-20mmHg, obtain product azoles humulone 13.3g, productive rate 78.7%, content 91.3%.
Claims (3)
1. the method for a synthetic azoles humulone, is characterized in that: add solvent acetonitrile or butanone in reactor, logical N
2, be cooled to-10-0 ℃, add while stirring 1-(the fluoro-4-chloro-phenyl-of 5-amino-2-)-3-methyl-4-difluoromethyl-1H-1, 2, 4-triazoline-5-ketone and cuprous chloride, drip concentrated hydrochloric acid in 20-50min, add again ethyl propenoate, then control temperature at 0-5 ℃, drip the diazo reagent nitrite tert-butyl in 0-4.0h, reaction 20-100min, solvent and unreacted ethyl propenoate are reclaimed in air distillation, by ethyl acetate, dilute again, the filtered and recycled cuprous chloride, in temperature, be finally 110-125 ℃, boil off impurity under the condition that pressure is 15-20mmHg, obtain product azoles humulone.
2. a synthetic method as claimed in claim 1, it is characterized in that: the consumption of reaction solvent acetonitrile or butanone is the 15-20 equivalent, its consumption all is expressed as corresponding to 1 molar equivalent 1-(the fluoro-4-chloro-phenyl-of 5-amino-2-)-3-methyl-4-difluoromethyl-1H-1,2, the molar equivalent of 4-triazoline-5-ketone, lower same, the consumption of concentrated hydrochloric acid is the 2.0-4.0 equivalent, the consumption of ethyl propenoate is the 1-15 equivalent, and the consumption of nitrite tert-butyl is the 1.0-1.5 equivalent.
3. a synthetic method as claimed in claim 1 is characterized in that: filtering the cuprous chloride that obtains can direct reuse, and reuse still has catalytic activity 6 times.
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| CN104926740A (en) * | 2014-03-31 | 2015-09-23 | 济南先达化工科技有限公司 | Preparation method of carfentrazone-ethyl |
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| WO1990002120A1 (en) * | 1988-08-31 | 1990-03-08 | Fmc Corporation | Herbicidal triazolinones |
| CN1193969A (en) * | 1995-08-21 | 1998-09-23 | Fmc有限公司 | Process for preparing herbicide ethyl 'alpha'-2-dichloro-5-[4-(difluoromethyl)-4,5-dihydro-3-methyl-5-oxo-1h-1,2,4-triazol-1-yl]-4-fluorobenzenepropanoate |
| CN102174026A (en) * | 2011-03-11 | 2011-09-07 | 浙江省诸暨合力化学对外贸易有限公司 | Preparation method of carfentrazone-ethyl |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO1990002120A1 (en) * | 1988-08-31 | 1990-03-08 | Fmc Corporation | Herbicidal triazolinones |
| CN1193969A (en) * | 1995-08-21 | 1998-09-23 | Fmc有限公司 | Process for preparing herbicide ethyl 'alpha'-2-dichloro-5-[4-(difluoromethyl)-4,5-dihydro-3-methyl-5-oxo-1h-1,2,4-triazol-1-yl]-4-fluorobenzenepropanoate |
| CN102174026A (en) * | 2011-03-11 | 2011-09-07 | 浙江省诸暨合力化学对外贸易有限公司 | Preparation method of carfentrazone-ethyl |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104926740A (en) * | 2014-03-31 | 2015-09-23 | 济南先达化工科技有限公司 | Preparation method of carfentrazone-ethyl |
| CN104926740B (en) * | 2014-03-31 | 2017-09-19 | 济南先达化工科技有限公司 | A kind of preparation method of azoles humulone |
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