CN109678767A - A kind of synthesis technology of herbicide tembotrions - Google Patents
A kind of synthesis technology of herbicide tembotrions Download PDFInfo
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- CN109678767A CN109678767A CN201811613707.4A CN201811613707A CN109678767A CN 109678767 A CN109678767 A CN 109678767A CN 201811613707 A CN201811613707 A CN 201811613707A CN 109678767 A CN109678767 A CN 109678767A
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- methyl
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- tembotrions
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- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 50
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 50
- 230000002363 herbicidal effect Effects 0.000 title claims abstract description 23
- 238000005516 engineering process Methods 0.000 title claims abstract description 21
- 239000004009 herbicide Substances 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
- 239000002904 solvent Substances 0.000 claims abstract description 38
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 27
- HROGGWHSSRQABB-UHFFFAOYSA-N 3-methyl-4-methylsulfonyl-2-(2,2,2-trifluoroethoxy)benzoic acid Chemical compound FC(COC1=C(C(=O)O)C=CC(=C1C)S(=O)(=O)C)(F)F HROGGWHSSRQABB-UHFFFAOYSA-N 0.000 claims abstract description 22
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 22
- YQYVOGFWLVVXMM-UHFFFAOYSA-N methyl 3-(bromomethyl)-2-chloro-4-methylsulfonylbenzoate Chemical class COC(=O)C1=CC=C(S(C)(=O)=O)C(CBr)=C1Cl YQYVOGFWLVVXMM-UHFFFAOYSA-N 0.000 claims abstract description 22
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003513 alkali Substances 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 14
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims abstract description 11
- MWFMGBPGAXYFAR-UHFFFAOYSA-N 2-hydroxy-2-methylpropanenitrile Chemical compound CC(C)(O)C#N MWFMGBPGAXYFAR-UHFFFAOYSA-N 0.000 claims abstract description 10
- HJSLFCCWAKVHIW-UHFFFAOYSA-N cyclohexane-1,3-dione Chemical compound O=C1CCCC(=O)C1 HJSLFCCWAKVHIW-UHFFFAOYSA-N 0.000 claims abstract description 10
- BBWCBPYXCNCYAT-UHFFFAOYSA-N methyl 2-chloro-3-methyl-4-methylsulfonylbenzoate Chemical class COC(=O)C1=CC=C(S(C)(=O)=O)C(C)=C1Cl BBWCBPYXCNCYAT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 7
- 238000001953 recrystallisation Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 17
- 235000019441 ethanol Nutrition 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical group C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052794 bromium Inorganic materials 0.000 claims description 8
- 239000012044 organic layer Substances 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 7
- 230000000630 rising effect Effects 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 5
- 239000005864 Sulphur Substances 0.000 claims description 5
- 238000005904 alkaline hydrolysis reaction Methods 0.000 claims description 5
- 230000020477 pH reduction Effects 0.000 claims description 5
- -1 Sulphur ketone Chemical class 0.000 claims description 4
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 claims description 3
- LULAYUGMBFYYEX-UHFFFAOYSA-N metachloroperbenzoic acid Natural products OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- YVLHCANJHJUCJK-UHFFFAOYSA-N methyl 2-methyl-4-methylsulfonylbenzoate Chemical class COC(=O)C1=CC=C(S(C)(=O)=O)C=C1C YVLHCANJHJUCJK-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical class OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 abstract description 7
- PVFOHMXILQEIHX-UHFFFAOYSA-N 8-[(6-bromo-1,3-benzodioxol-5-yl)sulfanyl]-9-[2-(2-bromophenyl)ethyl]purin-6-amine Chemical compound C=1C=2OCOC=2C=C(Br)C=1SC1=NC=2C(N)=NC=NC=2N1CCC1=CC=CC=C1Br PVFOHMXILQEIHX-UHFFFAOYSA-N 0.000 abstract 2
- 239000000843 powder Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 5
- 240000008042 Zea mays Species 0.000 description 5
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 5
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 5
- 235000005822 corn Nutrition 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 4
- 239000005578 Mesotrione Substances 0.000 description 4
- KPUREKXXPHOJQT-UHFFFAOYSA-N mesotrione Chemical compound [O-][N+](=O)C1=CC(S(=O)(=O)C)=CC=C1C(=O)C1C(=O)CCCC1=O KPUREKXXPHOJQT-UHFFFAOYSA-N 0.000 description 4
- KFUSEUYYWQURPO-UHFFFAOYSA-N 1,2-dichloroethene Chemical compound ClC=CCl KFUSEUYYWQURPO-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- QNEFNFIKZWUAEQ-UHFFFAOYSA-N carbonic acid;potassium Chemical compound [K].OC(O)=O QNEFNFIKZWUAEQ-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- ZUVPLKVDZNDZCM-UHFFFAOYSA-N 3-chloro-2-methylaniline Chemical compound CC1=C(N)C=CC=C1Cl ZUVPLKVDZNDZCM-UHFFFAOYSA-N 0.000 description 2
- 241000209504 Poaceae Species 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- ITGSCCPVERXFGN-UHFFFAOYSA-N isoxadifen Chemical compound C1C(C(=O)O)=NOC1(C=1C=CC=CC=1)C1=CC=CC=C1 ITGSCCPVERXFGN-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000009333 weeding Methods 0.000 description 2
- IBSQPLPBRSHTTG-UHFFFAOYSA-N 1-chloro-2-methylbenzene Chemical compound CC1=CC=CC=C1Cl IBSQPLPBRSHTTG-UHFFFAOYSA-N 0.000 description 1
- PNKKBIPGTDLSFF-UHFFFAOYSA-N 2-chloro-5-methyl-4-methylsulfonyl-3-(2,2,2-trifluoroethoxy)benzoic acid Chemical compound ClC1=C(C(=O)O)C=C(C(=C1OCC(F)(F)F)S(=O)(=O)C)C PNKKBIPGTDLSFF-UHFFFAOYSA-N 0.000 description 1
- WEKZLBGODVDBBZ-UHFFFAOYSA-N 2-methyl-4-methylsulfonylbenzoic acid Chemical compound CC1=CC(S(C)(=O)=O)=CC=C1C(O)=O WEKZLBGODVDBBZ-UHFFFAOYSA-N 0.000 description 1
- PJERCKGJJBCWEC-UHFFFAOYSA-N 2-prenyl-1,4-benzoquinone Chemical compound CC(C)=CCC1=CC(=O)C=CC1=O PJERCKGJJBCWEC-UHFFFAOYSA-N 0.000 description 1
- OPXYNEYEDHAXOM-UHFFFAOYSA-N 3-oxobutanenitrile Chemical compound CC(=O)CC#N OPXYNEYEDHAXOM-UHFFFAOYSA-N 0.000 description 1
- 241000207894 Convolvulus arvensis Species 0.000 description 1
- 244000214240 Galinsoga parviflora Species 0.000 description 1
- 235000018914 Galinsoga parviflora Nutrition 0.000 description 1
- 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 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 241001504654 Mustela nivalis Species 0.000 description 1
- 231100000674 Phytotoxicity Toxicity 0.000 description 1
- 239000005620 Tembotrione Substances 0.000 description 1
- 239000005622 Thiencarbazone Substances 0.000 description 1
- 241000159750 Urtica cannabina Species 0.000 description 1
- 240000005592 Veronica officinalis Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 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 description 1
- 208000006278 hypochromic anemia Diseases 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 231100000566 intoxication Toxicity 0.000 description 1
- 230000035987 intoxication Effects 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 231100001224 moderate toxicity Toxicity 0.000 description 1
- 230000017074 necrotic cell death Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- IUQAXCIUEPFPSF-UHFFFAOYSA-N tembotrione Chemical compound ClC1=C(COCC(F)(F)F)C(S(=O)(=O)C)=CC=C1C(=O)C1C(=O)CCCC1=O IUQAXCIUEPFPSF-UHFFFAOYSA-N 0.000 description 1
- GLDAZAQRGCSFNP-UHFFFAOYSA-N thiencarbazone Chemical compound O=C1N(C)C(OC)=NN1C(=O)NS(=O)(=O)C1=C(C)SC=C1C(O)=O GLDAZAQRGCSFNP-UHFFFAOYSA-N 0.000 description 1
- XSKZXGDFSCCXQX-UHFFFAOYSA-N thiencarbazone-methyl Chemical group COC(=O)C1=CSC(C)=C1S(=O)(=O)NC(=O)N1C(=O)N(C)C(OC)=N1 XSKZXGDFSCCXQX-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a kind of synthesis technology of herbicide tembotrions; it include: that the chloro- 3- methyl -4- methyl sulfonylbenzoic acid methyl esters of 2-, solvent, catalyst, hydrobromic acid 1) is first added; then hydrogen peroxide is added dropwise; it washes, be concentrated after reaction, recrystallization, obtaining the chloro- 3- bromomethyl -4- methyl sulfonylbenzoic acid methyl esters of bromo-derivative 2-；2) by bromo-derivative, alkali 1, catalyst, solvent, 2,2,2- trifluoroethanols are reacted, are filtered after reaction, are washed, concentration；Alkali 2, water is added, is acidified after reaction, filters, the chloro- 3- of etherate 2- (2,2,2- trifluoro ethoxy) methyl -4- methyl sulfonylbenzoic acid is dried to obtain in washing；3) solvent will be taken off after etherate, catalyst, thionyl chloride, solvent reaction；It is added 1, triethylamine is added dropwise in hydroresorcinol, solvent；Acetone cyanohydrin is added after reaction, washes, layering, oil reservoir takes off solvent, and solubilizer is recrystallized, and buff white solid tembotrions are dried to obtain in filtering.The present invention improves the yield of intermediate, more environmentally friendly, safer, reduction production cost.
Description
Technical field:
The invention belongs to the preparation fields of pesticide original medicine, and in particular to a kind of synthesis technology of herbicide tembotrions.
Background technique:
Herbicide tembotrions (Tembotrione), chemical name: 2- { chloro- 4- mesyl -3- [(2,2, the 2- trifluoros of 2-
Ethyoxyl) methyl] benzoyl } hexamethylene -1,3- diketone is by Beyer Co., Ltd's three ketones cornfield weeding developed in 2007
Agent, activity is higher than nitre sulphur ketone (mesotrione, mesotrione), to crop safety.Tembotrions are mainly used for corn field, are buds
HPPD (p-hydroxyphenypyruvate dioxydenase) inhibitor class herbicide afterwards, can block the life of prenyl quinone in plant body
Object synthesis, causes chlorosis, colour fading, tissue necrosis, finally dead within 2 weeks.Tembotrions herbicidal spectrum is wide, weeding optimum period is long, mainly
The various broadleaf weeds of middle and advanced stage and gramineae weed after target corn field bud, to Ji, field bindweed, Veronica, smallflower galinsoga herb, weasel hemp nettle
It is excellent with the preventive effects such as clearvers, and to succession crop without phytotoxicity, it is one of most important herbicide in american corn field, every season is maximum
Dosage is 100g/hm2, main dosage form are as follows: dispersible oil-suspending agent.
There are also mesotrione, sulphur humulone, benzobicylon etc., tembotrions for the triketone structure HPPD class herbicide developed at present
Activity be higher than mesotrione, compared to other kinds, tembotrions have a very strong killing effect to a variety of weeds, and noresidue is living
Property, there is stronger ability to resist splash erosion, and herbicidal spectrum is wider.
2007, tembotrions obtained registration in Austria first, joined safener isoxadifen in product
(isoxadifen), trade name Laudis, for preventing and kill off corn field gramineae weed and broadleaf weeds；In the same year, the product is also
Registration is obtained in the U.S. and Hungary；It is registered in Brazil within 2008；It is registered in Portugal within 2009.2010, tembotrions and thiophene
The compound product Capreno of ketone sulphur grand (thiencarbazone) is listed in the U.S., is obtained in Europe and Latin America thereafter further
Registration.
The patent No. CN1323292A of Beyer Co., Ltd, which is reported, synthesizes tembotrions by starting material of 2,6- dichlorotoleune
Technique, using NBS as bromating agent, has a large amount of solid when preparation 2- chloro- 3- bromomethyl -4- methyl sulfonylbenzoic acid methyl esters
It is useless to generate, and yield is relatively low, only 67%.
The patent No. CN105601548A of Heilongjiang University, which is reported, synthesizes ring by starting material of 3- chloro-2-methyl aniline
The technique of sulphur ketone is when preparing 2- chloro- 3- bromomethyl -4- methyl sulfonylbenzoic acid methyl esters, and using expensive NBS as bromination
Agent has a large amount of solid wastes and generates, and yield is relatively low, and only 75.2%.
The patent No. CN104292137A of Wuhan Engineering Univ, which is reported, synthesizes tembotrions by starting material of 2- chlorotoluene
Technique, when preparing 2- chloro- 3- bromomethyl -4- methyl sulfonylbenzoic acid methyl esters, using the biggish bromine of risk as bromine
Agent, yield is relatively low, and only 70%；Preparing the chloro- 3- of 2- (2,2,2- trifluoro ethoxy) methyl -4- methyl sulfonylbenzoic acid
When, used 2,2,2- trifluoroethanols can not be mass produced at present, can't buy raw material；When preparing tembotrions, make
Prohibitively expensive, the high production cost with cyano propanone price, and the chloro- 3- of intermediate state 2- (2,2,2- trifluoro ethoxy) methyl -4-
Methyl sulfonylbenzoic acid -3- oxo -1- hexamethylene enester is separately separated processing, causes technique cumbersome, and yield is relatively low, and only 69%.
The patent No. CN106008290A of Anhui agriculture limited liability company easy long reports the synthesis technology of tembotrions,
When preparing the chloro- 3- of 2- (2,2,2- trifluoro ethoxy) methyl -4- methyl sulfonylbenzoic acid, used 2,2,2- trifluoroethanols
It can not be mass produced at present, can't buy raw material；When preparing tembotrions, used expensive condensing agent, and dosage compared with
Greatly, synthesis cost is higher.
" pesticide " the 5th phase of volume 56 reports the synthesis technology of corn field herbicide tembotrions, in the synthesis chloro- 3- bromine first of 2-
When base -4- methyl sulfonylbenzoic acid methyl esters, using the biggish bromine of risk as bromating agent；In the synthesis chloro- 3- (2,2,2- of 2-
Trifluoro ethoxy) methyl -4- methyl sulfonylbenzoic acid when, having used sodium methoxide is raw material, and sodium methoxide is inflammable, explosive, right
Air and moisture-sensitive meet water and resolve into methanol and sodium hydroxide rapidly, and use condition is harsh in course of industrialization, in tembotrions
Synthesis when used acetonitrile, acetonitrile belongs to control class moderate toxicity chemicals and holds in the process of reproduction because of highly volatile
Easily cause slow poisoning accident.
Summary of the invention:
The purpose of the present invention is to shortcomings existing for the above method, provide a kind of synthesis of herbicide tembotrions
Technique, by improving its process route, replaces high risk chemistry using low dangerous chemical product from production safety angle
Product replace high poison chemicals using less toxic chemicals, simplify technical process, improve yield, reduce synthesis cost, reduce
Three waste discharge is suitble to industrial amplification production.
The present invention is achieved through the following technical solutions:
A kind of synthesis technology of herbicide tembotrions, includes following steps:
1) synthesis of the chloro- 3- bromomethyl -4- methyl sulfonylbenzoic acid methyl esters of 2-
Reaction flask is added in the chloro- 3- methyl -4- methyl sulfonylbenzoic acid methyl esters of 2-, solvent, catalyst, hydrobromic acid, 80
DEG C or less be added dropwise hydrogen peroxide, be added dropwise after the reaction was continued, LC tracks to fully reacting, is layered after fully reacting, organic layer water
It washes, is concentrated, solubilizer is recrystallized, and the chloro- 3- bromomethyl -4- methyl sulfonylbenzoic acid methyl esters of 2- is filtered to obtain；
2) synthesis of the chloro- 3- of 2- (2,2,2- trifluoro ethoxy) methyl -4- methyl sulfonylbenzoic acid
The chloro- 3- bromomethyl -4- methyl sulfonylbenzoic acid methyl esters of 2-, alkali 1, catalyst, solvent, 2,2,2 tfifluoroethyl alcohol are added
Enter reaction flask, reacted at 80 DEG C or less, LC tracks to fully reacting, filters after completion of the reaction, organic layer washing, concentration；
Add alkali 2, water in toward residue, in 80 DEG C or less progress alkaline hydrolysis, LC tracks to fully reacting, and hydrochloric acid acid is added dropwise after fully reacting
Change, filter, the chloro- 3- of 2- (2,2,2- trifluoro ethoxy) methyl -4- methyl sulfonylbenzoic acid is dried to obtain in washing；
3) synthesis of tembotrions
By the chloro- 3- of 2- (2,2,2- trifluoro ethoxy) methyl -4- methyl sulfonylbenzoic acid, catalyst, thionyl chloride, solvent
Reaction flask is added, temperature rising reflux reaction takes off solvent after completion of the reaction；By 1, reaction flask is added in hydroresorcinol, solvent, 30
DEG C or less triethylamine is added dropwise, LC tracks to fully reacting；After fully reacting, acetone cyanohydrin is added, LC tracks to fully reacting, instead
Water should be added afterwards completely to be washed, be layered, oil reservoir takes off solvent, and solubilizer is recrystallized, filtering, dry ecru is solid
Body tembotrions.
Preferably, in step 1), the chloro- 3- methyl -4- methyl sulfonylbenzoic acid methyl esters of 2-, catalyst, hydrobromic acid, hydrogen peroxide
Molar ratio be 1:0.01~0.1:1~2:1~2.
Further, in step 1), the catalyst is azodiisobutyronitrile or metachloroperbenzoic acid；The drop of hydrogen peroxide
Heating degree is 45~80 DEG C.
Further, in step 1), the reaction dissolvent is methylene chloride, 1,2- dichloroethanes or chloroform；The crystallization
Solvent is methanol, ethyl alcohol, isopropanol or n-butanol.
Preferably, in step 2), the chloro- 3- bromomethyl -4- methyl sulfonylbenzoic acid methyl esters of 2-, alkali 1, catalyst, 2,2,2-
Trifluoroethanol, alkali 2 molar ratio be 1:1~2:0.01~0.1:1~2:1~2.
Further, in step 2), the alkali 1 is potassium carbonate；The catalyst is three second of triethylene diamine or 2- methyl
Alkene diamines；The alkali 2 is sodium hydroxide, potassium hydroxide or lithium hydroxide.
Further, solvent described in step 2) is acetonitrile, DMF, acetone or tetrahydrofuran；Reaction temperature is 0~80 DEG C.
Preferably, in step 3), the chloro- 3- of 2- (2,2,2- trifluoro ethoxy) methyl -4- methyl sulfonylbenzoic acid, catalysis
Agent, thionyl chloride, hydroresorcinol, triethylamine, acetone cyanohydrin molar ratio be 1:0.01~0.1:1~2:1~2:2~3:
0.01~0.1.
Further, in step 3), the dropping temperature of triethylamine is 0~30 DEG C.
Further, in step 3), catalyst DMF；Recrystallisation solvent is methanol, ethyl alcohol, isopropanol or n-butanol.
Reaction equation according to the present invention is as follows:
The beneficial effects of the present invention are:
1. being with cheap hydrobromic acid when preparation 2- chloro- 3- bromomethyl -4- methyl sulfonylbenzoic acid methyl esters
Bromating agent reduces security risk, improves yield, reduces production cost.
2. when preparing the chloro- 3- of 2- (2,2,2- trifluoro ethoxy) methyl -4- methyl sulfonylbenzoic acid, in market
On 2,2, the 2- trifluoroethanols that are easy to get be raw material so that the technique has the feasibility of industrialized production.
3. replacing acetonitrile using DMF when the synthesis of tembotrions, low toxicity replaces high poison chemicals, reduces production process
Middle intoxication accident occurs.
4. being raw material without using inflammable, explosive, deliquescent sodium methoxide, production safety risk is reduced, it is easier to industry
Metaplasia produces.
Specific embodiment:
Present aspect is further described in detail below with reference to embodiment, but this explanation will not be constituted to present aspect
Limitation.
Embodiment 1
The present embodiment provides a kind of synthesis technologies of tembotrions, comprising the following steps:
1, the synthesis of the chloro- 3- bromomethyl -4- methyl sulfonylbenzoic acid methyl esters of 2-
By the chloro- 3- methyl -4- methyl sulfonylbenzoic acid methyl esters of 40g 2- (99.6%, 0.152mol), bis- chloroethene of 200ml
Alkane, 1g azodiisobutyronitrile (99%, 0.006mol), 46g hydrobromic acid (48%, 0.273mol) are added in 500ml reaction flask,
75~80 DEG C of dropwise addition 20.6g hydrogen peroxide (30%, 0.182mol), the reaction was continued after being added dropwise, and LC tracks to fully reacting, instead
It should be layered afterwards completely, organic layer washing, concentration, isopropanol are recrystallized, filtered, dried and to obtain 46.67g white powder, purity
99.0%, yield 89%.
2, the synthesis of the chloro- 3- of 2- (2,2,2- trifluoro ethoxy) methyl -4- methyl sulfonylbenzoic acid
By the chloro- 3- bromomethyl -4- methyl sulfonylbenzoic acid methyl esters of 30g 2- (99.0%, 0.0869mol), 18g potassium carbonate
(99%, 0.1289mol), 0.9g triethylene diamine (99%, 0.0079mol), 200ml tetrahydrofuran, 10.5g 2,2,2- tri-
Fluoroethanol (99%, 0.1039mol) is added in 500ml reaction flask, is reacted at 75~80 DEG C, and LC tracks to fully reacting,
It filters after completion of the reaction, filtrate concentration.6g sodium hydroxide (99%, 0.1485mol), 200ml water, 70~75 in toward residue
DEG C alkaline hydrolysis is carried out, LC tracks to fully reacting, and hydrochloric acid acidification is added dropwise after fully reacting, filters, and washing dries to obtain 27.6g white
Powder, purity 99.7%, yield 91.3%.
3, the synthesis of tembotrions
By the chloro- 3- of 27.4g 2- (2,2,2- trifluoro ethoxy) methyl -4- methyl sulfonylbenzoic acid (99.7%,
0.0788mol), 0.2g DMF (99%, 0.0027mol), 12.3g thionyl chloride (99%, 0.102mol), bis- chloroethene of 100ml
Alkane is added in 250ml reaction flask, and temperature rising reflux reaction takes off solvent after completion of the reaction.By 9.5g hydroresorcinol (99%,
0.084mol), reaction flask is added in 100ml dichloroethanes, in 25~30 DEG C of dropwise addition 18.5g triethylamines (99%, 0.18mol), LC
Track to fully reacting.It after fully reacting, is added 1g acetone cyanohydrin (95%, 0.011mol), LC tracks to fully reacting, reaction
Water is added after completely to be washed, is layered, oil reservoir takes off solvent, methanol is added to be recrystallized, and filters, and dries to obtain 30.3g cream colour
Color crystalline powder, purity 98.6%, yield 86%.
Embodiment 2
The present embodiment provides a kind of synthesis technologies of tembotrions, comprising the following steps:
1, the synthesis of the chloro- 3- bromomethyl -4- methyl sulfonylbenzoic acid methyl esters of 2-
By the chloro- 3- methyl -4- methyl sulfonylbenzoic acid methyl esters of 40g 2- (99.7%, 0.152mol), 200ml dichloromethane
Alkane, 0.5g azodiisobutyronitrile (99%, 0.003mol), 34g hydrobromic acid (48%, 0.202mol) are added in 500ml reaction flask,
In 45~50 DEG C of dropwise addition 25g hydrogen peroxide (30%, 0.22mol), the reaction was continued after being added dropwise, and LC tracks to fully reacting, instead
It should be layered afterwards completely, organic layer washing, concentration, ethyl alcohol are recrystallized, filtered, dried and to obtain 46g white powder, purity
99.8%, yield 88.5%.
2, the synthesis of the chloro- 3- of 2- (2,2,2- trifluoro ethoxy) methyl -4- methyl sulfonylbenzoic acid
By the chloro- 3- bromomethyl -4- methyl sulfonylbenzoic acid methyl esters of 35g 2- (99.8%, 0.102mol), 21.41g carbonic acid
Potassium (99%, 0.153mol), 1g triethylene diamine (99%, 0.008mol), 200ml DMF, 15.46g2,2,2- trifluoroethanol
(99%, 0.153mol) is added in 500ml reaction flask, is reacted at 70~75 DEG C, LC tracks to fully reacting, end of reaction
After filter, filtrate concentration.4.53g sodium hydroxide (99%, 0.112mol) in toward residue, 200ml water are carried out at 70~75 DEG C
Alkaline hydrolysis, LC track to fully reacting, and hydrochloric acid acidification is added dropwise after fully reacting, filters, and 31.82g white powder is dried to obtain in washing,
Purity 99.8%, yield 89.6%.
3, the synthesis of tembotrions
By the chloro- 3- of 30g 2- (2,2,2- trifluoro ethoxy) methyl -4- methyl sulfonylbenzoic acid (99.8%,
0.086mol), 0.3g DMF (99%, 0.004mol), 12.4g thionyl chloride (99%, 0.103mol), 100ml dichloroethanes
It is added in 250ml reaction flask, temperature rising reflux reaction takes off solvent after completion of the reaction.By 14.6g hydroresorcinol (99%,
0.129mol), reaction flask is added in 100ml methylene chloride, in 20~25 DEG C of dropwise addition 21.97g triethylamines (99%, 0.215mol),
LC tracks to fully reacting.After fully reacting, it is added 1g acetone cyanohydrin (95%, 0.011mol), LC tracks to fully reacting, instead
Water should be added afterwards completely to be washed, be layered, oil reservoir takes off solvent, ethyl alcohol is added to be recrystallized, and filters, dries to obtain 32.63g meters
Yellow crystalline powder, purity 98.1%, yield 84.1%.
Embodiment 3
The present embodiment provides a kind of synthesis technologies of tembotrions, comprising the following steps:
1, the synthesis of the chloro- 3- bromomethyl -4- methyl sulfonylbenzoic acid methyl esters of 2-
By the chloro- 3- methyl -4- methyl sulfonylbenzoic acid methyl esters of 26.46g 2- (99.6%, 0.1mol), bis- chloroethene of 200ml
500ml reaction is added in alkane, 0.174g metachloroperbenzoic acid (99%, 0.001mol), 16.88g hydrobromic acid (48%, 0.1mol)
In bottle, in 50~55 DEG C of dropwise addition 11.33g hydrogen peroxide (30%, 0.1mol), the reaction was continued after being added dropwise, and LC tracks to reaction
Completely, it is layered after fully reacting, organic layer washing, concentration, isopropanol are recrystallized, filtered, dried and to obtain 31.33g white powder
End, purity 98.0%, yield 90%.
2, the synthesis of the chloro- 3- of 2- (2,2,2- trifluoro ethoxy) methyl -4- methyl sulfonylbenzoic acid
By the chloro- 3- bromomethyl -4- methyl sulfonylbenzoic acid methyl esters of 34.5g 2- (99.0%, 0.1mol), 13.94g carbonic acid
Potassium (99%, 0.1mol), 0.226g triethylene diamine (99%, 0.001mol), 200ml acetone, 10.1g 2,2,2- trifluoro second
Alcohol (99%, 0.1mol) is added in 500ml reaction flask, is reacted at 0~5 DEG C, LC tracks to fully reacting, after completion of the reaction
Filtering, filtrate concentration.4.04g sodium hydroxide (99%, 0.1mol) in toward residue, 200ml water, in 70~75 DEG C of progress alkali
Solution, LC track to fully reacting, and hydrochloric acid acidification is added dropwise after fully reacting, filters, and 31.58g white powder is dried to obtain in washing, pure
Degree 99.3%, yield 90.5%.
3, the synthesis of tembotrions
By the chloro- 3- of 34.75g 2- (2,2,2- trifluoro ethoxy) methyl -4- methyl sulfonylbenzoic acid (99.7%,
0.1mol), 0.074g DMF (99%, 0.001mol), 12g thionyl chloride (99%, 0.1mol), 100ml dichloroethanes are added
In 250ml reaction flask, temperature rising reflux reaction takes off solvent after completion of the reaction.By 11.3g hydroresorcinol (99%,
0.1mol), reaction flask is added in 100ml dichloroethanes, and in 0~5 DEG C of dropwise addition 20.4g triethylamine (99%, 0.2mol), LC is tracked to
Fully reacting.After fully reacting, it is added 0.09g acetone cyanohydrin (95%, 0.001mol), LC tracks to fully reacting, has reacted
Water is added after complete to be washed, is layered, oil reservoir takes off solvent, methanol is added to be recrystallized, and filters, dries to obtain 37.94g ecru
Crystalline powder, purity 98.7%, yield 85%.
Embodiment 4
The present embodiment provides a kind of synthesis technologies of tembotrions, comprising the following steps:
1, the synthesis of the chloro- 3- bromomethyl -4- methyl sulfonylbenzoic acid methyl esters of 2-
By the chloro- 3- methyl -4- methyl sulfonylbenzoic acid methyl esters of 26.43g 2- (99.7%, 0.1mol), 200ml chloroform,
1.66g azodiisobutyronitrile (99%, 0.01mol), 33.75g hydrobromic acid (48%, 0.2mol) are added in 500ml reaction flask,
60~65 DEG C of dropwise addition 22.7g hydrogen peroxide (30%, 0.2mol), the reaction was continued after being added dropwise, and LC tracks to fully reacting, reaction
Layering after completely, organic layer washing, concentration, ethyl alcohol are recrystallized, are filtered, being dried and to be obtained 30.66g white powder, purity
98.8%, yield 88.7%.
2, the synthesis of the chloro- 3- of 2- (2,2,2- trifluoro ethoxy) methyl -4- methyl sulfonylbenzoic acid
By the chloro- 3- bromomethyl -4- methyl sulfonylbenzoic acid methyl esters of 34.2g 2- (99.8%, 0.1mol), 27.88g carbonic acid
Potassium (99%, 0.2mol), 2.26g triethylene diamine (99%, 0.01mol), 200ml DMF, 1.13g2,2,2- trifluoroethanol
(99%, 0.2mol) is added in 500ml reaction flask, is reacted at 20~25 DEG C, LC tracks to fully reacting, after completion of the reaction
Filtering, filtrate concentration.8.1g sodium hydroxide (99%, 0.2mol) in toward residue, 200ml water, in 70~75 DEG C of progress alkaline hydrolysis,
LC tracks to fully reacting, and hydrochloric acid acidification is added dropwise after fully reacting, filters, and 31.1g white powder, purity are dried to obtain in washing
99.5%, yield 89.3%.
3, the synthesis of tembotrions
By the chloro- 3- of 34.72g 2- (2,2,2- trifluoro ethoxy) methyl -4- methyl sulfonylbenzoic acid (99.8%,
0.1mol), 0.74g DMF (99%, 0.01mol), 24g thionyl chloride (99%, 0.2mol), 100ml dichloroethanes are added
In 250ml reaction flask, temperature rising reflux reaction takes off solvent after completion of the reaction.By 22.6g hydroresorcinol (99%,
0.2mol), reaction flask is added in 100ml methylene chloride, in 5~10 DEG C of dropwise addition 30.6g triethylamines (99%, 0.3mol), LC tracking
To fully reacting.After fully reacting, it is added 0.89g acetone cyanohydrin (95%, 0.01mol), LC tracks to fully reacting, has reacted
Water is added after complete to be washed, is layered, oil reservoir takes off solvent, ethyl alcohol is added to be recrystallized, and filters, dries to obtain 38.1g ecru
Crystalline powder, purity 98.7%, yield 85.4%.
Comparative example
1, the synthesis of the chloro- 3- bromomethyl -4- methyl sulfonylbenzoic acid methyl esters of 2-
The chloro- 3- methyl -4- methyl sulfonylbenzoic acid methyl esters of 13.1g (0.05mol) 2- is weighed in 500mL four-hole boiling flask,
180mL carbon tetrachloride is added, 8.8g (0.055mol) bromine is added dropwise in temperature rising reflux, and insulation reaction 4h stops reaction, cooling, mistake
Filter, filtrate are concentrated to give faint yellow solid 15g, yield 88%.
2, the synthesis of the chloro- 3- of 2- (2,2,2- trifluoro ethoxy) methyl -4- methyl sulfonylbenzoic acid
5.4g (0.1mol) sodium methoxide is claimed in 120mLDMF, is added in four-hole boiling flask, is cooled to 15 DEG C, trifluoro is added dropwise
After drop finishes, the chloro- 3- bromomethyl -4- methyl sulfonylbenzoic acid methyl esters of 2- is added in ethyl alcohol, and reaction overnight, steams DMF at room temperature, cold
But 100mL ethyl alcohol is added afterwards, 10%NaOH solution 40mL is added dropwise, flow back 1h after drop is complete, and end of reaction steams ethyl alcohol, with HCL tune
To acidity, yellow solid is precipitated, yield 83.2%.
3, the synthesis of tembotrions
34.6g (0.1mol) 2- chloro- 3- (2,2,2- trifluoro ethoxy) methyl -4- methyl sulfonylbenzoic acid is dissolved in
The thionyl chloride of 60g (0.5mol), back flow reaction 5h, then whole solvent and excessive chlorination out is added dropwise in methylene chloride in 200ml
The dissolution of 150ml acetonitrile is added in sulfoxide, raffinate, and 13.44g (0.12mol) 1, hydroresorcinol and 4 drop acetone cyanohydrins are then added.
16h is stirred at room temperature.Filtering, filtrate concentration, is added 150ml water, and after being adjusted to PH=2 with 2mol/L hydrochloric acid, filtering, drying are obtained yellow
Color solid 35g.Yield is 80%.
By embodiment it is found that hydrobromic acid is used to replace bromine as bromine during preparing tembotrions compared with comparative example
Agent is avoided using acetonitrile, the hazardous chemicals such as sodium methoxide, and the core of this patent is using hypotoxicity, low dangerous chemical product
Tembotrions are prepared, the factors such as risk factor in production process, slow poisoning are reduced；Implementing discovery by experiment simultaneously can take
It is also unexpected for obtaining higher yield.
Claims (10)
1. a kind of synthesis technology of herbicide tembotrions, includes following steps:
1) synthesis of the chloro- 3- bromomethyl -4- methyl sulfonylbenzoic acid methyl esters of 2-
By the chloro- 3- methyl -4- methyl sulfonylbenzoic acid methyl esters of 2-, solvent, catalyst, hydrobromic acid be added reaction flask, 80 DEG C with
Lower dropwise addition hydrogen peroxide, the reaction was continued after being added dropwise, and LC tracks to fully reacting, is layered after fully reacting, organic layer washing, dense
Contracting, solubilizer are recrystallized, and the chloro- 3- bromomethyl -4- methyl sulfonylbenzoic acid methyl esters of 2- is filtered to obtain；
2) synthesis of the chloro- 3- of 2- (2,2,2- trifluoro ethoxy) methyl -4- methyl sulfonylbenzoic acid
The chloro- 3- bromomethyl -4- methyl sulfonylbenzoic acid methyl esters of 2-, alkali 1, catalyst, solvent, 2,2,2 tfifluoroethyl alcohol are added anti-
Bottle is answered, is reacted at 80 DEG C or less, LC tracks to fully reacting, filters after completion of the reaction, organic layer washing, concentration；It is past surplus
Add alkali 2, water in excess, in 80 DEG C or less progress alkaline hydrolysis, LC tracks to fully reacting, and hydrochloric acid acidification, mistake are added dropwise after fully reacting
Filter, washing, dries to obtain the chloro- 3- of 2- (2,2,2- trifluoro ethoxy) methyl -4- methyl sulfonylbenzoic acid；
3) synthesis of tembotrions
The chloro- 3- of 2- (2,2,2- trifluoro ethoxy) methyl -4- methyl sulfonylbenzoic acid, catalyst, thionyl chloride, solvent are added
Reaction flask, temperature rising reflux reaction, takes off solvent after completion of the reaction；By 1, reaction flask is added in hydroresorcinol, solvent, 30 DEG C with
Lower dropwise addition triethylamine, LC track to fully reacting；After fully reacting, acetone cyanohydrin is added, LC tracks to fully reacting, reacted
Water is added after complete to be washed, is layered, oil reservoir takes off solvent, and solubilizer is recrystallized, and buff white solid ring is dried to obtain in filtering
Sulphur ketone.
2. the synthesis technology of herbicide tembotrions according to claim 1, which is characterized in that in step 1), the chloro- 3- first of 2-
Base -4- methyl sulfonylbenzoic acid methyl esters, catalyst, hydrobromic acid, hydrogen peroxide molar ratio be 1:0.01~0.1:1~2:1~2.
3. the synthesis technology of herbicide tembotrions according to claim 1 or 2, which is characterized in that described to urge in step 1)
Agent is azodiisobutyronitrile or metachloroperbenzoic acid；The dropping temperature of hydrogen peroxide is 45~80 DEG C.
4. the synthesis technology of herbicide tembotrions according to claim 1 or 2, which is characterized in that described anti-in step 1)
Answering solvent is methylene chloride, 1,2- dichloroethanes or chloroform；The recrystallisation solvent is methanol, ethyl alcohol, isopropanol or n-butanol.
5. the synthesis technology of herbicide tembotrions according to claim 1, which is characterized in that in step 2), the chloro- 3- bromine of 2-
Methyl -4- methyl sulfonylbenzoic acid methyl esters, alkali 1, catalyst, 2,2,2 tfifluoroethyl alcohol, alkali 2 molar ratio be 1:1~2:0.01
~0.1:1~2:1~2.
6. the synthesis technology of herbicide tembotrions according to claim 1 or 5, which is characterized in that in step 2), the alkali
1 is potassium carbonate；The catalyst is triethylene diamine or 2- methyl triethylene diamine；The alkali 2 is sodium hydroxide, potassium hydroxide
Or lithium hydroxide.
7. the synthesis technology of herbicide tembotrions according to claim 1 or 5, which is characterized in that molten described in step 2)
Agent is acetonitrile, DMF, acetone or tetrahydrofuran；Reaction temperature is 0~80 DEG C.
8. the synthesis technology of herbicide tembotrions according to claim 1, which is characterized in that in step 3), the chloro- 3- of 2-
(2,2,2- trifluoro ethoxy) methyl -4- methyl sulfonylbenzoic acid, catalyst, thionyl chloride, hydroresorcinol, triethylamine,
The molar ratio of acetone cyanohydrin is 1:0.01~0.1:1~2:1~2:2~3:0.01~0.1.
9. the synthesis technology of herbicide tembotrions according to claim 1 or 8, which is characterized in that in step 3), triethylamine
Dropping temperature be 0~30 DEG C.
10. according to claim 1 or the synthesis technology of herbicide tembotrions described in 9, which is characterized in that in step 3), catalysis
Agent is DMF；Recrystallisation solvent is methanol, ethyl alcohol, isopropanol or n-butanol.
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