CN108003133A - A kind of 2- hydroxyls -6- fluorine Thiochromone compound and its synthetic method and the application in weeding - Google Patents
A kind of 2- hydroxyls -6- fluorine Thiochromone compound and its synthetic method and the application in weeding Download PDFInfo
- Publication number
- CN108003133A CN108003133A CN201610949296.0A CN201610949296A CN108003133A CN 108003133 A CN108003133 A CN 108003133A CN 201610949296 A CN201610949296 A CN 201610949296A CN 108003133 A CN108003133 A CN 108003133A
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- CN
- China
- Prior art keywords
- compound
- fluorine
- formula
- alkyl
- thiochromone
- Prior art date
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- Pending
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- 238000010189 synthetic method Methods 0.000 title claims description 12
- 238000009333 weeding Methods 0.000 title description 10
- -1 fluorine Thiochromone compound Chemical class 0.000 claims abstract description 43
- 150000001875 compounds Chemical class 0.000 claims abstract description 40
- 230000002363 herbicidal effect Effects 0.000 claims abstract description 12
- 239000004009 herbicide Substances 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims abstract description 10
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 239000000460 chlorine Substances 0.000 claims abstract description 8
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 8
- 238000006467 substitution reaction Methods 0.000 claims abstract description 8
- 239000011737 fluorine Substances 0.000 claims abstract description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 6
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000004480 active ingredient Substances 0.000 claims abstract description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 3
- 239000011630 iodine Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical group O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical class CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 claims description 2
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 claims description 2
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 claims description 2
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical class CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- HTLZVHNRZJPSMI-UHFFFAOYSA-N N-ethylpiperidine Chemical compound CCN1CCCCC1 HTLZVHNRZJPSMI-UHFFFAOYSA-N 0.000 claims description 2
- MOFINMJRLYEONQ-UHFFFAOYSA-N [N].C=1C=CNC=1 Chemical group [N].C=1C=CNC=1 MOFINMJRLYEONQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 239000003085 diluting agent Substances 0.000 claims description 2
- 238000010413 gardening Methods 0.000 claims description 2
- 238000002955 isolation Methods 0.000 claims description 2
- USSBDBZGEDUBHE-UHFFFAOYSA-L magnesium;2-oxidooxycarbonylbenzoate Chemical compound [Mg+2].[O-]OC(=O)C1=CC=CC=C1C([O-])=O USSBDBZGEDUBHE-UHFFFAOYSA-L 0.000 claims description 2
- LULAYUGMBFYYEX-UHFFFAOYSA-N metachloroperbenzoic acid Natural products OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 238000007363 ring formation reaction Methods 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims 3
- HGNVEXMJZVUWJO-UHFFFAOYSA-N 3-methylhexan-3-amine Chemical compound CCCC(C)(N)CC HGNVEXMJZVUWJO-UHFFFAOYSA-N 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 150000004777 chromones Chemical class 0.000 claims 1
- 239000003937 drug carrier Substances 0.000 claims 1
- 229910052738 indium Inorganic materials 0.000 claims 1
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical class CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 229910001950 potassium oxide Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- 150000002576 ketones Chemical class 0.000 abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- 150000001408 amides Chemical class 0.000 abstract 1
- 230000004071 biological effect Effects 0.000 abstract 1
- 150000002148 esters Chemical group 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 10
- 230000003449 preventive effect Effects 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 0 C*c([n](C)c(I)n1)c1I Chemical compound C*c([n](C)c(I)n1)c1I 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 5
- YCDMZJGTEZGKPM-UHFFFAOYSA-N O1C=CC(C2=CC=CC=C12)=S.[Cl] Chemical compound O1C=CC(C2=CC=CC=C12)=S.[Cl] YCDMZJGTEZGKPM-UHFFFAOYSA-N 0.000 description 5
- TZIHFWKZFHZASV-UHFFFAOYSA-N anhydrous methyl formate Natural products COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 241000209510 Liliopsida Species 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- FLGZHHJNRZUPIL-UHFFFAOYSA-N chromene-4-thione Chemical class C1=CC=C2C(=S)C=COC2=C1 FLGZHHJNRZUPIL-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229930014626 natural product Natural products 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- 240000001592 Amaranthus caudatus Species 0.000 description 1
- 235000009328 Amaranthus caudatus Nutrition 0.000 description 1
- JBVKLEHZBZSXPT-QMMMGPOBSA-N CC(C)[C@H](CCNC(N)=C1C)C1=O Chemical compound CC(C)[C@H](CCNC(N)=C1C)C1=O JBVKLEHZBZSXPT-QMMMGPOBSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- MIADVEKJKCVMCN-UHFFFAOYSA-N Cc(c(C)c1)cc(C2O)c1NC(NC)=C2C(OC)=O Chemical compound Cc(c(C)c1)cc(C2O)c1NC(NC)=C2C(OC)=O MIADVEKJKCVMCN-UHFFFAOYSA-N 0.000 description 1
- DUAZFYUNWBILMU-UHFFFAOYSA-N Cc1c(C)[n](C)nc1C Chemical compound Cc1c(C)[n](C)nc1C DUAZFYUNWBILMU-UHFFFAOYSA-N 0.000 description 1
- VVJZQYADQJXKOC-UHFFFAOYSA-N Cc1nnc(N)[n]1C Chemical compound Cc1nnc(N)[n]1C VVJZQYADQJXKOC-UHFFFAOYSA-N 0.000 description 1
- 240000006122 Chenopodium album Species 0.000 description 1
- 235000009344 Chenopodium album Nutrition 0.000 description 1
- 244000058871 Echinochloa crus-galli Species 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
- 241000219926 Myrtaceae Species 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 241001529246 Platymiscium Species 0.000 description 1
- 235000010086 Setaria viridis var. viridis Nutrition 0.000 description 1
- 235000002594 Solanum nigrum Nutrition 0.000 description 1
- 240000002307 Solanum ptychanthum Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000004178 amaranth Substances 0.000 description 1
- 235000012735 amaranth Nutrition 0.000 description 1
- 230000001857 anti-mycotic effect Effects 0.000 description 1
- 239000002543 antimycotic Substances 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- JBDHZKLJNAIJNC-LLVKDONJSA-N clodinafop-propargyl Chemical group C1=CC(O[C@H](C)C(=O)OCC#C)=CC=C1OC1=NC=C(Cl)C=C1F JBDHZKLJNAIJNC-LLVKDONJSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 244000230342 green foxtail Species 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 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
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- YDWYMAHAWHBPPT-UHFFFAOYSA-N leptospermone Chemical compound CC(C)CC(=O)C1C(=O)C(C)(C)C(=O)C(C)(C)C1=O YDWYMAHAWHBPPT-UHFFFAOYSA-N 0.000 description 1
- PZTZKUAPDKQTOI-UHFFFAOYSA-N leptospermone Natural products CC(C)CC(=O)C1=C(O)C(C)(C)C(=O)C(C)(C)C1=O PZTZKUAPDKQTOI-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- RIVIDPPYRINTTH-UHFFFAOYSA-N n-ethylpropan-2-amine Chemical compound CCNC(C)C RIVIDPPYRINTTH-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229960003424 phenylacetic acid Drugs 0.000 description 1
- 239000003279 phenylacetic acid Substances 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
- C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D335/06—Benzothiopyrans; Hydrogenated benzothiopyrans
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
- A01N43/18—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with sulfur as the ring hetero atom
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Dentistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The present invention relates to a kind of 6 fluorine Thiochromone compound of 2 hydroxyl to have such as lower structure：Wherein R3It is ester, acid amides, ketone, C1‑C3The penta azacyclo of alkyl substitution；R4、R6It is independently selected from hydrogen, fluorine, chlorine, bromine or iodine；R5Selected from hydrogen, fluorine, chlorine, bromine, iodine, C1‑C6Oxyl, C1‑C6Hydrocarbon amino, C1‑C6Alkyl, phenoxy group, by one or more C1‑C6The phenoxy group of oxyl substitution.The compound of the present invention has broad-spectrum biological activity, is good herbicide；Activity experiment shows, under 85 grams of active ingredients/hectare dosage, part of compounds has good herbicide effect.
Description
Technical field
The present invention relates to a kind of antimycotic 2- hydroxyls -6- fluorine Thiochromone compound and its synthetic method with it in weeding
In application.
Background technology
The development trend of world today's pesticide is made a general survey of, herbicide is to study most rapid a kind of agriculturalization of most active, development
Product.At present, the herbicide of produced worldwide is wide in variety up to more than 300.Heterocyclic compound accounts for mainly in the development of herbicide
Status, accounts for 86%, with the in the majority of ultra high efficiency.Three ketones herbicide is more in the red fine layer platymiscium of Myrtaceae earliest
Poly- acetyl natural products leptospermone, this natural products are active to some broad-leaveds and grass, artificial as the beginning
Synthesize some derivatives and obtain patent in 1980.Nineteen eighty-two has synthesized the 1st kind sulphur humulone, and 1991 start pin
Sell, so as to start three ketones herbicide this frontier, then soon, by structural modification, synthesized another new work
The kind nitre sulphur ketone of property higher.While nitre sulphur ketone large-area applications, and synthesize more new high activity kinds, so as to open
The new situation of three ketones herbicide Cultivar development is created.
Activity research shows that Thiochromone compound has the thiochromone class of obvious activity of weeding, at present document report
Compound, more with synthesis obtain based on.To design and synthesize out more efficient, the wider array of Thiochromone compound of activity profile, root
Theoretical according to structural modification, we have carried out corresponding structural modification to benzo thiochromone.After 3 introduce different functional groups, then
Be changed into hydroxyl by 2, to it is to be synthesized go out a series of bioactivity and better choice and security with higher
- 6 fluorine Thiochromone compound of 2- hydroxyls.
The content of the invention
It is an object of the present invention to provide a kind of -6 fluorine Thiochromone compound of 2- hydroxyls and its synthetic method and in weeding
Using.
- 6 fluorine Thiochromone compound of 2- hydroxyls according to the present invention, its chemical constitution are as follows：
R3Selected from such as R3' or
Wherein R3' it is selected from one kind in five yuan of nitrogen azoles rings of formula (II)：
Wherein：J, K, L are separately selected from hydrogen, C1-C3Alkyl；
Wherein, Y is selected from C1-C6Oxyl, C1-C6Hydrocarbon amino, C1-C6Alkyl, phenyl, by one or more C1-C6
Alkyl or oxyl substitution phenyl, phenoxy group, by one or more C1-C6Alkyl or the phenoxy group of oxyl substitution；
R4、R6Separately selected from hydrogen, fluorine, chlorine, bromine or iodine；
R5Selected from hydrogen, fluorine, chlorine, bromine, iodine, C1-C6Oxyl, C1-C6Hydrocarbon amino, C1-C6Alkyl, phenoxy group, by 1
A or multiple C1-C6The phenoxy group of oxyl substitution；
2. compound according to claim 1, its feature compound includes its salt allowed on galenic pharmacy；
3. a kind of synthetic method of the formula of claim 1 (I) compound, it is characterized in that, compound (III) is dissolved in organic
In solvent, reacted with carbon disulfide, through condensation, after cyclization with C1-C6Halohydrocarbons reaction generation compound (V), compound (V)
Oxidized dose of oxidation generation compound (VI), then reacts to obtain solid product 2- hydroxyl -6- fluorine sulphur with alkali metal hydroxide
Chromone compounds；
The structural formula of the compound (III) is as follows：
The structural formula of the compound (V) is as follows：
The structural formula of the compound (VI) is as follows：
Wherein, X represents F or Cl；
R3、R4、R5、R6The same formula of definition (I)；
R7Selected from C1-C6Alkyl；
Z is selected from sulfinylSulfonyl
The organic solvent is selected from n,N-Dimethylformamide, n,N-dimethylacetamide, dimethyl sulfoxide, dioxane, second
At least one of nitrile, tetrahydrofuran, methanol, ethanol, isopropanol, tert-butyl alcohol.It is preferred that n,N-Dimethylformamide, dimethyl sulfoxide.
The oxidant is selected from manganese dioxide, potassium permanganate, potassium bichromate, hydrogen peroxide, benzoyl hydroperoxide, m-chloro peroxide
At least one of benzoic acid, magnesium monoperoxyphthalate or Peracetic acid.It is preferred that hydrogen peroxide, metachloroperbenzoic acid.
The alkali compounds is selected from alkali carbonate, alkali metal hydroxide, alkali metal acetate or triethylamine, two
In ethyl isopropylamine, N- methyl piperidines, N-ethylpiperidine, N-methylmorpholine, N-ethylmorpholine, pyridine, 4- picolines extremely
Few one kind.It is preferred that sodium hydroxide, potassium hydroxide, potassium carbonate, cesium carbonate.
The reaction can use each step product to be directly entered the one-step synthesis of reaction in next step without isolation or incite somebody to action
Often walk reaction product isolated and purified after enter in next step reaction step synthesis.
The synthetic method of the present invention is a kind of universal method, is suitable for synthesizing thiochromone compound and its derivative, to virtue
A variety of functional groups on ring have high tolerance, therefore in fact to the substituent in Thiochromone compound and its derivative
There is no particular restriction for number and species.
Formula (I) compound of the present invention further includes its salt allowed on pharmaceutics.
The present invention provides application of the 2- hydroxyls -6- fluorine Thiochromone compound as agricultural and gardening herbicide.
In the herbicide in addition to containing active ingredient 2- hydroxyl -6- fluorine Thiochromone compounds, also contain with medicine
Acceptable carrier, auxiliary agent and/or diluent, form composition.
Embodiment
The synthetic method of the present invention is illustrated below by specific embodiment.It should be noted that given here retouch
The embodiment just for the sake of the description present invention with embodiment is stated, technical staff is easier to understand the present invention, they
It is not intended to limit the scope of the present invention.
Embodiment 1, the synthetically prepared reaction equation of Formula V 1 are as follows：
Press step preparation：
2,4- bis- chloro- 5 fluorobenzoyl methyl acetate 22.4mmol, DMSO 30mL, NaOH are added in single-necked flask
45mmol, is warming up to 40 DEG C, CS is added dropwise at this temperature under stirring2The solution of the 5mL DMSO of 26.3mmol.Drop finishes, temperature control 40
DEG C stirring reaction.Reaction is finished, and is cooled to room temperature, and the 10mLDMSO solution of iodoethane 26.3mmol is added dropwise, and drop finishes, and room temperature reaction is extremely
Reaction is finished, and reaction solution is stirred down and is poured into 50mL frozen water, has a large amount of solids to separate out, solid is collected by filtration, is recrystallized in ethanol,
Obtain formula (V1) product 2- ethylmercapto groups fluoro- 7 chlorine thiochromone -3- methyl formate 16.8mmol of -6-, yield 75%.
1HNMR(DMSO-d6)：1.36 (t, 3H), 3.16 (q, 2H), 4.81 (s, 3H), 8.22 (d, 1H), 8.55 (d, 1H).
2~embodiment of embodiment 9：The preparation of formula (V) Thiochromone compound
Using (III) compound as raw material, preparing product formula (V) compound, (target product is formula (V2)~(V9) in table 1
Each compound), for preparation process with embodiment 1, reaction equation is as follows：
In 2~embodiment of embodiment 9, each group selection of product formula (V) Thiochromone compound and preparation reagent and inspection
Survey data and be listed in table 1.
Table 1
Embodiment 10：The synthetically prepared reaction equation of Formula IV 1 is as follows：
Prepare by the following step：
Into 100mL single-necked flasks, the fluoro- 7 chlorine thiochromone -3- methyl formate 10mmol of 2- ethylmercapto groups -6-, second are sequentially added
Sour 20mL, is heated to 65 DEG C, and 30% H is added dropwise2O2When 12mmol stirrings reaction 6 is small, adds sodium sulfite extraction and go out, be evaporated under reduced pressure
Solvent acetic acid is removed, then 50mL dichloromethane and the extraction of 50mL water, take dichloromethane layer, (50mL × 2) are washed twice with water,
Organic layer is recycled, is evaporated under reduced pressure to the fluoro- 7 chlorine thiochromone -3- methyl formates of formula (III16) product 2- second sulfinyls -6-
9.5mmol, yield 95%.
1HNMR(DMSO-d6)：1.28 (t, 3H), 3.06-3.18 (m, 1H), 3.31-3.43 (m, 1H), 3.87 (s, 3H),
8.16 (d, 1H), 8.60 (d, 1H).
Embodiment 11：The synthetically prepared reaction equation of Formula IV 2 is as follows
Prepare by the following step：
Into 100mL single-necked flasks, the fluoro- 7 chlorine thiochromone -3- methyl formates 10mmol of 2- ethylmercapto groups -6- are sequentially added, two
Chloromethanes 20mL, is heated to flowing back, and m-chloro peroxide phenylacetic acid mCPBA 22mmol are added dropwise, and stirring reaction is finished, and adds sodium sulfite
Extraction is gone out, and vacuum distillation removes solvent acetic acid, and then 50mL dichloromethane and the extraction of 50mL water, take dichloromethane layer, be washed with water
(50mL × 2) twice, recycle organic layer, are evaporated under reduced pressure to the fluoro- 7 chlorine thiochromone -3- first of formula (III17) product 2- second sulfo groups -6-
Sour methyl esters 9.7mmol, yield 97%.
1HNMR(DMSO-d6)：1.38 (t, 3H), 3.20 (q, 2H), 4.83 (s, 3H), 7.54 (d, 1H), 8.15 (d, 1H).
12~embodiment of embodiment 19：The preparation of formula (VI) Thiochromone compound
Respectively using (V2~V9) compound as raw material, product formula (VI3~VI10) compound is prepared, preparation process is the same as implementation
Example 10 or 11, reaction equation are as follows：
In 12~embodiment of embodiment 19, the selection of each group of product formula (VI) Thiochromone compound and preparations reagent with
Detection data are listed in table 2.
Table 2
Embodiment 20：The first synthetically prepared reaction of formula (I1) is as follows：
Preparation process is as follows：
Into 100mL single-necked flasks, the fluoro- 7- chlorine thiochromone -3- methyl formates of 2- second sulfinyls -6- are sequentially added
The THF of 1mmol, KOH1.5mmol (being dissolved in 1ml water) and 5mL, stirring reaction.Question response is finished, and adjusts PH to 6~7, separates out solid
Body, filters to obtain formula (I1) product 2- hydroxyls fluoro- 7- chlorine thiochromone -3- methyl formate 0.86mmol of -6-, yield 86%.
1HNMR(DMSO-d6)：3.74 (s, 3H), 8.14 (d, 1H), 8.36 (s, 1H),.
Embodiment 21：Second of synthetically prepared reaction of formula (I1) is as follows：
Preparation process is as follows：
Into 100mL single-necked flasks, the fluoro- 7- chlorine thiochromone -3- methyl formate 1mmol of 2- ethylsulfonyls -6- are sequentially added,
The THF of KOH1.5mmol (being dissolved in 1ml water) and 5mL, stirring reaction.Question response is finished, and adjusts PH to 6~7, separates out solid, takes out
Filter to obtain formula (I2) product 2- hydroxyls fluoro- 7- chlorine thiochromone -3- methyl formate 0.79mmol of -6-, yield 79%.
1HNMR(DMSO-d6)：3.74 (s, 3H), 8.14 (d, 1H), 8.36 (s, 1H),.
22~embodiment of embodiment 29：The preparation of formula (I) Thiochromone compound
Respectively using (VI) compound as raw material, prepare product formula (I) compound (target product be table 3 in formula (I2)~
(I9) each compound), preparation process is as follows with embodiment 20 or 21, reaction equation：
In 22~embodiment of embodiment 29, the selection of each group of product formula (I) Thiochromone compound and preparations reagent with
Detection data are listed in table 3.
Table 3
30 activity of weeding of embodiment is evaluated
Method is as follows：(1) in sectional area 64cm2Plastic tub alms bowl in quantitatively fill soil pressure and put down, be placed in Stainless steel basin, choose
Full seed, seed of the same size, divide monocotyledon weed (lady's-grass, barnyard grass, green bristlegrass) and broadleaf weed (black nightshade, lamb's-quarters, recessed
Head amaranth) divide alms bowl to sow, the 1/3 of alms bowl area is respectively accounted for, covers the thick thin scholars of 1cm, upper layer of soil infiltration is added water to from plastic tub alms bowl bottom, puts
In hot-house culture, material length to be tried to required leaf age carries out test process；(2) weighing a series of suitable provided by the invention has
2- hydroxyl -6- fluorine the Thiochromone compounds of weeding bioactivity, with acetone solution, add a small amount of Tween 80 emulsifying agent, stir
Mix uniformly, add proper amount of clear water, be configured to required concentration, if coordinative solvent and clear water are control；(3) processing mode：Unifacial leaf
Try material length to 1 heart stage of 1 leaf, dicotyledonous examination material length to 2 leaf periods and carry out after seedling cauline leaf process；(4) quantitatively moved by setting dosage
Taking liquid carries out cauline leaf spraying treatment, respectively using spray solvent and clear water to compare, while with the clodinafop-propargyl of same concentrations to stem
Leaf carries out spraying treatment, as standard control；(5) processing examination material, which is placed in greenhouse, cultivates；(6) soil is estimated after handling 15-30 days
Overground part growing state, according to investigation result, calculates preventive effect of each compound to weeds as follows：Preventive effect (%)=100
(control plant height-processing plant height)/control plant height；(7) activity of weeding classification is carried out according to preventive effect：A grades of preventive effect ＞ 90%, B grades anti-
Imitate 75~90%, C grades of preventive effects 50~75%, D grades of preventive effects 25~50%, E grades of preventive effect ＜ 25%.The result shows that partization of the invention
Compound has the clean property of A grades of weedings under 85g a.i./ha dosage to monocotyledon weed, and evaluation result is listed in Table 3 below.
Activity of weeding (cauline leaf process) of the 3. each compound of table under 85g a.i./ha dosage
Claims (8)
- It is 1. a kind of as the 2- hydroxyl -6- fluorine Thiochromone compounds of formula (I), its chemical constitution are as follows：R3Selected from such as R3' orWherein R3' it is selected from one kind in five yuan of nitrogen azoles rings of formula (II)：Wherein：J, K, L are separately selected from hydrogen, C1-C3Alkyl；Wherein, Y is selected from C1-C6Oxyl, C1-C6Hydrocarbon amino, C1-C6Alkyl, phenyl, by one or more C1-C6Alkyl Or oxyl substitution phenyl, phenoxy group, by one or more C1-C6Alkyl or the phenoxy group of oxyl substitution；R4、R6Separately selected from hydrogen, fluorine, chlorine, bromine or iodine；R5Selected from hydrogen, fluorine, chlorine, bromine, iodine, C1-C6Oxyl, C1-C6Hydrocarbon amino, C1-C6Alkyl, phenoxy group, by 1 or Multiple C1-C6The phenoxy group of oxyl substitution；
- 2. compound according to claim 1, its feature compound includes its salt allowed on galenic pharmacy；
- 3. a kind of synthetic method of the formula of claim 1 (I) compound, it is characterized in that, compound (III) is dissolved in organic solvent In, reacted with carbon disulfide, through condensation, after cyclization with C1-C6Halohydrocarbons reaction generation compound (V), compound (V) is through oxygen Agent oxidation generation compound (VI), then reacts to obtain solid product 2- hydroxyl -6- fluorine thiochromones with alkali metal hydroxide Class compound；The structural formula of the compound (III) is as follows：The structural formula of the compound (V) is as follows：The structural formula of the compound (VI) is as follows：Wherein, X represents F or Cl；R3、R4、R5、R6The same formula of definition (I)；R7Selected from C1-C6Alkyl；Z is selected from sulfinylSulfonyl
- 4. synthetic method according to claim 3, it is characterized in that the organic solvent is selected from n,N-Dimethylformamide, N, In N- dimethylacetylamides, dimethyl sulfoxide, dioxane, acetonitrile, tetrahydrofuran, methanol, ethanol, isopropanol, the tert-butyl alcohol extremely Few one kind；The oxidant is selected from manganese dioxide, potassium permanganate, potassium bichromate, hydrogen peroxide, benzoyl hydroperoxide, m-chloro peroxide At least one of benzoic acid, magnesium monoperoxyphthalate or Peracetic acid；The alkali compounds is selected from alkali metal carbonic acid Salt, alkali metal hydroxide, alkali metal acetate or triethylamine, diethylisopropylamide, N- methyl piperidines, N-ethylpiperidine, N- Methyl morpholine, N-ethylmorpholine,；At least one of pyridine, 4- picolines.
- 5. according to the synthetic method described in claim 3,4, it is characterized in that the organic solvent be selected from n,N-Dimethylformamide, Dimethyl sulfoxide；The oxidant is selected from hydrogen peroxide, metachloroperbenzoic acid；The alkali compounds is selected from sodium hydroxide, hydrogen Potassium oxide, potassium carbonate, cesium carbonate.
- 6. according to the synthetic method described in claim 3-5, it is characterized in that often step reaction product is directly entered without isolation The one-step synthesis of reaction or enter the substep of reaction in next step after the product that every step is reacted is isolated and purified in next step Synthetic method.
- A kind of 7. application of the 2- hydroxyls -6- fluorine Thiochromone compound described in claim 1 as agricultural and gardening herbicide.
- 8. application according to claim 7, contains active ingredient 2- hydroxyl -6- fluorine sulphur it is characterized in that being removed in the herbicide Outside chromone compounds, also containing pharmaceutically acceptable carrier, auxiliary agent and/or diluent, composition is formed.
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| US5378677A (en) * | 1992-01-23 | 1995-01-03 | Basf Aktiengesellschaft | Thiochromenone derivatives as antidotes, and herbicides containing them |
| CN101519402A (en) * | 2009-04-13 | 2009-09-02 | 南京工业大学 | Thiochromone compound, synthetic method and application thereof in preparing antifungal medicaments |
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2016
- 2016-10-28 CN CN201610949296.0A patent/CN108003133A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5378677A (en) * | 1992-01-23 | 1995-01-03 | Basf Aktiengesellschaft | Thiochromenone derivatives as antidotes, and herbicides containing them |
| CN101519402A (en) * | 2009-04-13 | 2009-09-02 | 南京工业大学 | Thiochromone compound, synthetic method and application thereof in preparing antifungal medicaments |
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| VIOLETTA CECCHETTI ET AL.: "4H-1-Benzothiopyran-4-one-3-carboxylic Acids and 3,4-Dihydro-2H-isothiazolo[5,4-b][1]benzothiopyran-3,4-diones as Quinolone Antibacterial Analogs", 《J.HETEROCYCLIC CHEM.》 * |
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