NO133455B - - Google Patents
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- Publication number
- NO133455B NO133455B NO280/73A NO28073A NO133455B NO 133455 B NO133455 B NO 133455B NO 280/73 A NO280/73 A NO 280/73A NO 28073 A NO28073 A NO 28073A NO 133455 B NO133455 B NO 133455B
- Authority
- NO
- Norway
- Prior art keywords
- chloro
- salt
- group
- acid
- halogen
- Prior art date
Links
- 239000000203 mixture Substances 0.000 claims description 57
- 239000002253 acid Substances 0.000 claims description 41
- 239000004009 herbicide Substances 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 18
- 230000002363 herbicidal effect Effects 0.000 claims description 18
- 150000002148 esters Chemical class 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 15
- -1 alkali metal salt Chemical class 0.000 claims description 14
- 239000004480 active ingredient Substances 0.000 claims description 7
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 150000001408 amides Chemical class 0.000 claims description 5
- 239000003085 diluting agent Substances 0.000 claims description 5
- 150000002825 nitriles Chemical class 0.000 claims description 5
- 125000003368 amide group Chemical group 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- WHKUVVPPKQRRBV-UHFFFAOYSA-N Trasan Chemical compound CC1=CC(Cl)=CC=C1OCC(O)=O WHKUVVPPKQRRBV-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 2
- YZHUMGUJCQRKBT-UHFFFAOYSA-M sodium chlorate Chemical compound [Na+].[O-]Cl(=O)=O YZHUMGUJCQRKBT-UHFFFAOYSA-M 0.000 claims description 2
- WNTGYJSOUMFZEP-UHFFFAOYSA-N 2-(4-chloro-2-methylphenoxy)propanoic acid Chemical compound OC(=O)C(C)OC1=CC=C(Cl)C=C1C WNTGYJSOUMFZEP-UHFFFAOYSA-N 0.000 claims 1
- 241001180873 Saposhnikovia divaricata Species 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- 238000009833 condensation Methods 0.000 claims 1
- 241000196324 Embryophyta Species 0.000 description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 19
- 239000000243 solution Substances 0.000 description 19
- 239000007787 solid Substances 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 17
- 239000007864 aqueous solution Substances 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 11
- HYJSGOXICXYZGS-UHFFFAOYSA-N benazolin Chemical compound C1=CC=C2SC(=O)N(CC(=O)O)C2=C1Cl HYJSGOXICXYZGS-UHFFFAOYSA-N 0.000 description 11
- 238000010992 reflux Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 10
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 150000007513 acids Chemical class 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 241000257303 Hymenoptera Species 0.000 description 7
- 235000013339 cereals Nutrition 0.000 description 7
- 238000004821 distillation Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 241001232700 Carex aquatilis Species 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- 240000006694 Stellaria media Species 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- MBFOZAKOORJAMK-UHFFFAOYSA-N 4-chloro-3h-1,3-benzothiazol-2-one Chemical compound C1=CC=C2SC(O)=NC2=C1Cl MBFOZAKOORJAMK-UHFFFAOYSA-N 0.000 description 4
- 239000005995 Aluminium silicate Substances 0.000 description 4
- 241000722731 Carex Species 0.000 description 4
- 235000012211 aluminium silicate Nutrition 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- QFMDFTQOJHFVNR-UHFFFAOYSA-N 1-[2,2-dichloro-1-(4-ethylphenyl)ethyl]-4-ethylbenzene Chemical compound C1=CC(CC)=CC=C1C(C(Cl)Cl)C1=CC=C(CC)C=C1 QFMDFTQOJHFVNR-UHFFFAOYSA-N 0.000 description 3
- SXOCCTHWTPGZHT-UHFFFAOYSA-N 2-(2-oxo-1,3-benzothiazol-3-yl)acetic acid Chemical compound C1=CC=C2SC(=O)N(CC(=O)O)C2=C1 SXOCCTHWTPGZHT-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 125000004494 ethyl ester group Chemical group 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 230000012010 growth Effects 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000001473 noxious effect Effects 0.000 description 3
- 230000008635 plant growth Effects 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000080 wetting agent Substances 0.000 description 3
- ROEHMJCRBWELOT-UHFFFAOYSA-N 2-(4-bromo-2-oxo-1,3-benzothiazol-3-yl)acetic acid Chemical compound C1=CC=C2SC(=O)N(CC(=O)O)C2=C1Br ROEHMJCRBWELOT-UHFFFAOYSA-N 0.000 description 2
- 241001290610 Abildgaardia Species 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 240000005702 Galium aparine Species 0.000 description 2
- 235000014820 Galium aparine Nutrition 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 244000292697 Polygonum aviculare Species 0.000 description 2
- 235000006386 Polygonum aviculare Nutrition 0.000 description 2
- 240000003059 Portulaca quadrifida Species 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 241000404538 Tripleurospermum maritimum subsp. inodorum Species 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- PQJJJMRNHATNKG-UHFFFAOYSA-N ethyl bromoacetate Chemical compound CCOC(=O)CBr PQJJJMRNHATNKG-UHFFFAOYSA-N 0.000 description 2
- 229940116333 ethyl lactate Drugs 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 229940088597 hormone Drugs 0.000 description 2
- 239000005556 hormone Substances 0.000 description 2
- 239000003701 inert diluent Substances 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 231100000208 phytotoxic Toxicity 0.000 description 2
- 230000000885 phytotoxic effect Effects 0.000 description 2
- 230000019612 pigmentation Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- RCIJACVHOIKRAP-UHFFFAOYSA-N sodium;1,4-dioctoxy-1,4-dioxobutane-2-sulfonic acid Chemical compound [Na+].CCCCCCCCOC(=O)CC(S(O)(=O)=O)C(=O)OCCCCCCCC RCIJACVHOIKRAP-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 208000024891 symptom Diseases 0.000 description 2
- ZZNDQCACFUJAKJ-UHFFFAOYSA-N 1-phenyltridecan-1-one Chemical compound CCCCCCCCCCCCC(=O)C1=CC=CC=C1 ZZNDQCACFUJAKJ-UHFFFAOYSA-N 0.000 description 1
- JQBRWVJTYLUPSX-UHFFFAOYSA-N 2-(6-chloro-2-oxo-1,3-benzothiazol-3-yl)acetic acid Chemical compound C1=C(Cl)C=C2SC(=O)N(CC(=O)O)C2=C1 JQBRWVJTYLUPSX-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- XOQAIUQIOPUHQP-UHFFFAOYSA-N 2-chloro-2-(2-oxo-1,3-benzothiazol-3-yl)acetic acid Chemical compound ClC(C(=O)O)N1C(SC2=C1C=CC=C2)=O XOQAIUQIOPUHQP-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- CVGSTWYNBBETDF-UHFFFAOYSA-N CCOC(C(N(C(C=CC=C1)=C1S1)C1=O)Cl)=O Chemical class CCOC(C(N(C(C=CC=C1)=C1S1)C1=O)Cl)=O CVGSTWYNBBETDF-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RENMDAKOXSCIGH-UHFFFAOYSA-N Chloroacetonitrile Chemical compound ClCC#N RENMDAKOXSCIGH-UHFFFAOYSA-N 0.000 description 1
- 241000254171 Curculionidae Species 0.000 description 1
- 244000166102 Eucalyptus leucoxylon Species 0.000 description 1
- 235000004694 Eucalyptus leucoxylon Nutrition 0.000 description 1
- 241000258937 Hemiptera Species 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 235000017879 Nasturtium officinale Nutrition 0.000 description 1
- 240000005407 Nasturtium officinale Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 244000273256 Phragmites communis Species 0.000 description 1
- 235000014676 Phragmites communis Nutrition 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 244000110797 Polygonum persicaria Species 0.000 description 1
- 235000004442 Polygonum persicaria Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 244000098338 Triticum aestivum Species 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- VXIVSQZSERGHQP-UHFFFAOYSA-N chloroacetamide Chemical compound NC(=O)CCl VXIVSQZSERGHQP-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- SSOVHFPWMPUQOS-UHFFFAOYSA-N cyanomethyl benzenesulfonate Chemical compound N#CCOS(=O)(=O)C1=CC=CC=C1 SSOVHFPWMPUQOS-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000036253 epinasty Effects 0.000 description 1
- 239000012259 ether extract Substances 0.000 description 1
- ARFLASKVLJTEJD-UHFFFAOYSA-N ethyl 2-bromopropanoate Chemical compound CCOC(=O)C(C)Br ARFLASKVLJTEJD-UHFFFAOYSA-N 0.000 description 1
- VEUUMBGHMNQHGO-UHFFFAOYSA-N ethyl chloroacetate Chemical compound CCOC(=O)CCl VEUUMBGHMNQHGO-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000001261 hydroxy acids Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 230000004660 morphological change Effects 0.000 description 1
- 230000031942 natural killer cell mediated cytotoxicity Effects 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 238000003359 percent control normalization Methods 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 150000003385 sodium Chemical class 0.000 description 1
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- OQFRATAOPGTAOP-UHFFFAOYSA-M sodium;1,4-di(nonoxy)-1,4-dioxobutane-2-sulfonate Chemical compound [Na+].CCCCCCCCCOC(=O)CC(S([O-])(=O)=O)C(=O)OCCCCCCCCC OQFRATAOPGTAOP-UHFFFAOYSA-M 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/026—Anodisation with spark discharge
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Electrochemical Coating By Surface Reaction (AREA)
Description
Ugressdrepere samt fremgangsmåte til fremstilling av disse. Weed killers and methods for their production.
Foreliggende oppfinnelse angår nye ugressdreperblandinger som som aktiv bestanddel inneholder visse nye benzoetiazol-forbindelser. The present invention relates to new herbicide mixtures which contain certain new benzothiazole compounds as an active ingredient.
Kontroll av ugress ved kjemiske midler er nå vanlig jordbruks- og havepraksis, men skjønt det er blitt utført et stort arbeid på det teoretiske område for kjemiske ugressdrepere, lider alle ugressdrepere som er tilgjengelige i øyeblikket av en eller an-nen ulempe. Dette angår særlig de så-kalte «selektive» ugressdrepere, dvs. ugressdrepere som kan brukes både på nyttevekster og ugress for å kontrollere ugresset uten å påvirke nyttevekstene. Det område for ugresskontroll som kan oppnås ved bruk av tilgjengelige selektive ugressdrepere er ikke helt adekvat. Det består derfor et kon-stant behov for forbedrede ugressdrepere. Weed control by chemical means is now common agricultural and horticultural practice, but although much work has been done in the theoretical area of chemical herbicides, all herbicides currently available suffer from one drawback or another. This particularly concerns the so-called "selective" weed killers, i.e. weed killers that can be used on both beneficial crops and weeds to control the weeds without affecting the beneficial crops. The range of weed control that can be achieved using available selective herbicides is not entirely adequate. There is therefore a constant need for improved weed killers.
Foreliggende oppfinnelse er basert på den oppdagelse at visse benzoetiazolderi-vater som hittil ikke er beskrevet har egenskaper som gjør dem potensielt verdifulle som ugressdrepere. Det er blitt funnet at 4-halogen-2-oksobenzoetiazolin-3-yleddiksyrer og deres derivater slik som definert i det følgende, har ugressdrepe-egenskaper av meget høy grad. Ved uttrykket derivater menes salter, estere, amider og nitriler av 4-halogen-2-oksobenzoe-tia-zolin-3-yleddiksyrer. The present invention is based on the discovery that certain benzoethiazole derivatives which have not been described so far have properties which make them potentially valuable as herbicides. It has been found that 4-halo-2-oxobenzothiazolin-3-yldiacids and their derivatives as defined below have very high weed killing properties. By the term derivatives are meant salts, esters, amides and nitriles of 4-halogen-2-oxobenzoe-thia-zolin-3-yldiacids.
4-halogen-2-oksobenzoetiazolin-3-yleddiksyrer og deres derivater (i det føl-gende kalt forbindelser ifølge oppfinnelsen) viser meget høy ugressdrepeaktivitet mot de viktige ugress: hønsegress, (Polygonum persicaria), klengemaur (Galium aparine) 4-Halogen-2-oxobenzothiazolin-3-yl diacids and their derivatives (hereinafter referred to as compounds according to the invention) show very high weed-killing activity against the important weeds: hen's weed (Polygonum persicaria), klengema ant (Galium aparine)
og vassarv (Stellaria media). Denne oppdagelse er et verdifullt bidrag til den kjemiske ugresskontroll, da ingen veletablerte selektive ugressdrepere av den type som regulerer planteveksten på en effektiv måte kontrollerer alle disse ugress. Således kontrollerer 2 : 4-diklorfenoksyeddiksyre (2:4-D) og 4-klor-2-metylfenoksyeddiksyre (M. C. P. A.), som er de mest anvendte hormon-ugressdrepere, ikke klengemaur i det hele tatt og har lav aktivitet mot vassarv og hønsegress. Alf a- (4-klor-2-metylf enoksy) - propionsyre (C.M.P.P.), som nylig er blitt innført som en selektiv ugressdreper, er meget effektiv mot klengemaur og vassarv, men kontrollerer ikke hønsegress. Forbin-delsene ifølge oppfinnelsen er ikke fytotoksiske likeoverfor kornvekster når de anvendes i mengder som er nødvendige for å kontrollere de tidligere nevnte ugress og når de anvendes på et veksttrinn for korn-vekstene hvor de velkjente selektive ugressdrepere normalt anvendes. and watercress (Stellaria media). This discovery is a valuable contribution to chemical weed control, as no well-established selective herbicide of the type that regulates plant growth effectively controls all of these weeds. Thus, 2 : 4-dichlorophenoxyacetic acid (2:4-D) and 4-chloro-2-methylphenoxyacetic acid (M.C.P.A.), which are the most widely used hormone herbicides, do not control ants at all and have low activity against water sedge and chickweed. Alf a-(4-chloro-2-methylphenoxy)-propionic acid (C.M.P.P.), which has recently been introduced as a selective herbicide, is very effective against ants and water sedges, but does not control chickweed. The compounds according to the invention are not phytotoxic to cereal crops when they are used in quantities necessary to control the previously mentioned weeds and when they are used at a growth stage for the cereal crops where the well-known selective herbicides are normally used.
Ifølge et trekk ved foreliggende oppfinnelse skaffes ugressblandinger som omfatter et 4-halogen-2-oksobenzoetiazolin-3-yleddiksyre eller et derivat av dette, som definert tidligere i forbindelse med et fortynningsmiddel eller en bærer. According to a feature of the present invention, weed mixtures are obtained which comprise a 4-halogen-2-oxobenzoethiazoline-3-ylacetic acid or a derivative thereof, as defined earlier in connection with a diluent or a carrier.
Uttrykket «ugressdrepeblandinger» skal bety ikke bare blandinger i en egnet form for påføring på planter, men også sterkt konsentrerte blandinger som forbrukeren kan fortynne med en egnet mengde vann eller annet fortynningsmiddel før anvendelse på planter. The term "herbicide mixtures" shall mean not only mixtures in a suitable form for application to plants, but also highly concentrated mixtures which the consumer can dilute with a suitable amount of water or other diluent before application to plants.
Salter av 4-halogen-2-oksobenzoetia-zolin-3-yleddiksyrer, som kan anvendes i blandingene ifølge oppfinnelsen omfatter salter dannet av uorganiske og organiske baser, slik som f. eks. metall, f. eks. natri-um og kalium, ammonium og organiske aminsalter. Salts of 4-halo-2-oxobenzoethia-zolin-3-yldiacids, which can be used in the mixtures according to the invention, include salts formed from inorganic and organic bases, such as e.g. metal, e.g. sodium and potassium, ammonium and organic amine salts.
Estere av 4-halogen-2-oksobenzoetia-zolin-3-yleddiksyrer, som kan anvendes i blandingene ifølge oppfinnelsen omfatter estere dannet av enkle alkoler, slik som metanol, etanol, propanol, butanol etc, langkjedede alkoholer, slik som heksyl, hep-tyl, oktyl, 3:5: 5-trimetylheksylalkohol etc, aralkanoler slik som benzylalkohol, glykolmonoetere, slik som 2-butoksyetyl og 2-2'-butoksyetoksyetyl-alkohol, og hydrok-sysyrederivater slik som etyllaktat. Esters of 4-halo-2-oxobenzoethia-zolin-3-yl diacids, which can be used in the mixtures according to the invention, include esters formed from simple alcohols, such as methanol, ethanol, propanol, butanol, etc., long-chain alcohols, such as hexyl, hep- tyl, octyl, 3:5:5-trimethylhexyl alcohol etc, aralkanols such as benzyl alcohol, glycol monoethers such as 2-butoxyethyl and 2-2'-butoxyethoxyethyl alcohol, and hydroxy acid derivatives such as ethyl lactate.
Naturen av fortynningsmidlene eller The nature of the diluents or
bærerne som skal anvendes i blandingene ifølge oppfinnelsen vil avhenge av de fysi-kalske egenskaper for de aktive bestanddeler. Typiske blandinger som faller innen-for dette trekk ved oppfinnelsen omfatter følgende: the carriers to be used in the mixtures according to the invention will depend on the physical properties of the active ingredients. Typical mixtures falling within this feature of the invention include the following:
a) Dispergerbare oppløsninger. En dispergerbar oppløsning omfatter en fast, vannuoppløselig forbindelse ifølge oppfinnelsen oppløst i et vann-blandbart oppløs-ningsmiddel, f. eks. aceton, med tilsetning av et dispergeringsmiddel, slik at en vandig dispersjon dannes ved fortynning med vann. b) Blandbare oljer. En blandbar olje omfatter en vann-uoppløselig forbindelse ifølge oppfinnelsen, hvilken kan være et fast stoff eller en væske oppløst i et vann-ublandbart oppløsningsmiddel, f. eks. et høytkokende kullvannstoff, med tilsetning av et emulgeringsmiddel, slik at det dannes en emulsjon ved fortynning med vann. I tilfelle av flytende, vannuoppløselige forbindelser ifølge oppfinnelsen, kan oppløs-ningsmidlet utelates hvis ønsket. Som et alternativ kan forbrukeren få en konsen-trert emulsjon erholdt fra en blandbar olje ved tilsetning av omtrent like stort volum vann. Silke konsentrerte emulsjoner for-tynnes med en tilsvarende mengde vann før anvendelsen for planter. c) Dispergerbare pulvere. Et dispergerbart pulver omfatter en vann-uoppløse-lig forbindelse ifølge oppfinnelsen i forbindelse med et fast inert fortynningsmiddel, f. eks. kaolin, og et dispergeringsmiddel. d) Støv. Et ugressdrepemiddel-støv omfatter en forbindelse ifølge oppfinnelsen a) Dispersible solutions. A dispersible solution comprises a solid, water-insoluble compound according to the invention dissolved in a water-miscible solvent, e.g. acetone, with the addition of a dispersing agent, so that an aqueous dispersion is formed by dilution with water. b) Miscible oils. A miscible oil comprises a water-insoluble compound according to the invention, which can be a solid or a liquid dissolved in a water-immiscible solvent, e.g. a high-boiling coal hydrogen, with the addition of an emulsifier, so that an emulsion is formed when diluted with water. In the case of liquid, water-insoluble compounds according to the invention, the solvent can be omitted if desired. As an alternative, the consumer can get a concentrated emulsion obtained from a miscible oil by adding an approximately equal volume of water. Silk concentrated emulsions are diluted with a corresponding amount of water before application to plants. c) Dispersible powders. A dispersible powder comprises a water-insoluble compound according to the invention in connection with a solid inert diluent, e.g. kaolin, and a dispersant. d) Dust. A herbicide dust comprises a compound according to the invention
i forbindelse med et fast, pulverformet fortynningsmiddel, som kan være et inert fortynningsmiddel, slik som kaolin eller et standard gjødningsmiddel. in conjunction with a solid, powdered diluent, which may be an inert diluent, such as kaolin or a standard fertilizer.
e) Vandige oppløsninger. Vann-opp-løselige forbindelser ifølge oppfinnelsen e) Aqueous solutions. Water-soluble compounds according to the invention
kan anvendes som vandige oppløsninger. can be used as aqueous solutions.
De dispergerbare oppløsninger, blandbare oljer, dispergerbare pulvere, og vandige oppløsninger som er beskrevet i det foregående kan også inneholde et fuktningsmiddel, hvis dette er ønskelig. The dispersible solutions, miscible oils, dispersible powders, and aqueous solutions described above may also contain a wetting agent, if this is desired.
4-halogen-2-oksobenzoetiazolin-3-yleddiksyrer er faste, vannuoppløselige forbindelser og kan derfor sammensettes som 4-halo-2-oxobenzoethiazoline-3-yl diacids are solid, water-insoluble compounds and can therefore be composed as
a) dispergerbare oppløsninger, b) blandbare oljer, c) dispergerbare pulvere og d) a) dispersible solutions, b) miscible oils, c) dispersible powders and d)
støv. Esterne av 4-halogen-2-oksobenzoe-tiazolin-3-yleddiksyrer er også vannuopp-løselige og, kan avhengig av alkoholdelen være faste eller flytende. De kan derfor sammensettes på samme måte som de frie syrer, med unntagelse av at de dispergerbare oppløsninger ikke er praktiske i tilfelle av flytende estere. Nitrilene og amid-ene av 4-halogen-2-oksobenzoetiazolin-3-yleddiksyrene er også vannuoppløselige, faste forbindelser og kan sammensettes på samme måte som syrene. I tilfelle av salter av 4-halogen-2-oksobenzoetiazolin-3-yled-diksyrer, kan de oppløselige salter, slik som silke som er dannet av alkalimetallbaser og enkle alkyl- og hydroksyalkylaminer, sammensettes som e) vandige oppløsninger. Det kan være hensiktsmessig å tilføre forbrukeren et salt i fast form, med eller uten tilsetning av et fuktningsmiddel, for å settes til en riktig mengde vann for å gi en oppløsning for påføring på planter. dust. The esters of 4-halo-2-oxobenzo-thiazolin-3-yldiacids are also water-soluble and, depending on the alcohol part, can be solid or liquid. They can therefore be composed in the same way as the free acids, with the exception that the dispersible solutions are not practical in the case of liquid esters. The nitriles and amides of the 4-halo-2-oxobenzoethiazoline-3-yldiacids are also water-insoluble, solid compounds and can be composed in the same way as the acids. In the case of salts of 4-halo-2-oxobenzothiazolin-3-yledoacetic acids, the soluble salts, such as silks formed from alkali metal bases and simple alkyl and hydroxyalkylamines, can be composed as e) aqueous solutions. It may be appropriate to supply the consumer with a salt in solid form, with or without the addition of a wetting agent, to be added to an appropriate amount of water to provide a solution for application to plants.
Konsentrasjonen av den aktive bestanddel i de fortynnede blandinger ifølge oppfinnelsen, hvilke påføres nyttevekstene for kontroll av ugress, er avhengig av den spesielle nyttevekst og ugress, som det er ønskelig å behandle, også av maskintypen som skal anvendes ved påføringen av blandingene, da både «lavvolum»- og «høy-volum»-sprøyter er vanlig brukt og krever blandinger som inneholder forskjellige kon-sentrasjoner av den aktive bestanddel. For ugresskontroll er den totale mengde aktiv bestanddel som anvendes pr. enhet areal av de nyttevekster som behandles av betydning. For kontroll av hønsegress, klengemaur og vassarv er det av betydning blitt funnet at anvendelse av 4-klor-2-oksobenzoetiazolin-3-yleddiksyre eller dens salter eller estere i en mengde på 28—112 g/mål syreekvivalent. Den nedre mengde på 28—56 g syreekvivalent pr. mål er tilstrekkelig til å kontrollere klengemaur og vassarv, men hønsegress synes mer motstandsdyktig og det fore-trekkes en mengde på minst 56 g syre-ekvivalent pr. mål for å sikre adekvat kontroll av dette ugress. Således vil en hensiktsmessig mengde for å sikre adekvat kontroll av alle tre ugressarter være ca. 56 g syreekvivalent pr. mål. The concentration of the active ingredient in the diluted mixtures according to the invention, which are applied to the beneficial plants for weed control, depends on the particular beneficial plant and weed that it is desired to treat, also on the type of machine to be used when applying the mixtures, as both " low-volume' and 'high-volume' syringes are commonly used and require mixtures containing different concentrations of the active ingredient. For weed control, the total amount of active ingredient used per unit area of the useful crops that are treated as important. The use of 4-chloro-2-oxobenzoethiazoline-3-yl acetic acid or its salts or esters in an amount of 28-112 g/measure of acid equivalent has been found to be important for the control of chicken weed, small hema ants and water sedges. The lower amount of 28-56 g acid equivalent per target is sufficient to control ants and water sedges, but hen grass seems more resistant and a quantity of at least 56 g acid equivalent per hectare is preferred. target to ensure adequate control of this weed. Thus, an appropriate amount to ensure adequate control of all three weed species will be approx. 56 g acid equivalent per goal.
Som angitt i det foregående, fremkal-ler forbindelsen ifølge oppfinnelsen ikke fytotoksiske symptomer i kornsorter når de anvendes på det riktige veksttrinn for kornsortene. Således kan i tilfelle av 4-klor-2-oksobenzoetiazolin-3-yleddiksyre og dens derivater, vårkorn sprøytes på et tidlig veksttrinn (f. eks. 1—5 blad) med 28 g pr. mål syreekvivalent for å kontrollere klengemaur og vassarv uten noen ødeleggelse av kornplantene. Med større mengder for å kontrollere hønsegress, klengemaur og vassarv, er det å foretrekke å forsinke sprøyt-ning inntil 5-blad-trinnet for å sikre fullstendig unngåelse av kornødeleggelse. Ved de velkjente hormon-selektive ugressdrepere, må sprøytning ikke utføres etter «skyte»-trinnet for kornsortene. As indicated above, the compound according to the invention does not cause phytotoxic symptoms in cereals when they are used at the correct growth stage for the cereals. Thus, in the case of 4-chloro-2-oxobenzothiazolin-3-ylacetic acid and its derivatives, spring wheat can be sprayed at an early growth stage (e.g. 1-5 leaves) with 28 g per target acid equivalent to control whiteflies and weevils without any damage to the cereal plants. With larger quantities to control chickenweed, sedge ants and reeds, it is preferable to delay spraying until the 5-leaf stage to ensure complete avoidance of grain damage. With the well-known hormone-selective herbicides, spraying must not be carried out after the "shoot" stage for the cereals.
Blandingene ifølge oppfinnelsen kan inneholde andre ugressdrepemidler, slik som 2 : 4-D, M.C.P.A. og C.M.P.P. i tillegg til de andre bestanddeler som beskrevet i det foregående. The mixtures according to the invention may contain other herbicides, such as 2 : 4-D, M.C.P.A. and C.M.P.P. in addition to the other components as described above.
En verdifull kombinasjon omfatter 4-halogen-2-oksobenzoetiazolin-3-yleddik-syre eller dens derivater som definert i det foregående i forbindelse med M.C.P.A. eller et egnet derivat av dette. Slike blandinger har ugressdrepe-aktivitet mot et stort an-tall ugress. Et betydelig trekk ved disse blandinger er at det er symptomer på at de vil kontrollere balderbrå (Matricaria inodora), et ugress som ikke kontrolleres hver-ken av 4-halogen-2-oksobenzoetiazolin-3-yleddiksyrer eller M.C.P.A. eller av dets derivater. Blandinger som inneholder en 4-halogen-2-oksobenzoetiazolin-3-yleddik-syre og M.C.P.A. eller egnede derivater av disse syrer i et forhold på 4-halogen-2-ok-sobenzoetiazolin-3-yleddiksyre: M.C.P.A. på mellom 1 : 1 og 1 : 4 er særlig egnet for å skaffe ugressdrepeaktivitet over et vidt spektrum. A valuable combination comprises 4-halo-2-oxobenzothiazolin-3-ylacetic acid or its derivatives as defined above in connection with M.C.P.A. or a suitable derivative thereof. Such mixtures have weed-killing activity against a large number of weeds. A significant feature of these mixtures is that there are symptoms that they will control knotweed (Matricaria inodora), a weed that is not controlled either by 4-halogen-2-oxobenzoethiazoline-3-yl diacids or M.C.P.A. or of its derivatives. Mixtures containing a 4-halo-2-oxobenzothiazolin-3-ylacetic acid and M.C.P.A. or suitable derivatives of these acids in a ratio of 4-halogen-2-oxo-benzothiazolin-3-ylacetic acid: M.C.P.A. of between 1:1 and 1:4 is particularly suitable for obtaining weed-killing activity over a wide spectrum.
En blanding som omfatter 4-halogen-2-oksobenzoetiazolin-3-yleddiksyre eller et derivat av dette som definert i det foregående i forbindelse med C.M.P.P eller et egnet derivat av disse, er også meget verdifull. Blandinger som inneholder en 4-halogen-2-oksobenzoetiazolin-3-yleddik-syre og C.M.P.P. eller egnede derivater av disse syrer i en mengde på 4-halogen-2-oksobenzoetiazolin-3-yleddiksyre: C.M.P.P. på mellom 1 : 2 og 1 : 8 er særlig egnet for å skaffe et ugressdrepemiddel med aktivitet over et vidt spektrum. A mixture comprising 4-halogen-2-oxobenzothiazolin-3-ylacetic acid or a derivative thereof as defined above in connection with C.M.P.P or a suitable derivative thereof is also very valuable. Mixtures containing a 4-halo-2-oxobenzothiazolin-3-ylacetic acid and C.M.P.P. or suitable derivatives of these acids in an amount of 4-halogen-2-oxobenzothiazolin-3-ylacetic acid: C.M.P.P. of between 1 : 2 and 1 : 8 is particularly suitable for obtaining a herbicide with activity over a wide spectrum.
Den meget høye ugressdrepemiddel-aktivitet ot klengemaur, vassarv og hønse-gress, som utvides av forbindelsen ifølge oppfinnelsen er meget overraskende, da en slik aktivitet ikke deles av nær beslektede 2-oksobenzoetiazolin-3-yleddiksyrer, som det vil sees i det følgende. The very high weed killer activity of ants, water sedges and hen-grass, which is extended by the compound according to the invention, is very surprising, as such activity is not shared by closely related 2-oxobenzothiazolin-3-yl diacids, as will be seen in the following.
En prøve som ble utviklet for å be-stemme ugress-drepemiddel-effektiviteten av forbindelser mot klengemaur, vassarv og hønsegress ble utført som følger: Fire like porsjoner av klengemaur, vassarv og hønsegress ble sprøytet med vandige emulsjoner av estere av forskjellige 2-oksobenzoetiazolin-3-yleddiksyrer eller med vandige oppløsninger av dietanolamin-saltene av disse syrer. En gradert serie på mengder ekvivalent med 28, 56 og 112 g fri syre pr. mål ble anvendt i et volum vann svarende til 90 1 pr. mål. Plantene grodde i potter under standardiserte betingelser og ble vurdert en måned etter behandling ved visuell undersøkelse, reaksjonen ble gradert ifølge følgende skala. A test designed to determine the weedicidal efficacy of compounds against sedge ants, sedges, and chickweed was conducted as follows: Four equal portions of sedges, sedges, and sedges were sprayed with aqueous emulsions of esters of various 2-oxobenzothiazoline- 3-yl diacids or with aqueous solutions of the diethanolamine salts of these acids. A graded series of quantities equivalent to 28, 56 and 112 g of free acid per measure was used in a volume of water corresponding to 90 1 per goal. The plants grew in pots under standardized conditions and were assessed one month after treatment by visual examination, the reaction being graded according to the following scale.
0 — Ingen synlig reaksjon. 0 — No visible reaction.
1 — Tvilsom reaksjon. 1 — Doubtful reaction.
2 — Avgjort reaksjon, men en reaksjon som ikke fører til noe permanent tap i størrelse, livskraft eller pigmentering eller antyder noen vesentlige morfologiske for-andringer, f. eks. forbigående epinasti. 2 — Definite reaction, but a reaction which does not lead to any permanent loss in size, vitality or pigmentation or suggests any significant morphological changes, e.g. transient epinasty.
3 — Mellomliggende reaksjon. 3 — Intermediate reaction.
4 — En utpreget plantevekstreaksjon som fører til tap i størrelse, livskraft eller pigmentering eller medfører en betydelig permanent forandring i plantens morfologi, men som ikke fører til dens død. 4 — A pronounced plant growth reaction which leads to a loss in size, vigor or pigmentation or causes a significant permanent change in the plant's morphology, but which does not lead to its death.
5 — Mellomliggende reaksjon. 5 — Intermediate reaction.
6 — Alvorlig plantevekstreaksjon, som ved slutten av undersøkelses-perioden på en måned resulterer i plantens død. 6 — Severe plant growth reaction, which at the end of the one-month study period results in the death of the plant.
De resultater som ble oppnådd med 4-halogen-2-oksobenzoetiazolin-3-yleddik-syrer og de tilsvarende usubstituerte, 5-klor-, 6-klor- og 4 : 6-diklorforbindelser er vist i tabell 1. The results obtained with 4-halogen-2-oxobenzoethiazolin-3-ylacetic acids and the corresponding unsubstituted, 5-chloro-, 6-chloro- and 4:6-dichloro compounds are shown in table 1.
Som angitt tidligere, er 4-halogen-2-oksobenzoetiazolin-3-yleddiksyrene og deres derivater nye forbindelser, og ifølge et videre trekk ved oppfinnelsen skaffes det en fremgangsmåte til fremstilling av en 4-halogen-2-oksobenzoetiazolin-3-yleddik-syre eller dens derivater som definert i det foregående med den generelle formel: As indicated earlier, the 4-halogen-2-oxobenzoethiazoline-3-ylacetic acids and their derivatives are new compounds, and according to a further feature of the invention, a method for the production of a 4-halogen-2-oxobenzoethiazoline-3-ylacetic acid is provided or its derivatives as defined above by the general formula:
hvori Z betyr et halogenatom og W betyr en karboksylgruppe eller et salt eller ester av denne, en amidgruppe eller en cyanogruppe, hvor et 4-halogen-2-oksobenzoe-tiazolin bringes til å reagere med en for- in which Z means a halogen atom and W means a carboxyl group or a salt or ester thereof, an amide group or a cyano group, where a 4-halo-2-oxobenzoe-thiazoline is reacted with a for-
bindelse som er valgt fra X-CH--Y og R'OCH2R" hvori X betyr et halogenatom, R' betyr en alkansulfonyl- eller arensulfo-nylgruppe, R" betyr en cyanogruppe og Y betyr en karboksylgruppe eller et salt eller en ester av denne, en amidgruppe eller en cyanogruppe, i nærvær av et alkalikonden-sasjonsmiddel, og hvis gruppen Y eller R" ikke svarer til den ønskede gruppe W, om-dannes Y eller R" til W ved hjelp av kjente fremgangsmåter. bond selected from X-CH--Y and R'OCH2R" wherein X means a halogen atom, R' means an alkanesulfonyl or arenesulfonyl group, R" means a cyano group and Y means a carboxyl group or a salt or an ester of this, an amide group or a cyano group, in the presence of an alkali condensing agent, and if the group Y or R" does not correspond to the desired group W, Y or R" is converted to W by means of known methods.
Ifølge et videre trekk ved oppfinnelsen skaffes en fremgangsmåte for fremstilling av en 4-halogen-2-oksobenzoetiazolin-3-yleddiksyre eller et derivat av denne som definert i det foregående, hvor 2-oksoben-zoetiazolin-3-yleddiksyre eller et derivat av denne halogeneres. According to a further feature of the invention, a method for the production of a 4-halogen-2-oxobenzothiazolin-3-ylacetic acid or a derivative thereof as defined above is provided, where 2-oxobenzothiazolin-3-ylacetic acid or a derivative thereof halogenated.
Som ventet fører halogenering av en 2-oksobenzoetiazolin-3-yleddiksyre eller et derivat av denne til en blanding av halogen As expected, halogenation of a 2-oxobenzothiazolin-3-ylacetic acid or a derivative thereof leads to a mixture of halogen
-2-oksobénzoetiazolin-3-yleddiksyrer eller derivater av disse, idet en slik blanding inneholder en mengde av den 4-halogen- -2-oxobenzothiazolin-3-yl diacids or derivatives thereof, such a mixture containing a quantity of the 4-halo-
isomere. I tillegg til de ønskede 4-halogen-isomere, fremstilles også 6-halogen-isomere. Skjønt den 6-halogen-isomere har langt mindre ugressdrepende aktivitet er imid-lertid denne ikke skadelig, og den rå blanding som inneholder en del av den ønskede 4-halogen-isomere kan anvendes i blandinger ifølge oppfinnelsen, som beskrevet i det foregående. isomers. In addition to the desired 4-halogen isomers, 6-halogen isomers are also produced. Although the 6-halogen isomer has far less weed-killing activity, this is nevertheless not harmful, and the crude mixture containing part of the desired 4-halogen isomer can be used in mixtures according to the invention, as described above.
Følgende eksempler illustrerer oppfinnelsen. The following examples illustrate the invention.
Ekesmpel 1. Example 1.
Ved fremstilling av etyl-4-klor-2-okso-benzoetiazolin-3-ylacetat, ble en blanding av 186 g 4-klor-2-oksobenzoetiazolin, 180 g etylbromacetat, 140 g kaliumkarbonat og 1 1 aceton oppvarmet under tilbakeløpskjø-ling i iy2 time. Reaksjonsblandingen ble filtrert og acetonet fjernet fra filtratet ved fordampning. Dette ga en olje som krystalliserte ved behandling med 300 cm<:i> etanol. Det faste stoff ble isolert og omkrystallisert fra etanol. Det erholdtes således etyl-4-klor-2-oksobenzoetialin-3-ylacetat In the preparation of ethyl 4-chloro-2-oxo-benzothiazolin-3-yl acetate, a mixture of 186 g of 4-chloro-2-oxobenzothiazoline, 180 g of ethyl bromoacetate, 140 g of potassium carbonate and 1 L of acetone was heated under reflux in iy2 hours. The reaction mixture was filtered and the acetone removed from the filtrate by evaporation. This gave an oil which crystallized on treatment with 300 cm<:i> of ethanol. The solid was isolated and recrystallized from ethanol. Ethyl 4-chloro-2-oxobenzoethialin-3-yl acetate was thus obtained
i form av et krystallinsk fast stoff, med smeltepunkt 78—79° C. (Funnet: C, 48,4; H, 3,8; N, 5,2. CuH„,ClNOaS krever C, 48,6, H 3,7; N, 5,2 pst.). in the form of a crystalline solid, with a melting point of 78-79° C. (Found: C, 48.4; H, 3.8; N, 5.2. CuH„,ClNOaS requires C, 48.6, H 3 .7; N, 5.2 per cent).
Eksempel 2. Example 2.
En blanding av 12 g 4-klor-2-oksoben-zoetiazol, 31 g etylkloracetat, 15 g kaliumkarbonat og 200 cm3 metyletylketon ble oppvarmet under tilbakeløpskjøling i 60 timer. Etter filtrering ble oppløsningsmid-let fjernet ved destillasjon under forminsket trykk og det etterlot en olje hvortil det ble satt 50 cm<:i> etanol. Avkjøling av denne blanding ga et krystallinsk fast stoff med smeltepunkt 78—79° C, identisk med det som ble erholdt i eksempel 1. A mixture of 12 g of 4-chloro-2-oxobenzothiazole, 31 g of ethyl chloroacetate, 15 g of potassium carbonate and 200 cm 3 of methyl ethyl ketone was heated under reflux for 60 hours. After filtration, the solvent was removed by distillation under reduced pressure and it left an oil to which was added 50 cm<:i> of ethanol. Cooling of this mixture gave a crystalline solid with a melting point of 78-79° C, identical to that obtained in example 1.
Eksempel 3. Example 3.
Natriumhydroksyd (200 cm<3> 1,075 N) ble satt dråpevis under omrøring til en blanding, oppvarmet under tilbakeløps-kjøling, av 54,3 g etyl-4-klor-2-oksobenzoe-tiazolin-3-ylacetat og 200 cm'<1> metanol. Metanol (180 cm<3>) ble fjernet ved destillasjon i løpet av 30 minutter og reaksjonsblandingen ble heilt i Hiter vann. Et lite bunnfall ble oppsamlet og filtratet ble ansyret til Congo-rødt. Ved avkjøling erholdtes et krystallinsk bunnfall. Omkrystalli-sasjon fra etylacetat ga 4-klor-2-oksoben-zoetiazolin-3-yleddiksyre i form av et krystallinsk fast stoff, sm.p. 193° C. (Funnet: C, 44,5; H, 2,4; N, 6,0. CnHcClNOaS krever C, 44,4; H, 2,5; N, 5,7 pst.). Sodium hydroxide (200 cm<3> 1.075 N) was added dropwise with stirring to a mixture, heated under reflux, of 54.3 g of ethyl 4-chloro-2-oxobenzoe-thiazolin-3-yl acetate and 200 cm'< 1> methanol. Methanol (180 cm<3>) was removed by distillation over 30 minutes and the reaction mixture was poured into hot water. A small precipitate was collected and the filtrate was acidified to Congo red. On cooling, a crystalline precipitate was obtained. Recrystallization from ethyl acetate gave 4-chloro-2-oxobenzo-zoetiazolin-3-ylacetic acid as a crystalline solid, m.p. 193° C. (Found: C, 44.5; H, 2.4; N, 6.0. CnHcClNOaS requires C, 44.4; H, 2.5; N, 5.7 per cent).
Eksempel 4. Example 4.
4-klor-2-oksobenzoetiazolin-3-yleddik-syre (5,0 g) ble oppvarmet under tilbake-løpskjøling med 15 cm<3> tionylklorid. Over-skudd av tionylklorid ble fjernet ved destillasjon under forminsket trykk. Det rå syreklorid ble destillert ved 1—2 mm (kokepunkt 110—130° C) slik at det ga en olje som krystalliserte ved henstand. Dette 4-klor-2-oksobenzoetiazolin-3-ylacetylklorid ble oppvarmet under tilbakeløpskjøling med metanol. Ved avkjøling erholdtes kry-staller. Disse ble oppsamlet og omkrystallisert fra metanol, slik at de ga metyl-4-klor-2-oksobenzoe-tiazolin-3-ylacetat, smeltepunkt 126—127° C. (Funnet: C, 46,3; 4-Chloro-2-oxobenzothiazolin-3-ylacetic acid (5.0 g) was heated under reflux with 15 cm<3> thionyl chloride. Excess thionyl chloride was removed by distillation under reduced pressure. The crude acid chloride was distilled at 1-2 mm (boiling point 110-130° C) so that it gave an oil which crystallized on standing. This 4-chloro-2-oxobenzothiazolin-3-ylacetyl chloride was heated under reflux with methanol. On cooling, crystals were obtained. These were collected and recrystallized from methanol, so that they gave methyl-4-chloro-2-oxobenzoe-thiazolin-3-yl acetate, melting point 126-127° C. (Found: C, 46.3;
H, 3,2. doHsClNO^S krever C, 46,7; H, 3,2 pst.). H, 3.2. doHsClNO^S requires C, 46.7; H, 3.2 per cent).
Eksempel 5. Example 5.
En blanding av 10 g 4-klor-2-oksoben-zoetiazolin-3-ylacetylklorid, 5 g 2-2'-butok-syetoksyetanol, 5 g pyridin og 200 cm3 eter ble oppvarmet under tilbakeløpskjøling i 2 timer. Reaksjonsblandingen ble vasket med iskald 5N-svovelsyre, vann, vandig natriumbikarbonat og vann i rekkefølge, og eteren ble deretter fjernet ved destillasjon. Det gummiaktige residuum ble destillert slik at det ga 2-2'-butoksyetoksyetyl-4-klor-2-oksobenzoetiazolin-3-ylacetat i form av en olje, kokepunkt 190° C/0,075 mm. (Funnet: C, 52,0; H, 5,6. CitHmCINObS krever C, 52,6; 5,7 pst.). A mixture of 10 g of 4-chloro-2-oxobenzene-zoethiazolin-3-ylacetyl chloride, 5 g of 2-2'-butoxyethoxyethanol, 5 g of pyridine and 200 cm 3 of ether was heated under reflux for 2 hours. The reaction mixture was washed with ice-cold 5N sulfuric acid, water, aqueous sodium bicarbonate, and water in sequence, and the ether was then removed by distillation. The gummy residue was distilled to give 2-2'-butoxyethoxyethyl-4-chloro-2-oxobenzothiazolin-3-yl acetate as an oil, b.p. 190° C./0.075 mm. (Found: C, 52.0; H, 5.6. CitHmCINObS requires C, 52.6; 5.7 percent).
Eksempel 6. Example 6.
4-brom-2-oksobenzoetiazolin (2,1 g), etylbromacetat (2 cm<3>), kaliumkarbonat (2 g) og aceton (80 cm<3>) ble oppvarmet under tilbakeløpskjøling i 1,5 time. Etter filtrering ble acetonet fjernet ved destillasjon og 30 cm<3> etanol ble satt til residuet. Det ble langsomt dannet et krystallinsk bunnfall og dette ble isolert og omkrystallisert fra etanol, slik at det ga etyl-4-brom-2-oksobenzoetiazolin-3-ylacetat, smeltepunkt 89,5—90° C. (Funnet: C, 41,6; H, 3,2. CnHioBrNOnS krever C, 41,8; H, 3,2 pst.). 4-Bromo-2-oxobenzoethiazoline (2.1 g), ethyl bromoacetate (2 cm<3>), potassium carbonate (2 g) and acetone (80 cm<3>) were heated under reflux for 1.5 hours. After filtration, the acetone was removed by distillation and 30 cm<3> of ethanol was added to the residue. A crystalline precipitate was slowly formed and this was isolated and recrystallized from ethanol, so that it gave ethyl-4-bromo-2-oxobenzothiazolin-3-yl acetate, melting point 89.5-90° C. (Found: C, 41, 6; H, 3.2. CnHioBrNOnS requires C, 41.8; H, 3.2 per cent).
Eksempel 7. Example 7.
En blanding av 1 g etyl-4-brom-2-okso-benzoetiazolin-3-ylacetat og 25 cm<3> 10-N. saltsyre ble oppvarmet under tilbakeløps-kjøling i 2 timer. Ved slutten av denne tid ble rqaksjonsblandingen ekstrahert med eter, og eterekstrakten ble ekstrahert med vandig natriumbikarbonat. Ansyring av natriumbikarbonatekstraktet ga et bunnfall, som ble oppsamlet og omkrystallisert fra etylacetat. Det erholdtes således 4-brom-2-oksobenzoetiazolin-3-yleddiksyre, med smeltepunkt 190,5—191° C. (Funnet: C, 37,4; H, 2,0. CnH.iBrNOaS krever C, 37,5; H, 2,1 pst.). A mixture of 1 g of ethyl-4-bromo-2-oxo-benzothiazolin-3-yl acetate and 25 cm<3> 10-N. hydrochloric acid was heated under reflux for 2 hours. At the end of this time, the reaction mixture was extracted with ether, and the ether extract was extracted with aqueous sodium bicarbonate. Acidification of the sodium bicarbonate extract gave a precipitate, which was collected and recrystallized from ethyl acetate. 4-bromo-2-oxobenzoethiazolin-3-ylacetic acid was thus obtained, with melting point 190.5-191° C. (Found: C, 37.4; H, 2.0. CnH.iBrNOaS requires C, 37.5; H, 2.1 per cent).
Eksempel 8. Example 8.
4-klor-2-oksobenzoetiazolin (18,5 g) i 100 cm<3> isobutanol og 30 cm<:l> toluol ble oppvarmet med natriumhydroksyd (4,5 g) og vannet fjernet ved azeotropisk destillasjon. Det erholdtes således en grøt av na-triumderivatet. Natriumkloracetat (12,8 g) ble satt til den avkjølte grøt og blandingen ble oppvarmet til 105° C i 3 timer. Det ble tilsatt 300 cm<3> vann og isobutanolet ble ekstrahert med eter. Den vandige fase ble surgjort og deretter gjort alkalisk med natriumbikarbonat. Det uoppløselige 4-klor-2-oksobenzoetiazolin ble fjernet ved filtrering og ansyring av filtratet ga en lys gul gummi som hurtig størknet. To omkry-stallisasjoner fra etylacetat ga 4-klor-2-ok-sobenxoetiazolin-3-yleddiksyre, identisk med den som ble oppnådd i eksempel 3. 4-Chloro-2-oxobenzothiazoline (18.5 g) in 100 cm<3> of isobutanol and 30 cm<:1> of toluene was heated with sodium hydroxide (4.5 g) and the water removed by azeotropic distillation. A slurry of the sodium derivative was thus obtained. Sodium chloroacetate (12.8 g) was added to the cooled mash and the mixture was heated to 105°C for 3 hours. 300 cm<3> of water was added and the isobutanol was extracted with ether. The aqueous phase was acidified and then made alkaline with sodium bicarbonate. The insoluble 4-chloro-2-oxobenzoethiazoline was removed by filtration and acidification of the filtrate gave a light yellow gum which quickly solidified. Two recrystallizations from ethyl acetate gave 4-chloro-2-oxobenzothiazolin-3-ylacetic acid, identical to that obtained in Example 3.
Eksempel 9. Example 9.
En blanding av 4-klor-2-oksobenzoetia-zolin (6,0 g), kloracetonitril (3 cm<3>), kaliumkarbonat (5 g) og aceton (50 cm<8>) ble oppvarmet under tilbakeløpskjøling i 6 timer. Acetonet ble fordampet og etanol ble tilsatt residuet og ga da et fast bunnfall. Dette ble omkrystallisert fra etanol og ga 4-klor-2-oksobenzoe-tiazolin-3-ylacetoni-tril, med smeltepunkt 160,5—161° C. (Funnet: C, 48,3; H, 2,3. CHbCINi.OS krever C, 48,1; H, 2,2 pst.). A mixture of 4-chloro-2-oxobenzoethiazoline (6.0 g), chloroacetonitrile (3 cm<3>), potassium carbonate (5 g) and acetone (50 cm<8>) was heated under reflux for 6 hours. The acetone was evaporated and ethanol was added to the residue, giving a solid precipitate. This was recrystallized from ethanol to give 4-chloro-2-oxobenzoe-thiazolin-3-ylacetonitrile, mp 160.5-161° C. (Found: C, 48.3; H, 2.3. CHbCINi. OS requires C, 48.1; H, 2.2 per cent).
Nitrilet (2 g) som var fremstilt som ovenfor og svovelsyre (30 cm<3> av 30 volumpst.) ble oppvarmet til 130—140° C i % time. Avkjøling av reaksjonsblandingen ga et bunnfall som ble isolert, vasket med vann og tørket, Produktet hadde et smeltepunkt på 193° C, og var identisk med den 4-klor-2-oksobenzoetiazolin-3-yleddiksyre som ble fremstilt i eksempel 3. The nitrile (2 g) which was prepared as above and sulfuric acid (30 cm<3> of 30 vol.) were heated to 130-140° C. for 1 hour. Cooling of the reaction mixture gave a precipitate which was isolated, washed with water and dried. The product had a melting point of 193° C, and was identical to the 4-chloro-2-oxobenzoethiazolin-3-ylacetic acid which was prepared in example 3.
Eksempel 10. Example 10.
En blanding av 4-klor-2-oksobenzo-etiazolin (7 g), 2-kloracetamid (3,5 g), kaliumkarbonat (10 g) og aceton (75 cm<3>) A mixture of 4-chloro-2-oxobenzo-ethiazoline (7 g), 2-chloroacetamide (3.5 g), potassium carbonate (10 g) and acetone (75 cm<3>)
ble oppvarmet under tilbakeløpskjøling i was heated under reflux i
12 timer. Reaksjonsblandingen ble helt i 12 hours. The reaction mixture was poured into
vann og det uoppløselige faste stoff ble oppsamlet og omkrystallisert to ganger fra iseddik og ga 4-klor-2-oksobenzoe-tiazolin-3-ylacetamid, med smeltepunkt 280—282° C (med dekomponering). (Funnet: C, 44,9; water and the insoluble solid was collected and recrystallized twice from glacial acetic acid to give 4-chloro-2-oxobenzoe-thiazolin-3-ylacetamide, m.p. 280-282°C (with decomposition). (Found: C, 44.9;
H, 3,1; N, 11,6. CoHtCIN^S krever C, 44,5; H, 3.1; N, 11.6. CoHtCIN^S requires C, 44.5;
H, 2,9; N, 11,3 pst.). H, 2.9; N, 11.3 per cent).
Amidet (3 g) som ble fremstilt ovenfor og svovelsyre (30 cm<3> av 70 volumpst. ble oppvarmet i 20 minutter ved 130—140° C. Reaksjonsproduktet ble avkjølt og ga et bunnfall som var isolert vasket med vann og tørket. Dette materiale, med smeltepunkt 193° C, var identisk med 4-klor-2-oksoben-zoetiazolin-3-yleddiksyre som ble fremstilt i eksempel 3. The amide (3 g) prepared above and sulfuric acid (30 cm<3> of 70% by volume were heated for 20 minutes at 130-140° C. The reaction product was cooled and gave a precipitate which was isolated, washed with water and dried. This material, with melting point 193° C, was identical to 4-chloro-2-oxoben-zoetiazolin-3-ylacetic acid which was prepared in example 3.
Eksempel 11. Example 11.
4-klor-2-oksobenzoetiazolin (9,3 g) ble oppløst i varm 2,2 N. natriumhydroksyd-oppløsning (22,8 cm<3>) og oppløsningen ble kokt under tilbakeløpskjøling. Det ble deretter tilsatt dråpevis 9,9 g cyanometyl-benzolsulfonat under omrøring. Etter at tilsetningen var fullstendig, ble reaksjonsproduktet kokt i 10 minutter til og deretter avkjølt. Det faste bunnfall som erholdtes på denne måte ble isolert ved filtrering og omkrystallisert fra etanol og ga 4-klor-2-oksobenzoetiazolin-3-ylacetonitril, smeltepunkt 160—161° C, og var identisk med det som ble oppnådd i eksempel 9. 4-Chloro-2-oxobenzothiazoline (9.3 g) was dissolved in hot 2.2 N sodium hydroxide solution (22.8 cm<3>) and the solution was boiled under reflux. 9.9 g of cyanomethylbenzenesulfonate were then added dropwise with stirring. After the addition was complete, the reaction product was boiled for another 10 minutes and then cooled. The solid precipitate obtained in this way was isolated by filtration and recrystallized from ethanol to give 4-chloro-2-oxobenzothiazolin-3-ylacetonitrile, melting point 160-161° C., and was identical to that obtained in Example 9.
Eksempel 12. Example 12.
Kalium-4-klor-2-oksobenzoetiazolin-3-ylacetat (28,2 g) og etylalfa-brompropio-nat (18,1 g) ble kokt under tilbakeløps-kjøling i etyllaktat (100 cm<3>) i 1 time. Reaksjonsblandingen ble avkjølt, helt i 1 liter vann og produktet ble ekstrahert med metylenklorid. Ekstrakten ble tørket over vannfritt magnesiumsulfat og oppløs-ningsmidlet fjernet ved destillasjon. Ved to destillasjoner i vakuum av residuet ble det oppnådd etylalfa-(4-klor-2-oksobenzo-etiazolin-3-ylacetoksy)-propionat, med kokepunkt 187—190° C/0,5 mm. (Funnet: C, 49,1; H, 4,2; N, 4,5. CmHuCINObS krever C, 49,0; H, 4,1; N, 4,1 pst.). Potassium 4-chloro-2-oxobenzothiazolin-3-yl acetate (28.2 g) and ethyl alpha-bromopropionate (18.1 g) were refluxed in ethyl lactate (100 cm<3>) for 1 hour. The reaction mixture was cooled, poured into 1 liter of water and the product was extracted with methylene chloride. The extract was dried over anhydrous magnesium sulfate and the solvent removed by distillation. By two distillations in vacuum of the residue, ethyl alpha-(4-chloro-2-oxobenzo-etiazolin-3-ylacetoxy)-propionate was obtained, with a boiling point of 187-190° C/0.5 mm. (Found: C, 49.1; H, 4.2; N, 4.5. CmHuCINObS requires C, 49.0; H, 4.1; N, 4.1 percent).
Eksempel 13. Example 13.
Etyl-2-oksobenzoetiazolin-3-ylacetat (11,9 g) ble oppløst i benzol (100 cm<3>) og en oppløsning av sulfurylklorid (6,8 g) i benzol (50 cm<3>) ble satt til dråpevis under : omrøring i 15 minutter. Temperaturen i i reaksjonsblandingen ble deretter langsomt i hevet inntil den kokte, hvoretter oppløs- i ningsmidlet ble fjernet ved fordampning, Det oljeaktige residuum krystalliserte ved : avkjøling og hadde smeltepunkt 78—83° C. Ethyl 2-oxobenzothiazolin-3-yl acetate (11.9 g) was dissolved in benzene (100 cm<3>) and a solution of sulfuryl chloride (6.8 g) in benzene (50 cm<3>) was added dropwise under: stirring for 15 minutes. The temperature of the reaction mixture was then slowly raised until it boiled, after which the solvent was removed by evaporation. The oily residue crystallized on cooling and had a melting point of 78-83° C.
Det faste stoff (13,6 g) som erholdtes på denne måte og som besto av en blanding av etyl-klor-2-oksobenzoetiazolin-3-ylace-tater ble oppløst i metanol (50 cm<3>) og oppløsningen ble oppvarmet til kokning. N.-natrium-hydroksyd (50 cm<3>) ble deretter satt dråpevis til under omrøring med en slik hastighet at det ikke oppsto noen uklarhet i oppløsningen. Metanolen ble til-latt å destillere langsomt under tilsetningen og endelig ble alt metanol fjernet på dampbad og den resterende oppløsning av-kjølt til 0° C ved tilsetning av is. Blandingen ble ansyret ved tilsetning av fortynnet saltsyre og det faste stoff ble isolert ved filtrering. Det hadde smeltepunkt 150 —160° C. Ved hjelp av infrarød analyse, ble det faste stoff bestemt til å inneholde omtrent 60 pst. 2-oksobenzoetiazolin-3-yleddiksyre, 20 pst. 6-klor-2-oksobenzo-etiazolin-3-yleddiksyre og 7 pst. 4-klor-2-oksobenzoetiazolin-3-yleddiksyre. The solid (13.6 g) thus obtained, which consisted of a mixture of ethyl chloro-2-oxobenzothiazolin-3-ylacetates, was dissolved in methanol (50 cm<3>) and the solution was heated to boiling. N-sodium hydroxide (50 cm<3>) was then added dropwise with stirring at such a rate that no turbidity occurred in the solution. The methanol was allowed to distill slowly during the addition and finally all the methanol was removed on a steam bath and the remaining solution cooled to 0°C by adding ice. The mixture was acidified by the addition of dilute hydrochloric acid and the solid was isolated by filtration. It had a melting point of 150-160° C. By means of infrared analysis, the solid was determined to contain about 60 percent 2-oxobenzothiazolin-3-ylacetic acid, 20 percent 6-chloro-2-oxobenzo-thiazolin-3- ylacetic acid and 7 percent 4-chloro-2-oxobenzoethiazoline-3-ylacetic acid.
Eksempel 14. Example 14.
Ved tilberedning av et ugressdrepemiddel-støv, ble 2,5 vektsdeler 4-klor-2-okso-benzoetiazolin-3-yleddiksyre grundig blandet med 97,5 vektsdeler kaolin. In the preparation of a herbicide dust, 2.5 parts by weight of 4-chloro-2-oxo-benzothiazolin-3-ylacetic acid was thoroughly mixed with 97.5 parts by weight of kaolin.
Lignende blandinger ble fremstilt idet det ble anvendt forbindelser ifølge oppfinnelsen, beskrevet i eksemplene 1, 4, 5, 6, 7, 9, 10 og 12, i stedet for 4-klor-2-oksobenzo-etiazolin-3-yleddiksyre. Similar mixtures were prepared using compounds according to the invention, described in Examples 1, 4, 5, 6, 7, 9, 10 and 12, instead of 4-chloro-2-oxobenzo-ethiazolin-3-ylacetic acid.
Eksempel 15. Example 15.
Ved fremstilling av et dispergerbart pulver ble 20 vektsdeler 4-klor-2-oksoben-zoetiazolin-3-yleddiksyre grundig blandet med 8 vektsdeler Belloid T. D. (varemerke for dispergeringsmiddel som er et konden-sat av formaldehyd og et alkylarylsulfonat) og 72 vektsdeler kaolin. Blandingen kan settes til vann og danne en dispersjon som egner seg for bruk som ugressdrepemiddel. In the preparation of a dispersible powder, 20 parts by weight of 4-chloro-2-oxobenzene-zoetiazolin-3-ylacetic acid were thoroughly mixed with 8 parts by weight of Belloid T.D. (trademark for a dispersant which is a condensate of formaldehyde and an alkylaryl sulphonate) and 72 parts by weight of kaolin. The mixture can be added to water and form a dispersion suitable for use as a herbicide.
Liknende blandinger ble fremstilt, idet det ble anvendt forbindelser ifølge oppfinnelsen, som er beskrevet i eksemplene 1, 4, 5, 6, 7, 9, 10 og 12 i stedet for 4-klor-2-okso-benzoetiazolin-3-yleddiksyre. Similar mixtures were prepared, using compounds according to the invention, which are described in examples 1, 4, 5, 6, 7, 9, 10 and 12 instead of 4-chloro-2-oxo-benzothiazolin-3-ylacetic acid.
Eksempel 16. Example 16.
Ved fremstilling av en ugressdrepemiddelblanding ble 4 g 4-klor-2-oksobenzoetia- In the preparation of a herbicide mixture, 4 g of 4-chloro-2-oxobenzoethia-
solin-3-yleddiksyre oppløst under oppvarm-ning i en oppløsning av 1,75 g dietanolamin i 50 cm3 vann. Oppløsningen ble fortynnet til 1000 cm<3> ved tilsetning av vann. Det ble således oppnådd en vandig oppløsning som inneholdt 0,4 vektspst. 4-klor-2-oksobenzo-etiazolin-3-yleddiksyre i form av sitt dietanolaminsalt. solin-3-ylacetic acid dissolved under heating in a solution of 1.75 g of diethanolamine in 50 cm3 of water. The solution was diluted to 1000 cm<3> by adding water. An aqueous solution containing 0.4% by weight was thus obtained. 4-Chloro-2-oxobenzo-etiazolin-3-ylacetic acid in the form of its diethanolamine salt.
Eksempel 17. Example 17.
Ved fremstilling av en ugressdrepemiddelblanding ble 4 g 4-klor-2-oksobenzo-etiazolin-3-yleddiksyre oppløst under opp-varmning i en oppløsning som inneholdt 1,75 g dietanolamin og 0,2 g Manoxol N (varemerke for et fuktemiddel som er natrium-dinonyl-sulfosuccinat) i 50 cm3 vann. Opp-løsningen ble fortynnet til 1000 cm<3> ved tilsetning av vann, for å oppnå en vandig oppløsning som inneholdt 0,4 vektspst. 4t klor-2-oksobenzoetiazolin-3-yleddiksyre i form av dens dietanolaminsalt. In the preparation of a herbicide mixture, 4 g of 4-chloro-2-oxobenzo-ethiazolin-3-ylacetic acid was dissolved under heating in a solution containing 1.75 g of diethanolamine and 0.2 g of Manoxol N (trademark for a wetting agent which is sodium dinonyl sulfosuccinate) in 50 cm3 of water. The solution was diluted to 1000 cm<3> by adding water, to obtain an aqueous solution containing 0.4 wt. 4t Chloro-2-oxobenzothiazolin-3-ylacetic acid in the form of its diethanolamine salt.
Eksempel 18. Example 18.
Ved fremstilling av en ugressdrepemiddelblanding ble 4 g 4-klor-2-oksobenzoetia-zolin-3-yleddiksyre oppløst under oppvarm-ning i 50 cm<3> av en vandig oppløsning som inneholdt 0,66 g natriumhydroksyd. Opp-løsningen ble fortynnet til 1000 cm<3> ved tilsetning av vann, slik at det erholdtes en vandig oppløsning som inneholdt 0,4 vektspst. 4-klor-2-oksobenzoetiazolin-3-yleddik-syre i form av dens natriumsalt. In the preparation of a herbicide mixture, 4 g of 4-chloro-2-oxobenzoethia-zolin-3-ylacetic acid was dissolved under heating in 50 cm<3> of an aqueous solution containing 0.66 g of sodium hydroxide. The solution was diluted to 1000 cm<3> by adding water, so that an aqueous solution containing 0.4% by weight was obtained. 4-Chloro-2-oxobenzothiazolin-3-ylacetic acid in the form of its sodium salt.
Eksempel 19. Example 19.
Ved fremstilling av en ugressdrepemiddelblanding ble 4 g 4-klor-2-oksobenzo-etiazolin-3-yleddiksyre oppløst under opp-varmning i 50 cm3 av en vandig oppløsning som inneholdt 0,66 g natriumhydroksyd og 0,2 g Manoxol N. Oppløsningen ble fortynnet til 1000 cm<3> ved tilsetning av vann. In the preparation of a herbicide mixture, 4 g of 4-chloro-2-oxobenzo-ethiazolin-3-ylacetic acid was dissolved under heating in 50 cm 3 of an aqueous solution containing 0.66 g of sodium hydroxide and 0.2 g of Manoxol N. The solution was diluted to 1000 cm<3> by adding water.
Liknende blandinger som de som er beskrevet i eksemplene 16—19 ble fremstilt idet det anvendtes 4-brom-2-oksobenzo-etiazolin-3-yleddiksyre i stedet for 4-klor-2-oksobenzoetiazolin-3-yleddiksyre. Mixtures similar to those described in Examples 16-19 were prepared using 4-bromo-2-oxobenzo-thiazolin-3-ylacetic acid instead of 4-chloro-2-oxobenzothiazolin-3-ylacetic acid.
Eksempel 20. Example 20.
Ved fremstilling av en dispergerbar oppløsning ble 8 g 4-klor-2-oksobenzoetia-zolin-3-yleddiksyre oppløst i 100 cm3 aceton inneholdende 2 g Belloid T. D. When preparing a dispersible solution, 8 g of 4-chloro-2-oxobenzoethia-zolin-3-ylacetic acid was dissolved in 100 cm3 of acetone containing 2 g of Belloid T.D.
Liknende blandinger ble fremstilt, idet det ble anvendt etyl- og metylestere av 4-klor-2-oksobenzoetiazolin-3-yleddiksyre og 4-brom-2-oksobenzoetiazolin-3-yleddik-syre og dens etylester i stedet for 4-klor-2-oksobenzoetiazolin-3-yleddiksyre. Similar mixtures were prepared, using ethyl and methyl esters of 4-chloro-2-oxobenzothiazolin-3-ylacetic acid and 4-bromo-2-oxobenzothiazolin-3-ylacetic acid and its ethyl esters instead of 4-chloro-2 -oxobenzothiazolin-3-ylacetic acid.
Eksempel 21. Example 21.
Ved fremstilling av en vandig emulsjon ble 4,5 g etyl-4-klor-2-oksobenzoetia-zolin-3-ylacetat blandet med 50 cm<3> xylol inneholdende 1 cm3 Ethylan S. E. (varemerke for emulgeringsmiddel som er en blanding av laurindietanolamid og et poly-etylenoksyd-kondensat av en oktylfenol). Blandingen ble fortynnet til 1000 cm<3> ved tilsetning av vann. In the preparation of an aqueous emulsion, 4.5 g of ethyl 4-chloro-2-oxobenzoethia-zolin-3-yl acetate was mixed with 50 cm<3> xylol containing 1 cm 3 of Ethylan S. E. (trademark for emulsifier which is a mixture of lauric diethanolamide and a polyethylene oxide condensate of an octylphenol). The mixture was diluted to 1000 cm<3> by adding water.
Eksempel 22. Example 22.
Ved fremstilling av konsentrerte vandige oppløsninger som egner seg for fortynning med vann for å oppnå ugressdre-pemiddelblandinger for påføring på planter, ble følgende bestanddeler anvendt. In the preparation of concentrated aqueous solutions suitable for dilution with water to obtain herbicide mixtures for application to plants, the following ingredients were used.
a) Natrium-4-klor-2-oksobenzoetia- a) Sodium 4-chloro-2-oxobenzoethia-
zolin-3-ylacetat 20 g s. e. zolin-3-yl acetate 20 g s. e.
Vann innntil 100 cm3, Water up to 100 cm3,
b) Dietanolamin-4-klor-2-oksoben-zoetiazolin-3-ylacetat 20 g s. e. b) Diethanolamine-4-chloro-2-oxobenzene-zoetiazolin-3-yl acetate 20 g s. e.
Vann inntil 100 cm<3>, Water up to 100 cm<3>,
(s. e. betyr syreekvivalent). (s. e. means acid equivalent).
Eksempel 23. Example 23.
Ved forsøk utført i marken for å under-søke videre 4-klor-2-oksobenzoetiazolin-3-yleddiksyre og dens etylester, ble det utført vanlige prøver. Prøvene 1, 2 og 3 oppsum-merer disse, «%-kontrollen» er basert på frisk vekt av arealdelene av ugress i disse tre prøver sammenliknet med ubehandlede kontroller. In experiments carried out in the field to investigate further 4-chloro-2-oxobenzothiazolin-3-ylacetic acid and its ethyl ester, ordinary tests were carried out. Samples 1, 2 and 3 summarize these, the "% control" is based on fresh weight of the area parts of weeds in these three samples compared to untreated controls.
Prøve 1. Plagsomt ugress — klenge-maure ( Galium aparine). Sample 1. Noxious weed — klenge-maure ( Galium aparine).
Prøve 3. Plagsomt ugress — vassarv ( Stellaria media). Sample 3. Noxious weeds — water sedge ( Stellaria media).
Ved denne prøve var det ikke mulig å gjøre en kvantitativ bestemmelse, men det ble oppnådd i det vesentlige 100 pst.'s eli-minering av ugresset ved anvendelse av etylesteren med 28, 56 og 112 g s. e. pr. mål, bestemt ved visuell inspeksjon av marken. In this test it was not possible to make a quantitative determination, but essentially 100% elimination of the weeds was achieved by using the ethyl ester with 28, 56 and 112 g s.e. per target, determined by visual inspection of the field.
Eksempel 24. Example 24.
En blanding som er egnet for anvendelse for planter etter fortynning med vann ble fremstilt med følgende bestanddeler : A mixture suitable for application to plants after dilution with water was prepared with the following ingredients:
I Dietanolaminsalt av 4-klor-2-okso- I Diethanolamine salt of 4-chloro-2-oxo-
' benzoetiazolin-3-yleddiksyre 10 g s. e. ' benzoethiazolin-3-ylacetic acid 10 g s. e.
Dietanolaminsalt av M.C.P.A. 20 g s. e. Vann inntil 100 cm<3>. Diethanolamine salt of M.C.P.A. 20 g s. e. Water up to 100 cm<3>.
Eksempel 25. Example 25.
Vandige oppløsninger av dietanol-aminsaltet av M.C.P.A., ble tilsatt forskjellige mengder av etyl-4-klor-2-oksobenzoe-tiazolin-3-ylacetat og Ethylan S. E. (varemerke for emulgeringsmiddel) i en blanding av like volum aceton og toluol for å gi en emulsjon inneholdende 100 vektspst. ester, idet vekten av Ethylan S.E. er halv-parten av esteren i hvert tilfelle. Blandinger inneholdende esteren og saltet i forhol-dene 1:4, 1:2 og 1:1 (syre-ekvivalent) Aqueous solutions of the diethanolamine salt of M.C.P.A., were added various amounts of ethyl 4-chloro-2-oxobenzoe-thiazolin-3-yl acetate and Ethylan S.E. (trademark for emulsifier) in a mixture of equal volumes of acetone and toluene to give a emulsion containing 100 wt. ester, the weight of Ethylan S.E. is half of the ester in each case. Mixtures containing the ester and the salt in the ratios 1:4, 1:2 and 1:1 (acid equivalent)
ble fremstilt. Vanlige små områdeprøver was produced. Regular small area samples
ble utført med disse blandinger, hvilke ble were carried out with these mixtures, which were
fortynnet med vann før bruk og ble påført diluted with water before use and applied
i mengder som svarte til 45 l/mål. Prøve-detaljene var som følger, idet ugresskon-trollen ble betegnet med samme reaksjons- in amounts equivalent to 45 l/measure. The test details were as follows, as the weed control was designated with the same reaction
angivelser på 0—6 som ble anvendt ved prøvene som beskrevet tidligere i beskri-velsen. Ugresskontroll hvor det ble anvendt bare etyl-4-klor-2-oksobenzoetiazolin-3-ylacetat er også vist. indications of 0-6 which were used in the tests as described earlier in the description. Weed control using only ethyl 4-chloro-2-oxobenzoethiazolin-3-yl acetate is also shown.
Prøve 4. Plagsomt ugress — balderbrå Sample 4. Noxious weeds — knotweed
( Matricaria inodora). (Matricaria inodora).
Eksempel 26. Example 26.
En blanding som egner seg for på-føring på planter etter fortynning med A mixture suitable for application to plants after dilution with
vann ble fremstilt med følgende bestanddeler: Dietanolaminsalt av 4-klor-2-okso-benzoetiazolin-3-yleddiksyre 5 g s. e. water was prepared with the following ingredients: Diethanolamine salt of 4-chloro-2-oxo-benzothiazolin-3-ylacetic acid 5 g s. e.
Dietanolaminsalt av C.M.P.P. 20 g s. e. Diethanolamine salt of C.M.P.P. 20 g s.e.
Vann inntil 100 cm<3>. Water up to 100 cm<3>.
Claims (7)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19722203445 DE2203445A1 (en) | 1972-01-25 | 1972-01-25 | MOLDED ALUMINUM OBJECT WITH OXIDE SURFACE |
Publications (2)
Publication Number | Publication Date |
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NO133455B true NO133455B (en) | 1976-01-26 |
NO133455C NO133455C (en) | 1976-05-05 |
Family
ID=5833984
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Application Number | Title | Priority Date | Filing Date |
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NO280/73A NO133455C (en) | 1972-01-25 | 1973-01-24 |
Country Status (7)
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US (1) | US3862892A (en) |
JP (1) | JPS4883042A (en) |
CH (1) | CH594070A5 (en) |
DE (1) | DE2203445A1 (en) |
FR (1) | FR2169259B1 (en) |
IT (1) | IT978434B (en) |
NO (1) | NO133455C (en) |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS60159195A (en) * | 1984-01-30 | 1985-08-20 | Pentel Kk | Thin film body of aluminum oxide |
JPS60181295A (en) * | 1984-02-27 | 1985-09-14 | Pentel Kk | Manufacture of aluminum or aluminum alloy substrate having oxide film |
JPS62199797A (en) * | 1986-02-25 | 1987-09-03 | Deitsupusoole Kk | Flexible metal-ceramic composite material and its production |
DE4104847A1 (en) * | 1991-02-16 | 1992-08-20 | Friebe & Reininghaus Ahc | Prodn. of uniform ceramic layers on metal surfaces by spark discharge - partic. used for metal parts of aluminium@, titanium@, tantalum, niobium, zirconium@, magnesium@ and their alloys with large surface areas |
DE4239391C2 (en) * | 1991-11-27 | 1996-11-21 | Electro Chem Eng Gmbh | Objects made of aluminum, magnesium or titanium with an oxide ceramic layer filled with fluoropolymers and process for their production |
DE4139006C3 (en) * | 1991-11-27 | 2003-07-10 | Electro Chem Eng Gmbh | Process for producing oxide ceramic layers on barrier layer-forming metals and objects produced in this way from aluminum, magnesium, titanium or their alloys with an oxide ceramic layer |
KR100482862B1 (en) * | 1994-11-16 | 2005-04-15 | 가부시키가이샤 고베 세이코쇼 | Surface treatment for vacuum chamber made of aluminum or its alloy |
US5720866A (en) * | 1996-06-14 | 1998-02-24 | Ara Coating, Inc. | Method for forming coatings by electrolyte discharge and coatings formed thereby |
US6245436B1 (en) | 1999-02-08 | 2001-06-12 | David Boyle | Surfacing of aluminum bodies by anodic spark deposition |
US6197178B1 (en) | 1999-04-02 | 2001-03-06 | Microplasmic Corporation | Method for forming ceramic coatings by micro-arc oxidation of reactive metals |
US20060207884A1 (en) * | 2005-03-17 | 2006-09-21 | Volodymyr Shpakovsky | Method of producing corundum layer on metal parts |
DE102007046775A1 (en) * | 2007-09-27 | 2009-04-02 | Friedrich-Schiller-Universität Jena | Generating nanocrystalline metallic oxide and metal mixed oxide layers on barrier layer-forming metals e.g. aluminum of substrate, comprises anodically degreasing the substrate in galvanic electrolysis and then anodizing in electrolytes |
TWI465301B (en) * | 2012-09-25 | 2014-12-21 | Univ Southern Taiwan Sci & Tec | Preparation device of porous alumina template |
CN105706231A (en) * | 2013-10-24 | 2016-06-22 | 罗杰斯公司 | Thermal management circuit materials, method of manufacture thereof, and articles formed therefrom |
CN112345691B (en) * | 2020-12-07 | 2022-08-19 | 武汉海斯普林科技发展有限公司 | Method for detecting content of chloride ions in electrolyte solute of aluminum electrolytic capacitor |
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US2346658A (en) * | 1938-12-02 | 1944-04-18 | Brennan | Corrosion resistant coating |
US3293158A (en) * | 1963-09-17 | 1966-12-20 | Mcneill William | Anodic spark reaction processes and articles |
FR1595008A (en) * | 1968-12-11 | 1970-06-08 | ||
US3531385A (en) * | 1968-12-13 | 1970-09-29 | Matsushita Electric Ind Co Ltd | Method of forming electrical insulating film on aluminium metals |
-
1972
- 1972-01-25 DE DE19722203445 patent/DE2203445A1/en active Pending
-
1973
- 1973-01-22 US US325765A patent/US3862892A/en not_active Expired - Lifetime
- 1973-01-23 CH CH93473A patent/CH594070A5/xx not_active IP Right Cessation
- 1973-01-24 IT IT19565/73A patent/IT978434B/en active
- 1973-01-24 NO NO280/73A patent/NO133455C/no unknown
- 1973-01-25 JP JP48010616A patent/JPS4883042A/ja active Pending
- 1973-01-25 FR FR7302655A patent/FR2169259B1/fr not_active Expired
Also Published As
Publication number | Publication date |
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US3862892A (en) | 1975-01-28 |
IT978434B (en) | 1974-09-20 |
FR2169259A1 (en) | 1973-09-07 |
DE2203445A1 (en) | 1973-08-02 |
FR2169259B1 (en) | 1976-04-09 |
NO133455C (en) | 1976-05-05 |
JPS4883042A (en) | 1973-11-06 |
CH594070A5 (en) | 1977-12-30 |
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