CA2155861A1 - Effervescent pesticide tablet with metal perborate - Google Patents
Effervescent pesticide tablet with metal perborateInfo
- Publication number
- CA2155861A1 CA2155861A1 CA 2155861 CA2155861A CA2155861A1 CA 2155861 A1 CA2155861 A1 CA 2155861A1 CA 2155861 CA2155861 CA 2155861 CA 2155861 A CA2155861 A CA 2155861A CA 2155861 A1 CA2155861 A1 CA 2155861A1
- Authority
- CA
- Canada
- Prior art keywords
- group
- alkyl
- amino
- methyl
- alkoxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000000575 pesticide Substances 0.000 title claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 13
- 239000002184 metal Substances 0.000 title claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 22
- 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 claims description 17
- 229910052801 chlorine Inorganic materials 0.000 claims description 17
- 229910052731 fluorine Inorganic materials 0.000 claims description 17
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 17
- 229910052708 sodium Inorganic materials 0.000 claims description 17
- 239000011734 sodium Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 229910052794 bromium Inorganic materials 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 239000007916 tablet composition Substances 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
- -1 NHCH3 Chemical group 0.000 claims description 9
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical compound O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 9
- 125000000262 haloalkenyl group Chemical group 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 6
- 125000001188 haloalkyl group Chemical group 0.000 claims description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 5
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 125000004995 haloalkylthio group Chemical group 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- YROXIXLRRCOBKF-UHFFFAOYSA-N sulfonylurea Chemical class OC(=N)N=S(=O)=O YROXIXLRRCOBKF-UHFFFAOYSA-N 0.000 claims description 4
- 239000005496 Chlorsulfuron Substances 0.000 claims description 3
- 239000005584 Metsulfuron-methyl Substances 0.000 claims description 3
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 3
- 125000004414 alkyl thio group Chemical group 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- VJYIFXVZLXQVHO-UHFFFAOYSA-N chlorsulfuron Chemical compound COC1=NC(C)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=CC=2)Cl)=N1 VJYIFXVZLXQVHO-UHFFFAOYSA-N 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 239000004009 herbicide Substances 0.000 claims description 3
- 239000002917 insecticide Substances 0.000 claims description 3
- RSMUVYRMZCOLBH-UHFFFAOYSA-N metsulfuron methyl Chemical group COC(=O)C1=CC=CC=C1S(=O)(=O)NC(=O)NC1=NC(C)=NC(OC)=N1 RSMUVYRMZCOLBH-UHFFFAOYSA-N 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 239000005586 Nicosulfuron Substances 0.000 claims description 2
- 101100054666 Streptomyces halstedii sch3 gene Proteins 0.000 claims description 2
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 2
- 125000005210 alkyl ammonium group Chemical group 0.000 claims description 2
- 230000000844 anti-bacterial effect Effects 0.000 claims description 2
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 claims description 2
- 239000003899 bactericide agent Substances 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- NSWAMPCUPHPTTC-UHFFFAOYSA-N chlorimuron-ethyl Chemical group CCOC(=O)C1=CC=CC=C1S(=O)(=O)NC(=O)NC1=NC(Cl)=CC(OC)=N1 NSWAMPCUPHPTTC-UHFFFAOYSA-N 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 2
- ZINJLDJMHCUBIP-UHFFFAOYSA-N ethametsulfuron-methyl Chemical group CCOC1=NC(NC)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=CC=2)C(=O)OC)=N1 ZINJLDJMHCUBIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- RTCOGUMHFFWOJV-UHFFFAOYSA-N nicosulfuron Chemical compound COC1=CC(OC)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=CN=2)C(=O)N(C)C)=N1 RTCOGUMHFFWOJV-UHFFFAOYSA-N 0.000 claims description 2
- 125000004076 pyridyl group Chemical group 0.000 claims description 2
- FZMKKCQHDROFNI-UHFFFAOYSA-N sulfometuron Chemical compound CC1=CC(C)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=CC=2)C(O)=O)=N1 FZMKKCQHDROFNI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- XOPFESVZMSQIKC-UHFFFAOYSA-N triasulfuron Chemical compound COC1=NC(C)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=CC=2)OCCCl)=N1 XOPFESVZMSQIKC-UHFFFAOYSA-N 0.000 claims description 2
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims 11
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 4
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 claims 4
- 125000004767 (C1-C4) haloalkoxy group Chemical group 0.000 claims 3
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims 3
- 125000005083 alkoxyalkoxy group Chemical group 0.000 claims 3
- 125000006559 (C1-C3) alkylamino group Chemical group 0.000 claims 2
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 claims 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 2
- 229910052700 potassium Inorganic materials 0.000 claims 2
- 239000011591 potassium Substances 0.000 claims 2
- 125000006650 (C2-C4) alkynyl group Chemical group 0.000 claims 1
- 125000006645 (C3-C4) cycloalkyl group Chemical group 0.000 claims 1
- 239000005472 Bensulfuron methyl Substances 0.000 claims 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- BGNQYGRXEXDAIQ-UHFFFAOYSA-N Pyrazosulfuron-ethyl Chemical compound C1=NN(C)C(S(=O)(=O)NC(=O)NC=2N=C(OC)C=C(OC)N=2)=C1C(=O)OCC BGNQYGRXEXDAIQ-UHFFFAOYSA-N 0.000 claims 1
- 229940100389 Sulfonylurea Drugs 0.000 claims 1
- 125000004687 alkyl sulfinyl alkyl group Chemical group 0.000 claims 1
- 125000004688 alkyl sulfonyl alkyl group Chemical group 0.000 claims 1
- 125000006350 alkyl thio alkyl group Chemical group 0.000 claims 1
- 125000005133 alkynyloxy group Chemical group 0.000 claims 1
- XMQFTWRPUQYINF-UHFFFAOYSA-N bensulfuron-methyl Chemical group COC(=O)C1=CC=CC=C1CS(=O)(=O)NC(=O)NC1=NC(OC)=CC(OC)=N1 XMQFTWRPUQYINF-UHFFFAOYSA-N 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 239000000417 fungicide Substances 0.000 claims 1
- 125000004438 haloalkoxy group Chemical group 0.000 claims 1
- 239000011777 magnesium Substances 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- DTVOKYWXACGVGO-UHFFFAOYSA-N methyl 2-[(4,6-dimethoxypyrimidin-2-yl)carbamoylsulfamoyl]-6-(trifluoromethyl)pyridine-3-carboxylate Chemical compound COC(=O)C1=CC=C(C(F)(F)F)N=C1S(=O)(=O)NC(=O)NC1=NC(OC)=CC(OC)=N1 DTVOKYWXACGVGO-UHFFFAOYSA-N 0.000 claims 1
- ZTYVMAQSHCZXLF-UHFFFAOYSA-N methyl 2-[[4,6-bis(difluoromethoxy)pyrimidin-2-yl]carbamoylsulfamoyl]benzoate Chemical compound COC(=O)C1=CC=CC=C1S(=O)(=O)NC(=O)NC1=NC(OC(F)F)=CC(OC(F)F)=N1 ZTYVMAQSHCZXLF-UHFFFAOYSA-N 0.000 claims 1
- LOQQVLXUKHKNIA-UHFFFAOYSA-N thifensulfuron Chemical compound COC1=NC(C)=NC(NC(=O)NS(=O)(=O)C2=C(SC=C2)C(O)=O)=N1 LOQQVLXUKHKNIA-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 8
- 238000009472 formulation Methods 0.000 abstract description 4
- 239000007938 effervescent tablet Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 8
- QYPPRTNMGCREIM-UHFFFAOYSA-N methylarsonic acid Chemical compound C[As](O)(O)=O QYPPRTNMGCREIM-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 7
- 239000004615 ingredient Substances 0.000 description 7
- 241000282320 Panthera leo Species 0.000 description 6
- 239000002274 desiccant Substances 0.000 description 6
- 159000000000 sodium salts Chemical class 0.000 description 5
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 239000000080 wetting agent Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910052925 anhydrite Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- BSFODEXXVBBYOC-UHFFFAOYSA-N 8-[4-(dimethylamino)butan-2-ylamino]quinolin-6-ol Chemical compound C1=CN=C2C(NC(CCN(C)C)C)=CC(O)=CC2=C1 BSFODEXXVBBYOC-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical group OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000007884 disintegrant Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- 229940060367 inert ingredients Drugs 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 150000004682 monohydrates Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003871 sulfonates Chemical class 0.000 description 2
- GXEKYRXVRROBEV-FBXFSONDSA-N (1r,2s,3r,4s)-7-oxabicyclo[2.2.1]heptane-2,3-dicarboxylic acid Chemical compound C1C[C@@H]2[C@@H](C(O)=O)[C@@H](C(=O)O)[C@H]1O2 GXEKYRXVRROBEV-FBXFSONDSA-N 0.000 description 1
- XQEMNBNCQVQXMO-UHFFFAOYSA-M 1,2-dimethyl-3,5-diphenylpyrazol-1-ium;methyl sulfate Chemical compound COS([O-])(=O)=O.C[N+]=1N(C)C(C=2C=CC=CC=2)=CC=1C1=CC=CC=C1 XQEMNBNCQVQXMO-UHFFFAOYSA-M 0.000 description 1
- YIKWKLYQRFRGPM-UHFFFAOYSA-N 1-dodecylguanidine acetate Chemical class CC(O)=O.CCCCCCCCCCCCN=C(N)N YIKWKLYQRFRGPM-UHFFFAOYSA-N 0.000 description 1
- GOCUAJYOYBLQRH-UHFFFAOYSA-N 2-(4-{[3-chloro-5-(trifluoromethyl)pyridin-2-yl]oxy}phenoxy)propanoic acid Chemical class C1=CC(OC(C)C(O)=O)=CC=C1OC1=NC=C(C(F)(F)F)C=C1Cl GOCUAJYOYBLQRH-UHFFFAOYSA-N 0.000 description 1
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 1
- 101000742062 Bos taurus Protein phosphatase 1G Chemical class 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- NDUPDOJHUQKPAG-UHFFFAOYSA-N Dalapon Chemical class CC(Cl)(Cl)C(O)=O NDUPDOJHUQKPAG-UHFFFAOYSA-N 0.000 description 1
- 239000005644 Dazomet Substances 0.000 description 1
- 239000005630 Diquat Substances 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- XVOKUMIPKHGGTN-UHFFFAOYSA-N Imazethapyr Chemical class OC(=O)C1=CC(CC)=CN=C1C1=NC(C)(C(C)C)C(=O)N1 XVOKUMIPKHGGTN-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000002169 Metam Substances 0.000 description 1
- 239000005916 Methomyl Substances 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical class [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 101150054429 Tprn gene Proteins 0.000 description 1
- 239000005848 Tribasic copper sulfate Substances 0.000 description 1
- 101150046432 Tril gene Proteins 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 238000010669 acid-base reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- NUFNQYOELLVIPL-UHFFFAOYSA-N acifluorfen Chemical class C1=C([N+]([O-])=O)C(C(=O)O)=CC(OC=2C(=CC(=CC=2)C(F)(F)F)Cl)=C1 NUFNQYOELLVIPL-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- OTSAMNSACVKIOJ-UHFFFAOYSA-N azane;carbamoyl(ethoxy)phosphinic acid Chemical compound [NH4+].CCOP([O-])(=O)C(N)=O OTSAMNSACVKIOJ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- QZXCCPZJCKEPSA-UHFFFAOYSA-N chlorfenac Chemical compound OC(=O)CC1=C(Cl)C=CC(Cl)=C1Cl QZXCCPZJCKEPSA-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000003869 coulometry Methods 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- QAYICIQNSGETAS-UHFFFAOYSA-N dazomet Chemical compound CN1CSC(=S)N(C)C1 QAYICIQNSGETAS-UHFFFAOYSA-N 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- IWEDIXLBFLAXBO-UHFFFAOYSA-N dicamba Chemical class COC1=C(Cl)C=CC(Cl)=C1C(O)=O IWEDIXLBFLAXBO-UHFFFAOYSA-N 0.000 description 1
- OGGXGZAMXPVRFZ-UHFFFAOYSA-N dimethylarsinic acid Chemical class C[As](C)(O)=O OGGXGZAMXPVRFZ-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- SYJFEGQWDCRVNX-UHFFFAOYSA-N diquat Chemical compound C1=CC=[N+]2CC[N+]3=CC=CC=C3C2=C1 SYJFEGQWDCRVNX-UHFFFAOYSA-N 0.000 description 1
- 210000002304 esc Anatomy 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- XXOYNJXVWVNOOJ-UHFFFAOYSA-N fenuron Chemical compound CN(C)C(=O)NC1=CC=CC=C1 XXOYNJXVWVNOOJ-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- BGZZWXTVIYUUEY-UHFFFAOYSA-N fomesafen Chemical compound C1=C([N+]([O-])=O)C(C(=O)NS(=O)(=O)C)=CC(OC=2C(=CC(=CC=2)C(F)(F)F)Cl)=C1 BGZZWXTVIYUUEY-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical class OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- AFCCDDWKHLHPDF-UHFFFAOYSA-M metam-sodium Chemical compound [Na+].CNC([S-])=S AFCCDDWKHLHPDF-UHFFFAOYSA-M 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- UHXUZOCRWCRNSJ-QPJJXVBHSA-N methomyl Chemical compound CNC(=O)O\N=C(/C)SC UHXUZOCRWCRNSJ-QPJJXVBHSA-N 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- BMLIZLVNXIYGCK-UHFFFAOYSA-N monuron Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C=C1 BMLIZLVNXIYGCK-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- JXTHEWSKYLZVJC-UHFFFAOYSA-N naptalam Chemical compound OC(=O)C1=CC=CC=C1C(=O)NC1=CC=CC2=CC=CC=C12 JXTHEWSKYLZVJC-UHFFFAOYSA-N 0.000 description 1
- HVFSJXUIRWUHRG-UHFFFAOYSA-N oic acid Natural products C1CC2C3CC=C4CC(OC5C(C(O)C(O)C(CO)O5)O)CC(O)C4(C)C3CCC2(C)C1C(C)C(O)CC(C)=C(C)C(=O)OC1OC(COC(C)=O)C(O)C(O)C1OC(C(C1O)O)OC(COC(C)=O)C1OC1OC(CO)C(O)C(O)C1O HVFSJXUIRWUHRG-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000000361 pesticidal effect Effects 0.000 description 1
- DHHVAGZRUROJKS-UHFFFAOYSA-N phentermine Chemical compound CC(C)(N)CC1=CC=CC=C1 DHHVAGZRUROJKS-UHFFFAOYSA-N 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000001253 polyvinylpolypyrrolidone Substances 0.000 description 1
- 229920000523 polyvinylpolypyrrolidone Polymers 0.000 description 1
- 235000013809 polyvinylpolypyrrolidone Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- FFSSWMQPCJRCRV-UHFFFAOYSA-N quinclorac Chemical class ClC1=CN=C2C(C(=O)O)=C(Cl)C=CC2=C1 FFSSWMQPCJRCRV-UHFFFAOYSA-N 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- JGFYQVQAXANWJU-UHFFFAOYSA-M sodium fluoroacetate Chemical compound [Na+].[O-]C(=O)CF JGFYQVQAXANWJU-UHFFFAOYSA-M 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- NTWXWSVUSTYPJH-UHFFFAOYSA-M sodium;1,4-bis(2-methylpropoxy)-1,4-dioxobutane-2-sulfonate Chemical compound [Na+].CC(C)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(C)C NTWXWSVUSTYPJH-UHFFFAOYSA-M 0.000 description 1
- UELAIMNOXLAYRW-UHFFFAOYSA-M sodium;1,4-dicyclohexyloxy-1,4-dioxobutane-2-sulfonate Chemical compound [Na+].C1CCCCC1OC(=O)C(S(=O)(=O)[O-])CC(=O)OC1CCCCC1 UELAIMNOXLAYRW-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 125000004964 sulfoalkyl group Chemical group 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- LITQZINTSYBKIU-UHFFFAOYSA-F tetracopper;hexahydroxide;sulfate Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Cu+2].[Cu+2].[Cu+2].[Cu+2].[O-]S([O-])(=O)=O LITQZINTSYBKIU-UHFFFAOYSA-F 0.000 description 1
- REEQLXCGVXDJSQ-UHFFFAOYSA-N trichlopyr Chemical class OC(=O)COC1=NC(Cl)=C(Cl)C=C1Cl REEQLXCGVXDJSQ-UHFFFAOYSA-N 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
- 235000009529 zinc sulphate Nutrition 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- 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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
-
- 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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Toxicology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
An effervescent tablet formulation about 0.1 % to 75 % of a water-soluble pesticide and about 25 % to 99.9 % of an anhydrous metal perborate salt characterized by rapid breakup in cold water.
Description
, 215$861 TITLE
EFFERVESCENT PESTICIDE TABLET WITH METAL PERBORATE
WO 90/00007 discloses pesticidal tablets comprising an acid and a base which react upon contact with water to produce the ~ff~.vc3c~ reaction that 5 causes the pestici(l~ to rapidly lis~erse. The present tablets differ from those of WO 90/00007 in several iullpo~ aspects inrlu(ling the fact that it is the reaction of al-hydlous perborate salts with water that produces the ef~lvesccnl re~ction SUMMARY OF THE INVENTION
This invention conce~lls a tablet formulation colll~lisillg, by total weight of the formulation, about 0.1% to 75% of a water-soluble pesticide which is solid at room lelllp~turt, and 25% to 99.9% of an al~hydr~us metal ~cll,ol~le salt.
By "tablet formulation" is meant the tablet made from the composition described herein, as well as the colllposilion formulated in acconl~lcc with this disclosure but not in taUet form. By "anlly~ous metal perborate salt" is meant asodium, lithium, or pol~ salt having a water content less than about 2% by weight as det~rnin~ by coulometric meas~ .nent.
Plcfe.l~d ranges of the composition are 10% to 70%, and more p~fcll~d 30% to 60%, of the pesticide, and 30% to 90%, and more plcfell~d 40% to 70%, of the anhydrous metal perborate.
Conlc.llplated water-soluble, solid pesticides include those sele~lc;l from the following classes, in~lu(ling mi~tures tl.cn,of. herbicides, fimgici(1çs, b~çterici~le~, and insecticides. Plcfe~lcd pe~l ;cide~ are those having a melting point of at least about 75C and solubility in pH 7 water at 20C of at least about 2% by weight.
FY~mples of snit~ble water-soluble pesticides in~lucle: insecticides such as methomyl and o~amyl; f~ln~isides such as dodine salts, phosell,yl-Al, k~s~ mycin, and valid~y~ ; bactericides such as ~llcptoll.ycin and tribasic copper sulfate; and herbicides such as sulfonylurea salts, acifluorfen salts, ammonium ~nlf~ te, amitrole, bromo~cynil salts, cacodylic acid salts, clopyralidsalts, calcium salt of methylarsonic acid, dalapon salts, dazomet, dicamba salts, 30 difenzoquat methyl sulfate, diquat, 2-methyl-4,6-diilro~,.lol salts, disodium salt of methylarsonic acid, endothall, fenac, salt of fenuron and trichloroacetic acid, flulo~y~yl salts, fomesafen, fosamine ammonium, glyphosate salts, haloxyfop salts, h~flurate, im~7~-lnin salts, imazethapyr salts, io~ynil sodium salt, monoammonium salt of methylarsonic acid, (4-chloro-2-mell-ylphe.lo~y)acetic 35 acid salts, MCPP salts, mecoplup salts, mefl~ salts, metam sodium, monuron 2l5586`
WO 94/17660 ~ PCT/US94/00068 salt, monosodium salt of methylarsonic acid, naptalam, p~raq~l~t salts, picloramsalts, quinchlorac salts, sodium 2-chloro-6-[(4,6-dimetho~y-2-pyrimidinyl)thio]l,enzoale, trichloro&cclic acid salts, triclopyr salts, (2,4-dichlolo~he.lo~y)acetic acid salts, and 4-(2,4-dichloropheno~y)l~ulal~oic acid.
S Contemplated sul~n~lurca salts have the formula:
EFFERVESCENT PESTICIDE TABLET WITH METAL PERBORATE
WO 90/00007 discloses pesticidal tablets comprising an acid and a base which react upon contact with water to produce the ~ff~.vc3c~ reaction that 5 causes the pestici(l~ to rapidly lis~erse. The present tablets differ from those of WO 90/00007 in several iullpo~ aspects inrlu(ling the fact that it is the reaction of al-hydlous perborate salts with water that produces the ef~lvesccnl re~ction SUMMARY OF THE INVENTION
This invention conce~lls a tablet formulation colll~lisillg, by total weight of the formulation, about 0.1% to 75% of a water-soluble pesticide which is solid at room lelllp~turt, and 25% to 99.9% of an al~hydr~us metal ~cll,ol~le salt.
By "tablet formulation" is meant the tablet made from the composition described herein, as well as the colllposilion formulated in acconl~lcc with this disclosure but not in taUet form. By "anlly~ous metal perborate salt" is meant asodium, lithium, or pol~ salt having a water content less than about 2% by weight as det~rnin~ by coulometric meas~ .nent.
Plcfe.l~d ranges of the composition are 10% to 70%, and more p~fcll~d 30% to 60%, of the pesticide, and 30% to 90%, and more plcfell~d 40% to 70%, of the anhydrous metal perborate.
Conlc.llplated water-soluble, solid pesticides include those sele~lc;l from the following classes, in~lu(ling mi~tures tl.cn,of. herbicides, fimgici(1çs, b~çterici~le~, and insecticides. Plcfe~lcd pe~l ;cide~ are those having a melting point of at least about 75C and solubility in pH 7 water at 20C of at least about 2% by weight.
FY~mples of snit~ble water-soluble pesticides in~lucle: insecticides such as methomyl and o~amyl; f~ln~isides such as dodine salts, phosell,yl-Al, k~s~ mycin, and valid~y~ ; bactericides such as ~llcptoll.ycin and tribasic copper sulfate; and herbicides such as sulfonylurea salts, acifluorfen salts, ammonium ~nlf~ te, amitrole, bromo~cynil salts, cacodylic acid salts, clopyralidsalts, calcium salt of methylarsonic acid, dalapon salts, dazomet, dicamba salts, 30 difenzoquat methyl sulfate, diquat, 2-methyl-4,6-diilro~,.lol salts, disodium salt of methylarsonic acid, endothall, fenac, salt of fenuron and trichloroacetic acid, flulo~y~yl salts, fomesafen, fosamine ammonium, glyphosate salts, haloxyfop salts, h~flurate, im~7~-lnin salts, imazethapyr salts, io~ynil sodium salt, monoammonium salt of methylarsonic acid, (4-chloro-2-mell-ylphe.lo~y)acetic 35 acid salts, MCPP salts, mecoplup salts, mefl~ salts, metam sodium, monuron 2l5586`
WO 94/17660 ~ PCT/US94/00068 salt, monosodium salt of methylarsonic acid, naptalam, p~raq~l~t salts, picloramsalts, quinchlorac salts, sodium 2-chloro-6-[(4,6-dimetho~y-2-pyrimidinyl)thio]l,enzoale, trichloro&cclic acid salts, triclopyr salts, (2,4-dichlolo~he.lo~y)acetic acid salts, and 4-(2,4-dichloropheno~y)l~ulal~oic acid.
S Contemplated sul~n~lurca salts have the formula:
2 G;~ M
w~ l J is selected from the group R2~ ~ ~1CH3-- SJ~
S~ 5 '1~ ~ R7 J-4 ~ ~ J-6 `R6 R N R9)lN~N
~15586 1~.
Wo 94/17660 PCT/US94/00068 R~ R10 ~ R9 R5 6 R8 R8 ~ R8 J-10 J-ll J-12 ~7 I R6 R I
R is selected from the group H and CH3;
Rl is selected from the group F, Cl, Br, N02, Cl-C4 alkyl, Cl-C4 haloaLkyl, C3-C4 cycloaLyl, C2-C4 haloalkenyl, Cl-C4 alkoxy, Cl-C4 haloaLo~y, C2-C4 alko~yaLo~y, C02R12, C(o)NRl3Rl4, So2NRl5Rl6, S(o)nR17, C(O)Rl8, CH2CN and L;
R2 is selected from the group H, F, Cl, Br, CN, CH3, OCH3, SCH3, CF3 and OCF2H;
R3 is selected from the group Cl, NO2, CO2CH3, CO2CH2CH3, SO2N(CH3)2, SO2CH3, So2cH2cH3~ OCH3, and OCH2CH3 R4 is sele~ l~,d from the group Cl-C3 aLyl, Cl-C2 haloalkyl, Cl-C2 alko~cy, C2-C4 h~loAlk~nyl, F, Cl, Br, NO2, CO2R12, C(o)NR13R14, So2NR15R16, S(o)nR17, C(O)R18 and L;
R5 is selected from the group H, F, Cl, Br and CH3;
R6 is selected from the group Cl-C3 aLkyl, Cl-C2 alkoxy, C2-C4 haloalkenyl, F, Cl, Br, C02R12, C(o)NRl3R14, So2NRl5Rl6 S(o)nRl7, C(O)R18 and L;
R7 is selected from the group H, F, Cl, CH3 and CF3;
R8 is selected from the group H, Cl-C3 aLkyl and pyridyl;
R9 is selected from the group Cl-C3 alkyl, Cl-C2 alko~y, F, Cl, Br, N02, C02R12, So2NR15R16, S(o)nRl7~ OCF2H, C(O)R18, C2-C4 haloalkenyl and L;
WO 94/17660 ~,~55Qo PCTIU594/00068 R10 is selected from the group H, Cl, F, Br, Cl-C3 aL~yl and Cl-C2 alko~cy;
Rll is selected from the group H, Cl-C3 alkyl, Cl-C2 aLko~cy, C2-C4 haloalkenyl, F, Cl, Br, C02R12, C(o)NR13Rl4, So2NRl5Rl6 S(o)nR17, C(O)R18 and L;
R12 is selected from the group allyl and pr~dr~,yl and Cl-C3 optionally sub~ uled by at least one member indepPn~lPntly selected from halogen, Cl-C2 alko~cy and CN;
R13 is sclccled from the group H, Cl-C3 a,ll~yl and Cl-C2 alko~cy;
R14 is Cl-C2 aL~cyl;
R15 is selecled from the group H, Cl-C3 alkyl, Cl-C2 alko~y, allyl and cyclopropyl;
R16 is selected from the group H and Cl-C3 alkyl;
R17 is selected from the group Cl-C3 aL~yl, Cl-C3 haloalkyl, allyl and yl;
R18 is selected from the group Cl-C4 alkyl, Cl-C4 haloalkyl and C3-Cs cycloalkyl optionally sub~ ul~d by halogen;
nisO, 1 or2;
M is a cation;
L is Rj N N
N~N
Rj is selected from the group H and Cl-C3 alkyl;
W is selected from the group O and S;
X is selected from the group H, Cl-C4 alkyl, Cl-C4 alko~y, Cl-C4 haloalko~cy, Cl-C4 haloalkyl, Cl-C4 haloalkylthio, Cl-C4 alkylthio, halogen, C2-C5 alko~cyalkyl, C2-Cs alko~cyalko~cy, amino, Cl-C3 alkylamino and di(Cl-C3 aL~cyl)amino;
Y is selected from the group H, Cl-C4 aLkyl, Cl-C4 alko~y, Cl-C4 haloaL~co~y, Cl-C4 aLkylthio, Cl-C4 haloalkylthio, C2-C5 alkoxyalkyl, C2-C5 aLko~yaLkoxy, amino, Cl-C3 aLkylamino, di(Cl-C3 alkyl)amino, C3-C4 alkenyloxy, C3-C4 aLkynyloxy, C2-C5 alkylthioaLkyl, C2-C5 aLkylsulfinylaLkyl, C2-Cs aLkylsulfonylalkyl, wO 94/17660 2 ~ S S 8 6 I PCT/US94/00068 Cl-C4 haloaLkyl, C2-C4 aLkynyl, C3-Cs cycloalkyl, azido and cyano;
and Z is selected from the group CH and N;
provided that i) when one or both of X and Y is Cl haloalko~cy, then Z is 5 CH; and ii) when X is halogen, then Z is CH and Y is OCH3, OCH2CH3, N(OCH3)CH3, NHCH3, N(CH3)2 or OCF2H.
Pl~rcll~ d active in~ ,d;~nl~, are salts of the following s-wÇonylw. as,.
chlorsulfuron; sulfometuron; chlorimuron ethyl; metsulfuron methyl; methyl 2-[[[[(4~6-d~lelhw~y-2-pyrimi~linyl)-amino]c~lJollyl]-amino]sulfonyl]-6-10 (trifluolulllelllyl)-3-pyri~ ec~'uuAylate; ethametsulfuron methyl; triasulfuron;
ethyl 5-[[[[(4~6-dimethoxy-2-pyrimitlinyl)amino]carbonyl]-amino]sulfonyl]
methyl-lH-pyrazole4-ca.l,u~late; N-[[(4,6-dimetho~cy-2-pyrimidinylamino]ca,~,ullyl]-3-(ethyls-wfonyl)-2-pyrirlin~s~1fonamide;
tl.;r~ ..lfuron; llib~ .lwull methyl; bens-wfuron methyl; nicosulfuron; methyl 2-15 [[[[[4~6-bis(difluorometho~y)-2-pyrimitlinyl]amino]ca~bu~ l]amino]sulfonyl]-benzoate; methyl 2-[[[[[4-dimethylamino)-6-(2,2,2-trifluoroethoxy)-1,3,5-triazin-2-yl]amino]-cd~ yl]amino]sulfonyl]-3-methyl'L~ 74;~; and N-[[(4,6-~1imetho~y-2-pyrimidinyl)amino]calbollyl]-l-methyl-4-(2-methyl-2H-tetra yl)-lH-yyl~ol~-s-sulforl~mi~
Plcrcll~d salts are the sodium, yOlAP~ , c~ inm~ m~g.~ ~;.. , ammonium and alkylammonium salts of a s-wÇûllylw-,a. Most yl~,f .l~d sulÇull.~lw~a salts are the sodium and calcium salts of hi~.lwun methyl, the pol~s;~.. salt of !I.;r~ --lfilron methyl, the ammonium salt of chlorsulfuron and the ~OIA~S;~ salt of metsulfuron methyl.
DETAILED DESCRIPTION OF THE INVENTION
The most common method for applying pestici(les is as aqueous solutions or dis~ ions which are sprayed onto the field or crop using ground or aerial spray rigs. A tablet cont~ining the pestic~ l COl.lpOlle.-l iS an crr~clive form for introducing the pesticide into the water in the spray tank. It is ~ub~ lly i llpossible to obtain rapid break-up of a tablet willluul the use of errc. v~scence.
Rapid break-up in water is desirable for the conve.~nce of the ~lu~cl~ who require quick lwll~uulld times for the lulep~lion of the spray solutions and dispersions.
Known cr~vcsc~ pesti~ tablets co.. ~ e a water-insoluble pesticide, 35 an organic acid and a co~lJon~lc or bic~l,ondle base. The acid and base react in 2l5s86~\l WO 94/17660 PCT/US94/00068 ~
an aqueous ellvilu~ ent to produce carbon dio-Aide gas which aids in the break-up of the tablet and dispersion of the pesticide. However, the rate of the acid-base effervescent reaction slows .~ignific~ntly when the tablet co~ uliSeS a water-soluble pesticide. A soft "hydrogel" is believed to form around the tablet to S inhibit water from CO.~ g the tablet and f~ilit~ting the ~cl ;ol--Disintegration rates are ll,~cfolc too slow for pr~ctic~l appli~ ~tion.~. In cases where the pe~icide is a water-soluble metal salt, the acid in the tablet may react with the pestici(le to give the water-insoluble acid form.
No hydrogel formation or precipitate is obs~. ved in the reaction of the 10 tablets of the present invention with water. Effervesce~-ce begins i~ uusly and complete disi~ gl~lion occurs in less than 10 mimltes~ most often in less than 5 minnteS using even the cold water drawn from wells in the early spring. A clear aqueous solution forms with the pesticide homogeneously dissolved therein.
Inert ingredients up to about 74.9% of the total weight of the colllposilion lS can be employed. Such inert ingredients are colll~olle.l~, comrlemPnt~ry to the pestici-l , which are known in the tablet art to illlprovc tablet ~ le~ ralion rate, di~el~ibility, stability during storage, and the like. E-Aamples of optional colllponenl~ include a m~ng~npse~ copper or iron salt catalyst; a di~c~ ll, a disintegrant; an anionic or noniollic wetting agent; a flow aid, and a desiccant.
20 The amounts and types of such ill~;lcdienls will be readily detçrmin ah le by one skilled in the ~ lc~ e art given the disclosure herein.
The crr~. v~,scenl reaction is due to the ~Ihy~`~us metal perborate reacting with the water to liberate oxygen. Any such colllpoul~d which is collll,~tiUe with the pesticide and liberates o-Aygen upon hydration is ~u;lu~le for the tablets of the 25 present invention. The ~>rtrc.l~d colll,uoulld is ~lly~`ous sodium lu~ lbolale (also known as sodium l,~,uAylll~tabol. tc, NaB03).
Metal ~.l,or~lc is commonly available commercially as the monohydrate.
The monohydrate must be coll~ d to its a~hydl~ous state in order for the effervescent reaction to occur. The conv~ ion of the metal pell,olale 30 monohy~llale to its anhy~ us form can be accol..pli~hPd by oven-drying the granules at 135C for 24 hours in a vacuum oven with a llillugcll bleed to obtain a uiC of 1.33 A 103 Pascal. The sodium ~lluulale is spread in a layer less than 2 cm in thickness to facilitate drying. As a result of the drying, sodium pell,ol~le has been found to change color from white to yellow.
215586:~
The success of the drying procedure can be tested by bl~n-ling the dried sample to a homogenous mi~ture, and then dlu~i~g a small amount of the mi~ture into a beaker of water. If all the m~tçris~1 reacts (i.e., er~l~esces) on the surface of the water, and no residue (i.e., monohr&d~e) falls to the bottom of the 5 beaker, then the al~hrd~,us state was achieved.
If small amounts of the monollydl~le pe.l,o,dte are not col~ t~d to the anhydrous form during drying, a metal salt can be added in catalytic amounts to dccollll)ose the Illonohrd-~le to produce o~ygen and other products.
Monohr(l,~te which is not de~oy. d by a catalyst will not e~f sce when 10 cûnla~ d with water, but it does &ssolve within the time .~f ce~ y for disintegration of the tablet (i.e., less than 10 min~)tes). Pl~fe.l~d catalyst salts include m~n~nPse, copper or iron metal o~ides or carbonates. Most pl`tr~ d is iron (II) o~ide.
Di*,c,~.~ds can be added to aid the initial dis~.ion of the particles of the 15 active ingredient which are liberated during ~ eg~t;on of the tablet. Suitable di~. l~.~lts include sûdium, llOl~-.~.iulll and c~lcillm salts of l~al~h~ 1c.~r sulfonic acid form~ldfçhyde Co~ f..~.C~'~t~,S, lithinm, sodium, pol~ ...., c~lcillm, and ammonium salts of lignoslll rolldl~s such as Polyfon H0 and Lignosol TSF0;
sodium, pot~!s;.. and ammonium salts of polyacrylates and c~u'l,o~ylates, e.g., 20 Tamol 731 SD~9; sodium salts of maleic anhydride-isobulylene co~olyllle. ., and water soluble nonionic polyllle.~. such as polyvinyl~yllùli-ionP7 polyethylene o~ides and cçllnlose d~;~/ali~s. ~l~,f~ d di~ .alllS indude the sodium, S;-~--, ammonium and c~ lm salts of ~ lPnç sulfonic acid fonn~ Phyde c~ es, with the ammonium salts, ~ e~-;rir~lly Lomar PWA~9, 25 more pl~f~l~d.
Disintegrants façilit~te pe.l~ ~lion of the water into the interior of the tablet through a wiclcing or swelling action. Water-insoluble cross-linked polyvinylpolypyrrolidone is apleÇe.l~d~ ;..t~
A wetting agent can be used to control the size of the oxygen bubbles 30 fonned during the acid-base reaction The anionic w~lling agents include alkyll>el~el~c sulfonates, alkyl and dialkylnaphth~l~n~ sulfûnales, alkyl and alcohol sulfates, sulfoalkyl~mi-les, c~l,oAylates, alpha-olefin sulfonates and dialkyl sulfosuccillales. The no~ionic wetting agents include acetylenic diols, ethylene o~cide-propylene o~ide copolymers, alkylpl~ ol etho~ylates, 35 ~i~.ly-lpl~ ûl etho~ylates, fatty acid etho~cylates, alcohol etho~ylates, soll,i 215S86 1~
fatty acid ester ethoxylates and castor oil ethoxylates. The pre~.-cd wetting agents are sodium dialkyl sulfosuccinates of which sodium diisobutyl sulfosuccinate (Molld-.~t¢ MB-100), sodium diamyl sulfosuccin~te and sodium dicyclohexyl sulfosuccinate are more ~e~
S Flow aids can be added to facilitate Ll~lsr~r of th~ dry ingredients from the feed hopper to the tablet die. Suitable flow aids include silica and ~ tom~ceous earth.
A dessic~nt is another optional cc,lllpon~,nl of the formulation of the i~venlioll. As in~ te~l in Example 2 below, a tablet in a sealed conl~in~--without a ~lessi~nt remains er~.~scelll after storage. However, if a dessicant is desirable, it can be r~trm~l to the tablet, or Llcol,uolated into the tablet matri~c.
Tntçm~l desiccants can be those which "rhrmin~lly bind" water in that they undergo chemical re ~ction~ with water to form a new colll~uulld. An example of this type of material is CaO which reacts with water to form Ca(OH)2. Other m~trri~ senl;~;ve of those which react in this manner are mAg.. e~;.. oxide and boric anhydride.
The int~rn~l desir-c~nt can also be of the type which "physically adsorb"
water and are sdected from the group cQ~ ;ng of highly-dis,u~l~ed silicilic acids such as silica gel; ~lnminllm oxide; clays such as montmorillonite; and amorphous and crystalline ~lnminosilir~tes such as molecular sieves and zeolites.
20 Combin~tion~ of these desicc~nt~ with those that form hy~oAides and hydlahs can be used. Kirk-Othmer's Encyclopedia of Chemical Technology (3rd ed., Vol. 8, p 115) desclibes desiccants suitable for use in the tablet formulation of this invention as Type 1 and Type 4 ~l~si~c~nt~ Either type can be employed, singly or in combination, as long as the desiccant does not e~cpand when it picks-25 up water. Such expansion causes the tablet to crack or crumble on long termstorage.
~ ntrrn~l desiccants suitable for the tablet formulation of this invention also include m~teri~l~ that chrmir~lly bind water, not in the sense of a rh~mir~l l~ a~lion that forms a hyd~ ide, but in the sense of a ch~mi~l reaction that 30 produces a hydrate. Repl~s~ ;ve of useful tlesicc~nt~ that form hydrates are CaSO4, NaOAc, MgSO4, Na2SO4, CaC12. and ZnSO4. Repl~selllalive of the hydrate-forming reaction is that undergone by CaC12 to form CaC12-6H20. One or more desiccants from each group, the hydroxide-forming and the hydrate-forming, can be employed, alone or in combination, cl~ p- n.1i.~g on the particular 35 plol,c.Lies sought by the formnl~tQr.
In addition, inert fillers such as sugar or clay can be added as long as they do not affect the ch~m~ stability of the active ingreLe.lt(s). ~teri~l~ such as glid~nts, anti-adl~ nls, and lubricants can also be employed to facilitate production in the tablet press. For e~cample, lllbri~nt~ such as m~
S ~le~le or boric acid can be used. Such lnkri~rnt~ and anti-a Il~ nls can be brushed onto the die surface or ulcol~oralcd into the formnl~tion The tablets are typically pl~altd in the following manner. The solid water-soluble pestici~lç is passed through a 30 mesh screen to remove oversized particles. Granular &~hr<~ous sodium p.,lb(Jl~tC ~ d as described above is 10 blended with the pesti~ide and, if desired, the inert ~ng~-1;P~ i. The blend can be milled, e.g., in an air or h - nmçrmill, or compacted into tablet form wilhoul milling. Blends which are not milled and thereby co,l,plise larger particle sizes are desirable for rapid tablet break-up.
The tablets can be pl~al~d using con~ ;0n~l tablet-making equipment.
15 Their diameter can vary from about 1 cm or less, to 7.5 cm, dep~nr1ing on thetablet weight desired. Flat-faced, beveled-edge p---.-~hf s, with or wilhoul a breakline, produce alll~Clivc tablets.
Tablets are formed in a hydraulic press with a capacilr of 18,000 kg of force. ~l~.Si~ul~.S b~ .~n about 3.43~107 to 6.86~107 Pascals produce tablet 20 which remain intact during storage and h~n-lling and break-up rapidly. Break-up times are l~terminçd by dr~-ng a tablet, typically 7.5 g into 1000 mL of water.The "end point" of final dissolution is dçtçrmin~d by the cess~lio~ of the CL~ ' CS~ ;1 ;o~ ~ .
The tablets described in the following FY~Tnrles were 3.5 cm in diameter, 25 and were made with a hand-o~e.~.ted hydraulic press at a pr~ of 525 kg/cm2.
The following ingredients were milled for 1 minute in a CRC~ analytical labol~lolr mill.
F.amrle 1 2 3 4 Ingredient Wei~ht (g) tlil~. llulull methyl, sodium salt 4.00 4.00 4.00 4.00 al~}.rdlous sodium ~ellJûlale 4.00 4.00 3.52 4.00 des~ic~nt molecular sievesç~tçrn~l 0.48 CaS04 - - -e~ternal W O 94/17660 215 S 8 6 ~ lo PCTrJS94/00068 The milled ingredients, referred to hert,~ r as the pr~mi~çs, were blended well and aged for 3 weeks at 45C in sealed glass jars. In P.~mrles 1 and 4, the molecular sieves and CaS04 were packaged s~dl~lely and added to the glass jars æ çl~tPrn~l dessi~ . The jar co..~ ;ng the premix of P.Y~mple 2 5 conl~led no dessicant, and the premi~ of F.~mple 3 had the molecular sieves incGl~olaled into the formulation. The premi~es were then cooled, and 7.5 g of each premi~ was tabletted. The tablets were added to water and dissolution timeswere measured. The reslllting ~ueous mi~tures were passed through a stack of 50, 100, and 200 mesh screens. Particulate residue was dPtPrminPd by visual 10 i~l~e~ lion of the screens.
F~mrle Dissolution time (min.) Residue Amount 5.25 None 2 4.32 None 3 4.90 Light 4 4.88 None The color suggested the residue was the molecular sieves.
The following ingl~die~ were blended willloul a milling step.
Ingredient Weight (g) tril~c,luron methyl, sodium salt 4.00 a,~dluus sodium pc.l.oldte 4.00 A tablet was made from 7.5 grams of the premi~. The tablet wæ added to 25 water and the dissolution time was --e&~ul~ d. The rçs llting aqueous mi~ture was passed through a stack of 50, 100, and 200 mesh screens. No residue was found upon visual i,l~e~;lion of the screens.
E~ample Dissolution time (min.) Residue Amount 3.80 None 2l5586l The following ingredients were blended, milled and made into a tablet as described in Examples 1-4.
~ Example 6 7 Ingredient Weight (g) Lbc.luloll methyl, sodium salt 4.00 4.00 d~lhyCl~CIuS sodiumpe.l~ol~le 3.98 3.98 catalyst cupric c~l~l.dl~ 0.02 cupric oxide - 0.02 Tablets were made from 7.5 grams of the premixes. The tablets were added to water and the dissolution times were me~,d. The resulting aqueous mi~tures were passed through a stack of 50, 100, and 200 mesh screens.
Particulate residue was det~rmined by visual i,l~eclion of the screens.
p~mple Dissolution time (min.) Residue Amount 6 4.25 None 7 4.92 None lOne thin u ldissol~cd flake was obse.~ed, and it passed through the screens.
w~ l J is selected from the group R2~ ~ ~1CH3-- SJ~
S~ 5 '1~ ~ R7 J-4 ~ ~ J-6 `R6 R N R9)lN~N
~15586 1~.
Wo 94/17660 PCT/US94/00068 R~ R10 ~ R9 R5 6 R8 R8 ~ R8 J-10 J-ll J-12 ~7 I R6 R I
R is selected from the group H and CH3;
Rl is selected from the group F, Cl, Br, N02, Cl-C4 alkyl, Cl-C4 haloaLkyl, C3-C4 cycloaLyl, C2-C4 haloalkenyl, Cl-C4 alkoxy, Cl-C4 haloaLo~y, C2-C4 alko~yaLo~y, C02R12, C(o)NRl3Rl4, So2NRl5Rl6, S(o)nR17, C(O)Rl8, CH2CN and L;
R2 is selected from the group H, F, Cl, Br, CN, CH3, OCH3, SCH3, CF3 and OCF2H;
R3 is selected from the group Cl, NO2, CO2CH3, CO2CH2CH3, SO2N(CH3)2, SO2CH3, So2cH2cH3~ OCH3, and OCH2CH3 R4 is sele~ l~,d from the group Cl-C3 aLyl, Cl-C2 haloalkyl, Cl-C2 alko~cy, C2-C4 h~loAlk~nyl, F, Cl, Br, NO2, CO2R12, C(o)NR13R14, So2NR15R16, S(o)nR17, C(O)R18 and L;
R5 is selected from the group H, F, Cl, Br and CH3;
R6 is selected from the group Cl-C3 aLkyl, Cl-C2 alkoxy, C2-C4 haloalkenyl, F, Cl, Br, C02R12, C(o)NRl3R14, So2NRl5Rl6 S(o)nRl7, C(O)R18 and L;
R7 is selected from the group H, F, Cl, CH3 and CF3;
R8 is selected from the group H, Cl-C3 aLkyl and pyridyl;
R9 is selected from the group Cl-C3 alkyl, Cl-C2 alko~y, F, Cl, Br, N02, C02R12, So2NR15R16, S(o)nRl7~ OCF2H, C(O)R18, C2-C4 haloalkenyl and L;
WO 94/17660 ~,~55Qo PCTIU594/00068 R10 is selected from the group H, Cl, F, Br, Cl-C3 aL~yl and Cl-C2 alko~cy;
Rll is selected from the group H, Cl-C3 alkyl, Cl-C2 aLko~cy, C2-C4 haloalkenyl, F, Cl, Br, C02R12, C(o)NR13Rl4, So2NRl5Rl6 S(o)nR17, C(O)R18 and L;
R12 is selected from the group allyl and pr~dr~,yl and Cl-C3 optionally sub~ uled by at least one member indepPn~lPntly selected from halogen, Cl-C2 alko~cy and CN;
R13 is sclccled from the group H, Cl-C3 a,ll~yl and Cl-C2 alko~cy;
R14 is Cl-C2 aL~cyl;
R15 is selecled from the group H, Cl-C3 alkyl, Cl-C2 alko~y, allyl and cyclopropyl;
R16 is selected from the group H and Cl-C3 alkyl;
R17 is selected from the group Cl-C3 aL~yl, Cl-C3 haloalkyl, allyl and yl;
R18 is selected from the group Cl-C4 alkyl, Cl-C4 haloalkyl and C3-Cs cycloalkyl optionally sub~ ul~d by halogen;
nisO, 1 or2;
M is a cation;
L is Rj N N
N~N
Rj is selected from the group H and Cl-C3 alkyl;
W is selected from the group O and S;
X is selected from the group H, Cl-C4 alkyl, Cl-C4 alko~y, Cl-C4 haloalko~cy, Cl-C4 haloalkyl, Cl-C4 haloalkylthio, Cl-C4 alkylthio, halogen, C2-C5 alko~cyalkyl, C2-Cs alko~cyalko~cy, amino, Cl-C3 alkylamino and di(Cl-C3 aL~cyl)amino;
Y is selected from the group H, Cl-C4 aLkyl, Cl-C4 alko~y, Cl-C4 haloaL~co~y, Cl-C4 aLkylthio, Cl-C4 haloalkylthio, C2-C5 alkoxyalkyl, C2-C5 aLko~yaLkoxy, amino, Cl-C3 aLkylamino, di(Cl-C3 alkyl)amino, C3-C4 alkenyloxy, C3-C4 aLkynyloxy, C2-C5 alkylthioaLkyl, C2-C5 aLkylsulfinylaLkyl, C2-Cs aLkylsulfonylalkyl, wO 94/17660 2 ~ S S 8 6 I PCT/US94/00068 Cl-C4 haloaLkyl, C2-C4 aLkynyl, C3-Cs cycloalkyl, azido and cyano;
and Z is selected from the group CH and N;
provided that i) when one or both of X and Y is Cl haloalko~cy, then Z is 5 CH; and ii) when X is halogen, then Z is CH and Y is OCH3, OCH2CH3, N(OCH3)CH3, NHCH3, N(CH3)2 or OCF2H.
Pl~rcll~ d active in~ ,d;~nl~, are salts of the following s-wÇonylw. as,.
chlorsulfuron; sulfometuron; chlorimuron ethyl; metsulfuron methyl; methyl 2-[[[[(4~6-d~lelhw~y-2-pyrimi~linyl)-amino]c~lJollyl]-amino]sulfonyl]-6-10 (trifluolulllelllyl)-3-pyri~ ec~'uuAylate; ethametsulfuron methyl; triasulfuron;
ethyl 5-[[[[(4~6-dimethoxy-2-pyrimitlinyl)amino]carbonyl]-amino]sulfonyl]
methyl-lH-pyrazole4-ca.l,u~late; N-[[(4,6-dimetho~cy-2-pyrimidinylamino]ca,~,ullyl]-3-(ethyls-wfonyl)-2-pyrirlin~s~1fonamide;
tl.;r~ ..lfuron; llib~ .lwull methyl; bens-wfuron methyl; nicosulfuron; methyl 2-15 [[[[[4~6-bis(difluorometho~y)-2-pyrimitlinyl]amino]ca~bu~ l]amino]sulfonyl]-benzoate; methyl 2-[[[[[4-dimethylamino)-6-(2,2,2-trifluoroethoxy)-1,3,5-triazin-2-yl]amino]-cd~ yl]amino]sulfonyl]-3-methyl'L~ 74;~; and N-[[(4,6-~1imetho~y-2-pyrimidinyl)amino]calbollyl]-l-methyl-4-(2-methyl-2H-tetra yl)-lH-yyl~ol~-s-sulforl~mi~
Plcrcll~d salts are the sodium, yOlAP~ , c~ inm~ m~g.~ ~;.. , ammonium and alkylammonium salts of a s-wÇûllylw-,a. Most yl~,f .l~d sulÇull.~lw~a salts are the sodium and calcium salts of hi~.lwun methyl, the pol~s;~.. salt of !I.;r~ --lfilron methyl, the ammonium salt of chlorsulfuron and the ~OIA~S;~ salt of metsulfuron methyl.
DETAILED DESCRIPTION OF THE INVENTION
The most common method for applying pestici(les is as aqueous solutions or dis~ ions which are sprayed onto the field or crop using ground or aerial spray rigs. A tablet cont~ining the pestic~ l COl.lpOlle.-l iS an crr~clive form for introducing the pesticide into the water in the spray tank. It is ~ub~ lly i llpossible to obtain rapid break-up of a tablet willluul the use of errc. v~scence.
Rapid break-up in water is desirable for the conve.~nce of the ~lu~cl~ who require quick lwll~uulld times for the lulep~lion of the spray solutions and dispersions.
Known cr~vcsc~ pesti~ tablets co.. ~ e a water-insoluble pesticide, 35 an organic acid and a co~lJon~lc or bic~l,ondle base. The acid and base react in 2l5s86~\l WO 94/17660 PCT/US94/00068 ~
an aqueous ellvilu~ ent to produce carbon dio-Aide gas which aids in the break-up of the tablet and dispersion of the pesticide. However, the rate of the acid-base effervescent reaction slows .~ignific~ntly when the tablet co~ uliSeS a water-soluble pesticide. A soft "hydrogel" is believed to form around the tablet to S inhibit water from CO.~ g the tablet and f~ilit~ting the ~cl ;ol--Disintegration rates are ll,~cfolc too slow for pr~ctic~l appli~ ~tion.~. In cases where the pe~icide is a water-soluble metal salt, the acid in the tablet may react with the pestici(le to give the water-insoluble acid form.
No hydrogel formation or precipitate is obs~. ved in the reaction of the 10 tablets of the present invention with water. Effervesce~-ce begins i~ uusly and complete disi~ gl~lion occurs in less than 10 mimltes~ most often in less than 5 minnteS using even the cold water drawn from wells in the early spring. A clear aqueous solution forms with the pesticide homogeneously dissolved therein.
Inert ingredients up to about 74.9% of the total weight of the colllposilion lS can be employed. Such inert ingredients are colll~olle.l~, comrlemPnt~ry to the pestici-l , which are known in the tablet art to illlprovc tablet ~ le~ ralion rate, di~el~ibility, stability during storage, and the like. E-Aamples of optional colllponenl~ include a m~ng~npse~ copper or iron salt catalyst; a di~c~ ll, a disintegrant; an anionic or noniollic wetting agent; a flow aid, and a desiccant.
20 The amounts and types of such ill~;lcdienls will be readily detçrmin ah le by one skilled in the ~ lc~ e art given the disclosure herein.
The crr~. v~,scenl reaction is due to the ~Ihy~`~us metal perborate reacting with the water to liberate oxygen. Any such colllpoul~d which is collll,~tiUe with the pesticide and liberates o-Aygen upon hydration is ~u;lu~le for the tablets of the 25 present invention. The ~>rtrc.l~d colll,uoulld is ~lly~`ous sodium lu~ lbolale (also known as sodium l,~,uAylll~tabol. tc, NaB03).
Metal ~.l,or~lc is commonly available commercially as the monohydrate.
The monohydrate must be coll~ d to its a~hydl~ous state in order for the effervescent reaction to occur. The conv~ ion of the metal pell,olale 30 monohy~llale to its anhy~ us form can be accol..pli~hPd by oven-drying the granules at 135C for 24 hours in a vacuum oven with a llillugcll bleed to obtain a uiC of 1.33 A 103 Pascal. The sodium ~lluulale is spread in a layer less than 2 cm in thickness to facilitate drying. As a result of the drying, sodium pell,ol~le has been found to change color from white to yellow.
215586:~
The success of the drying procedure can be tested by bl~n-ling the dried sample to a homogenous mi~ture, and then dlu~i~g a small amount of the mi~ture into a beaker of water. If all the m~tçris~1 reacts (i.e., er~l~esces) on the surface of the water, and no residue (i.e., monohr&d~e) falls to the bottom of the 5 beaker, then the al~hrd~,us state was achieved.
If small amounts of the monollydl~le pe.l,o,dte are not col~ t~d to the anhydrous form during drying, a metal salt can be added in catalytic amounts to dccollll)ose the Illonohrd-~le to produce o~ygen and other products.
Monohr(l,~te which is not de~oy. d by a catalyst will not e~f sce when 10 cûnla~ d with water, but it does &ssolve within the time .~f ce~ y for disintegration of the tablet (i.e., less than 10 min~)tes). Pl~fe.l~d catalyst salts include m~n~nPse, copper or iron metal o~ides or carbonates. Most pl`tr~ d is iron (II) o~ide.
Di*,c,~.~ds can be added to aid the initial dis~.ion of the particles of the 15 active ingredient which are liberated during ~ eg~t;on of the tablet. Suitable di~. l~.~lts include sûdium, llOl~-.~.iulll and c~lcillm salts of l~al~h~ 1c.~r sulfonic acid form~ldfçhyde Co~ f..~.C~'~t~,S, lithinm, sodium, pol~ ...., c~lcillm, and ammonium salts of lignoslll rolldl~s such as Polyfon H0 and Lignosol TSF0;
sodium, pot~!s;.. and ammonium salts of polyacrylates and c~u'l,o~ylates, e.g., 20 Tamol 731 SD~9; sodium salts of maleic anhydride-isobulylene co~olyllle. ., and water soluble nonionic polyllle.~. such as polyvinyl~yllùli-ionP7 polyethylene o~ides and cçllnlose d~;~/ali~s. ~l~,f~ d di~ .alllS indude the sodium, S;-~--, ammonium and c~ lm salts of ~ lPnç sulfonic acid fonn~ Phyde c~ es, with the ammonium salts, ~ e~-;rir~lly Lomar PWA~9, 25 more pl~f~l~d.
Disintegrants façilit~te pe.l~ ~lion of the water into the interior of the tablet through a wiclcing or swelling action. Water-insoluble cross-linked polyvinylpolypyrrolidone is apleÇe.l~d~ ;..t~
A wetting agent can be used to control the size of the oxygen bubbles 30 fonned during the acid-base reaction The anionic w~lling agents include alkyll>el~el~c sulfonates, alkyl and dialkylnaphth~l~n~ sulfûnales, alkyl and alcohol sulfates, sulfoalkyl~mi-les, c~l,oAylates, alpha-olefin sulfonates and dialkyl sulfosuccillales. The no~ionic wetting agents include acetylenic diols, ethylene o~cide-propylene o~ide copolymers, alkylpl~ ol etho~ylates, 35 ~i~.ly-lpl~ ûl etho~ylates, fatty acid etho~cylates, alcohol etho~ylates, soll,i 215S86 1~
fatty acid ester ethoxylates and castor oil ethoxylates. The pre~.-cd wetting agents are sodium dialkyl sulfosuccinates of which sodium diisobutyl sulfosuccinate (Molld-.~t¢ MB-100), sodium diamyl sulfosuccin~te and sodium dicyclohexyl sulfosuccinate are more ~e~
S Flow aids can be added to facilitate Ll~lsr~r of th~ dry ingredients from the feed hopper to the tablet die. Suitable flow aids include silica and ~ tom~ceous earth.
A dessic~nt is another optional cc,lllpon~,nl of the formulation of the i~venlioll. As in~ te~l in Example 2 below, a tablet in a sealed conl~in~--without a ~lessi~nt remains er~.~scelll after storage. However, if a dessicant is desirable, it can be r~trm~l to the tablet, or Llcol,uolated into the tablet matri~c.
Tntçm~l desiccants can be those which "rhrmin~lly bind" water in that they undergo chemical re ~ction~ with water to form a new colll~uulld. An example of this type of material is CaO which reacts with water to form Ca(OH)2. Other m~trri~ senl;~;ve of those which react in this manner are mAg.. e~;.. oxide and boric anhydride.
The int~rn~l desir-c~nt can also be of the type which "physically adsorb"
water and are sdected from the group cQ~ ;ng of highly-dis,u~l~ed silicilic acids such as silica gel; ~lnminllm oxide; clays such as montmorillonite; and amorphous and crystalline ~lnminosilir~tes such as molecular sieves and zeolites.
20 Combin~tion~ of these desicc~nt~ with those that form hy~oAides and hydlahs can be used. Kirk-Othmer's Encyclopedia of Chemical Technology (3rd ed., Vol. 8, p 115) desclibes desiccants suitable for use in the tablet formulation of this invention as Type 1 and Type 4 ~l~si~c~nt~ Either type can be employed, singly or in combination, as long as the desiccant does not e~cpand when it picks-25 up water. Such expansion causes the tablet to crack or crumble on long termstorage.
~ ntrrn~l desiccants suitable for the tablet formulation of this invention also include m~teri~l~ that chrmir~lly bind water, not in the sense of a rh~mir~l l~ a~lion that forms a hyd~ ide, but in the sense of a ch~mi~l reaction that 30 produces a hydrate. Repl~s~ ;ve of useful tlesicc~nt~ that form hydrates are CaSO4, NaOAc, MgSO4, Na2SO4, CaC12. and ZnSO4. Repl~selllalive of the hydrate-forming reaction is that undergone by CaC12 to form CaC12-6H20. One or more desiccants from each group, the hydroxide-forming and the hydrate-forming, can be employed, alone or in combination, cl~ p- n.1i.~g on the particular 35 plol,c.Lies sought by the formnl~tQr.
In addition, inert fillers such as sugar or clay can be added as long as they do not affect the ch~m~ stability of the active ingreLe.lt(s). ~teri~l~ such as glid~nts, anti-adl~ nls, and lubricants can also be employed to facilitate production in the tablet press. For e~cample, lllbri~nt~ such as m~
S ~le~le or boric acid can be used. Such lnkri~rnt~ and anti-a Il~ nls can be brushed onto the die surface or ulcol~oralcd into the formnl~tion The tablets are typically pl~altd in the following manner. The solid water-soluble pestici~lç is passed through a 30 mesh screen to remove oversized particles. Granular &~hr<~ous sodium p.,lb(Jl~tC ~ d as described above is 10 blended with the pesti~ide and, if desired, the inert ~ng~-1;P~ i. The blend can be milled, e.g., in an air or h - nmçrmill, or compacted into tablet form wilhoul milling. Blends which are not milled and thereby co,l,plise larger particle sizes are desirable for rapid tablet break-up.
The tablets can be pl~al~d using con~ ;0n~l tablet-making equipment.
15 Their diameter can vary from about 1 cm or less, to 7.5 cm, dep~nr1ing on thetablet weight desired. Flat-faced, beveled-edge p---.-~hf s, with or wilhoul a breakline, produce alll~Clivc tablets.
Tablets are formed in a hydraulic press with a capacilr of 18,000 kg of force. ~l~.Si~ul~.S b~ .~n about 3.43~107 to 6.86~107 Pascals produce tablet 20 which remain intact during storage and h~n-lling and break-up rapidly. Break-up times are l~terminçd by dr~-ng a tablet, typically 7.5 g into 1000 mL of water.The "end point" of final dissolution is dçtçrmin~d by the cess~lio~ of the CL~ ' CS~ ;1 ;o~ ~ .
The tablets described in the following FY~Tnrles were 3.5 cm in diameter, 25 and were made with a hand-o~e.~.ted hydraulic press at a pr~ of 525 kg/cm2.
The following ingredients were milled for 1 minute in a CRC~ analytical labol~lolr mill.
F.amrle 1 2 3 4 Ingredient Wei~ht (g) tlil~. llulull methyl, sodium salt 4.00 4.00 4.00 4.00 al~}.rdlous sodium ~ellJûlale 4.00 4.00 3.52 4.00 des~ic~nt molecular sievesç~tçrn~l 0.48 CaS04 - - -e~ternal W O 94/17660 215 S 8 6 ~ lo PCTrJS94/00068 The milled ingredients, referred to hert,~ r as the pr~mi~çs, were blended well and aged for 3 weeks at 45C in sealed glass jars. In P.~mrles 1 and 4, the molecular sieves and CaS04 were packaged s~dl~lely and added to the glass jars æ çl~tPrn~l dessi~ . The jar co..~ ;ng the premix of P.Y~mple 2 5 conl~led no dessicant, and the premi~ of F.~mple 3 had the molecular sieves incGl~olaled into the formulation. The premi~es were then cooled, and 7.5 g of each premi~ was tabletted. The tablets were added to water and dissolution timeswere measured. The reslllting ~ueous mi~tures were passed through a stack of 50, 100, and 200 mesh screens. Particulate residue was dPtPrminPd by visual 10 i~l~e~ lion of the screens.
F~mrle Dissolution time (min.) Residue Amount 5.25 None 2 4.32 None 3 4.90 Light 4 4.88 None The color suggested the residue was the molecular sieves.
The following ingl~die~ were blended willloul a milling step.
Ingredient Weight (g) tril~c,luron methyl, sodium salt 4.00 a,~dluus sodium pc.l.oldte 4.00 A tablet was made from 7.5 grams of the premi~. The tablet wæ added to 25 water and the dissolution time was --e&~ul~ d. The rçs llting aqueous mi~ture was passed through a stack of 50, 100, and 200 mesh screens. No residue was found upon visual i,l~e~;lion of the screens.
E~ample Dissolution time (min.) Residue Amount 3.80 None 2l5586l The following ingredients were blended, milled and made into a tablet as described in Examples 1-4.
~ Example 6 7 Ingredient Weight (g) Lbc.luloll methyl, sodium salt 4.00 4.00 d~lhyCl~CIuS sodiumpe.l~ol~le 3.98 3.98 catalyst cupric c~l~l.dl~ 0.02 cupric oxide - 0.02 Tablets were made from 7.5 grams of the premixes. The tablets were added to water and the dissolution times were me~,d. The resulting aqueous mi~tures were passed through a stack of 50, 100, and 200 mesh screens.
Particulate residue was det~rmined by visual i,l~eclion of the screens.
p~mple Dissolution time (min.) Residue Amount 6 4.25 None 7 4.92 None lOne thin u ldissol~cd flake was obse.~ed, and it passed through the screens.
Claims (8)
1. A tablet formulation comprising, by total weight, about (1) 0.1% to 75% of a water-soluble pesticide that has a melting point of at least 75° and n solubility in PH 7 water at 20°C of at least about 2% by weight, and (2) 25% to 99.9% of an anhydrous metal perborate salt selected from the group sodium, lithium, and potassium per borate having a water content less than about 2% by weight.
2. A tablet formulation according to Claim 1 comprising 10 to 70% of a pesticide and 30 to 90% of a perborate salt.
3. A tablet formulation according to Claim 2 comprising 20 to 60% of a pesticide and 40 to 70% of a perborate salt.
4. A tablet formulation according to Claim 1 wherein the pesticide is selected from at least one member of the group herbicides, fungicides, bactericides, and insecticides.
5. A tablet formulation according to Claim4 wherein the pesticide is a sulfonylurea salt having the formula wherein J is selected from the group , , , , , , or ;
R is selected from the group H and CH3;
R1 is selected from the group F, Cl, Br, NO2, C1-C4 alkyl, C1-C4 haloalkyl, C3-C4 cycloalkyl, C2-C4 haloalkenyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkoxyalkoxy, CO2R12, C(O)NR13R14, SO2NR15R16, S(O)nR17, C(O)R18, CH2CN and L;
R2 is selected from the group H, F, Cl, Br, CN, CH3, OCH3, SCH3, CF3 and OCF2H;
R3 is selected from the group Cl, NO2, CO2CH3, CO2CH2CH3, SO2N(CH3)2, SO2CH3, SO2CH2CH3, OCH3, and OCH2CH3 R4 is selected from the group C1-C3 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy, C2-C4 haloalkenyl, F, C1, Br, NO2, CO2R12, C(O)NR13R14, SO2NR15R16, S(O)nR17, C(O)R18 and L;
R5 is selected from the group H, F, Cl, Br and CH3;
R6 is selected from the group C1-C3 alkyl, C1-C2 alkoxy, C2-C4 haloalkenyl, F, Cl, Br, CO2R12, C(O)NR13R14, SO2NR15R16, S(O)nR17, C(O)R18 and L;
R7 is selected from the group H, F, Cl, CH3 and CF3;
R8 is selected from the group H, C1-C3 alkyl and pyridyl;
R9 is selected from the group C1-C3 alkyl, C1-C2 alkoxy, F, Cl, Br, NO2, CO2R12, SO2NR15R16, S(O)nR17, OCF2H, C(O)R18, C2-C4 haloalkenyl and L;
R10 is selected from the group H, Cl, F, Br, C1-C3 alkyl and C1-C2 alkoxy;
R11 is selected from the group H, C1-C3 alkyl, C1-C2 alkoxy, C2-C4 haloalkenyl, F, Cl, Br, CO2R12, C(O)NR13R14, SO2NR15R16, S(O)nR17, C(O)R18 and L;
R12 is selected from the group allyl and propargyl and C1-C3 optionally substituted by at least one member independently selected from halogen, C1-C2 alkoxy and CN;
R13 is selected from the group H, C1-C3 alkyl and C1-C2 alkoxy;
R14 is C1-C2 alkyl;
R15 is selected from the group H, C1-C3 alkyl, C1-C2 alkoxy, allyl and cyclopropyl;
R16 is selected from the group H and C1-C3 alkyl;
R17 is selected from the group C1-C3 alkyl, C1-C3 haloalkyl, allyl and propargyl;
R18 is selected from the group C1-C4 alkyl, C1-C4 haloalkyl and C3-C5 cycloalkyl optionally substituted by halogen;
n is 0, 1 or 2;
M is a cation;
L is Rj is selected from the group H and C1-C3 alkyl;
W is selected from the group O and S;
X is selected from the group H, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 haloalkyl, C1-C4 haloalkylthio, C1-C4 alkylthio, halogen, C2-C5 alkoxyalkyl, C2-C5 alkoxyalkoxy, amino, C1-C3 alkylamino and di(C1-C3 alkyl)amino;
Y is selected from the group H, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 haloalkylthio, C2-C5 alkoxyalkyl, C2-C5 alkoxyalkoxy, amino, C1-C3 alkylamino, di(C1-C3 alkyl)amino, C3-C4 alkenyloxy, C3-C4 alkynyloxy, C2-C5 alkylthioalkyl, C2-C5 alkylsulfinylalkyl, C2-C5 alkylsulfonylalkyl, C1-C4 haloalkyl, C2-C4 alkynyl, C3-C5 cycloalkyl, azido and cyano;
and Z is selected from the group CH and N;
provided that i) when one or both of X and Y is C1 haloalkoxy, then Z is CH; and ii) when X is halogen, then Z is CH and Y is OCH3, OCH2CH3, N(OCH3)CH3, NHCH3, N(CH3)2 or OCF2H.
R is selected from the group H and CH3;
R1 is selected from the group F, Cl, Br, NO2, C1-C4 alkyl, C1-C4 haloalkyl, C3-C4 cycloalkyl, C2-C4 haloalkenyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkoxyalkoxy, CO2R12, C(O)NR13R14, SO2NR15R16, S(O)nR17, C(O)R18, CH2CN and L;
R2 is selected from the group H, F, Cl, Br, CN, CH3, OCH3, SCH3, CF3 and OCF2H;
R3 is selected from the group Cl, NO2, CO2CH3, CO2CH2CH3, SO2N(CH3)2, SO2CH3, SO2CH2CH3, OCH3, and OCH2CH3 R4 is selected from the group C1-C3 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy, C2-C4 haloalkenyl, F, C1, Br, NO2, CO2R12, C(O)NR13R14, SO2NR15R16, S(O)nR17, C(O)R18 and L;
R5 is selected from the group H, F, Cl, Br and CH3;
R6 is selected from the group C1-C3 alkyl, C1-C2 alkoxy, C2-C4 haloalkenyl, F, Cl, Br, CO2R12, C(O)NR13R14, SO2NR15R16, S(O)nR17, C(O)R18 and L;
R7 is selected from the group H, F, Cl, CH3 and CF3;
R8 is selected from the group H, C1-C3 alkyl and pyridyl;
R9 is selected from the group C1-C3 alkyl, C1-C2 alkoxy, F, Cl, Br, NO2, CO2R12, SO2NR15R16, S(O)nR17, OCF2H, C(O)R18, C2-C4 haloalkenyl and L;
R10 is selected from the group H, Cl, F, Br, C1-C3 alkyl and C1-C2 alkoxy;
R11 is selected from the group H, C1-C3 alkyl, C1-C2 alkoxy, C2-C4 haloalkenyl, F, Cl, Br, CO2R12, C(O)NR13R14, SO2NR15R16, S(O)nR17, C(O)R18 and L;
R12 is selected from the group allyl and propargyl and C1-C3 optionally substituted by at least one member independently selected from halogen, C1-C2 alkoxy and CN;
R13 is selected from the group H, C1-C3 alkyl and C1-C2 alkoxy;
R14 is C1-C2 alkyl;
R15 is selected from the group H, C1-C3 alkyl, C1-C2 alkoxy, allyl and cyclopropyl;
R16 is selected from the group H and C1-C3 alkyl;
R17 is selected from the group C1-C3 alkyl, C1-C3 haloalkyl, allyl and propargyl;
R18 is selected from the group C1-C4 alkyl, C1-C4 haloalkyl and C3-C5 cycloalkyl optionally substituted by halogen;
n is 0, 1 or 2;
M is a cation;
L is Rj is selected from the group H and C1-C3 alkyl;
W is selected from the group O and S;
X is selected from the group H, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 haloalkyl, C1-C4 haloalkylthio, C1-C4 alkylthio, halogen, C2-C5 alkoxyalkyl, C2-C5 alkoxyalkoxy, amino, C1-C3 alkylamino and di(C1-C3 alkyl)amino;
Y is selected from the group H, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 haloalkylthio, C2-C5 alkoxyalkyl, C2-C5 alkoxyalkoxy, amino, C1-C3 alkylamino, di(C1-C3 alkyl)amino, C3-C4 alkenyloxy, C3-C4 alkynyloxy, C2-C5 alkylthioalkyl, C2-C5 alkylsulfinylalkyl, C2-C5 alkylsulfonylalkyl, C1-C4 haloalkyl, C2-C4 alkynyl, C3-C5 cycloalkyl, azido and cyano;
and Z is selected from the group CH and N;
provided that i) when one or both of X and Y is C1 haloalkoxy, then Z is CH; and ii) when X is halogen, then Z is CH and Y is OCH3, OCH2CH3, N(OCH3)CH3, NHCH3, N(CH3)2 or OCF2H.
6. A tablet formulation according to Claim 5 wherein the metal cation of the sulfonylurea salt is selected from the group sodium, potassium, calcium, magnesium, ammonium and alkylammonium.
7. A tablet formulation according to Claim 6 wherein the sulfonylurea is selected from the group: chlorsulfuron; sulfometuron; chlorimuron ethyl;
metsulfuron methyl; methyl 2-[[[[(4,6-dimethoxy-2-pyrimidinyl)-amino]carbonyl]-amino]sulfonyl]-6-(trifluoromethyl)-3-pyridinecarboxylate;
ethametsulfuron methyl; triasulfuron; ethyl 5-[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]-amino]sulfonyl]-1-methyl-1H-pyrazole-4-carboxylate; N-[[(4,6-dimethoxy-2-pyrimidinylamino]carbonyl]-3-(ethylsulfonyl)-2-pyridinesulfonamide; thifensulfuron; tribemuron methyl;
bensulfuron methyl; nicosulfuron; methyl 2-[[[[[4,6-bis(difluoromethoxy)-2-pyrimidinyl]amino]carbonyl]amino]sulfonyl]-benzoate;methyl 2-[[[[[4-dimethylamino)-6-(2,2,2-trifluoroethoxy)-1,3,5-triazin-2-yl]amino]-carbonyl]amino]sulfonyl]-3-methylbenzoate; and N-[[(4,6-dimethoxy-2-pyrimidinyl)amino]calbonyl]-1-methyl-4-(2-methyl-2H-tetrazol-5-yl)-1H-pyrazole-5-sulfonamide.
metsulfuron methyl; methyl 2-[[[[(4,6-dimethoxy-2-pyrimidinyl)-amino]carbonyl]-amino]sulfonyl]-6-(trifluoromethyl)-3-pyridinecarboxylate;
ethametsulfuron methyl; triasulfuron; ethyl 5-[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]-amino]sulfonyl]-1-methyl-1H-pyrazole-4-carboxylate; N-[[(4,6-dimethoxy-2-pyrimidinylamino]carbonyl]-3-(ethylsulfonyl)-2-pyridinesulfonamide; thifensulfuron; tribemuron methyl;
bensulfuron methyl; nicosulfuron; methyl 2-[[[[[4,6-bis(difluoromethoxy)-2-pyrimidinyl]amino]carbonyl]amino]sulfonyl]-benzoate;methyl 2-[[[[[4-dimethylamino)-6-(2,2,2-trifluoroethoxy)-1,3,5-triazin-2-yl]amino]-carbonyl]amino]sulfonyl]-3-methylbenzoate; and N-[[(4,6-dimethoxy-2-pyrimidinyl)amino]calbonyl]-1-methyl-4-(2-methyl-2H-tetrazol-5-yl)-1H-pyrazole-5-sulfonamide.
8. A tablet formulation according to Claim 1 in the form of a tablet.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US1575893A | 1993-02-10 | 1993-02-10 | |
| US08/015,758 | 1993-02-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2155861A1 true CA2155861A1 (en) | 1994-08-18 |
Family
ID=21773434
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2155861 Abandoned CA2155861A1 (en) | 1993-02-10 | 1994-01-06 | Effervescent pesticide tablet with metal perborate |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0683627A1 (en) |
| JP (1) | JPH08506578A (en) |
| AU (1) | AU5963694A (en) |
| CA (1) | CA2155861A1 (en) |
| WO (1) | WO1994017660A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2337055A (en) * | 1998-05-08 | 1999-11-10 | Procter & Gamble | Effervescent particle |
| JP2001247411A (en) * | 2000-03-09 | 2001-09-11 | Tomono Agrica Co Ltd | Pest control agent |
| JP6061627B2 (en) * | 2012-02-20 | 2017-01-18 | 大日本除蟲菊株式会社 | Fly larvae control agent and fly larvae control method using the same |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1244815B (en) * | 1962-11-17 | 1967-07-20 | Albert Ag Chem Werke | Method for improving the rate of dissolution of crushed grains consisting of plant nutrients in soil fluid |
| US3421842A (en) * | 1965-09-30 | 1969-01-14 | Fmc Corp | Process for producing effervescent perborate compounds |
| GB1424084A (en) * | 1973-06-11 | 1976-02-04 | Holloway Ltd E R | Bactericidal compositions |
| JPS6034482B2 (en) * | 1977-08-03 | 1985-08-09 | 日本パ−オキサイド株式会社 | Oxygen gas generation method |
| GB2095694B (en) * | 1981-03-31 | 1984-08-01 | Hollaway E R Ltd | Tooth cleaning compositions |
| ZA828968B (en) * | 1981-12-08 | 1983-11-30 | Warner Lambert Co | Denture cleanser |
| AU626551B2 (en) * | 1988-06-28 | 1992-08-06 | E.I. Du Pont De Nemours And Company | Tablet formulations of pesticides |
-
1994
- 1994-01-06 JP JP6518027A patent/JPH08506578A/en active Pending
- 1994-01-06 CA CA 2155861 patent/CA2155861A1/en not_active Abandoned
- 1994-01-06 AU AU59636/94A patent/AU5963694A/en not_active Abandoned
- 1994-01-06 EP EP94905579A patent/EP0683627A1/en not_active Ceased
- 1994-01-06 WO PCT/US1994/000068 patent/WO1994017660A1/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08506578A (en) | 1996-07-16 |
| AU5963694A (en) | 1994-08-29 |
| EP0683627A1 (en) | 1995-11-29 |
| WO1994017660A1 (en) | 1994-08-18 |
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