US2922738A - Fungicidal compositions - Google Patents
Fungicidal compositions Download PDFInfo
- Publication number
- US2922738A US2922738A US511762A US51176255A US2922738A US 2922738 A US2922738 A US 2922738A US 511762 A US511762 A US 511762A US 51176255 A US51176255 A US 51176255A US 2922738 A US2922738 A US 2922738A
- Authority
- US
- United States
- Prior art keywords
- acid
- group
- xanthates
- phosphorus
- diorganotin
- 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.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title description 43
- 230000000855 fungicidal effect Effects 0.000 title description 16
- -1 METHYLENE COMPOUNDS Chemical class 0.000 claims description 23
- 239000012991 xanthate Substances 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 16
- 241000233866 Fungi Species 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 13
- 239000011574 phosphorus Substances 0.000 claims description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims description 13
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 claims description 9
- 150000003017 phosphorus Chemical class 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 claims description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 3
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 3
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 3
- GQZXNSPRSGFJLY-UHFFFAOYSA-N hydroxyphosphanone Chemical compound OP=O GQZXNSPRSGFJLY-UHFFFAOYSA-N 0.000 claims description 2
- 229940046817 hypophosphorus acid Drugs 0.000 claims description 2
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 claims description 2
- KJDGFQJCHFJTRH-YONAWACDSA-N 16-Ketoestradiol Chemical class OC1=CC=C2[C@H]3CC[C@](C)([C@H](C(=O)C4)O)[C@@H]4[C@@H]3CCC2=C1 KJDGFQJCHFJTRH-YONAWACDSA-N 0.000 claims 1
- 229930194542 Keto Natural products 0.000 claims 1
- 238000009472 formulation Methods 0.000 description 24
- 239000004480 active ingredient Substances 0.000 description 23
- 150000001875 compounds Chemical class 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 125000000217 alkyl group Chemical group 0.000 description 11
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 11
- 239000002270 dispersing agent Substances 0.000 description 11
- 150000002148 esters Chemical class 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 10
- 239000004094 surface-active agent Substances 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 8
- 230000003750 conditioning effect Effects 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 231100000674 Phytotoxicity Toxicity 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 125000000962 organic group Chemical group 0.000 description 6
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 5
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 5
- 239000000443 aerosol Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000000575 pesticide Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 4
- 241000227653 Lycopersicon Species 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 239000002671 adjuvant Substances 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- GJNVWSZVPRSEIH-UHFFFAOYSA-N C(CCC)OC(=S)SCCCC.C(CCC)[Sn]CCCC Chemical compound C(CCC)OC(=S)SCCCC.C(CCC)[Sn]CCCC GJNVWSZVPRSEIH-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 240000003768 Solanum lycopersicum Species 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 239000003350 kerosene Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- OJVAMHKKJGICOG-UHFFFAOYSA-N 2,5-hexanedione Chemical compound CC(=O)CCC(C)=O OJVAMHKKJGICOG-UHFFFAOYSA-N 0.000 description 2
- 241000213004 Alternaria solani Species 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 241000233622 Phytophthora infestans Species 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 2
- 241000607479 Yersinia pestis Species 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000006184 cosolvent Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 2
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 150000002085 enols Chemical group 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 208000014674 injury Diseases 0.000 description 2
- 125000000468 ketone group Chemical group 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 230000000361 pesticidal effect Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- LYRCQNDYYRPFMF-UHFFFAOYSA-N trimethyltin Chemical class C[Sn](C)C LYRCQNDYYRPFMF-UHFFFAOYSA-N 0.000 description 2
- SBXWFLISHPUINY-UHFFFAOYSA-N triphenyltin Chemical compound C1=CC=CC=C1[Sn](C=1C=CC=CC=1)C1=CC=CC=C1 SBXWFLISHPUINY-UHFFFAOYSA-N 0.000 description 2
- RFCAUADVODFSLZ-UHFFFAOYSA-N 1-Chloro-1,1,2,2,2-pentafluoroethane Chemical compound FC(F)(F)C(F)(F)Cl RFCAUADVODFSLZ-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical compound CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 244000075850 Avena orientalis Species 0.000 description 1
- 235000007319 Avena orientalis Nutrition 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- IVHVNMLJNASKHW-UHFFFAOYSA-M Chlorphonium chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CC1=CC=C(Cl)C=C1Cl IVHVNMLJNASKHW-UHFFFAOYSA-M 0.000 description 1
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-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 group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 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 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920004890 Triton X-100 Polymers 0.000 description 1
- 239000013504 Triton X-100 Substances 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000000642 acaricide Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- FAMUPMBATZGWOV-UHFFFAOYSA-M bromo(triphenyl)stannane Chemical compound C=1C=CC=CC=1[Sn](C=1C=CC=CC=1)(Br)C1=CC=CC=C1 FAMUPMBATZGWOV-UHFFFAOYSA-M 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000035613 defoliation Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- ONKUFCYOWCZCSR-UHFFFAOYSA-N didodecyltin Chemical compound CCCCCCCCCCCC[Sn]CCCCCCCCCCCC ONKUFCYOWCZCSR-UHFFFAOYSA-N 0.000 description 1
- RMYCHSWWYRUKHO-UHFFFAOYSA-N diethyl(phenyl)tin Chemical compound CC[Sn](CC)C1=CC=CC=C1 RMYCHSWWYRUKHO-UHFFFAOYSA-N 0.000 description 1
- BLBIZNCSZLTDPW-UHFFFAOYSA-N dihydrogenphosphite Chemical compound OP(O)[O-] BLBIZNCSZLTDPW-UHFFFAOYSA-N 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- PWEVMPIIOJUPRI-UHFFFAOYSA-N dimethyltin Chemical compound C[Sn]C PWEVMPIIOJUPRI-UHFFFAOYSA-N 0.000 description 1
- KUCPUSUXIGWHFB-UHFFFAOYSA-N diphenyltin Chemical class C=1C=CC=CC=1[Sn]C1=CC=CC=C1 KUCPUSUXIGWHFB-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- OVBPIULPVIDEAO-LBPRGKRZSA-N folic acid Chemical compound C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-LBPRGKRZSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 208000037824 growth disorder Diseases 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- WMIYKQLTONQJES-UHFFFAOYSA-N hexafluoroethane Chemical compound FC(F)(F)C(F)(F)F WMIYKQLTONQJES-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000003906 humectant Substances 0.000 description 1
- 239000003864 humus Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 208000006278 hypochromic anemia Diseases 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 230000003902 lesion Effects 0.000 description 1
- 239000012669 liquid formulation Substances 0.000 description 1
- 150000004668 long chain fatty acids Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- BRQVULKQFDNFJE-UHFFFAOYSA-N methyl(phenyl)tin Chemical compound C[Sn]C1=CC=CC=C1 BRQVULKQFDNFJE-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- WSGCRAOTEDLMFQ-UHFFFAOYSA-N nonan-5-one Chemical compound CCCCC(=O)CCCC WSGCRAOTEDLMFQ-UHFFFAOYSA-N 0.000 description 1
- VEXCRASZSGCQSY-UHFFFAOYSA-M o-methyl triphenylstannylsulfanylmethanethioate Chemical compound C=1C=CC=CC=1[Sn](C=1C=CC=CC=1)(SC(=S)OC)C1=CC=CC=C1 VEXCRASZSGCQSY-UHFFFAOYSA-M 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920001470 polyketone Polymers 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- OMKVZYFAGQKILB-UHFFFAOYSA-M potassium;butoxymethanedithioate Chemical compound [K+].CCCCOC([S-])=S OMKVZYFAGQKILB-UHFFFAOYSA-M 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910052903 pyrophyllite Inorganic materials 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000004763 spore germination Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- JNZRDLWZFWFSBK-UHFFFAOYSA-N tribenzyltin Chemical compound C=1C=CC=CC=1C[Sn](CC=1C=CC=CC=1)CC1=CC=CC=C1 JNZRDLWZFWFSBK-UHFFFAOYSA-N 0.000 description 1
- PIILXFBHQILWPS-UHFFFAOYSA-N tributyltin Chemical compound CCCC[Sn](CCCC)CCCC PIILXFBHQILWPS-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000002569 water oil cream Substances 0.000 description 1
- 239000004563 wettable powder Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
-
- 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
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/22—Tin compounds
Definitions
- This invention relates to fungicidal compositions and more particularly to new and potent tin-containing fungicidal compositions characterized by an essential lack of phytotoxicity'. This invention also relates to the use of such compositionsin combating fungi.
- An object of this invention is to provide new fungicidal compositions.
- a further object is to provide new fungicidal compositions coupling a high degree of fungitoxicity with an essential lack of phytotoxicity.
- Still another object is to provide a new means for combating fungi.
- fungicidal compositions comprising a conditioning agent and as a principal active ingredient a material selected from the class consisting of diorganotin enolates, triorganotin enolates, diorganotin esters of phosphorus acids, triorganotin esters of phosphorus acids, diorganotin xanthates and triorganotin xanthates.
- a specific outstanding aspect of the invention resides in the provision of the fungicidal compositions comprising a conditioning agent and as a principal active ingredient a dialkyltin enolate, particularly dibutyltin diacetylacetonate.
- compositions are exceedingly useful in combating fungi when they are applied to the Such treatment, therefore, constitutes one aspect of our invention.
- materials We have found our materials to be especially useful in controlling and eliminating fungi which infest vegetation since the compounds completely lack phytoxicity, as nearly as can be I determined.
- the active ingredients of this invention comprise or ganotin salts containing 2 to 3 organo groups directly attached to tin.
- organo groups are preferably hydrocarbon groups such as alkyl, aryl and alkenyl radi- However, they can also be substituted, as with halogen atoms.
- the alkyl groups have preferably 1-16 carbon atoms and the aryl groups 6-10 carbon atoms.
- the two or three organo groups in the molecule can be the same or they can be different. When different they can be selected from more than one of the above mentioned types of organo groups.
- dialkyltin salts trialkyltin salts, diaryltin salts, triaryltin salts, alkylaryltin salts, dialkylaryltin salts, diarylalkyltin salts, etc.
- an active ingredient such as a trimethyltin salt, a dibutyltin salt, a methylpropylhexyltin salt, a dimethylbenzyltin salt, a diphenyltin salt, etc.
- our active ingredients when our active ingredients is an enolate it can be in general prepared from any compound capableof existing in enol form. We find that especially good results are obtained when our active ingredient is derived from the enolic form of a ketone such as acetone, methylethylketone, dibutylketone, acetylacetone or acetonylacetone. That is, it can be prepared from monoketones and polyketones, especially diketones, particularly fi-diketones and u-diketones.
- Other enols which may be used to form our enolates include active methylene compounds, particularly those inwhich a methylene group is located be,-
- These compounds can readily be formed as for example by merely mixing the enolic compound and the dior triorganotin halide in alkaline solution 'such'as aqueous sodium hydroxide, aqueous sodium vcarbonate and even dilute aqueous ammonium hydroxidesolution, as is shown in the following example.
- Example 1 Dibutyltin diacetylacetonate was prepared in good yield by merely mixing acetylacetone and dibutyltin dichloride in substantially 2:1 molar proportion for a period of a few minutes at room temperature in dilute ammonium hydroxide solution.
- triphenyltin cyclohexanonate by reacting triphenyltin bromide with cyclohexanone" at room temperature in 2 percent aqueous sodium carbonate solution, etc.
- our active ingredient is an ester of a phosphorus acid it can be an ester of either a trivalent or a pentavalent phosphorus acid including phosphoric acid, phosphorus acid, pyrophosphoric acid, hypophosphorus'acid, primary and secondary phosphonous and phosphonic
- the compound may be composed so that the phosphorus acid is either completely esterified with an organotin radical; partially esterified with an organotin radical and partially esterified with a hydrocarbon radical;or partially esterified with an organotin radical andhaving the remainder of its hydrogen atoms unesterified.
- any 'or all of the oxygen atoms in the phosphorus acid may be replaced with sulfur atoms so that our active ingredients encompass esters of thiophosphorus acids as well as their oxygenated analogs.
- organotin esters of phosphorus acids include trimethyltin phosphite, triamyltin phosphite, tribenzyltin monohydrogenphosphite, di-
- the phosphorus-containing materials of this invention may be prepared conveniently by condensing; a dior triorganotin halide with an alkali metal 101? other q as the conditioning agent.
- xanthate ingredients include dibutyltin dimethylxanthate, dibutyltin dibutylxanthate, dimethyltin didodecyl- ,xanthate, triphenyltin methylxanthate, methyl diphenylmethylxanthate, methyltolyltin dioctylxanthate, di- -tolyltin diphenylxanthate and the like. Theymay be prepared conveniently by reaction of the dior triorganotin salt corresponding to the xanthate desired with the corresponding xanthate salt as the following example indicates.
- Our preferred xanthate ingredients are dialkyltin dialkylxanthates.
- Example HI Dibutyltin dibutylxanthate.--To a stirred solution of 30.4 parts of dibutyltin dichloride in 320 parts of methanol was added a solution of 37.8 parts of potassium n-butylxanthate in 160 parts of methanol over a period of 1 hour with rapid agitation. An oil layer was then separated from the turbid solution and was withdrawn, filtered through a siliceous filter aid to remove the slight degree of turbidity which was present, following which the oily layer was heated at 100 to remove last traces of the alcohol solvent. The residue from this distillation was dibutyltin dibutylxanthate, a yellow viscous oil which was found by analysis to contain 19.3 percent sulfur and 19.4 percent tin.
- conditioning agents with which we admix our active ingredients are of the type also known in the art as pest control adjuvants, extenders, and modifiers as well as dispersants, dispersing agents, surface-active agents, etc.
- such formulations comprise both the liquid and solid types as well as the Aerosol type of formulation.
- the liquid type of formulation can have water, an organic solvent, an oil-Water emulsion and the like
- the liquid ingredient of the formulation may further contain a surface-active agent such as a detergent, a soap or other wetting agent.
- a surface-active agent such as a detergent, a soap or other wetting agent.
- conditioning agent include solid carriers such as talc, pyrophyllite, Attaclay, kieselguhr, chalk, diatomaceous earth, and the like; and various mineral powders such as calcium carbonate and the like which act as a dispersant, as a carrier, and in' some 7 instances perform the function of a surface-active agent.
- solid conditioning agents include solid carriers such as talc, pyrophyllite, Attaclay, kieselguhr, chalk, diatomaceous earth, and the like; and various mineral powders such as calcium carbonate and the like which act as a dispers
- these wettable powders include the activeingredient, a surface-active agent and an inert carrier such as soybean flour, sulfur, calcium, mica, talc, humus and the like.
- an inert carrier such as soybean flour, sulfur, calcium, mica, talc, humus and the like.
- Such formulations provide the advantage of permitting storage and transportation of the pesticides in readilyhandled form and permit further dilution by simple admixture with water to provide finished liquid formulations at the time of application.
- formulations which comprise our active ingredient in combination with a conditioning agent provide liquid, solid and aerosol formulations in a form adapted to be readily applied to the material to be treated.
- liquid compositions either solutions or dispersions
- the solid formulations also frequently contain a surfaceactive dispersing agent in amount suflicient to render the composition readily dispersable in water for aqueous spray application.
- the solid formulations also frequently contain a surfaceactive dispersing agent in amount suificient to impart When dust application is desired a surface-active dispersing agent can be omitted. In this case the formulation will still contain a solid carrier, extender or diluent as conditioning agent.
- the surface-active dispersing agents referred to herein are sometimes known as wetting, dispersing or penetrating agents. They are agents which cause the formulations to be easily dispersed in water. They can be of the anionic, cationic or non-ionic type and include salts of long chain fatty acids, sulfonated oils-both vegetable and animalpetroleum oils, sulfates of long chain alcohols, phosphates of long chain alcohols, various polyethylene oxides and condensation products of ethylene oxide with alcohols and phenols, quaternary ammonium salts and the like. The surface-active agent will usually be present to the extent of 0.1 to 5 percent of the formulation.
- the active ingredients can also be dispersed or suspended in various organic solvents such as alcohols, ketones, hydrocarbons, petroleum cuts such as kerosene, dimethylformamide and the like.
- a surfaceactive dispersing agent is usually present to provide ready dispersability with water.
- Example IV A formulation of dibutyltin diacetylacetonate is prepared by adding with vigorous agitation 10 parts of this material to 1000 parts of water containing one part of Tween-80. This concentrated dispersion is further diluted 1000 times by the addition of water to obtain a formulation of suitable concentration for application. Thus, the resulting dispersion contains 10 p.p.m. of our pesticide in the water dispersion.
- the solubility of the active ingredients of this invention in organic solvents is such that it can be applied advantageously in the form of solution in this type of solvent, and for certain uses this method of application is preferred.
- solution may be the most practical method for applying a protective film by brushing, spraying, or dipping.
- the choice of an appropriate solvent is determined largely by the concentration of active ingredient which it is desired to employ, by the volatility required in a solvent, the spreading or flow characteristics thereof, and by the nature of the material being treated.
- Example V A solution consisting of parts of tri-n-propyltin trithiophosphate in 250 parts of cyclohexanone is prepared by stirring the two constituents for a period of 2 minutes at a temperature of about 25 C. This concentrated solution, suitable for storage or transportation, is further diluted with 99,750 parts of kerosene to form a final dilution of 50 p.p.m. suitable for application.
- Example VI A mixture of 100 parts of dibutyltin dimethylxanthate, 1000 parts of Attaclay, and 0.1 part of Nacconol is intimately mixed in an L-shaped blender. The percent wettable powder thus prepared produces a satisfactory water suspension when 11 parts are stirred into 10,000 parts of water to produce a suspension containing 100 p.p.m. active ingredient.
- Example VII An oil-in-water emulsion is prepared by dissolving 10 parts of dibutyltin di(diphenyldithiophosphate) in 1000 parts of kerosene. This solution is dispersed with vigorous agitation in 99,000 parts of water containing 1 part of Triton X-100 to provide a dispersion containing 10 p.p.m. of active agent.
- an adherent or sticking agent such as vegetable oils, naturally occurring gums, and other adhesives
- these formulations can be employed in admixture with other pesticidal materials or other biocides, such as insecticides, larvicides, bactericides, vermicides, miticides, or with other materials which it is desired to apply along with our pesticides.
- our compounds also find effective use when formulated in Aerosol type formulations; that is, when mixed with a liquid of low boiling point that changes to a gas when released from a confined space.
- this type diluent are fluorinated hydrocarbons such as tetrafluoromethane and hexafluoroethane; mixed halogenated compounds containing fluorine and chlorine, such as difluorodichloromethane, pentafluorochloroethane; or ethylene substituted with both these halogens.
- Compounds containing fluorine and bromine are also applicable, as, for example, trifiuorobromomethane.
- Aerosol formulations comprise introducing our new compounds into a pressure cylinder and later introducing the liquefied diluent under pressure, followed by mixing the cylinder to obtain uniform solution. If desired, smaller containers can then be filled from the cylinder in which the formulation is made up. In many cases it is desirable to add a second solvent to the low boiling material of the type described above, so as to more readily dissolve our compounds. Examples of such cosolvents are benzene, acee tone, carbon tetrachloride, butyl acetate, Cellosolve, and the like.
- Example IX Into a cylinder rated at 500 p.s.i. working pressure, is introduced 10 parts of triphenyltin phenylxanthate. The cylinder is then made pressure-tight except for one opening, through which is introduced a mixture of 50 parts acetone and 50 parts dichlorodifluoromethane from a container at 2000 p.s.i. The cylinder into which the in-' gredients are introduced is then sealed off and inverted to give a uniform Aerosol solution of our active materials in the mixture of cosolvents.
- Tomato foliage disease test measures the percent control of early blight fungus, Alternaria solani, and late blight fungus, Phytophthora infestans. The chemicals are evaluated at concentrations of 2000 and 400 p.p.m. Chemicals showing good results at these concentrations are tested at successively lower concentrations to determine effective dosages. Tomato plants are sprayed with formulations of the active materials, allowed to dry and along with untreated controls are sprayed with a spore suspension of conidia of Alternaria solani or sporangia of Phytophthora infestans. The plants are held in a saturated atmosphere for 24 hours at 70 F. for early blight and 60 F.
- Tomato watering test-Potted tomato plants of the same variety as used in the foliage spray test are watered with 50 ml. of a one percent formulation of the test chemical. Plant effects are observed after ten days and are recorded as described in the foliage spray test.
- Method of combating fungi comprising treating the locus of the fungi with amaterial selected from the class consisting of diorganotin enolates, triorganotin enolates, diorganotin esters of phosphorus acids, triorganotin esters of phosphorus acids, diorganotin Xanthates, and triorganotin x anthates wherein said organo group is selected from the group consisting of alkyl groups having 1 to 6 carbon atoms and aryl groups having 6 to 10 carbon atoms and wherein said phosphorus acidis selected from the group consisting of phosphoric acid, phosphorus acid, pyrophosphoric acid, hypophosphorus acid, phosphonous acid, phosphonic acid, and metaphosphoric acid and wherein said enolate is selected from the group consisting of monoketones, u-diketones, fi-diketones, keto esters and active methylene compounds wherein a methylene radical is between two carb
- Method of combating fungi comprising treating the locus of the fungi with a material selected from the class consisting of dialkyltin p-keto ester enolate wherein the alkyl group has 1 to 16 carbon atoms.
- Method of combating fungi comprising treating the locus of the fungi with dibutyltin diacetylacetonate.
- Fungicidal composition comprising a dispersing agent as a Vfungicidaladjuvant and a surface-active agent and as a principal active ingredient a material selected from the class consisting of diorganotin enolates, triorganotin enolates, diorganotin esters of phosphorus acids, triorganotin esters of phosphorus acids, diorganotin xanthates, and triorganotin Xanthates wherein said organo group is selected from the group consisting of alkyl groups having 1 to 6 carbon atorns and aryl groups havacidtis 'selectedffi'om'the group consisting ,of phosphoric acid, phosphorus i'acidf pyrophosphorie'facid b passes; pho rus r.acid, phosphon'ous .acid, phosphonidacid, and metaphosphoric "and and wherein said enolate 'is selected from
- a fungicidal composition comprising a dispersing agent as a fungicidal adjuvant and a surface-active agent and as a principal active ingredient a material selected from the group'consi'sting of a dialkyltin thiophosphate ester, a dialkyltin dialkyl xanthate, and a dialkyltin fiketo ester enolate wherein said alkyl groups have 1 to 16 carbon atoms. 7
- fungicidal composition comprising adispersing agent as a fungicidal adjuvant and a surface-active agent and as a principal active ingredient a dialkyltin fl-keto ester enolate wherein the alkyl group has 1 to 16 carbon atoms.
- a fungicidal composition comprising a dispersing agent as a fungicidal adjuvant and a surface-active agent and as a principal activeingredient dibutyltin diacetylacetonate.
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Description
locus of the fungi.
v cals.
FUNGICIDAL COMPOSITIONS No Drawing. Application May 27 1955 Serial No. 511,762
7 Claims. (Cl. 167- -22 This invention relates to fungicidal compositions and more particularly to new and potent tin-containing fungicidal compositions characterized by an essential lack of phytotoxicity'. This invention also relates to the use of such compositionsin combating fungi. I 2 An object of this invention is to provide new fungicidal compositions. A further object is to provide new fungicidal compositions coupling a high degree of fungitoxicity with an essential lack of phytotoxicity. Still another object is to provide a new means for combating fungi.
The above and other objects are accomplished by the present invention which resides in providing fungicidal compositions comprising a conditioning agent and as a principal active ingredient a material selected from the class consisting of diorganotin enolates, triorganotin enolates, diorganotin esters of phosphorus acids, triorganotin esters of phosphorus acids, diorganotin xanthates and triorganotin xanthates. A specific outstanding aspect of the invention resides in the provision of the fungicidal compositions comprising a conditioning agent and as a principal active ingredient a dialkyltin enolate, particularly dibutyltin diacetylacetonate.
We have found that such compositions are exceedingly useful in combating fungi when they are applied to the Such treatment, therefore, constitutes one aspect of our invention. We have found our materials to be especially useful in controlling and eliminating fungi which infest vegetation since the compounds completely lack phytoxicity, as nearly as can be I determined.
The active ingredients of this invention comprise or ganotin salts containing 2 to 3 organo groups directly attached to tin. Such organo groups are preferably hydrocarbon groups such as alkyl, aryl and alkenyl radi- However, they can also be substituted, as with halogen atoms. The alkyl groups have preferably 1-16 carbon atoms and the aryl groups 6-10 carbon atoms. The two or three organo groups in the molecule can be the same or they can be different. When different they can be selected from more than one of the above mentioned types of organo groups. That is to say, we provide dialkyltin salts, trialkyltin salts, diaryltin salts, triaryltin salts, alkylaryltin salts, dialkylaryltin salts, diarylalkyltin salts, etc. Thus we provide an active ingredient such as a trimethyltin salt, a dibutyltin salt, a methylpropylhexyltin salt, a dimethylbenzyltin salt, a diphenyltin salt, etc.
When our active ingredients is an enolate it can be in general prepared from any compound capableof existing in enol form. We find that especially good results are obtained when our active ingredient is derived from the enolic form of a ketone such as acetone, methylethylketone, dibutylketone, acetylacetone or acetonylacetone. That is, it can be prepared from monoketones and polyketones, especially diketones, particularly fi-diketones and u-diketones. Other enols which may be used to form our enolates include active methylene compounds, particularly those inwhich a methylene group is located be,-
United States Patent 2,922,738 Patented Jan. 26, i960 "ice acetylacetonate, didodecyltin diacetylacetonate, dibutyltin diacetylacetonate tributyltin acetylacetonate, .triphenyltin acetylacetonate, ethylditolyltin acetylacetonate, dibutyltin diacetonylacetonate, methyl-a-naphth'yltin 'diacetonylacetonate, diphenylhexyltin acetonylacetonate, di-
' acids, metaphosphoric acid and the like.
methylphenyltin acetonate, triisopropyltin methylethyl ketonate, diethylphenyltin cyclopentanonate, triethyltin ethylacetoacetate, methyldodecylhexyltin diethylm'alonate, and the like. Y
These compounds can readily be formed as for example by merely mixing the enolic compound and the dior triorganotin halide in alkaline solution 'such'as aqueous sodium hydroxide, aqueous sodium vcarbonate and even dilute aqueous ammonium hydroxidesolution, as is shown in the following example.
Example 1 Dibutyltin diacetylacetonate was prepared in good yield by merely mixing acetylacetone and dibutyltin dichloride in substantially 2:1 molar proportion for a period of a few minutes at room temperature in dilute ammonium hydroxide solution.
Likewise we prepare triphenyltin cyclohexanonate by reacting triphenyltin bromide with cyclohexanone" at room temperature in 2 percent aqueous sodium carbonate solution, etc.
When our active ingredient is an ester of a phosphorus acid it can be an ester of either a trivalent or a pentavalent phosphorus acid including phosphoric acid, phosphorus acid, pyrophosphoric acid, hypophosphorus'acid, primary and secondary phosphonous and phosphonic Furthermore the compound may be composed so that the phosphorus acid is either completely esterified with an organotin radical; partially esterified with an organotin radical and partially esterified with a hydrocarbon radical;or partially esterified with an organotin radical andhaving the remainder of its hydrogen atoms unesterified. Furthermore, any 'or all of the oxygen atoms in the phosphorus acid may be replaced with sulfur atoms so that our active ingredients encompass esters of thiophosphorus acids as well as their oxygenated analogs. I
Specific examples of our organotin esters of phosphorus acids include trimethyltin phosphite, triamyltin phosphite, tribenzyltin monohydrogenphosphite, di-
,hexyltolyltin dihydrogenphosphite, trilauryltin trithiophosphite, tri-fl-naphthyltin phosphate, ethyldiamyltin acids whose remaining free hydrogens are esterified with alkyl, cycloalkyl or aryl groups, are preferred v The phosphorus-containing materials of this invention may be prepared conveniently by condensing; a dior triorganotin halide with an alkali metal 101? other q as the conditioning agent.
metal solvent of the corresponding phosphorus acid as the following example illustrates.
, I i I V I Example 11 I V Di-butyltin (dimethylcyclohexyl .dithiophosphate) .,A mixture of 18.2 parts of dibutyltin dichloride and 432 --parts of potassium dimethylcyclohexyl, dithiophosphate in200 parts of petroleum ether was stirred at room Preparation of other phosphorus-containing materials of this invention can be effected in a similar way. Further examples of preparations of such materials can be found in. US. Patent 2,630,436. 'Similarly the xanthates of this invention can have as the xanth'ate portion'of the molecule a radical derived from any alkyl or aryl 'xanthat'e. Typical examples, of our xanthate ingredients include dibutyltin dimethylxanthate, dibutyltin dibutylxanthate, dimethyltin didodecyl- ,xanthate, triphenyltin methylxanthate, methyl diphenylmethylxanthate, methyltolyltin dioctylxanthate, di- -tolyltin diphenylxanthate and the like. Theymay be prepared conveniently by reaction of the dior triorganotin salt corresponding to the xanthate desired with the corresponding xanthate salt as the following example indicates. Our preferred xanthate ingredients are dialkyltin dialkylxanthates.
Example HI Dibutyltin dibutylxanthate.--To a stirred solution of 30.4 parts of dibutyltin dichloride in 320 parts of methanol was added a solution of 37.8 parts of potassium n-butylxanthate in 160 parts of methanol over a period of 1 hour with rapid agitation. An oil layer was then separated from the turbid solution and was withdrawn, filtered through a siliceous filter aid to remove the slight degree of turbidity which was present, following which the oily layer was heated at 100 to remove last traces of the alcohol solvent. The residue from this distillation was dibutyltin dibutylxanthate, a yellow viscous oil which was found by analysis to contain 19.3 percent sulfur and 19.4 percent tin.
The other xanthates of the present invention can be i made by similar methods. r
The conditioning agents with which we admix our active ingredients are of the type also known in the art as pest control adjuvants, extenders, and modifiers as well as dispersants, dispersing agents, surface-active agents, etc.
Their purpose is to extend the active ingredient to assure its eflicacious penetration or application onto the locus being treated and to adapt the active .ingredients for ready and efiicient application to pests and to the loci of the fungi using conventional equipment.
In general such formulations comprise both the liquid and solid types as well as the Aerosol type of formulation. The liquid type of formulation can have water, an organic solvent, an oil-Water emulsion and the like The liquid ingredient of the formulation may further contain a surface-active agent such as a detergent, a soap or other wetting agent. It is also intended that the term conditioning agent include solid carriers such as talc, pyrophyllite, Attaclay, kieselguhr, chalk, diatomaceous earth, and the like; and various mineral powders such as calcium carbonate and the like which act as a dispersant, as a carrier, and in' some 7 instances perform the function of a surface-active agent. I Among the preferred formulations employing solid conditioning agents are those known as wettable powders.
water dispersability to the compositions.
In general these wettable powders include the activeingredient, a surface-active agent and an inert carrier such as soybean flour, sulfur, calcium, mica, talc, humus and the like. In preparing such concentrated wettable powders it is preferred to employ between about 0.1 and 5 percent of the surface-active agent based upon the amount of active ingredient used and up to about percent of the inert solid carrier based upon the total amount of the formulation. Such formulations provide the advantage of permitting storage and transportation of the pesticides in readilyhandled form and permit further dilution by simple admixture with water to provide finished liquid formulations at the time of application.
Thus the formulations which comprise our active ingredient in combination with a conditioning agent provide liquid, solid and aerosol formulations in a form adapted to be readily applied to the material to be treated.
.The liquid compositions, either solutions or dispersions,
frequently contain a surface-active dispersing agent in amount suflicient to render the composition readily dispersable in water for aqueous spray application. The solid formulations also frequently contain a surfaceactive dispersing agent in amount suificient to impart When dust application is desired a surface-active dispersing agent can be omitted. In this case the formulation will still contain a solid carrier, extender or diluent as conditioning agent.
The surface-active dispersing agents referred to herein are sometimes known as wetting, dispersing or penetrating agents. They are agents which cause the formulations to be easily dispersed in water. They can be of the anionic, cationic or non-ionic type and include salts of long chain fatty acids, sulfonated oils-both vegetable and animalpetroleum oils, sulfates of long chain alcohols, phosphates of long chain alcohols, various polyethylene oxides and condensation products of ethylene oxide with alcohols and phenols, quaternary ammonium salts and the like. The surface-active agent will usually be present to the extent of 0.1 to 5 percent of the formulation.
The active ingredients can also be dispersed or suspended in various organic solvents such as alcohols, ketones, hydrocarbons, petroleum cuts such as kerosene, dimethylformamide and the like. In this case a surfaceactive dispersing agent is usually present to provide ready dispersability with water.
Typical of such formulations of this invention are described in the following examples in which all parts are parts by weight.
Example IV A formulation of dibutyltin diacetylacetonate is prepared by adding with vigorous agitation 10 parts of this material to 1000 parts of water containing one part of Tween-80. This concentrated dispersion is further diluted 1000 times by the addition of water to obtain a formulation of suitable concentration for application. Thus, the resulting dispersion contains 10 p.p.m. of our pesticide in the water dispersion.
The solubility of the active ingredients of this invention in organic solvents, furthermore, is such that it can be applied advantageously in the form of solution in this type of solvent, and for certain uses this method of application is preferred. For example, in treating cloth, leather, or other fibrous articles, it is preferred to apply the pesticides dissolved in a volatile solvent. Afteruse the volatile solvent evaporates, leaving the pesticidal agents, impregnated throughout the surface of the article and in thedispersed form which has been found to be most advantageous. Likewise, in applying the pesticides to. smooth surfaces, as, for example, in treating wood or other surfaces, .2. solution may be the most practical method for applying a protective film by brushing, spraying, or dipping. The choice of an appropriate solvent is determined largely by the concentration of active ingredient which it is desired to employ, by the volatility required in a solvent, the spreading or flow characteristics thereof, and by the nature of the material being treated.
' Example V A solution consisting of parts of tri-n-propyltin trithiophosphate in 250 parts of cyclohexanoneis prepared by stirring the two constituents for a period of 2 minutes at a temperature of about 25 C. This concentrated solution, suitable for storage or transportation, is further diluted with 99,750 parts of kerosene to form a final dilution of 50 p.p.m. suitable for application.
Example VI A mixture of 100 parts of dibutyltin dimethylxanthate, 1000 parts of Attaclay, and 0.1 part of Nacconol is intimately mixed in an L-shaped blender. The percent wettable powder thus prepared produces a satisfactory water suspension when 11 parts are stirred into 10,000 parts of water to produce a suspension containing 100 p.p.m. active ingredient.
Example VII Example VIII An oil-in-water emulsion is prepared by dissolving 10 parts of dibutyltin di(diphenyldithiophosphate) in 1000 parts of kerosene. This solution is dispersed with vigorous agitation in 99,000 parts of water containing 1 part of Triton X-100 to provide a dispersion containing 10 p.p.m. of active agent.
In addition, we have found that we can incorporate an adherent or sticking agent, such as vegetable oils, naturally occurring gums, and other adhesives, in our active ingredient formulations. Likewise, we can employ humectants in our formulations. Furthermore, these formulations can be employed in admixture with other pesticidal materials or other biocides, such as insecticides, larvicides, bactericides, vermicides, miticides, or with other materials which it is desired to apply along with our pesticides.
Our compounds also find effective use when formulated in Aerosol type formulations; that is, when mixed with a liquid of low boiling point that changes to a gas when released from a confined space. Examples of this type diluent are fluorinated hydrocarbons such as tetrafluoromethane and hexafluoroethane; mixed halogenated compounds containing fluorine and chlorine, such as difluorodichloromethane, pentafluorochloroethane; or ethylene substituted with both these halogens. Compounds containing fluorine and bromine are also applicable, as, for example, trifiuorobromomethane. Other materials such as carbon dioxide, sulfur dioxide, hydrogen sulfide, and ammonia can be used, and of these carbon dioxide is preferred. One method of preparing such Aerosol formulations comprises introducing our new compounds into a pressure cylinder and later introducing the liquefied diluent under pressure, followed by mixing the cylinder to obtain uniform solution. If desired, smaller containers can then be filled from the cylinder in which the formulation is made up. In many cases it is desirable to add a second solvent to the low boiling material of the type described above, so as to more readily dissolve our compounds. Examples of such cosolvents are benzene, acee tone, carbon tetrachloride, butyl acetate, Cellosolve, and the like.
Example IX Into a cylinder rated at 500 p.s.i. working pressure, is introduced 10 parts of triphenyltin phenylxanthate. The cylinder is then made pressure-tight except for one opening, through which is introduced a mixture of 50 parts acetone and 50 parts dichlorodifluoromethane from a container at 2000 p.s.i. The cylinder into which the in-' gredients are introduced is then sealed off and inverted to give a uniform Aerosol solution of our active materials in the mixture of cosolvents.
The fungicidal effectiveness of our compounds can be demonstrated by the following tests.
Tomato foliage disease test.--The tomato foliage disease test measures the percent control of early blight fungus, Alternaria solani, and late blight fungus, Phytophthora infestans. The chemicals are evaluated at concentrations of 2000 and 400 p.p.m. Chemicals showing good results at these concentrations are tested at successively lower concentrations to determine effective dosages. Tomato plants are sprayed with formulations of the active materials, allowed to dry and along with untreated controls are sprayed with a spore suspension of conidia of Alternaria solani or sporangia of Phytophthora infestans. The plants are held in a saturated atmosphere for 24 hours at 70 F. for early blight and 60 F. for late blight to permit spore germination and infection before removal to the greenhouse. After 2w 4 days lesion counts are made on the three uppermost fully expanded leaves. This test method is a modification of that described by McCallan and Wellman (Contrib. Boyce Thompson, 13(3) :93'134, July-September 1943).
In such tests the ED95 of typical compounds of this invention were found to be as follows:
ED-95 Against Early Blight ED-95 Against Blight Compound p.p.m.
p.p.m. Dibutyltin acetylacetonate Dibutyltin dimethylcyclohexylthiophosphate Dibutyltin dibutylxanthate Hoe NOIW
corn, variety Early Golden Orange; oats, variety Clydesdale; and tomato, variety Bonny Best. Phytotoxicity, at the end of 10 days, is rated on a scale from 0 to 11. The grades are based on the percent leaf area destroyed: 0=no injury; 1:0. to 3; 2:3 to 6; 3:6 to 12; 4=12 to 25; 5:25 to 50; 6:50 to 75; 7:75 to 87; 8:87 to 94; 9:94 to 97; 10:97 to 100; and at 11 the plant is dead. Other responses such as stunting, chlorosis, defoliation, and formative effects are noted. Chemicals which are rated 10 or more on one of the test plants are retested in dosage series to determine the level of their activity.
Tomato watering test-Potted tomato plants of the same variety as used in the foliage spray test are watered with 50 ml. of a one percent formulation of the test chemical. Plant effects are observed after ten days and are recorded as described in the foliage spray test.
In such tests the three compounds listed in the above table showed no phytotoxicity (phytotoxicity rating of 0) in each test with the exception that dibutyltin dimethylcyclohexylthiophosphate did show up to 3 percent injury (phytotoxicity rating of l) in the tomato soil watering test.
Similar fungitoxicity and phytotoxicity results are obtained with the other active ingredients of this invention.
ssl im 1. Method of combating fungi comprising treating the locus of the fungi with amaterial selected from the class consisting of diorganotin enolates, triorganotin enolates, diorganotin esters of phosphorus acids, triorganotin esters of phosphorus acids, diorganotin Xanthates, and triorganotin x anthates wherein said organo group is selected from the group consisting of alkyl groups having 1 to 6 carbon atoms and aryl groups having 6 to 10 carbon atoms and wherein said phosphorus acidis selected from the group consisting of phosphoric acid, phosphorus acid, pyrophosphoric acid, hypophosphorus acid, phosphonous acid, phosphonic acid, and metaphosphoric acid and wherein said enolate is selected from the group consisting of monoketones, u-diketones, fi-diketones, keto esters and active methylene compounds wherein a methylene radical is between two carboxylic groups, and wherein said Xanthate is selected from the group consisting of alkyl Xauthates and aryl Xanthates.
2, Method of combating fungi comprising treating the locus of the fungi with a material selected from the class consisting of dialkyltin p-keto ester enolate wherein the alkyl group has 1 to 16 carbon atoms.
3. Method of combating fungi comprising treating the locus of the fungi with dibutyltin diacetylacetonate.
, 4. Fungicidal composition comprising a dispersing agent as a Vfungicidaladjuvant and a surface-active agent and as a principal active ingredient a material selected from the class consisting of diorganotin enolates, triorganotin enolates, diorganotin esters of phosphorus acids, triorganotin esters of phosphorus acids, diorganotin xanthates, and triorganotin Xanthates wherein said organo group is selected from the group consisting of alkyl groups having 1 to 6 carbon atorns and aryl groups havacidtis 'selectedffi'om'the group consisting ,of phosphoric acid, phosphorus i'acidf pyrophosphorie'facid b passes; pho rus r.acid, phosphon'ous .acid, phosphonidacid, and metaphosphoric "and and wherein said enolate 'is selected from the group consistingof monoketones, 'a-diketones, fi-diketones, keto esters and active methylene compounds wherein a methylene radical is between two carboxylic groups, and wherein said xanthate is selected from the groupconsisting of alkyl xanthates and aryl xanthatcs.
5. A fungicidal composition comprising a dispersing agent as a fungicidal adjuvant and a surface-active agent and as a principal active ingredient a material selected from the group'consi'sting of a dialkyltin thiophosphate ester, a dialkyltin dialkyl xanthate, and a dialkyltin fiketo ester enolate wherein said alkyl groups have 1 to 16 carbon atoms. 7
6.'A fungicidal compositioncomprising adispersing agent as a fungicidal adjuvant and a surface-active agent and as a principal active ingredient a dialkyltin fl-keto ester enolate wherein the alkyl group has 1 to 16 carbon atoms..
7. A fungicidal composition comprising a dispersing agent as a fungicidal adjuvant and a surface-active agent and as a principal activeingredient dibutyltin diacetylacetonate.
References Cited in the file of this patent UNITED STATES PATENTS 1,736,448 Liebknecht Nov. 19, 1929 2,107,298 Kilgore: Feb. 8, 1938 2,150,759 Carter Mar. 14, 1939 2,278,965 Van Peski et a1. Apr. .7, 1942 2,702,777 Kerr et a1. Feb. 22, 1955
Claims (1)
1. METHOD OF COMBATING FUNGI COMPRISING TREATING THE LOCUS OF THE FUNGI WITH A MATERIAL SELECTED FROM THE CLASS CONSISTING OF DIORGANOTIN ENOLATES, TRIORGANOTIN ENOLATES, DIORGANOTIN ESTERS OF PHOSPHORUS ACIDS, TRIORGANOTIC ESTERS OF PHOSPHORUS ACIDS, DIORGANOTIN XANTHATES, AND TRIORGANOTIN XANTHATES WHEREIN SAID ORGANO GROUP IS SELECTED FROM THE GROUP CONSISTING OF ALKYL GROUPS HAVING 1 TO 6 CARBON ATOMS AND ARYL GROUPS HAVING 6 TO 10 CARBON ATOMS AND WHEREIN SAID PHOSPHORUS ACID IS SELECTED FROM THE GROUP CONSISTING OF PHOSPHORIC ACID, PHOSPHORUS ACID, PYROPHOSPHORIC ACID, HYPOPHOSPHORUS ACID, PHOSPHONOUS ACID, KPHOSPHONIC ACID, AND METAPHOSPHORIC ACID AND WHEREIN SAID ENOLATE IS SELECTED FROM THE GROUP CONSISTING OF MONOKETONES, A-DIKETONES, B-DIKETONES, KETO ESTERS AND ACTIVE METHYLENE COMPOUNDS WHEREIN A METHYLENE RADICAL IS BETWEEN TWO CARBOXYLIC GROUPS, AND WHEREIN SAID XANTHATE IS SELECTED FROM THE GROUP CONSISTING OF ALKYL XANTHATES AND ARYL XANTHATES.
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US511762A US2922738A (en) | 1955-05-17 | 1955-05-27 | Fungicidal compositions |
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US509099A US3435118A (en) | 1955-05-17 | 1955-05-17 | Dibutyltin diacetate as a fungicidal agent |
US511762A US2922738A (en) | 1955-05-17 | 1955-05-27 | Fungicidal compositions |
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Cited By (26)
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US2957785A (en) * | 1957-06-07 | 1960-10-25 | Permachem Corp | Aqueous metastable dispersion of tetravalent organo-tin compounds treating process |
US3105000A (en) * | 1961-05-25 | 1963-09-24 | Dow Chemical Co | Organo-tin and organo-sulphur parasiticides |
US3120550A (en) * | 1960-05-27 | 1964-02-04 | Dow Chemical Co | Organo-tin and lead chelates |
US3127432A (en) * | 1960-10-03 | 1964-03-31 | Monsanto Chemicals | Organic phosphorus-aluminum compounds and method of preparation |
US3128296A (en) * | 1960-10-03 | 1964-04-07 | Monsanto Chemicals | Organic phosphinyloxyaluminum compounds and the preparation thereof |
US3140977A (en) * | 1960-05-27 | 1964-07-14 | Philips Corp | Fungicidal compositions containing triphenyl compounds |
US3214453A (en) * | 1960-08-25 | 1965-10-26 | Nease Chemical Company Inc | Bis-tributyltin carbonate and a method for the preparation thereof |
US3222158A (en) * | 1960-05-26 | 1965-12-07 | Frank J Sowa | Organotin compositions |
US3277132A (en) * | 1962-06-13 | 1966-10-04 | Wild Samuel | Tin(ii) salts of orthophosphoric-mono-(beta-aminoethanol)ester |
US3287103A (en) * | 1960-05-26 | 1966-11-22 | Frank J Sowa | Method of controlling weeds |
US3448131A (en) * | 1966-03-30 | 1969-06-03 | Union Carbide Corp | Process for preparing trihydrocarbyltin acetoacetates |
US4371651A (en) * | 1980-08-14 | 1983-02-01 | Phoenix Chemical Corporation | Stabilizer compositions and polyvinyl halide resin compositions containing 1,3-dicarbonyl compounds |
WO1986002369A1 (en) * | 1984-10-09 | 1986-04-24 | Interface Research Corporation | Microbiocidal composition and method of preparation thereof |
US4908209A (en) * | 1983-08-16 | 1990-03-13 | Interface, Inc. | Biocidal delivery system of phosphate ester and method of preparation thereof |
US4935232A (en) * | 1983-08-16 | 1990-06-19 | Interface Research Corporation | Microbiocidal composition and method of preparation thereof |
US4957948A (en) * | 1988-05-05 | 1990-09-18 | Interface, Inc. | Biocidal protective coating for heat exchanger coils |
US5024840A (en) * | 1984-03-08 | 1991-06-18 | Interface, Inc. | Antimicrobial carpet and carpet tile |
US5032310A (en) * | 1983-08-16 | 1991-07-16 | Interface, Inc. | Microbiocidal cleansing and disinfecting formulations and preparation thereof |
US5133933A (en) * | 1983-08-16 | 1992-07-28 | Interface Research Corporation | Microbiocidal preservative |
US5474739A (en) * | 1978-02-04 | 1995-12-12 | Interface, Inc. | Microbiocidal composition |
US5587407A (en) * | 1988-09-09 | 1996-12-24 | Interface, Inc. | Biocidal polymeric coating for heat exchanger coils |
US5635192A (en) * | 1988-05-05 | 1997-06-03 | Interface, Inc. | Biocidal polymeric coating for heat exchanger coils |
US20080175930A1 (en) * | 2007-01-22 | 2008-07-24 | Shireen Baseeth | Water Dispersible Compositions and Methods of Using the Water Dispersible Compositions |
US20100105804A1 (en) * | 2006-12-01 | 2010-04-29 | Hans-Detlef Deike | One-component mold growth-inhibiting sanitary joint sealant |
US10665899B2 (en) | 2017-07-17 | 2020-05-26 | NOHMs Technologies, Inc. | Phosphorus containing electrolytes |
US10868332B2 (en) | 2016-04-01 | 2020-12-15 | NOHMs Technologies, Inc. | Modified ionic liquids containing phosphorus |
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US2150759A (en) * | 1938-01-28 | 1939-03-14 | Roscoe H Carter | Insecticidal and fungicidal compositions |
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Cited By (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2957785A (en) * | 1957-06-07 | 1960-10-25 | Permachem Corp | Aqueous metastable dispersion of tetravalent organo-tin compounds treating process |
US3287103A (en) * | 1960-05-26 | 1966-11-22 | Frank J Sowa | Method of controlling weeds |
US3222158A (en) * | 1960-05-26 | 1965-12-07 | Frank J Sowa | Organotin compositions |
US3140977A (en) * | 1960-05-27 | 1964-07-14 | Philips Corp | Fungicidal compositions containing triphenyl compounds |
US3120550A (en) * | 1960-05-27 | 1964-02-04 | Dow Chemical Co | Organo-tin and lead chelates |
US3214453A (en) * | 1960-08-25 | 1965-10-26 | Nease Chemical Company Inc | Bis-tributyltin carbonate and a method for the preparation thereof |
US3128296A (en) * | 1960-10-03 | 1964-04-07 | Monsanto Chemicals | Organic phosphinyloxyaluminum compounds and the preparation thereof |
US3127432A (en) * | 1960-10-03 | 1964-03-31 | Monsanto Chemicals | Organic phosphorus-aluminum compounds and method of preparation |
US3105000A (en) * | 1961-05-25 | 1963-09-24 | Dow Chemical Co | Organo-tin and organo-sulphur parasiticides |
US3277132A (en) * | 1962-06-13 | 1966-10-04 | Wild Samuel | Tin(ii) salts of orthophosphoric-mono-(beta-aminoethanol)ester |
US3448131A (en) * | 1966-03-30 | 1969-06-03 | Union Carbide Corp | Process for preparing trihydrocarbyltin acetoacetates |
US5474739A (en) * | 1978-02-04 | 1995-12-12 | Interface, Inc. | Microbiocidal composition |
US4371651A (en) * | 1980-08-14 | 1983-02-01 | Phoenix Chemical Corporation | Stabilizer compositions and polyvinyl halide resin compositions containing 1,3-dicarbonyl compounds |
US4935232A (en) * | 1983-08-16 | 1990-06-19 | Interface Research Corporation | Microbiocidal composition and method of preparation thereof |
US5032310A (en) * | 1983-08-16 | 1991-07-16 | Interface, Inc. | Microbiocidal cleansing and disinfecting formulations and preparation thereof |
US5133933A (en) * | 1983-08-16 | 1992-07-28 | Interface Research Corporation | Microbiocidal preservative |
US4908209A (en) * | 1983-08-16 | 1990-03-13 | Interface, Inc. | Biocidal delivery system of phosphate ester and method of preparation thereof |
US5024840A (en) * | 1984-03-08 | 1991-06-18 | Interface, Inc. | Antimicrobial carpet and carpet tile |
WO1986002369A1 (en) * | 1984-10-09 | 1986-04-24 | Interface Research Corporation | Microbiocidal composition and method of preparation thereof |
US5639464A (en) * | 1988-05-05 | 1997-06-17 | Interface, Inc. | Biocidal polymeric coating for heat exchanger coils |
US4957948A (en) * | 1988-05-05 | 1990-09-18 | Interface, Inc. | Biocidal protective coating for heat exchanger coils |
US5635192A (en) * | 1988-05-05 | 1997-06-03 | Interface, Inc. | Biocidal polymeric coating for heat exchanger coils |
US5587407A (en) * | 1988-09-09 | 1996-12-24 | Interface, Inc. | Biocidal polymeric coating for heat exchanger coils |
US20100105804A1 (en) * | 2006-12-01 | 2010-04-29 | Hans-Detlef Deike | One-component mold growth-inhibiting sanitary joint sealant |
US20080175930A1 (en) * | 2007-01-22 | 2008-07-24 | Shireen Baseeth | Water Dispersible Compositions and Methods of Using the Water Dispersible Compositions |
US8906431B2 (en) * | 2007-01-22 | 2014-12-09 | Archer Daniels Midland Company | Water dispersible compositions and methods of using the water dispersible compositions |
US10868332B2 (en) | 2016-04-01 | 2020-12-15 | NOHMs Technologies, Inc. | Modified ionic liquids containing phosphorus |
US11489201B2 (en) | 2016-04-01 | 2022-11-01 | NOHMs Technologies, Inc. | Modified ionic liquids containing phosphorus |
US10665899B2 (en) | 2017-07-17 | 2020-05-26 | NOHMs Technologies, Inc. | Phosphorus containing electrolytes |
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