US3340265A - Quaternary ammonium salts of acetylenenic carboxylic acids - Google Patents
Quaternary ammonium salts of acetylenenic carboxylic acids Download PDFInfo
- Publication number
- US3340265A US3340265A US362559A US36255964A US3340265A US 3340265 A US3340265 A US 3340265A US 362559 A US362559 A US 362559A US 36255964 A US36255964 A US 36255964A US 3340265 A US3340265 A US 3340265A
- Authority
- US
- United States
- Prior art keywords
- alkyl
- quaternary ammonium
- carbon atoms
- benzyl
- solution
- Prior art date
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- Expired - Lifetime
Links
- 150000003242 quaternary ammonium salts Chemical class 0.000 title claims description 5
- 150000001735 carboxylic acids Chemical class 0.000 title description 4
- BQDKCWCMDBMLEH-UHFFFAOYSA-N 2-octynoic acid Chemical compound CCCCCC#CC(O)=O BQDKCWCMDBMLEH-UHFFFAOYSA-N 0.000 claims description 8
- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims description 8
- 241000607142 Salmonella Species 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 150000004665 fatty acids Chemical class 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 241000191967 Staphylococcus aureus Species 0.000 claims description 3
- AWJUIBRHMBBTKR-UHFFFAOYSA-O isoquinolin-2-ium Chemical compound C1=[NH+]C=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-O 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- -1 alkyl-benzyl trimethyl ammonium chlorides Chemical class 0.000 description 37
- 125000000217 alkyl group Chemical group 0.000 description 19
- 239000000047 product Substances 0.000 description 18
- 125000004432 carbon atom Chemical group C* 0.000 description 17
- 239000000243 solution Substances 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 241001031074 Ongokea gore Species 0.000 description 12
- 239000002253 acid Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000002906 microbiologic effect Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000344 soap Substances 0.000 description 5
- KWLVIGJGNBJKPA-UHFFFAOYSA-N Isanolic acid Chemical compound OC(=O)CCCCCCC(O)C#CC#CCCCCC=C KWLVIGJGNBJKPA-UHFFFAOYSA-N 0.000 description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- SLRMQYXOBQWXCR-UHFFFAOYSA-N 2154-56-5 Chemical group [CH2]C1=CC=CC=C1 SLRMQYXOBQWXCR-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 241000233866 Fungi Species 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000003385 bacteriostatic effect Effects 0.000 description 3
- 230000004071 biological effect Effects 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 101100172132 Mus musculus Eif3a gene Proteins 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000004599 antimicrobial Substances 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- ODRZUUBZEIXMOS-UHFFFAOYSA-N benzyl-ethyl-dimethylazanium Chemical compound CC[N+](C)(C)CC1=CC=CC=C1 ODRZUUBZEIXMOS-UHFFFAOYSA-N 0.000 description 2
- 150000001649 bromium compounds Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- OASRDXXKKGHDJZ-UHFFFAOYSA-N octadec-17-en-9,11-diynoic acid Chemical compound OC(=O)CCCCCCCC#CC#CCCCCC=C OASRDXXKKGHDJZ-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000011012 sanitization Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- BLSQLHNBWJLIBQ-OZXSUGGESA-N (2R,4S)-terconazole Chemical compound C1CN(C(C)C)CCN1C(C=C1)=CC=C1OC[C@@H]1O[C@@](CN2N=CN=C2)(C=2C(=CC(Cl)=CC=2)Cl)OC1 BLSQLHNBWJLIBQ-OZXSUGGESA-N 0.000 description 1
- QLAJNZSPVITUCQ-UHFFFAOYSA-N 1,3,2-dioxathietane 2,2-dioxide Chemical compound O=S1(=O)OCO1 QLAJNZSPVITUCQ-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 241000228245 Aspergillus niger Species 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 241001031075 Ongokea Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 241000918585 Pythium aphanidermatum Species 0.000 description 1
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 229940064004 antiseptic throat preparations Drugs 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000000022 bacteriostatic agent Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000011449 brick 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
- 239000004566 building material Substances 0.000 description 1
- 125000006487 butyl benzyl group Chemical group 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 235000013351 cheese Nutrition 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 125000006182 dimethyl benzyl group Chemical group 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- BFDFJIJWIIIZJB-HPWRNOGASA-M ethyl-dimethyl-[(z)-octadec-9-enyl]azanium;bromide Chemical compound [Br-].CCCCCCCC\C=C/CCCCCCCC[N+](C)(C)CC BFDFJIJWIIIZJB-HPWRNOGASA-M 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 230000002538 fungal effect Effects 0.000 description 1
- 229940089256 fungistat Drugs 0.000 description 1
- 230000001408 fungistatic effect Effects 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
- 238000000227 grinding Methods 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000005555 metalworking Methods 0.000 description 1
- 125000005528 methosulfate group Chemical group 0.000 description 1
- 125000006178 methyl benzyl group Chemical group 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 230000017066 negative regulation of growth Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000010665 pine oil Substances 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 125000003198 secondary alcohol group Chemical group 0.000 description 1
- 239000008149 soap solution Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 230000000699 topical effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000002759 woven fabric 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
- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/02—Amines; Quaternary ammonium compounds
- A01N33/12—Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
- C07C57/18—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon triple bonds as unsaturation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/40—Unsaturated compounds
- C07C59/42—Unsaturated compounds containing hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D217/00—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems
- C07D217/02—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with only hydrogen atoms or radicals containing only carbon and hydrogen atoms, directly attached to carbon atoms of the nitrogen-containing ring; Alkylene-bis-isoquinolines
- C07D217/10—Quaternary compounds
Definitions
- Z is the cation of a microbiologically active qua ternary ammonium compound
- R is the residue of a saturated or monoor poly-unsaturated hydrocarbon chain
- R is a carbon atom or the residue of a saturated or mono or poly-unsaturated hydrocarbon or secondary alcohol group
- either R or R" may contain further acetylenic linkages
- R and R" comprise, in all, from 7 to 21 carbon atoms.
- acetylenic acids are octynoic acid and the like; and isanic acid whose structure is reported to be:
- the fatty acids from isano oil contain about 46% of isanic acid and about 44% of isanolic acid along with other fatty acids. For descriptive purposes, this mixture will hereinafter be referred to as isano acid.
- R is an alkyl or alkaralkyl radical containing from 8 to 22 carbon atoms or an alkyl phenoxy ethoxy ethyl radical in which R is an alkyl radical containing from 8 to 9 carbon atoms and in which the-phenyl radical may be substituted by a methyl group;
- R and R are methyl or ethyl radicals or members of a heterocyclic ring system such as pyridine, isoquinoline, pyrrolidine and morpholine;
- R is a methyl radical or a benzyl group or a substituted-benzyl group such, for example, as a monochlorobenzyl radical or a dichlorobenzyl radical or mixture thereof or a methyl benzyl, dimethyl benzyl, ethyl benzyl, diethyl benzyl, isopropyl benzyl, tertiary butyl benzyl or another benzyl radical containing from 1 to
- R and R are members of a morpholine or pyrrolidine ring
- R is a methyl, ethyl, propyl or butyl group.
- R' is the same radical as R.
- X in the above formula corresponds to a halide radical such as chloride, bromide or iodide or to any other water-soluble anion such as methosulfate.
- the compounds of this invention may be prepared by mixing aqueous solutions of the quaternary ammonium salts or hydroxides with an aqueous solution of the acetylenic carboxylic acid in question or any of its water-soluble salts.
- the organic product layer is separated from the aqueous layer (as with a separatory funnel) since two distinct phases are formed. Separation may be facilitated by the addition of an organic solvent immiscible with water.
- the product layer may be washed with water to remove any residual by-product salt or unreacted materials.
- the solvent if any, may be evaporated and the product air or vacuum dried to a paste, wax, oil or solid.
- Non-aqueous solvents facilitate the separation of by-product inorganic salt and reduce the need for vacuum drying to get an anhydrous product.
- a non-aqueous medium it is usually necessary to add a small amount of water to facilitate ionic reaction.
- the product may be used, if desired, without drying since any entrapped water is irrelevant to the microbiological activity of the compounds. In other applications, removal of water may be essential for reasons not related to biological activity.
- An alternative method for the preparation of compounds especially applicable to the treatment of fabric, ropes, net, woven and non-woven fabric and reticulated or convoluted materials involves a two-step process.
- the method of adjustment of solution concentration to achieve the required pickup is well known to those skilled in the art.
- the order of treatment may be reversed without affecting the biological activity or durability of the product on the material.
- the products of this invention may be formulated as water dispersions by dissolving them in a water miscible organic solvent such as acetone or methanol and diluting with water or by dissolving them in emulsifiable oils such, for example, as sulfonated castor oil or pine oil and diluting with water.
- emulsifying agents such, for example, as ethylene oxide condensates of alkyl phenols may be used with or without organic solvents.
- the. compounds of this invention exhibit high microbiological activity despite their relative insolubility in water. Because of their unusual combination of physical and microbiological properties, they can be used to impart laundry-resistant anti-microbial characteristics to textiles. They can also be used as the active agent in antimildew finishes for textiles which are resistant to leaching with water.
- the compounds have low Water solubility, they are compatible with various organic solvents, plasticizers and high molecular weight compounds. Consequently, they may be incorporated as anti-microbial agents in synthetic resins and plastics.
- the compounds are compatible with natural and synthetic rubber latices. Therefore, they may be used to prepare bacteriostatic films and molded objects deposited from such latices.
- the compounds can be incorporated into cutting and grinding fluids without precipitation. Also, they blend well with non-ionic and anionic surface active agents. In such compositions they retain their microbiological activity.
- microbiological activity of our compounds has been evaluated for microbiological stasis by the Stand ard Tube Dilution Test, the technique for which is common knowledge to those skilled in the art.
- a Difco Bacto CSMA Broth #0826 was used in the study. This test is used to determine the lowest concentration of microbiologically active compounds which will inhibit the growth of the organism in question. For a wide range of applications, the inhibition of growth rather than outright kill is satisfactory.
- the Tube Dilution Test consists in placing 9 cc. of the CSMA Broth in a test tube which is then sterilized in an autoclave.
- One cc. solution of the microbiologically active compound at an appropriate concentration is added to the test tube which is then inoculated with 0.1 cc. of a twenty-four hour old culture of the organism under study.
- the test tube is then incubated at 37 C.
- Example I Isano oil was saponified with alcoholic potassium hydroxide to produce the potash soap. The excess alkali and the alcohol were removed and the solution was adjusted to 10% concentration by weight.
- Example II An aliquot of the solution of isano soap of Example I was reacted in the same manner with a chemically equivalent amount of a 10% solution of a commercial grade of alkyl dimethylbenzyl ammonium chloride (Onyx Chemical Corporations ETC-824 in which the alkyl distribution is 60% C 30% C 5% C 5% C On separating and drying, a brown paste of alkyl dimethyl benzyl ammonium salt of isano acid was recovered in 96% of the theoretical yield.
- a commercial grade of alkyl dimethylbenzyl ammonium chloride Onyx Chemical Corporations ETC-824 in which the alkyl distribution is 60% C 30% C 5% C 5% C
- a brown paste of alkyl dimethyl benzyl ammonium salt of isano acid was recovered in 96% of the theoretical yield.
- Example lII Similarly, an aliquot of the isano soap solution of Example I was reacted with a chemically equivalent amount of an aqueous-alcohol solution of a commercial grade of alkyl isoquinolinium bromide. The alcohol was removed by evaporation and the residual mixture, with the additin of benzene, was transferred to a separatory funnel. The organic product layer was removed and vacuum dried to yield the theoretical amount of alkyl isoquinolinium salt of isano acid as a dark brown paste.
- Example IV A 20% aqueous solution of potassium alpha-octynoate was prepared. An aliquot of this solution containing 0.045 molecular weights of the compound was reacted with a chemically equivalent amount of the alkyl dimethyl ethyl-benzyl ammonium chloride solution of Example I. Benzene was added and the mixture was separated in a separatory funnel. The organic product layer was removed and vacuum dried. The alkyl dimethyl ethyl-benzyl ammonium alpha-octynoate was obtained in the theoretical yield as a viscous orange liquid.
- Example V An aliquot of the solution of potassium octynoate of Example IV was reacted in the same manner with a chemically equivalent amount of the solution of alkyl dimethyl benzyl ammonium chloride of Example II.
- Example VI An aliquot of the solution of potassium octynoate of Example IV was reacted with a chemically equivalent amount of the aqueous-alcohol solution of alkyl isoquinolinium bromide of Example III. The alcohol was evaporated off, benzene was added to facilitate phase separation, and the organic product layer was removed and vacuum dried. The theoretical yield of alkyl isoquinolinium alphaoctynoate was obtained as a dark brown viscous liquid.
- alkyl dimethyl ethyl-benzyl ammonium salt of isano acid said alkyl having 8 to 22 carbon atoms.
- alkyl dimethyl benzyl ammonium salt of isano acid said alkyl having 8 to 22 carbon atoms.
- alkyl isoquinolinium salt of isano acid said alkyl having 8 to 22 carbon atoms.
- Alkyl dimethyl ethyl-benzyl ammonium alphaoctynoate said alkyl having 8 to 22 carbon atoms.
- Alkyl dimethyl benzyl ammonium alpha-octynoate said alkyl having 8 to 22 carbon atoms.
- Alkyl isoquinolinium alpha-octynoate said alkyl having 8 to 22 carbon atoms.
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Description
Unimd States Paten 3,340,265 QUATERNARY AMMONIUM SALTS F ACETYLENIC CARBOXYLIC ACIDS Reginald L. Wakeman, Philadelphia, Pa., and E. Griflin Shay, Belle Mead, N.J., assignors, by mesne assignments, to Millmaster Onyx Corporation, New York, N.Y., a corporation of New York No Drawing. Filed Apr. 23, 1964, Ser. No. 362,559
7 Claims. (Cl. 260-286) The object of the present invention is the preparation of relatively water-insoluble, microbiologically active compounds by reaction of certain quaternary ammonium hydroxides or their water-soluble salts with acetylenic carboxylic acids or their water-soluble salts.
The products of this invention conform, in general, to the following structure:
wherein Z is the cation of a microbiologically active qua ternary ammonium compound; R is the residue of a saturated or monoor poly-unsaturated hydrocarbon chain; and R is a carbon atom or the residue of a saturated or mono or poly-unsaturated hydrocarbon or secondary alcohol group; and either R or R" may contain further acetylenic linkages; and R and R" comprise, in all, from 7 to 21 carbon atoms.
Typical of these acetylenic acids are octynoic acid and the like; and isanic acid whose structure is reported to be:
CH CH(CH -CEC-'CEC(CH COOH and isanolic acid whose structure is reported to be:
CH (CH CH=CH-CEC- CEC' CH CH (OH) (CH COOH as well as other acids such as may be found in isano oil or boleko or ongokea oil or other acetylenic oil derived from the fruits of related species of plants.
The fatty acids from isano oil contain about 46% of isanic acid and about 44% of isanolic acid along with other fatty acids. For descriptive purposes, this mixture will hereinafter be referred to as isano acid.
Typical examples of the quaternary ammonium compounds which may be used in this invention are the alkyl trimethyl ammonium chlorides, alkyl-benzyl trimethyl ammonium chlorides, alkyl dimethyl benzyl ammonium chlorides, alkyl dimethyl menaphthyl ammonium chlorides, alkyl dimethyl substituted-benzyl ammonium chlorides in which the benzyl radical is substituted with one or more side chains containing from 1 to carbon atoms such, for example, as methyl, dimethyl, ethyl and the like and in which the carbon atoms may all be in the same or different side chains or in which the benzyl radical bears one, two or more halogen atoms such as chlorine or bromine, alkyl pyridinium chlorides, alkyl isoquinolinium chlorides and bromides, alkyl lower-alkyl pyrrolidinium chlorides, alkyl lower-alkyl morpholinium chlorides in all of which the alkyl group may have from 8 to 22 carbon atoms and the lower-alkyl group may have from 1 to 4 carbon atoms and alkyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride in which the alkyl radical may be iso-octyl or nonyl and in which the phenyl radical may, if desired, be substituted by a methyl radical. Various other analogs of these quaternaries may also be employed such, for example, as cetyl dimethyl ethyl am- .monium bromide or oleyl dimethyl ethyl ammonium bromide.
In general, the quaternary ammonium compounds useful in this invention are the higher alkyl quaternary ammonium hydroxides, halides (chlorides and bromides),
3346 265 Patented Sept. 5, 1967 sulfates, methosulfates and the like possessing the following formula:
where R is an alkyl or alkaralkyl radical containing from 8 to 22 carbon atoms or an alkyl phenoxy ethoxy ethyl radical in which R is an alkyl radical containing from 8 to 9 carbon atoms and in which the-phenyl radical may be substituted by a methyl group; R and R are methyl or ethyl radicals or members of a heterocyclic ring system such as pyridine, isoquinoline, pyrrolidine and morpholine; R is a methyl radical or a benzyl group or a substituted-benzyl group such, for example, as a monochlorobenzyl radical or a dichlorobenzyl radical or mixture thereof or a methyl benzyl, dimethyl benzyl, ethyl benzyl, diethyl benzyl, isopropyl benzyl, tertiary butyl benzyl or another benzyl radical containing from 1 to 5 carbon atoms as side chains, either as a single side chain or a multiplicity of side chains including mixtures thereof or a menaphthyl group or hydrogenated menaphthyl group. When R and R are members of a morpholine or pyrrolidine ring, R is a methyl, ethyl, propyl or butyl group. When R and R are members of an unsaturated heterocyclic ring such as pyridine or isoquinoline, R' is the same radical as R. X in the above formula corresponds to a halide radical such as chloride, bromide or iodide or to any other water-soluble anion such as methosulfate.
In general, we prefer to use such quaternary ammonium compounds which have a phenol coefficient of at least with respect to both Staphylococcus aureus and Salmonella typhosa at 20 C. when determined by the standard method given in the Official Methods of Analysis of the Association of Official Agricultural Chemists, ninth edition (1960), pages 63 et seq.
The compounds of this invention may be prepared by mixing aqueous solutions of the quaternary ammonium salts or hydroxides with an aqueous solution of the acetylenic carboxylic acid in question or any of its water-soluble salts.
After thorough mixing, the organic product layer is separated from the aqueous layer (as with a separatory funnel) since two distinct phases are formed. Separation may be facilitated by the addition of an organic solvent immiscible with water. The product layer may be washed with water to remove any residual by-product salt or unreacted materials. The solvent, if any, may be evaporated and the product air or vacuum dried to a paste, wax, oil or solid.
It is not necessary to use an aqueous medium. Any solvent or solvent mixture in which the starting materials are soluble will be satisfactory. Non-aqueous solvents facilitate the separation of by-product inorganic salt and reduce the need for vacuum drying to get an anhydrous product. When a non-aqueous medium is employed, it is usually necessary to add a small amount of water to facilitate ionic reaction.
The product may be used, if desired, without drying since any entrapped water is irrelevant to the microbiological activity of the compounds. In other applications, removal of water may be essential for reasons not related to biological activity.
An alternative method for the preparation of compounds especially applicable to the treatment of fabric, ropes, net, woven and non-woven fabric and reticulated or convoluted materials involves a two-step process. In
0 the first step, the material is passed through a bath contreated material is then passed through a second bath wherein the concentration of quaternary ammonium compound is such that the material pickup will result in an equivalent amount of quaternary ammonium compound reacting with the anionic moiety, depositing the product in the most intimate way on the surface and in the interstices, convolutions and reticulations of the material.
The method of adjustment of solution concentration to achieve the required pickup is well known to those skilled in the art. The order of treatment may be reversed without affecting the biological activity or durability of the product on the material. The products of this invention may be formulated as water dispersions by dissolving them in a water miscible organic solvent such as acetone or methanol and diluting with water or by dissolving them in emulsifiable oils such, for example, as sulfonated castor oil or pine oil and diluting with water. In preparing aqueous dispersions, emulsifying agents such, for example, as ethylene oxide condensates of alkyl phenols may be used with or without organic solvents.
It is surprising that the. compounds of this invention exhibit high microbiological activity despite their relative insolubility in water. Because of their unusual combination of physical and microbiological properties, they can be used to impart laundry-resistant anti-microbial characteristics to textiles. They can also be used as the active agent in antimildew finishes for textiles which are resistant to leaching with water.
Although the compounds have low Water solubility, they are compatible with various organic solvents, plasticizers and high molecular weight compounds. Consequently, they may be incorporated as anti-microbial agents in synthetic resins and plastics. The compounds are compatible with natural and synthetic rubber latices. Therefore, they may be used to prepare bacteriostatic films and molded objects deposited from such latices.
The compounds can be incorporated into cutting and grinding fluids without precipitation. Also, they blend well with non-ionic and anionic surface active agents. In such compositions they retain their microbiological activity.
It will be understood that the properties of the products described herein will vary depending upon the nature of the cationic quaternary ammonium compound used in their preparation as well as the anionic compound reacted therewith.
The chemical, physical and biological properties of the products of our invention make them especially appropriate for the following applications when suitably incorporated in active amounts in an appropriate vehicle, binder, medium or substrate:
(1) Mildewproofing fabric, canvas, ropes, textiles, awnings, sails, tenting and other woven and non-woven reticulated materials.
(2) Paint mildewstats.
(3) Jet plane fuel additive to control growth of microorganisms.
(4) Odor preservative agents for clothes and shoes.
(5) Mildew retardant and odor suppressant for shoes and other leather products.
(6) Topical antiseptics.
(7) Antidandruff agents.
(8) Disinfection agents for hair and gut of man and beast.
(9) Bacteriostatic furniture dressing.
(10) Surface finishes for stone, plaster, tile, cement, brick and other inorganic building materials to retard growth of microorganism, fungi, mold and algae.
(11) Wool preservative.
(12) Plant and tree spray to combat fungi.
(13) Antimycotic agents for soap wrappers.
(14) Self-sanitizing brushes.
(15) Mildewproofing agent in and on plastic and film.
(16) Mildewproofing of cellulosics, cardboard, fibreboard, paper and cordage.
(17) Contact biostat for application to film, waxes and cloth to preserve cheese, meats and vegetables and other food products.
(18) Algal inhibition, especially on surfaces and in solution where low foaming is desirable.
(19) Paper pulp slime control.
(20) Sanitizing agent for rug, carpet, curtains.
(21) Egg preservation.
(22) Adhesive preservation.
(23) Preservation of latex paints.
(24) Preservation of metal-working compounds.
(25) Additives for soap and for both anionic and nonionic detergents in liquid, bar, powder, bead, solution and other forms to impart bacteriostatic and fungi-static properties thereto.
(26) Bacteriostatic agents for household laundry softener-s.
(27) Algastat and bacteriostat in recirculated water for cooling towers, air conditions and humidifiers.
(28) Bacteriostat and algastat for flood waters and brines used in secondary oil recovery.
(29) Fungistat for seed and soil treatment against damping-off.
The microbiological activity of our compounds has been evaluated for microbiological stasis by the Stand ard Tube Dilution Test, the technique for which is common knowledge to those skilled in the art. A Difco Bacto CSMA Broth #0826 was used in the study. This test is used to determine the lowest concentration of microbiologically active compounds which will inhibit the growth of the organism in question. For a wide range of applications, the inhibition of growth rather than outright kill is satisfactory.
Briefly put, the Tube Dilution Test consists in placing 9 cc. of the CSMA Broth in a test tube which is then sterilized in an autoclave. One cc. solution of the microbiologically active compound at an appropriate concentration is added to the test tube which is then inoculated with 0.1 cc. of a twenty-four hour old culture of the organism under study. The test tube is then incubated at 37 C.
for forty-eight hours and observed for bacterial growth.
The same procedure is followed for fungi. In such tests, however, the tubes are incubated for fourteen days at a temperature suitable for optimum fungal growth, usually 25 C.
This invention is illustrated by, but not restricted to, the followingexamples:
Example I Isano oil was saponified with alcoholic potassium hydroxide to produce the potash soap. The excess alkali and the alcohol were removed and the solution was adjusted to 10% concentration by weight.
An aliquot of this solution containing 0.0782 equivalent weights of the soap was agitated vigorously while adding a chemically equivalent amount of a solution of a commercial grade of alkyl dimethyl ethyl-benzyl ammonium chloride (Onyx Chemical Corporations ETC-471 in which the alkyl distribution is 50% C 30% C 17% C 3% C The mixture was transferred to a separatory funnel along with a little benzene and the organic product layer was removed and dried in vacuo. The alkyl dimethyl ethyl-benzyl ammonium salt of isano acid was recovered in theoretical yield as a light brown viscous liquid.
Example II An aliquot of the solution of isano soap of Example I was reacted in the same manner with a chemically equivalent amount of a 10% solution of a commercial grade of alkyl dimethylbenzyl ammonium chloride (Onyx Chemical Corporations ETC-824 in which the alkyl distribution is 60% C 30% C 5% C 5% C On separating and drying, a brown paste of alkyl dimethyl benzyl ammonium salt of isano acid was recovered in 96% of the theoretical yield.
Example lII Similarly, an aliquot of the isano soap solution of Example I was reacted with a chemically equivalent amount of an aqueous-alcohol solution of a commercial grade of alkyl isoquinolinium bromide. The alcohol was removed by evaporation and the residual mixture, with the additin of benzene, was transferred to a separatory funnel. The organic product layer was removed and vacuum dried to yield the theoretical amount of alkyl isoquinolinium salt of isano acid as a dark brown paste.
Example IV A 20% aqueous solution of potassium alpha-octynoate was prepared. An aliquot of this solution containing 0.045 molecular weights of the compound was reacted with a chemically equivalent amount of the alkyl dimethyl ethyl-benzyl ammonium chloride solution of Example I. Benzene was added and the mixture was separated in a separatory funnel. The organic product layer was removed and vacuum dried. The alkyl dimethyl ethyl-benzyl ammonium alpha-octynoate was obtained in the theoretical yield as a viscous orange liquid.
Example V An aliquot of the solution of potassium octynoate of Example IV was reacted in the same manner with a chemically equivalent amount of the solution of alkyl dimethyl benzyl ammonium chloride of Example II. The product, alkyl dimethyl benzyl ammonium alpha-octynoate, was a viscous orange liquid in 99% of the theoretical yield.
Example VI An aliquot of the solution of potassium octynoate of Example IV was reacted with a chemically equivalent amount of the aqueous-alcohol solution of alkyl isoquinolinium bromide of Example III. The alcohol was evaporated off, benzene was added to facilitate phase separation, and the organic product layer was removed and vacuum dried. The theoretical yield of alkyl isoquinolinium alphaoctynoate was obtained as a dark brown viscous liquid.
Example VII When tested by the Standard Tube Dilution Test described above, these products gave the following values for static dilution. (S.a.=Staphyl0c0ccus aureus, S.t. =Salmonella typhosa, A.n.=Aspergillus niger.)
We claim:
1. A quaternary ammonium salt of a carboxylic fatty acid having at least one acetylenic linkage and from 8 to 18 carbon atoms, wherein the quaternary ammonium cation is derived from a quaternary ammonium compound having a phenol coeflicient of at least with respect to both Staphylococcus aureus and Salmonella typhosa at 20 C. and having at least one alkyl having 8 to 22 carbon atoms on the quaternary nitrogen.
2. The alkyl dimethyl ethyl-benzyl ammonium salt of isano acid said alkyl having 8 to 22 carbon atoms.
3. The alkyl dimethyl benzyl ammonium salt of isano acid said alkyl having 8 to 22 carbon atoms.
4. The alkyl isoquinolinium salt of isano acid said alkyl having 8 to 22 carbon atoms.
5. Alkyl dimethyl ethyl-benzyl ammonium alphaoctynoate said alkyl having 8 to 22 carbon atoms.
6. Alkyl dimethyl benzyl ammonium alpha-octynoate said alkyl having 8 to 22 carbon atoms.
7. Alkyl isoquinolinium alpha-octynoate said alkyl having 8 to 22 carbon atoms.
References Cited Schwartz et al.: Surface Active Agents and Detergents, vol. II, Inter-science, 1-958, pp. 222 and 230 relied upon.
ALEX MAZEL, Primary Examiner.
DONALD G. DAUS, Assistant Examiner.
Claims (2)
1. A QUATERNARY AMMONIUM SALT OF A CARBOXYLIC FATTY ACID HAVING AT LEAST ONE ACETYLENIC LINKAGE AND FROM 8 TO 18 CARBON ATOMS, WHEREIN THE QUARTERNARY AMMONIUM CATION IS DERIVED FROM A QUATERNARY AMMONIUM COMPOUND HAVING A PHENOL COEFFICIENT OF AT LEAST 100 WITH RESPECT TO BOTH STAPHYLOCOCCUS AUREUS AND SALMONELLA TYPHOSA AT 20*C. AND HAVING AT LEAST ONE ALKYL HAVING 8 TO 22 CARBON ATOMS ON THE QUATERNARY NITROGEN.
7. ALKYL ISOQUINOLINIUM ALPHA-OCTYNOATE SAID ALKYL HAVING 8 TO 22 CARBON ATOMS.
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3471423A (en) * | 1966-11-07 | 1969-10-07 | Gen Tire & Rubber Co | Polyurethane materials having biocidal properties and their production |
US3507872A (en) * | 1965-08-11 | 1970-04-21 | Ciba Ltd | Indolyl-quinolinium dyestuffs |
US4587025A (en) * | 1982-06-30 | 1986-05-06 | Mobil Oil Corporation | Zwitterionic quaternary ammonium carboxylates, their metal salts and lubricants containing same |
KR20180008743A (en) | 2015-07-13 | 2018-01-24 | 가부시키가이샤 상기 | Powder for forming a tooth surface film containing fired apatite |
-
1964
- 1964-04-23 US US362559A patent/US3340265A/en not_active Expired - Lifetime
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None * |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3507872A (en) * | 1965-08-11 | 1970-04-21 | Ciba Ltd | Indolyl-quinolinium dyestuffs |
US3471423A (en) * | 1966-11-07 | 1969-10-07 | Gen Tire & Rubber Co | Polyurethane materials having biocidal properties and their production |
US4587025A (en) * | 1982-06-30 | 1986-05-06 | Mobil Oil Corporation | Zwitterionic quaternary ammonium carboxylates, their metal salts and lubricants containing same |
KR20180008743A (en) | 2015-07-13 | 2018-01-24 | 가부시키가이샤 상기 | Powder for forming a tooth surface film containing fired apatite |
KR20180009347A (en) | 2015-07-13 | 2018-01-26 | 가부시키가이샤 상기 | Powder for forming a tooth surface film containing fired apatite |
KR20200060535A (en) | 2015-07-13 | 2020-05-29 | 가부시키가이샤 상기 | Tooth-surface-membrane-forming powder containing sintered apatite |
KR20200062357A (en) | 2015-07-13 | 2020-06-03 | 가부시키가이샤 상기 | Tooth-surface-membrane-forming powder containing sintered apatite |
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Owner name: MILLMASTER ONYX GROUP, INC., A DE CORP. Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:KEWANEE INDUSTRIES, INC.;REEL/FRAME:004139/0909 Effective date: 19830407 Owner name: BARCLAYS AMERICAN, 1 BUSINESS CREDIT, INC. 111 FOU Free format text: SECURITY INTEREST;ASSIGNOR:MILLMASTER ONYX GROUP, INC., A DE CORP.;REEL/FRAME:004139/0941 Effective date: 19821222 |