US3299073A - Quaternary ammonium aromatic amino sulfonates - Google Patents
Quaternary ammonium aromatic amino sulfonates Download PDFInfo
- Publication number
- US3299073A US3299073A US323598A US32359863A US3299073A US 3299073 A US3299073 A US 3299073A US 323598 A US323598 A US 323598A US 32359863 A US32359863 A US 32359863A US 3299073 A US3299073 A US 3299073A
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- US
- United States
- Prior art keywords
- product
- alkyl
- quaternary ammonium
- biostasis
- aromatic amino
- Prior art date
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- Expired - Lifetime
Links
- -1 Quaternary ammonium aromatic amino sulfonates Chemical class 0.000 title description 50
- ZFCMISKWVFUWHP-UHFFFAOYSA-N 2-dodecylisoquinolin-2-ium Chemical compound C1=CC=CC2=C[N+](CCCCCCCCCCCC)=CC=C21 ZFCMISKWVFUWHP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 150000003863 ammonium salts Chemical group 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 239000000047 product Substances 0.000 description 46
- 238000010790 dilution Methods 0.000 description 21
- 239000012895 dilution Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 21
- 241000228245 Aspergillus niger Species 0.000 description 19
- 150000001875 compounds Chemical class 0.000 description 14
- 125000004432 carbon atom Chemical group C* 0.000 description 13
- 239000000203 mixture Substances 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
- 125000000217 alkyl group Chemical group 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 241000607142 Salmonella Species 0.000 description 10
- 241000191967 Staphylococcus aureus Species 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 230000002906 microbiologic effect Effects 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 229920000126 latex Polymers 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 239000011550 stock solution Substances 0.000 description 6
- 241000233866 Fungi Species 0.000 description 5
- 125000000129 anionic group Chemical group 0.000 description 5
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 150000003254 radicals Chemical group 0.000 description 5
- MSJLMQTXVKCUCD-UHFFFAOYSA-M 2-dodecylisoquinolin-2-ium;bromide Chemical compound [Br-].C1=CC=CC2=C[N+](CCCCCCCCCCCC)=CC=C21 MSJLMQTXVKCUCD-UHFFFAOYSA-M 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 239000004816 latex Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- ULUIMLJNTCECJU-UHFFFAOYSA-N 3-amino-4-hydroxybenzenesulfonate;hydron Chemical compound NC1=CC(S(O)(=O)=O)=CC=C1O ULUIMLJNTCECJU-UHFFFAOYSA-N 0.000 description 3
- ZAJAQTYSTDTMCU-UHFFFAOYSA-N 3-aminobenzenesulfonic acid Chemical compound NC1=CC=CC(S(O)(=O)=O)=C1 ZAJAQTYSTDTMCU-UHFFFAOYSA-N 0.000 description 3
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000003385 bacteriostatic effect Effects 0.000 description 3
- 230000004071 biological effect Effects 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229940074995 bromine Drugs 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 229910052602 gypsum Inorganic materials 0.000 description 3
- 239000010440 gypsum Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 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
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 101100172132 Mus musculus Eif3a gene Proteins 0.000 description 2
- 231100000674 Phytotoxicity Toxicity 0.000 description 2
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000004599 antimicrobial Substances 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 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
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000011499 joint compound Substances 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
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000000123 paper 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
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 238000011012 sanitization Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- KSVSZLXDULFGDQ-UHFFFAOYSA-M sodium;4-aminobenzenesulfonate Chemical compound [Na+].NC1=CC=C(S([O-])(=O)=O)C=C1 KSVSZLXDULFGDQ-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229950000244 sulfanilic acid Drugs 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- TXVWTOBHDDIASC-UHFFFAOYSA-N 1,2-diphenylethene-1,2-diamine Chemical compound C=1C=CC=CC=1C(N)=C(N)C1=CC=CC=C1 TXVWTOBHDDIASC-UHFFFAOYSA-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
- KBVDUUXRXJTAJC-UHFFFAOYSA-N 2,5-dibromothiophene Chemical compound BrC1=CC=C(Br)S1 KBVDUUXRXJTAJC-UHFFFAOYSA-N 0.000 description 1
- NSMMFSKPGXCMOE-UHFFFAOYSA-N 2-[2-(2-sulfophenyl)ethenyl]benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1C=CC1=CC=CC=C1S(O)(=O)=O NSMMFSKPGXCMOE-UHFFFAOYSA-N 0.000 description 1
- ZMCHBSMFKQYNKA-UHFFFAOYSA-N 2-aminobenzenesulfonic acid Chemical compound NC1=CC=CC=C1S(O)(=O)=O ZMCHBSMFKQYNKA-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- CEUIDYDXEWYQNC-UHFFFAOYSA-N 4-(methylamino)naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(NC)=CC=C(S(O)(=O)=O)C2=C1 CEUIDYDXEWYQNC-UHFFFAOYSA-N 0.000 description 1
- BFKVAIPNQYGUDQ-UHFFFAOYSA-N 6,6-diamino-3-(2-phenylethenyl)cyclohexa-2,4-diene-1,2-disulfonic acid Chemical compound NC1(C(C(=C(C=C1)C=CC1=CC=CC=C1)S(=O)(=O)O)S(=O)(=O)O)N BFKVAIPNQYGUDQ-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 208000001840 Dandruff Diseases 0.000 description 1
- 241000462639 Epilachna varivestis Species 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical class [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 240000005038 Spathoglottis aurea Species 0.000 description 1
- 241000191940 Staphylococcus Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 241001459572 Trichophyton interdigitale Species 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 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
- 229920000180 alkyd Polymers 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 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
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000002585 base 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
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 125000001246 bromo group Chemical group Br* 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
- 150000001804 chlorine Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- PNZDZRMOBIIQTC-UHFFFAOYSA-N ethanamine;hydron;bromide Chemical compound Br.CCN PNZDZRMOBIIQTC-UHFFFAOYSA-N 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
- 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
- 239000000295 fuel oil Substances 0.000 description 1
- 230000002538 fungal effect Effects 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 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
- ACGUYXCXAPNIKK-UHFFFAOYSA-N hexachlorophene Chemical compound OC1=C(Cl)C=C(Cl)C(Cl)=C1CC1=C(O)C(Cl)=CC(Cl)=C1Cl ACGUYXCXAPNIKK-UHFFFAOYSA-N 0.000 description 1
- 229960004068 hexachlorophene Drugs 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 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
- 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
- 150000007522 mineralic acids Chemical class 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
- 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
- 125000000913 palmityl 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])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
- 239000006072 paste Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000002062 proliferating 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
- 239000002453 shampoo Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 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
- SZYJELPVAFJOGJ-UHFFFAOYSA-N trimethylamine hydrochloride Chemical class Cl.CN(C)C SZYJELPVAFJOGJ-UHFFFAOYSA-N 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
- 238000005406 washing Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S424/00—Drug, bio-affecting and body treating compositions
- Y10S424/04—Dandruff
Definitions
- the object of the present invention is the preparation of microbiologically active compounds by reaction of certain quaternary ammonium hydroxides or their salts of inorganic acids with aromatic amino sulfonic acids or their salts, and substituted aromatic amino sulfonic acids containing chlorine, bro-mine, or hydroxyl groups attached to the aromatic nucleus.
- the quaternary ammonium compounds used in the process of this invention contain at least one carbon chain having from 8 to 22 carbon atoms.
- the quaternary nitrogen atom may be a member of a fiveor six-membered heterocyclic ring such as pyridine, isoquinoline, morpholine, or pyrrolidine if desired.
- quaternary ammonium compounds are alkyl trimethyl ammonium chlorides, alkyl bcnzyl trimethyl ammonium chlorides, alkyl dimethyl benzyl ammonium chlorides, alkyl di-rnethyl menaphthyl ammonium chlorides, alkyl dimethyl substituted bcnzyl ammonium chlorides in which.
- the bcnzyl radical is substituted with one or more side chains containing from 1 to 4 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 bcnzyl radical bears one, two or more halogen atoms such as chlorine or bromine, alkyl pyridinium chlorides, al-kyl 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 phen'oxyethyl dimethyl benzylammonium chloride in which the alkyl radical may be isooctyl or nonyl and in which the phenyl radical may, if desired, contain a substituent
- Various other analogs of these quaternaries may also be employed such
- microbiologically active quaternary ammonium compounds of the preceding types are not compatiblei.e., lose their microbiological activity-in the presence of anionic materials, particularly anionic surface active agents such as soaps.
- A is an aromatic hydrocarbon nucleus containing from 6 to 14 carbon atoms and possessing at least one single or condensed benzene ring system
- X is hydrogen, an alkali metal, NH.,, or other anion of a watersoluble ionizable salt of the aforesaid sulfonic acid
- Y and Y are H or lower alkyl radicals containing from 1 to 4 carbon atoms
- m and n are small whole numbers between 1 and 4
- both the SO X and 3,299,373 Patented Jan. 17, 1967 groups are nuclear substituents and wherein A may also contain other nuclear substituted groups such as chloro-, bromo-, iodo-, or hydroxyl radicals.
- aromatic amino sulfonic acids we may mention o-amino benzene sulfonic acid, p-amino benzene sulfonic acid, m-amino benzene sulfonic acid and substituted amino benzene sulfonic acid containing ringsubstituted chlorine, bromine, or hydroxyl radicals such, for example, as o-amino phenol-p-sulfonic acid, amino naphthol sulfonic acids such, for example, as l-amino-2- naphthol-4-su1fonic acid and its various isomers, Z-aminonaphthalene-l-sulfonic acid, 4-amino-naphthalene-l'sulfonic acid, 3-amino-na-phthalene-lsulfonic acid, 4-methylamino-naphthalene-l-sulfonic acid, S-amino-naphthalene-l-s
- more than one acidic hydrogen is present in the molecule, as for example in disulfonic acids or hydroxyl sulfonic acids, either one or all of the acidic hydrogens from either sulfonic acid radicals or hydroxyl groups may be converted to the form of quaternary ammonium salts.
- the quaternary ammonium compounds useful in this invention are the higher alkyl quaternary ammonium hydroxides, halides (chlorides and bromides), sulfates, methosulfates and the like possessing the following formula:
- 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 bcnzyl group or a substituted benzyl group such, for example, as a monochlorobenzyl radical or a dichlorobenzyl radical or mixture thereof or a methyl bcnzyl, dimethyl bcnzyl, ethyl benzyl, diethyl bcnzyl, isopropyl benzyl, tertiary butyl benzyl or another
- R and R" are members of a morpholine or pyrrolidine ring
- R' is a methyl, ethyl, propyl, or butyl group.
- R and R are members of an unsaturated hetcrocyclic ring such as pyridine or isoquinolin-e
- 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 of the anions hereinabove listed, such as methosulf-ate.
- 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 acid in question or any of its water-soluble salts.
- the organic product layer is separated from the aqueous layer (as with a separator-y 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
- 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 re lated 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 material is passed through a bath containing the anionic moiety. Excess solution is removed by methods well known to those skilled in the art.
- the treated 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 as, for example, 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 anti-mildew 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.
- 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 microbiological 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.
- Example I A stock solution was prepared containing 10 weight percent of the sodium salt of metanilic acid. To a vigorously agitated aliquot of this solution containing 0.294 equivalent weight of the compound was added the chemical equivalent weight of a 10 weight percent solution of alkyl dimethyl ethyl benzyl ammonium chloride in which the alkyl distribution is 50% C 30% C 17% C 3% C (BTC471 manufactured by the Onyx ChemicalCorporation). The agitated mixture was poured into a separatory funnel. The mixture separated into two phases. The organic product layer was removed and vacuum dried to yield a brown paste of alkyl dimethyl ethyl benzyl ammonium metanilate in 87.6 percent theoretical yield.
- Example II An aliquot of the stock solution in Example I containing 0.067 equivalent of sodium metanilate was vigorously agitated while a chemical equivalent amount of alkyl dimethyl benzyl ammonium chloride (Onyx Chemical Corporation; BTC-824, in which the alkyl radicalcorresponds to C14, C15, C12, and C 3) in l the form of a weight percent solution was slowly added.
- alkyl dimethyl benzyl ammonium chloride Onyx Chemical Corporation; BTC-824, in which the alkyl radicalcorresponds to C14, C15, C12, and C 3
- Biostasis was evaluated against Staphylococcus aureus, Salmonella typhosa, and Aspergillus niger by the Standard Tube Dilution Test described above. The product showed biostasis at the dilutions shown: S. aureus, 1:1.000,000; S. typhosa, 1:100,000; A. niger, 1100.000.
- Example IV A stock solution was prepared containing 10 weight percent of the sodium salt of sulfanilic acid. To a vigorously agitated aliquot of this solution containing 0.0315 equivalent weights of the compound was added the chemical equivalent weight of a 10 weight percent solution of the alkyl dimethyl ethyl benzyl ammonium chloride of Example I. The agitated mixture was poured into a separatory funnel. The mixture separated into two phases. The organic product layer was removed and vacuum dried to yield an alkyl dimethyl ethyl benzyl ammonium s'ul-fanilate as a yellow paste in 78 percent theoretical yield.
- Biostasis was evaluated against Staphylococcus aureus, Salmonella typhosa, and Aspergillus niger by the Standard Tube Dilution Test described above. The product showed biostasis at the dilutions as given: S. aureus, 1:l00,000; S. typhosa, 1:100,000; A. niger, 1:10,000.
- Example V An aliquot of the stock solution in Example I containing 0.0315 equivalent of sodium sulfanilate was vigorously agitated while a chemical equivalent amount of the alkyl dimethyl benzyl ammonium chloride of Example II in the form of a 10 weight percent solution was slowly added. The agitated mixture was then poured into a separatory funnel. The mixture separated into two phases. The organicproduct layer was removed and vacuum dried to yield a yellow paste of alkyl dimethyl benzyl ammonium sulfanilate in 81 percent theoretical yield.
- Biostasis was evaluated against Staphylococcus aureus, Salmonella typhosa, and Aspergillus niger by the Standard Tube Dilution Test described above. The product showed biostasis at the dilutions as given: S. aureus, 1:l0,000,000; S. typhosa, 1: 100,000; A. niger, 1:l00,000.
- Example VI An aliquot of the stock solution in Example I containing 0.308 equivalent of sodium sulfanilate was vigorously agitated while a chemical equivalent amount of lauryl isoquinolinium bromide of Example III in the form of a 10 weight percent solution was slowly added. Benzene was added to the agitated mixture which was then poured into a separatory funnel. T he rnixture separated into two phases. The organic product layer was removed and the benzene evaporated on a steam bath. The product was vacuum dried to' yield lauryl isoquinolinium sulfanilate as a dark red paste in 87 percent theoretical yield.
- Biostasis was evaluated against Staphylococcus aureus, Salmonella typhosa, and Aspergillus niger by the Standdard Tube Dilution Test described above. The product showed biostasis at the dilutions as given: S. aureus, l:10,000,000; S. typhosa, 1:1000,000; A. niger, 1:100,000.
- the product of this example was also found effective in the control of dandruff when incorporated in shampoos.
- Example VII Two tenths part of the product of Example VI and 99.8 parts of a commercial grade of gypsum joint cement containing no mold inhibitor were blended and pasted up with suflicient water to make a heavy dough which was applied by spatula to a 3-inch by 6-inch piece of fibreboard.
- Another fibreboard sample was coated with the same gypsum joint cement paste containing no inhibitor.
- Example VIII In a 500 ml. separatory funnel were placed grams of a 10% solution of the sodium salt of l-amino-Z-naphthol-4-sulfonic acid and grams of a 10% solution of the alkyl dimethyl ethyl benzyl ammonium chloride of Example I. The funnel was well shaken and then 50 ml. of benzene added to facilitate layer separation. The product layer was separated, the benzene evaporated on a steam bath and then placed in a vacuum oven to dry. The product was a black paste of alkyl dimethyl ethyl benzyl ammonium 1-amino-2-naphthol-4-sulfonate (20 grams88% yield).
- Biostasis was evaluated against Staphylococcus aureus, Salmonella typhosa, and Aspergillus niger by the Standard Tube Dilution Test described above. The product showed biostasis at the dilutions as given: S. aureus, 1:100,000,000; S. typhosa, 1:100,000,000; A. niger, 1210,000.
- Biostasis was evaluated against Staphylococcus tllll'LllS, Salmonella typhosa, and Aspergillus niger by the Standard Tube Dilution Test described above. The product showed biostasis at the dilutions as given: S. aureas, l:l00,000; S. typhosa, l:100,000; A. niger, 1:10,000.
- Example X In a 1 liter separatory funnel were placed 330 grams of a 10% solution of the disodium salt of 4,4-diamino stilbene-2,2-disulfonic acid and 220 grams of alkyl dimethyl ethyl benzyl ammonium chloride identical to that used in Example VIII above. Using the technique of Example VIII, 30 grams of a yellow solid (70% yield) was obtained.
- Biostasis was evaluated against Staphylococcus aureus, Salmonella typhosa, and Aspergillus niger by the Standard Tube Dilution Test described above. The product showed biostasis at the dilutions as given: S. aureus, 121,000,000; S. typhosa, 1:l00,000; A. niger, 1:l00,000.
- Biostasis was evaluated against Staphylococcus aureus, Salmonella typhosa, and Aspergillus niger by the Standard Tube Dilution Test described above. The product showed biostasis at the dilutions as given: S. aureus, 1:1,000,000; S. typhosa, l:1,000,000; A. niger, l:100,000.
- Example XI In a 500 ml. separatory funnel were placed 180 grams one mole equivalent of quaternary, the corresponding of a 10% solution of alkyl dimethyl ethyl benzyl am-monium chloride (identical to that used in Example VIII) and 60 grams of a 10% solution of the disodium salt of o-amino phenol-p-sulfonic acid. The funnel was well shaken and then layer separation allowed to occur. The product layer was dried in a vacuum oven to give 22.5 grams (98% yield) of a dark brown paste.
- This product was the salt of alkyl dimethyl ethyl benzyl ammonium chloride and o-amino phenol-p-sulfonic acid in which both hydroxyl and sulfonic acid groups were converted to their corresponding quaternary ammonium salts.
- Biostasis was evaluated against Staphylococcus aureus, Salmonella typhosa, and Aspergillus niger by the Standard Tube Dilution Test described above. The product showed biostasis at the dilutions as given: S. aureus, 1: 1,000,000; S. typhosa, l:l,000,000; A, niger, 1: 100,000.
- Example XII A 25 weight percent solution of the product of 'Example II was prepared in ethylene glycol mono -butyl ether and mixed with a commercial grade of alkyd base paint containing no other'fungicide in the ratio of 4 parts by weight of this solution to 96 .parts by weight of paint. Strips of filter paper out to 1 inch by 4 inches were coated with this paint and allowed to dry. They were then inoculated with a culture of Pullularia pa/lulans and held in an incubator at 25 C. and relative humidity for three Weeks. At the end of this time, no fungus growth was visible.
- Example XIII Four parts of the 25% solution of the product of Example II prepared according to Example III were added to 96 parts of a latex acrylic type paint with thorough stirring and the latex emulsion thus treated was inoculated. with a culture of Pullularia pallalans and incubated as in Example XII. At the end of three weeks, no fungus growth was visible in the latex.
- the products of this invention are useful in the control of plant diseases and plant pests. They exhibit little or no phytotoxicity when dipped or sprayed onto plant foliage in the form of 0.1% active solutions or dispersions. Thus, for example, there is no phytotoxicity observed by application of such concentrations of the product of Example II to Woods Prolific Lima Beans, whereas such application affords marked control of Mexican bean beetles feeding on the foliage.
- a quaternary ammonium aromatic amino sulfonate in which the quaternary nitrogen atom is linked to at least one straight-chain alkyl having 12 to 18 carbon atoms.
- Alkyl dimethyl ethyl-benzyl ammonium metanilate in which the alkyl has 12 to 18 carbon atoms.
- Alkyl dimethyl benzyl ammonium metanilate in which the alkyl has 12 to 18 carbon atoms.
Description
methyl radical.
United States Patent 3,299,073 QUATERNARY AMMONIUM AROMATIC AMINO SULFONATES Reginald L. Wakeman, Philadelphia, Pa., and Joseph F.
Coates,Washington, D.C., assignors, by mesne assignments, to Millmaster Onyx Corporation, New York, N.Y., a corporation of New York NoDrawing. Filed Nov. 14, 1963, Ser. No. 323,598 7 Claims. (Cl. 260-286) The object of the present invention is the preparation of microbiologically active compounds by reaction of certain quaternary ammonium hydroxides or their salts of inorganic acids with aromatic amino sulfonic acids or their salts, and substituted aromatic amino sulfonic acids containing chlorine, bro-mine, or hydroxyl groups attached to the aromatic nucleus.
The quaternary ammonium compounds used in the process of this invention contain at least one carbon chain having from 8 to 22 carbon atoms. The quaternary nitrogen atom may be a member of a fiveor six-membered heterocyclic ring such as pyridine, isoquinoline, morpholine, or pyrrolidine if desired.
Typical examples of these quaternary ammonium compounds are alkyl trimethyl ammonium chlorides, alkyl bcnzyl trimethyl ammonium chlorides, alkyl dimethyl benzyl ammonium chlorides, alkyl di-rnethyl menaphthyl ammonium chlorides, alkyl dimethyl substituted bcnzyl ammonium chlorides in which. the bcnzyl radical is substituted with one or more side chains containing from 1 to 4 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 bcnzyl radical bears one, two or more halogen atoms such as chlorine or bromine, alkyl pyridinium chlorides, al-kyl 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 phen'oxyethyl dimethyl benzylammonium chloride in which the alkyl radical may be isooctyl or nonyl and in which the phenyl radical may, if desired, contain a substituent Various other analogs of these quaternaries may also be employed such, for example, as cetyl dimetliyl ethyl ammonium bromide or oleyl dimethyl ethyl ammonium bromide.
It has generally been thought that microbiologically active quaternary ammonium compounds of the preceding types are not compatiblei.e., lose their microbiological activity-in the presence of anionic materials, particularly anionic surface active agents such as soaps.
We have found, however, that contrary to general belief the reaction of mic'robiologically active water-soluble quaternary ammonium compounds with aromatic amino sulfonic acids of the aforementioned types, or with watersolu'ble salts of such acids, yields products which in many cases are equally as active microbiologically as the parent quaternary ammonium compounds from which they are derived. In many cases they are more active.
wherein A is an aromatic hydrocarbon nucleus containing from 6 to 14 carbon atoms and possessing at least one single or condensed benzene ring system, X is hydrogen, an alkali metal, NH.,, or other anion of a watersoluble ionizable salt of the aforesaid sulfonic acid, Y and Y are H or lower alkyl radicals containing from 1 to 4 carbon atoms, and m and n are small whole numbers between 1 and 4, and wherein both the SO X and 3,299,373 Patented Jan. 17, 1967 groups are nuclear substituents and wherein A may also contain other nuclear substituted groups such as chloro-, bromo-, iodo-, or hydroxyl radicals.
As suitable aromatic amino sulfonic acids we may mention o-amino benzene sulfonic acid, p-amino benzene sulfonic acid, m-amino benzene sulfonic acid and substituted amino benzene sulfonic acid containing ringsubstituted chlorine, bromine, or hydroxyl radicals such, for example, as o-amino phenol-p-sulfonic acid, amino naphthol sulfonic acids such, for example, as l-amino-2- naphthol-4-su1fonic acid and its various isomers, Z-aminonaphthalene-l-sulfonic acid, 4-amino-naphthalene-l'sulfonic acid, 3-amino-na-phthalene-lsulfonic acid, 4-methylamino-naphthalene-l-sulfonic acid, S-amino-naphthalene-l-sulfonic acid and the like including their chloro, 'bromo, and hydroxy-substituted derivatives. We may also use more complex aromatic amino sulfonic acids such, for example, as 4,4-diamino stilbene-disulfonic acid. Where more than one acidic hydrogen is present in the molecule, as for example in disulfonic acids or hydroxyl sulfonic acids, either one or all of the acidic hydrogens from either sulfonic acid radicals or hydroxyl groups may be converted to the form of quaternary ammonium salts.
The quaternary ammonium compounds useful in this invention are the higher alkyl quaternary ammonium hydroxides, halides (chlorides and bromides), 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 bcnzyl group or a substituted benzyl group such, for example, as a monochlorobenzyl radical or a dichlorobenzyl radical or mixture thereof or a methyl bcnzyl, dimethyl bcnzyl, ethyl benzyl, diethyl bcnzyl, isopropyl benzyl, tertiary butyl benzyl or another bcnzyl radical containing from 1 to 4 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 hetcrocyclic ring such as pyridine or isoquinolin-e, 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 of the anions hereinabove listed, such as methosulf-ate.
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 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 separator-y 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 re lated 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 the first step, the material is passed through a bath containing the anionic moiety. Excess solution is removed by methods well known to those skilled in the art. The treated 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 as, for example, 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 anti-mildew 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 quaternary ammonium compound used in their preparation as well as the aromatic amino sulfonic acid or salt 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:
(l) Mildewproofing fabric, canvas, ropes, textiles,
awnings, sails, tenting and other woven and nonwoven 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) Antidandruif 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 microorganisms, 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, waxe 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.
The microbiological activity of our compounds'has been evaluated for microbiological stasis by the Standard 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 appli cations, 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 microbiological 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 tubeis 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.
The invention is illustrated by, but not restricted to, the following examples:
Example I A stock solution was prepared containing 10 weight percent of the sodium salt of metanilic acid. To a vigorously agitated aliquot of this solution containing 0.294 equivalent weight of the compound was added the chemical equivalent weight of a 10 weight percent solution of alkyl dimethyl ethyl benzyl ammonium chloride in which the alkyl distribution is 50% C 30% C 17% C 3% C (BTC471 manufactured by the Onyx ChemicalCorporation). The agitated mixture was poured into a separatory funnel. The mixture separated into two phases. The organic product layer was removed and vacuum dried to yield a brown paste of alkyl dimethyl ethyl benzyl ammonium metanilate in 87.6 percent theoretical yield.
lution Test described above.
When dissolved in sopropanol and added to fuel oil to the extent of 1250 parts per million, this product prevented the growth of bacteria in contaminated oil.
:Biostasis of this product was evaluated against Staphylococcus aureus, Salmonella typhosa, Aspergillus niger, and T richophyton interdigitale by the Standard Tube Di- The product showed biostasis at the dilutions as given: S. aureus, l:1,000,000; S. typhosa, l:1,000,000; A. niger, 1:l00,000; T. interdigitale, 1:500,000. Example II An aliquot of the stock solution in Example I containing 0.067 equivalent of sodium metanilate was vigorously agitated while a chemical equivalent amount of alkyl dimethyl benzyl ammonium chloride (Onyx Chemical Corporation; BTC-824, in which the alkyl radicalcorresponds to C14, C15, C12, and C 3) in l the form of a weight percent solution was slowly added. The organic'product was removed and vacuum dried to yield alkyl dimethyl benzyl ammonium metanilate An aliquot of the stock solution in Example I containing 0.067 equivalent of sodium metanilate was vigorously agitated while a chemical equivalent amount of lauryl isoqu inolinium bromide (Onyx Chemical Corporation, Isothan Q-75 in the form of a 10 weight percent solution was slowly added. The agitated mixture was then poured intoa separatory funnel. The mixture separated into two phases. The organic product layer was removed and the product was vacuum dried to yield a dark brown paste of lauryl isoquinolinium nietanilate in 81.5 percent theoreticalyield.
Biostasis was evaluated against Staphylococcus aureus, Salmonella typhosa, and Aspergillus niger by the Standard Tube Dilution Test described above. The product showed biostasis at the dilutions shown: S. aureus, 1:1.000,000; S. typhosa, 1:100,000; A. niger, 1100.000.
Example IV A stock solution was prepared containing 10 weight percent of the sodium salt of sulfanilic acid. To a vigorously agitated aliquot of this solution containing 0.0315 equivalent weights of the compound was added the chemical equivalent weight of a 10 weight percent solution of the alkyl dimethyl ethyl benzyl ammonium chloride of Example I. The agitated mixture was poured into a separatory funnel. The mixture separated into two phases. The organic product layer was removed and vacuum dried to yield an alkyl dimethyl ethyl benzyl ammonium s'ul-fanilate as a yellow paste in 78 percent theoretical yield.
Biostasis was evaluated against Staphylococcus aureus, Salmonella typhosa, and Aspergillus niger by the Standard Tube Dilution Test described above. The product showed biostasis at the dilutions as given: S. aureus, 1:l00,000; S. typhosa, 1:100,000; A. niger, 1:10,000.
Example V An aliquot of the stock solution in Example I containing 0.0315 equivalent of sodium sulfanilate was vigorously agitated while a chemical equivalent amount of the alkyl dimethyl benzyl ammonium chloride of Example II in the form of a 10 weight percent solution was slowly added. The agitated mixture was then poured into a separatory funnel. The mixture separated into two phases. The organicproduct layer was removed and vacuum dried to yield a yellow paste of alkyl dimethyl benzyl ammonium sulfanilate in 81 percent theoretical yield.
Biostasis was evaluated against Staphylococcus aureus, Salmonella typhosa, and Aspergillus niger by the Standard Tube Dilution Test described above. The product showed biostasis at the dilutions as given: S. aureus, 1:l0,000,000; S. typhosa, 1: 100,000; A. niger, 1:l00,000.
Example VI An aliquot of the stock solution in Example I containing 0.308 equivalent of sodium sulfanilate was vigorously agitated while a chemical equivalent amount of lauryl isoquinolinium bromide of Example III in the form of a 10 weight percent solution was slowly added. Benzene was added to the agitated mixture which was then poured into a separatory funnel. T he rnixture separated into two phases. The organic product layer was removed and the benzene evaporated on a steam bath. The product was vacuum dried to' yield lauryl isoquinolinium sulfanilate as a dark red paste in 87 percent theoretical yield.
Biostasis was evaluated against Staphylococcus aureus, Salmonella typhosa, and Aspergillus niger by the Standdard Tube Dilution Test described above. The product showed biostasis at the dilutions as given: S. aureus, l:10,000,000; S. typhosa, 1:1000,000; A. niger, 1:100,000.
This product, when incorporated in soap at the 2% level, resulted in a bacteriostatic soap showing activity against Staphylococcus aureus comparable to that of hexachlorophene in a hand-washing test.
The product of this example was also found effective in the control of dandruff when incorporated in shampoos.
Example VII Two tenths part of the product of Example VI and 99.8 parts of a commercial grade of gypsum joint cement containing no mold inhibitor were blended and pasted up with suflicient water to make a heavy dough which was applied by spatula to a 3-inch by 6-inch piece of fibreboard.
Another fibreboard sample was coated with the same gypsum joint cement paste containing no inhibitor.
Both samples, after hardening, were placed in a desiccator with the bottom covered with water and out of reach of the samples. A moldy piece of gypsum-coated fibreboard was placed in the desiccator which was then closed. Within three days, the untreated sample showed heavy mold growth, whereas the sample containing the product of Example VI was completely barren of such growth after two weeks.
Example VIII In a 500 ml. separatory funnel were placed grams of a 10% solution of the sodium salt of l-amino-Z-naphthol-4-sulfonic acid and grams of a 10% solution of the alkyl dimethyl ethyl benzyl ammonium chloride of Example I. The funnel was well shaken and then 50 ml. of benzene added to facilitate layer separation. The product layer was separated, the benzene evaporated on a steam bath and then placed in a vacuum oven to dry. The product was a black paste of alkyl dimethyl ethyl benzyl ammonium 1-amino-2-naphthol-4-sulfonate (20 grams88% yield).
Biostasis was evaluated against Staphylococcus aureus, Salmonella typhosa, and Aspergillus niger by the Standard Tube Dilution Test described above. The product showed biostasis at the dilutions as given: S. aureus, 1:100,000,000; S. typhosa, 1:100,000,000; A. niger, 1210,000.
Example IX Using the technique of Example VIII above, the sodium salt of 1=amino-2-naphthol-4-sulfonic acid was reacted with a chemically equivalent amount of the alkyl dimethyl benzyl ammonium chloride of Example II. The product, alkyl dimethyl benzyl ammonium 1amino-2- 7 naphthol-4-sulfonate, was a black solid and was obtained in 94% yield.
Biostasis was evaluated against Staphylococcus tllll'LllS, Salmonella typhosa, and Aspergillus niger by the Standard Tube Dilution Test described above. The product showed biostasis at the dilutions as given: S. aureas, l:l00,000; S. typhosa, l:100,000; A. niger, 1:10,000.
Example X In a 1 liter separatory funnel were placed 330 grams of a 10% solution of the disodium salt of 4,4-diamino stilbene-2,2-disulfonic acid and 220 grams of alkyl dimethyl ethyl benzyl ammonium chloride identical to that used in Example VIII above. Using the technique of Example VIII, 30 grams of a yellow solid (70% yield) was obtained.
Biostasis was evaluated against Staphylococcus aureus, Salmonella typhosa, and Aspergillus niger by the Standard Tube Dilution Test described above. The product showed biostasis at the dilutions as given: S. aureus, 121,000,000; S. typhosa, 1:l00,000; A. niger, 1:l00,000.
In a similar manner, the'4,4-diamino stilbene-2,2'-disulfonic acid was reacted with alkyl dimethyl benzyl ammonium chloride (identical to that used in Example IX above). The product was a yellow solid obtained in 81% yield.
Biostasis was evaluated against Staphylococcus aureus, Salmonella typhosa, and Aspergillus niger by the Standard Tube Dilution Test described above. The product showed biostasis at the dilutions as given: S. aureus, 1:1,000,000; S. typhosa, l:1,000,000; A. niger, l:100,000.
Using the same technique, the lauryl isoquinolinium bromide of Example IH was reacted with an equimolar quantity of 4,4'-diamino stilbene-2,2-disulfonic' acid to give a red powder in 86% yield.
All three of these products were quaternary ammonium salts of the diamino stilbene 'disulfonic acid. By a similar technique, using the mono sodium salt and only monosalts may be made.
Example XI In a 500 ml. separatory funnel were placed 180 grams one mole equivalent of quaternary, the corresponding of a 10% solution of alkyl dimethyl ethyl benzyl am-monium chloride (identical to that used in Example VIII) and 60 grams of a 10% solution of the disodium salt of o-amino phenol-p-sulfonic acid. The funnel was well shaken and then layer separation allowed to occur. The product layer was dried in a vacuum oven to give 22.5 grams (98% yield) of a dark brown paste. This product was the salt of alkyl dimethyl ethyl benzyl ammonium chloride and o-amino phenol-p-sulfonic acid in which both hydroxyl and sulfonic acid groups were converted to their corresponding quaternary ammonium salts.
Biostasis was evaluated against Staphylococcus aureus, Salmonella typhosa, and Aspergillus niger by the Standard Tube Dilution Test described above. The product showed biostasis at the dilutions as given: S. aureus, 1: 1,000,000; S. typhosa, l:l,000,000; A, niger, 1: 100,000.
Example XII A 25 weight percent solution of the product of 'Example II was prepared in ethylene glycol mono -butyl ether and mixed with a commercial grade of alkyd base paint containing no other'fungicide in the ratio of 4 parts by weight of this solution to 96 .parts by weight of paint. Strips of filter paper out to 1 inch by 4 inches were coated with this paint and allowed to dry. They were then inoculated with a culture of Pullularia pa/lulans and held in an incubator at 25 C. and relative humidity for three Weeks. At the end of this time, no fungus growth was visible.
Example XIII Four parts of the 25% solution of the product of Example II prepared according to Example III were added to 96 parts of a latex acrylic type paint with thorough stirring and the latex emulsion thus treated was inoculated. with a culture of Pullularia pallalans and incubated as in Example XII. At the end of three weeks, no fungus growth was visible in the latex.
.In general, the products of this invention are useful in the control of plant diseases and plant pests. They exhibit little or no phytotoxicity when dipped or sprayed onto plant foliage in the form of 0.1% active solutions or dispersions. Thus, for example, there is no phytotoxicity observed by application of such concentrations of the product of Example II to Woods Prolific Lima Beans, whereas such application affords marked control of Mexican bean beetles feeding on the foliage.
We claim:
1. A quaternary ammonium aromatic amino sulfonate in which the quaternary nitrogen atom is linked to at least one straight-chain alkyl having 12 to 18 carbon atoms.
2. Alkyl dimethyl ethyl-benzyl ammonium metanilate in which the alkyl has 12 to 18 carbon atoms.
3. Lauryl isoquinolinium metanilate.
4. Alkyl dimethyl benzyl ammonium metanilate in which the alkyl has 12 to 18 carbon atoms.
References Cited by the Examiner UNITED STATES PATENTS 3/1958 Slack 260-313 6/1963 Coker 260567.6 XR
ALEX MAZEL, Primary Examiner.
NICHOLAS s. RIZZO, HENRY R. JILES,
Examiners.
DONALD G. DAUS, Assistant Examiner.
Claims (2)
1. A QUATERNARY AMMONIUM AROMATIC AMINO SULFONATE IN WHICH THE QUATERNARY NITROGEN ATOM IS LINKED TO AT LEAST ONE STRAIGHT-CHAIN ALKYL HAVING 12 TO 18 CARBON ATOMS.
3. LAURYL ISOQUINOLINIUM METANILATE.
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US323598A US3299073A (en) | 1963-11-14 | 1963-11-14 | Quaternary ammonium aromatic amino sulfonates |
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US323598A US3299073A (en) | 1963-11-14 | 1963-11-14 | Quaternary ammonium aromatic amino sulfonates |
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US3299073A true US3299073A (en) | 1967-01-17 |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3961092A (en) * | 1974-05-03 | 1976-06-01 | Forest Joseph G | Method for preserving high moisture content agricultural grains |
US3962475A (en) * | 1974-05-03 | 1976-06-08 | Forest Joseph G | Method for preserving high moisture content agricultural grains |
US4588522A (en) * | 1982-04-24 | 1986-05-13 | Hoechst Aktiengesellschaft | Betaine-amine oxides, a process for their preparation and their use as surfactants |
EP0357417A1 (en) * | 1988-09-01 | 1990-03-07 | Glaxo Group Limited | Lactam derivatives |
US5084096A (en) * | 1989-04-06 | 1992-01-28 | Pavel Stovicek | Biocidal compositions based on polymers of dihydroxy quaternary ammonium salts |
US5833741A (en) * | 1997-01-16 | 1998-11-10 | Lonza Inc. | Waterproofing and preservative compositons for wood |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2827466A (en) * | 1953-02-17 | 1958-03-18 | May & Baker Ltd | Bis-quaternary ammonium salts of amsonic acid |
US3092547A (en) * | 1959-03-13 | 1963-06-04 | Burroughs Wellcome Co | Methods of treating oxyurid worms with quaternary ammonium compounds |
-
1963
- 1963-11-14 US US323598A patent/US3299073A/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2827466A (en) * | 1953-02-17 | 1958-03-18 | May & Baker Ltd | Bis-quaternary ammonium salts of amsonic acid |
US3092547A (en) * | 1959-03-13 | 1963-06-04 | Burroughs Wellcome Co | Methods of treating oxyurid worms with quaternary ammonium compounds |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3961092A (en) * | 1974-05-03 | 1976-06-01 | Forest Joseph G | Method for preserving high moisture content agricultural grains |
US3962475A (en) * | 1974-05-03 | 1976-06-08 | Forest Joseph G | Method for preserving high moisture content agricultural grains |
US4588522A (en) * | 1982-04-24 | 1986-05-13 | Hoechst Aktiengesellschaft | Betaine-amine oxides, a process for their preparation and their use as surfactants |
EP0357417A1 (en) * | 1988-09-01 | 1990-03-07 | Glaxo Group Limited | Lactam derivatives |
US5084096A (en) * | 1989-04-06 | 1992-01-28 | Pavel Stovicek | Biocidal compositions based on polymers of dihydroxy quaternary ammonium salts |
US5833741A (en) * | 1997-01-16 | 1998-11-10 | Lonza Inc. | Waterproofing and preservative compositons for wood |
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