US3726968A - The inhibition of perspiration with sodium tetraphenylboron - Google Patents
The inhibition of perspiration with sodium tetraphenylboron Download PDFInfo
- Publication number
- US3726968A US3726968A US00121591A US3726968DA US3726968A US 3726968 A US3726968 A US 3726968A US 00121591 A US00121591 A US 00121591A US 3726968D A US3726968D A US 3726968DA US 3726968 A US3726968 A US 3726968A
- Authority
- US
- United States
- Prior art keywords
- sodium
- lithium
- antiperspirant
- compounds
- tetraarylboron
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 83
- 239000011734 sodium Substances 0.000 title claims abstract description 83
- 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 title claims abstract description 77
- 230000005764 inhibitory process Effects 0.000 title description 9
- 238000000034 method Methods 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 abstract description 68
- 239000003213 antiperspirant Substances 0.000 abstract description 64
- 230000001166 anti-perspirative effect Effects 0.000 abstract description 63
- 229910052744 lithium Inorganic materials 0.000 abstract description 59
- 239000000203 mixture Substances 0.000 abstract description 56
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 52
- -1 aluminum chlorhydrates Chemical class 0.000 description 38
- 239000000463 material Substances 0.000 description 20
- 239000000243 solution Substances 0.000 description 20
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 17
- 229910052796 boron Inorganic materials 0.000 description 17
- 239000002904 solvent Substances 0.000 description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 150000001768 cations Chemical class 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 8
- 239000004615 ingredient Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000003380 propellant Substances 0.000 description 8
- 239000002537 cosmetic Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 239000000969 carrier Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000003974 emollient agent Substances 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000000443 aerosol Substances 0.000 description 4
- 229940009840 aluminum chlorhydrate Drugs 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 150000001639 boron compounds Chemical class 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 235000019388 lanolin Nutrition 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004166 Lanolin Substances 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XQOZFAAKQVWOCE-UHFFFAOYSA-N [Li]C1=CC=CC=C1C Chemical compound [Li]C1=CC=CC=C1C XQOZFAAKQVWOCE-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000005907 alkyl ester group Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000003937 drug carrier Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 230000002452 interceptive effect Effects 0.000 description 3
- 229940039717 lanolin Drugs 0.000 description 3
- YAMQOOCGNXAQGW-UHFFFAOYSA-M magnesium;methylbenzene;bromide Chemical compound [Mg+2].[Br-].CC1=CC=CC=[C-]1 YAMQOOCGNXAQGW-UHFFFAOYSA-M 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 239000000375 suspending agent Substances 0.000 description 3
- MXSVLWZRHLXFKH-UHFFFAOYSA-N triphenylborane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 MXSVLWZRHLXFKH-UHFFFAOYSA-N 0.000 description 3
- QSSXJPIWXQTSIX-UHFFFAOYSA-N 1-bromo-2-methylbenzene Chemical compound CC1=CC=CC=C1Br QSSXJPIWXQTSIX-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- ROFFHGJHENUAMX-UHFFFAOYSA-N CC1=CC=CC=C1[Na] Chemical compound CC1=CC=CC=C1[Na] ROFFHGJHENUAMX-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910020808 NaBF Inorganic materials 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 125000005036 alkoxyphenyl group Chemical group 0.000 description 2
- 210000001099 axilla Anatomy 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- MOOAHMCRPCTRLV-UHFFFAOYSA-N boron sodium Chemical compound [B].[Na] MOOAHMCRPCTRLV-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 2
- 210000000245 forearm Anatomy 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 159000000002 lithium salts Chemical group 0.000 description 2
- YRHYCMZPEVDGFQ-UHFFFAOYSA-N methyl decanoate Chemical compound CCCCCCCCCC(=O)OC YRHYCMZPEVDGFQ-UHFFFAOYSA-N 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000003381 solubilizing effect Effects 0.000 description 2
- 210000004243 sweat Anatomy 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- UJPMYEOUBPIPHQ-UHFFFAOYSA-N 1,1,1-trifluoroethane Chemical compound CC(F)(F)F UJPMYEOUBPIPHQ-UHFFFAOYSA-N 0.000 description 1
- DLKQHBOKULLWDQ-UHFFFAOYSA-N 1-bromonaphthalene Chemical compound C1=CC=C2C(Br)=CC=CC2=C1 DLKQHBOKULLWDQ-UHFFFAOYSA-N 0.000 description 1
- QMYGFTJCQFEDST-UHFFFAOYSA-N 3-methoxybutyl acetate Chemical group COC(C)CCOC(C)=O QMYGFTJCQFEDST-UHFFFAOYSA-N 0.000 description 1
- QJPJQTDYNZXKQF-UHFFFAOYSA-N 4-bromoanisole Chemical compound COC1=CC=C(Br)C=C1 QJPJQTDYNZXKQF-UHFFFAOYSA-N 0.000 description 1
- TUXYZHVUPGXXQG-UHFFFAOYSA-N 4-bromobenzoic acid Chemical compound OC(=O)C1=CC=C(Br)C=C1 TUXYZHVUPGXXQG-UHFFFAOYSA-N 0.000 description 1
- HIQIXEFWDLTDED-UHFFFAOYSA-N 4-hydroxy-1-piperidin-4-ylpyrrolidin-2-one Chemical compound O=C1CC(O)CN1C1CCNCC1 HIQIXEFWDLTDED-UHFFFAOYSA-N 0.000 description 1
- 240000008025 Alternanthera ficoidea Species 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- CAQWNKXTMBFBGI-UHFFFAOYSA-N C.[Na] Chemical compound C.[Na] CAQWNKXTMBFBGI-UHFFFAOYSA-N 0.000 description 1
- XOCKQIWLQMQYFW-UHFFFAOYSA-N COc1ccc([Na])cc1 Chemical compound COc1ccc([Na])cc1 XOCKQIWLQMQYFW-UHFFFAOYSA-N 0.000 description 1
- SGNBVLSWZMBQTH-FGAXOLDCSA-N Campesterol Natural products O[C@@H]1CC=2[C@@](C)([C@@H]3[C@H]([C@H]4[C@@](C)([C@H]([C@H](CC[C@H](C(C)C)C)C)CC4)CC3)CC=2)CC1 SGNBVLSWZMBQTH-FGAXOLDCSA-N 0.000 description 1
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- BTEISVKTSQLKST-UHFFFAOYSA-N Haliclonasterol Natural products CC(C=CC(C)C(C)(C)C)C1CCC2C3=CC=C4CC(O)CCC4(C)C3CCC12C BTEISVKTSQLKST-UHFFFAOYSA-N 0.000 description 1
- 241000282375 Herpestidae Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000005640 Methyl decanoate Substances 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- TVIVFOCKMSMZOJ-UHFFFAOYSA-N OC(=O)c1ccc([Na])cc1 Chemical compound OC(=O)c1ccc([Na])cc1 TVIVFOCKMSMZOJ-UHFFFAOYSA-N 0.000 description 1
- 239000004264 Petrolatum Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 235000019485 Safflower oil Nutrition 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229930182558 Sterol Natural products 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- 241000270666 Testudines Species 0.000 description 1
- FYOQEFGAZKEPGG-UHFFFAOYSA-N [Li]C1=CC=C(C)C=C1 Chemical compound [Li]C1=CC=C(C)C=C1 FYOQEFGAZKEPGG-UHFFFAOYSA-N 0.000 description 1
- CSCHZBSMAFRBKU-UHFFFAOYSA-N [Li]C1=CC=CC(OC)=C1OC Chemical compound [Li]C1=CC=CC(OC)=C1OC CSCHZBSMAFRBKU-UHFFFAOYSA-N 0.000 description 1
- UDPCZKKCDJCTGI-UHFFFAOYSA-N [Na]C#CC1=CC=CC=C1 Chemical compound [Na]C#CC1=CC=CC=C1 UDPCZKKCDJCTGI-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- WWHZEXDIQCJXSV-UHFFFAOYSA-N aluminum;trihypochlorite Chemical class [Al+3].Cl[O-].Cl[O-].Cl[O-] WWHZEXDIQCJXSV-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- SGNBVLSWZMBQTH-PODYLUTMSA-N campesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CC[C@@H](C)C(C)C)[C@@]1(C)CC2 SGNBVLSWZMBQTH-PODYLUTMSA-N 0.000 description 1
- 235000000431 campesterol Nutrition 0.000 description 1
- 125000004181 carboxyalkyl group Chemical group 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 235000012000 cholesterol Nutrition 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000012612 commercial material Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- BCLJZFLDSCTULJ-UHFFFAOYSA-N decyl formate Chemical compound CCCCCCCCCCOC=O BCLJZFLDSCTULJ-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 229940052296 esters of benzoic acid for local anesthesia Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229940006487 lithium cation Drugs 0.000 description 1
- OTUADNSYEBSXHE-UHFFFAOYSA-N lithium;1,3,5-tri(propan-2-yl)benzene-6-ide Chemical compound [Li+].CC(C)C1=CC(C(C)C)=[C-]C(C(C)C)=C1 OTUADNSYEBSXHE-UHFFFAOYSA-N 0.000 description 1
- RBWRWAUAVRMBAC-UHFFFAOYSA-M magnesium;methoxybenzene;bromide Chemical compound [Mg+2].[Br-].COC1=CC=[C-]C=C1 RBWRWAUAVRMBAC-UHFFFAOYSA-M 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000001457 metallic cations Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 229940105132 myristate Drugs 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- 229940066842 petrolatum Drugs 0.000 description 1
- ANRQGKOBLBYXFM-UHFFFAOYSA-M phenylmagnesium bromide Chemical compound Br[Mg]C1=CC=CC=C1 ANRQGKOBLBYXFM-UHFFFAOYSA-M 0.000 description 1
- 230000001766 physiological 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
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000003813 safflower oil Substances 0.000 description 1
- 235000005713 safflower oil Nutrition 0.000 description 1
- KZJWDPNRJALLNS-VJSFXXLFSA-N sitosterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CC[C@@H](CC)C(C)C)[C@@]1(C)CC2 KZJWDPNRJALLNS-VJSFXXLFSA-N 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 150000003432 sterols Chemical class 0.000 description 1
- 235000003702 sterols Nutrition 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- 230000000699 topical effect Effects 0.000 description 1
- YFDAMRSZJLWUSQ-UHFFFAOYSA-N tris(2-methylphenyl)borane Chemical compound CC1=CC=CC=C1B(C=1C(=CC=CC=1)C)C1=CC=CC=C1C YFDAMRSZJLWUSQ-UHFFFAOYSA-N 0.000 description 1
- HHIFJGNVQGOIPS-UHFFFAOYSA-N tris(4-methoxyphenyl)borane Chemical compound C1=CC(OC)=CC=C1B(C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 HHIFJGNVQGOIPS-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q15/00—Anti-perspirants or body deodorants
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/58—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/027—Organoboranes and organoborohydrides
Definitions
- compositions which are designed to inhibit or reduce unwanted perspiration, especially in the axillae.
- Such compositions generally contain one or moreingredients which inhibit or arrest perspiration flow when appliedto human skin.
- antiperspirant ingredients are thought to react with the sweat duct by any of a variety of mechanisms and to stop perspiration flow either by a physiological action, or by a physical plugging of the sweat duct orifice.
- commercially available antiperspirant ingredients have been limited almost exclusively to the partially hydrated acid salts of polyvalent metals, for example the aluminum chlorhydrates, aluminum chloralcoholate compounds, zirconium halide hydrates and the like.
- the antiperspirant compounds currently employed all suffer from various defects which limit their utility in wherein M is selected from the group consisting of lithium cation and sodium cation and wherein each sub-' stituent R is an aromatic group having the formula day-to-day cosmetic use.
- M is selected from the group consisting of lithium cation and sodium cation and wherein each sub-' stituent R is an aromatic group having the formula day-to-day cosmetic use.
- the acid salts of the polyvalent metals sometimes cause an acid reaction on the skin which deteriorates clothing coming in contact therewith.
- Certain of the known antiperspirant compounds are not sufficiently stable to insure reasonable product shelf life and can cause unacceptable discolorations of clothing and skin after storage.
- it is widely recognized that some antiperspirant 'compounds' appar ently are not effective when applied to certain individuals. For these reasons, there is a continuing search for new, effective antiperspirant compounds capable of being formulated into cosmetically acceptable compositions.
- the present invention is based on the unexpected utility of sodium and lithium tetraarylboron compounds as antiperspirants.
- This invention thus encompasses antiperspirant compositions comprising tetraarylboron compounds of thetype hereinafter disclosed,
- compositions being substantially free from interfering amines and cations.
- antiperspirant as used herein encompasses materials that either inhibit, or stop, perspiration flow when applied to the surface of the human skin.
- the instant invention encompasses an antiperspirant composition
- an antiperspirant composition comprising: l an amount sufficient to inhibit perspiration (at least about 0.01 percent, by weight, preferably from about 1 percent to about 20 percent, by weight) of a tetraarylboron compound having the general formula MBR wherein R is: hydrogen; lower alkyl (e.g., methyl, ethyl, propyl, butyl, isopropyl,'t-butyl, pentyl, hexyl,
- lower alkoxyl e.g., methoxyl, ethoxyl,
- This invention also encompasses a method for inhibiting perspiration comprising applying to the human skin an effective amount of a tetraarylboron compound of formula (I), above.
- aryl lithium or aryl sodium compound which is reacted with the triarylboron compound can be prepared, for example, by the reaction of lithium or sodium with an aryl halide in the manner well-known in the art.
- aryl sodium and aryl lithium compounds can be prepared by a metal exchange reaction involving an alkyl metallic compound (e.g., methyl sodium or methyl lithium) with an aromatic compound such as benzene, toluene, naphthalene and the like in the manner described by Rochow, et al., The Chemistry of Organometallic Compounds, J. Wiley and Sons, Chapter 4.
- alkyl metallic compound e.g., methyl sodium or methyl lithium
- aromatic compound such as benzene, toluene, naphthalene and the like
- the aryl sodium or aryl lithium compound is then allowed to react with the triarylboron compound, 8R with the formation of the corresponding sodium or lithium tetrarylboron product.
- the triarylboron compound, 8R with the formation of the corresponding sodium or lithium tetrarylboron product.
- addition of phenyl lithium to an ethereal solution of triphenylboron gives lithium tetraphenylboron.
- a general procedure for the preparation of the complex metal tetrarylboron salts of formula (I) is described more fully in British Pat. 705,719 l954), incorporated herein by reference.
- the sodium or lithium tetraarylboron compounds of formula (I) are applied to the human skin in an amount sufficient to inhibit perspiration.
- the requisite amount of a sodium or lithium tetraaryl compound of formula (I) will vary since the antiperspirant response to these materials will vary between individuals applying same.
- perspiration, especially axillary perspiration will be inhibited when at least about LOug. of the sodium or lithium tetraarylboron compound is applied per mm of skin. In some instances less materials will be needed. Most generally, from about 0.1 g. to 5 g.
- an antiperspirant composition as hereinafter described, containing from about 0.01 percent to about 20 percent, by weight, of a sodium or lithium tetraarylboron of formula (I) will be applied to a skin area of about 24 cm with good antiperspirant results. More or less of such compositions can be used, depending on the individual.
- tetraarylboron compound of formula (I) it is not necessary that the tetraarylboron compound of formula (I) be dissolved prior to application to effect its antiperspirant action, and, hence, when such materials are applied to human skin in the form ofa power or dust they exhibit a high degree of antiperspirant activity.
- sodium or lithium tetraarylboron compounds of formula (I) are applied as powders in the manner of this invention their state of aggregation is of no consequence in that they perform their antiperspirant function regardless of particle size.
- cosmetically acceptable antiperspirant dusts comprising sodium or lithium tetraarylboron compounds of formula (I) should preferably have said boron compound in the state of aggregation smaller than about 37 microns.
- compatible and pharmaceutically acceptable carriers are suitable for this purpose.
- compatible is meant that such carriers are substantially free from cations other than sodium and lithium cations and free from amines having a basic dissociation constant (K of or greater, since the compounds of formula (I) precipitate the cations of essentially all of the metals of the periodic chart, other than sodium and lithium, and
- amines having K s of lO', or greater are suitable for repeated application to human skin with little, or no, untoward physiological effects.
- the sodium or lithium tetrarylboron compounds of formula (I) can be applied to the skin as a solution containing an effective amount, i.e., greater than about 0.01 percent, by weight, preferably about 1 percent to about 20 percent, by weight, of said tetraarylboron compound.
- an effective amount i.e., greater than about 0.01 percent, by weight, preferably about 1 percent to about 20 percent, by weight, of said tetraarylboron compound.
- solvent carriers for the sodium and lithium tetraarylborons is not limited other than that they be compatible and pharmaceutically acceptable, as herein defined.
- solvents which can be used herein to prepare solutions of the compounds of formula (I) for antiperspirant use.
- water can be used for this purpose.
- water When water is employed as a solvent for the tetraarylboron compounds to provide aqueous antiperspirant formulations, it should first be carefully deionized by standard deionization techniques to render it substantially free of metal cations.
- Non-amine chelating agents can also be used to remove such interfering cations.
- Another procedure which can be used to advantage is to add to the solvent an excess of the sodium or lithium tetraarylboron compound over that desired in the composition, said excess being calculated to precipitate and remove the contaminating metal ions present in the water.
- solvents suitable for use with the tetraarylboron compounds of formula (I) to provide antiperspirant compositions in solution form include: alcohols, especially alcohols having from one to about 16 carbon atoms; esters, especially those liquid esters of lower organic acids and alcohols having from about one to about 16 carbon atoms; polyoxyalkylene materials, for example polyoxyethylene in the molecular weight range from about 50 to about 10,000.
- Non-limiting examples of compatible, pharmaceutically acceptable solvents suitable for use in preparing antiperspirant compositions containing sodium or lithium tetraarylboron compounds of formula (I) in solution include: ethyl alcohol, isopropyl alcohol, butanol, isobutanol, 2- ethyll-hexanol, hexadecanol, methyl propionate, ethyl formate, decyl formate, methyl decanoate, isopropyl myristate and the like.
- Especially preferred compatible, pharmaceutically acceptable carriers which are solvents for use herein in the preparation of antiperspirant compositions wherein the sodium or lithium tetraarylboron compound of formula (I) is dissolved are water, especially deionized water, ethyl alcohol, isopropyl alcohol, polyoxyethylene and mixtures thereof.
- the sodium and lithium tetraarylboron compounds of formula (I) can be formulated in antiperspirant compositions wherein said tetraarylboron compound is not dissolved in the carrier but is merely suspended therein in particulate form.
- a composition comprising greater than about 0.01 percent, by weight, preferably from about 1 percent to about 20 percent, by weight, of a particulate sodium or lithium tetraarylboron compound of formula (1) and a compatible, pharmaceutically acceptable solid or liquid carrier in which said boron compound is essentially insoluble provides an effective antiperspirant Composition.
- Suitable non-solubilizing carriers include such exemplary materials as: waxes, for instance the high molecular weight esters obtained from various plant and animal sources; oils, for example sunflower oil, turtle oil, minkoil, safflower oil, civet oil, and other oils commonly employed in cosmetic applications; high molecular weight alcoholic materials, for example sterols such as B-sitosterol and campesterol and materials such as cholesterol; lanolin and the commercially available alkylated and alkanolylated lanolins which are commonly employed in cosmetic formulations; higher molecular weight polyoxyalkylene materials which are semi-solid or waxy solids; and high molecular weight waxy hydrocarbons, e.g., petrolatum. Carboxyalkyl celluloses and high molecular weight polyoxyalkylene materials can also be used herein as gelling agents. Such materials are suitable herein, singly and in mixtures, both by virtue of their compatibility and their pharmaceutical acceptability. I
- non-solubilizing carrier materials useful herein fall within that class of compounds commonly referred to as skin emollients.
- skin emollients As is "recognized in the art, such emollient materials are often employed in conjunction with many of the materials hereinabove referred to as solvents for the sodium and lithium tetraarylboron compounds.
- solvents for the sodium and lithium tetraarylboron compounds Such combinations of the solvent materials and emollient materials also provide carrier mixtures suitable for use herein in the formulation of antiperspirant compositions containing the sodium or lithium tetraarylboron compounds of formula (1).
- Still another class of carriers which are suitably employed with the sodium and lithium tetraarylboron compounds include those halogenated, i.e., chlorinated, fluorinated and chloro-fluorinated, lower molecular weight hydrocarbons which are commercially used as propellants. Many of these materials have vapor pressures of 1 atmosphere, or greater, at temperatures of about 20C, and above, but ,are commonly li'quified under pressure and employed as propellants in aerosol cosmetic formulations. These liq'uified gases can be employed to propel antiperspirant solutions of the sodium or lithium tetraarylboron compound by mixing said solution with the liquified propellant gas under pressure.
- halogenated i.e., chlorinated, fluorinated and chloro-fluorinated, lower molecular weight hydrocarbons which are commercially used as propellants.
- Many of these materials have vapor pressures of 1 atmosphere, or greater, at temperatures of about 20C, and above, but ,are commonly
- the undissolved, solid sodium or lithium tetraarylboron compound can be suspended in the pressurized liquified gas, itself.
- antiperspirant compositions comprising liquified propellant gases and antiperspirant ingredients also contain one or more emoll'ients of the type hereinbefore noted.
- Such compositions comprising a dissolved or undissolved sodium or lithium tetraarylboron compound of formula (I), a liquified propellant gas and one or more of said emollient materials are also within the scope of this invention.
- Antiperspirant compositions comprising from about 0.1 percent to 10 percent, by weight, of an undissolved sodium or lithium tetraarylboron compound of formula (I) in combination with from about percent to percent by weight of liquified propellant gas, from about 2 percent to about 10 percent, by weight, of a compatible, pharmaceutically acceptable emollient as hereinabove disclosed and from about 0.1 percent to 2 percent, by weight, of a suspending agent capable of maintaining the particulate matter in a more-or-less stable suspension are preferred embodiments herein.
- Suspending agents such as fumed colloidal silica or oleophilic Bentonite clays can be employed herein in the manner well-known to those skilled in the art to help stabilize such aerosol antiperspirant compositions containing the antiperspirant compounds of formula (I).
- antiperspirant compositions comprising a sodium or lithium tetraarylboron compound of formula (I) in combination with all manner of pharmaceutically acceptable emollients, propellants, solvents and suspending agents, and mixtures thereof, which are substantially free from interfering metal cations and amines can be prepared.
- the sodium and lithium tetraarylboron antiperspirant compounds of formula (I) can therefore be employed in antiperspirant formulations such as sprays, sticks, rollons, aerosols and the like.
- All manner of additives commonly found in cosmetic formulations can be employed in the preparation of said compositions to provide more cosmetically acceptable products if such additives are substantially free from dissolved cations other than lithium or sodium cations and amines of the type hereinbefore defined.
- the resulting tri-o-tolylboron compound is recovered by vacuum distillation.
- a solution of o-tolyl lithium is prepared from lithium shot and o-tolyl bromide in diethyl ether according to the procedure of F. Hein, et al., Z. Anorg. Chem., 141, 161 (1924).
- the solution of o-tolyl lithium is admixed with an ethereal solution of the tri-o-tolylboron (40C, 24 hours) and the ether removed by vacuum distillation to provide crystals of lithium tetra- (o-tolyl)boron.
- the o-tolyl lithium is replaced by four equivalents o-tolyl sodium, prepared in analogous fashion using sodium metal, and the BF Et- O is replaced by one equivalent of NaBF and the sodium tetra-(o-tolyl)boron compound is thereby secured.
- the o-tolylmagnesium bromide is replaced by an equivalent amount of p-methoxyphenyl-magnesium bromide prepared by the reaction of p-methoxyphenyl bromide with magnesium turnings in diethyl ether.
- the resulting tri-(p-methoxyphenyl)boron is allowed to react with p-methoxyphenyl sodium 1:1 mole basis) in diethyl ether and the resulting sodium tetra-(p-methoxy-phenyl)boron is recovered by crystallization.
- Sodium tetra-(p-methlbenzoate)boron is prepared in like fashion by reacting BF3-Et O with the Grignard reagent prepared from the methyl ester of p-bromobenzoic acid and subsequently reacting the triarylboron compound with the methyl ester of p-carboxyphenyl sodium.
- a-naphthyltriphenylboron is prepared by allowing a 0.321 molar mixture of boron trifluoride etherate and phenyl magnesium bromide to react and then mixing the resulting triphenylboron with a-naphthyl lithium, prepared from a-bromonaphthalene and lithium wire.
- lithium triphenyl-p-tolyboron from triphenylboron and p-tolyl lithium
- lithium phenyltri-a-naphthylboron from tri-a-naphthylmagnesium bromide, boron trifluoride etherate and phenyl lithium.
- sodium and lithium tetraarylboron compounds of formula (I) can be prepared by reacting a triarylboron compound with the desired aryllithium or arylsodium compound.
- a triarylboron compound with the desired aryllithium or arylsodium compound.
- the aryl group is phenyl, carboxyphenyl, i.e., benzoic acid derivatives, alkyl esters of benzoic acid, or alkoxyphenyl groups are most preferred.
- Substituent groups on the phenyl ring can be at any of the ortho, para or meta positions with equivalent antiperspirant results.
- alkoxyl and alkyl ester derivatives of the tetraphenyl boron compounds having lower alkyl groups i.e., those containing from about one to l0, more preferably one to six, carbon atoms.
- substituent on the phenyl ring is carboxyl, i.e., benzoic acid
- the sodium or lithium salt form of the acid is also suitable herein.
- Examples of such preferred antiperspirants include compounds of formula (I) wherein substituent R is a lower alkyl ester of benzoic acid, especially the ortho-, metaand para-methylbenzoates, and the lower alkoxyphenyl derivatives especially ortho-, paraand meta-methoxyphenyl groups; the sodium salts of these are preferred.
- the sodium tetraphenylboron is replaced by an equivalent amount of lithium tetra-(p-butoxyphenyl)boron, sodium tetra-(para-t-butoxyphenyl)boron sodium tetra-(o-tolyl)boron, sodium tetra-(p-methylbenzoate)boron, sodium tetra-(pmethoxyphenyl)boron, sodium tetra-(p-carboxy-phenyl)boron and sodium tetra-(o-decyloxyphenyl)boron, respectively, and equivalent antiperspirant compositions are secured.
- EXAMPLE IV Aerosol Solution Antiperspirant Percent By Weight Ingredient 20 Sodium tetraphenylboron 20 Ethyl alcohol isopropyl alcohol (2:1 volume mixture) 0. l Hexchlorophene 0.7 Perfume Balance Propellant* Dichlorodifluoromethane and trifuloroethane, 60:40 weight mixture.
- the sodium tetraphenylboron is replaced by an equivalent amount of sodium tetra-(p-methylbenzoate)boron, sodium tetra-(mmethylbenzoate)boron and sodium tetra-(o-methylbenzoate)boron, respectively, and equivalent antiperspirant compositions are secured.
- the sodium tetraphenylboron is replaced by an equivalent amount of lithium tetra-(o-ethoxyphenyl)boron, lithium tetra-(a-carboxyl)boron, respectively, and equivalent antiperspirant compositions are secured.
- EXAMPLE VI Roll-on Antiperspirant Percent By Weight Ingredient 5 Sodium tetraphenylboron 50 Ethyl alcohol 20 Lanolin 20 Isopro yl myristate 0.1 Hexch orophene 0.5 Perfume Balance lsopropyl alcohol Application of about 0.01 g/cm of the above composition to the skin gives good antiperspirant results.
- the sodium tetraphenylboron is replaced by an equivalent amount of sodium tetra-(p-carboxyphenyl)boron sodium salt form, and sodium tetra-(o-carboxyphenyl)boron, lithium salt form, and equivalent antiperspirant compositions are secured.
- TEST 1 A 5% (wt.) solution of sodium tetraphenylboron was prepared by dissolving 0.5 g. of sodium tetraphenylboron (commercial material) in 9.5 g. of deionized water. In the test procedure, 1 ml. of the above solution was applied to a l in. square cotton patch which was affixed to the inner forearm of test subjects for one hour. Following this patching procedure, the volunteers were placed in a hot room at 110F and 47 percent relative humidity for a few minutes and the perspiration inhibition on the test portion of the arm was visually estimated using a phenolphthalein test cream by comparing the patched portion with the surrounding forearm skin. The results on three test subjects were as follows:
- Subject 2 100% inhibition 90 inhibition
- Aluminum chlorhydrate the most commonly used antiperspirant compound, generally gives perspiration inhibition scores of 50 percent to percent in similar tests.
- TEST 2 In the following test, the overall antiperspirant efficacy of sodium tetraphenylboron was assessed over a five day test period and compared with the antiperspirant effectiveness of aluminum chlorhydrate, a commonly used antiperspirant, on the same test subjects and under the same test each
- the historical perspiration flow from three volunteers was assessed by daily perspiration collections using cotton pads at a temperature of 1 10F and 47 percent relative humidity under conditions wherein the subject exercised for five minutes and then walked for five minutes during axillary perspiration collection; the collected perspiration was weighed to establish each volunteer's normal (historical) perspiration flow under these conditions.
- tetraarylboron compounds of formula (I), especially sodium tetraphenyl boron provide superior antiperspirant activity when applied to human skin.
- a method for inhibiting perspiration comprising applying a perspiration inhibiting effective amount of sodium tetraphenylboron to human skin.
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Abstract
Antiperspirant compositions containing sodium or lithium tetraarylboron compounds as antiperspirant agents.
Description
ilnified States Paiem [191 Loomans 5] Apr. 10, 1973 [54] THE INHIBITION OF PERSPIRATION [56] References Cited WHTH SODIUM TETRAPHENYLB RON 0 UNITED STATES PATENTS [75] Inventor: Maurice E. Loomans, Green Town- 2 853 525 9/1958 W al 260/606 5 B v ittla et Hamilton Ohm 2,982,785 5/1961 McKenzie et a1. ..260/606.5 B [73] Assignee: The Procter & Gamble Com an 3,062,708 11/1962 Updegraff ..260/606.5 B
Cincinnati, Ohio Primary ExaminerStanley J. Friedman Flled: 5, 1971 Assistant Examiner-Donald B. Meyer [21] Appl' No.2 121,591 Attorney-Jack D. Schaeffer and Richard C. White [57] ABSTRACT [52] US. Cl ..424/65, 424/47 Antipersplrant compositions containing sodium or [51] Int. Cl. ..A61k 7/00 lithium tetraarylboron compounds as antiperspiram [58] Field of Search ..424/47, 185, 65; a ems 2 Claims, N0 Drawings I BACKGROUND OF THE INVENTION This invention relates to novel compositions for topical application to human skin to inhibit perspiration.
One of the most widely used types of cosmetic compositions are the antiperspirants which are designed to inhibit or reduce unwanted perspiration, especially in the axillae. Such compositions generally contain one or moreingredients which inhibit or arrest perspiration flow when appliedto human skin. These antiperspirant ingredients are thought to react with the sweat duct by any of a variety of mechanisms and to stop perspiration flow either by a physiological action, or by a physical plugging of the sweat duct orifice. Heretofore, commercially available antiperspirant ingredients have been limited almost exclusively to the partially hydrated acid salts of polyvalent metals, for example the aluminum chlorhydrates, aluminum chloralcoholate compounds, zirconium halide hydrates and the like. i
The antiperspirant compounds currently employed all suffer from various defects which limit their utility in wherein M is selected from the group consisting of lithium cation and sodium cation and wherein each sub-' stituent R is an aromatic group having the formula day-to-day cosmetic use. For example, the acid salts of the polyvalent metals sometimes cause an acid reaction on the skin which deteriorates clothing coming in contact therewith. Certain of the known antiperspirant compounds are not sufficiently stable to insure reasonable product shelf life and can cause unacceptable discolorations of clothing and skin after storage. At the same time, it is widely recognized that some antiperspirant 'compounds' appar ently are not effective when applied to certain individuals. For these reasons, there is a continuing search for new, effective antiperspirant compounds capable of being formulated into cosmetically acceptable compositions.
Therefore, it is a primary object of this invention to provide new and effective antiperspirant compositions. It is a further object to provide antiperspirant compositions comprising certain tetraarylboron compounds in combination with certain suitable carriers. These and other objects are obtained by the present invention as will become apparent from the following disclosure.
SUMMARY OF THE INVENTION The present invention is based on the unexpected utility of sodium and lithium tetraarylboron compounds as antiperspirants. This invention thus encompasses antiperspirant compositions comprising tetraarylboron compounds of thetype hereinafter disclosed,
said compositions being substantially free from interfering amines and cations. (The term antiperspirant as used herein encompasses materials that either inhibit, or stop, perspiration flow when applied to the surface of the human skin.)
DETAILED DESCRIPTION OF THE INVENTION In one of its embodiments, the instant invention encompasses an antiperspirant composition comprising: l an amount sufficient to inhibit perspiration (at least about 0.01 percent, by weight, preferably from about 1 percent to about 20 percent, by weight) of a tetraarylboron compound having the general formula MBR wherein R is: hydrogen; lower alkyl (e.g., methyl, ethyl, propyl, butyl, isopropyl,'t-butyl, pentyl, hexyl,
7 and the like); lower alkoxyl (e.g., methoxyl, ethoxyl,
propoxyl, butoxyl, isopropoxyl, t-butoxyl and the like); carboxyalkyl ester, wherein alkyl is C to C or carboxyl; and (2) a compatible, pharmaceutically acceptable carrier as hereinafter detailed. Compounds of formula (I) wherein R is phenyl and R is hydrogen, lower alkoxyl, carboxyl and carboxyalkyl ester, with alkyl being about C to C are preferred for use herein.
This invention also encompasses a method for inhibiting perspiration comprising applying to the human skin an effective amount of a tetraarylboron compound of formula (I), above.
Sodium tetraphenylboron, which is preferred for use 9 the resulting triarylboron compound, all in the manner described by Wittig, et al., Ann. 563, l 10 (1949). The aryl lithium or aryl sodium compound which is reacted with the triarylboron compound can be prepared, for example, by the reaction of lithium or sodium with an aryl halide in the manner well-known in the art. Alternatively, aryl sodium and aryl lithium compounds can be prepared by a metal exchange reaction involving an alkyl metallic compound (e.g., methyl sodium or methyl lithium) with an aromatic compound such as benzene, toluene, naphthalene and the like in the manner described by Rochow, et al., The Chemistry of Organometallic Compounds, J. Wiley and Sons, Chapter 4. By these general procedures are preparedsuch compounds as phenyl lithium, o-tolyl sodium, mtolyl lithium, lithium, diethoxyphenyl sodium, dimethoxyphenyl lithium, a-naphthyl lithium, B- naphthyl lithium, 2,4,6-triisopropyl-phenyl lithium, tetrabutylphenyl lithium, xylyl sodium, naphthyl sodium, phenylethynyl sodium, B-naphthylmethyl sodium and the like. Specific references to the preparation of these and other aryl lithium and aryl sodium compounds are found at page 73 of Rochow, et al., above. The aryl sodium or aryl lithium compound is then allowed to react with the triarylboron compound, 8R with the formation of the corresponding sodium or lithium tetrarylboron product. For example, as described by Wittig, et al., above, addition of phenyl lithium to an ethereal solution of triphenylboron gives lithium tetraphenylboron. A general procedure for the preparation of the complex metal tetrarylboron salts of formula (I) is described more fully in British Pat. 705,719 l954), incorporated herein by reference.
It is also possible to prepare tetraarylboron compounds having mixed aryl groups; this is achieved by reacting an aryl'sodium or aryl lithium compound with a triarylboron compound having different aryl groups. Such materials are also of use herein. References describing the preparation of various sodium and lithium tetraarylboron compounds having mixed aryl groups, e.g., lithium triphenyl-a-naphthylboron, lithium phenyl-tri-oc-naphthylboron, lithium triphenyl-ptolylboron, lithium di-(o-tolyl)diphenylboron, and the like, are found in W. Gerrard, The Organic Chemistry of Boron, 1961 Academic Press, pages 239 and 240. Still another process suitable for preparing compounds of formula (I) suitable for use herein involves reacting NaBF, with four equivalents of an aryl Grignard reagent of the type noted above. It may therefore be seen that any of the sodium and lithium tetrarylboron compounds of formula (I) which are suitable for use in the practice of this invention can be prepared by wellknown methods.
To effect the antiperspirant activity of the sodium or lithium tetraarylboron compounds of formula (I) in the manner of this invention said compounds are applied to the human skin in an amount sufficient to inhibit perspiration. The requisite amount of a sodium or lithium tetraaryl compound of formula (I) will vary since the antiperspirant response to these materials will vary between individuals applying same. In most cases, perspiration, especially axillary perspiration, will be inhibited when at least about LOug. of the sodium or lithium tetraarylboron compound is applied per mm of skin. In some instances less materials will be needed. Most generally, from about 0.1 g. to 5 g. of an antiperspirant composition, as hereinafter described, containing from about 0.01 percent to about 20 percent, by weight, of a sodium or lithium tetraarylboron of formula (I) will be applied to a skin area of about 24 cm with good antiperspirant results. More or less of such compositions can be used, depending on the individual.
It is not necessary that the tetraarylboron compound of formula (I) be dissolved prior to application to effect its antiperspirant action, and, hence, when such materials are applied to human skin in the form ofa power or dust they exhibit a high degree of antiperspirant activity. When the sodium or lithium tetraarylboron compounds of formula (I) are applied as powders in the manner of this invention their state of aggregation is of no consequence in that they perform their antiperspirant function regardless of particle size. For most cosmetic applications it is desirable that materials applied to the skin be impalpable. Therefore, cosmetically acceptable antiperspirant dusts comprising sodium or lithium tetraarylboron compounds of formula (I) should preferably have said boron compound in the state of aggregation smaller than about 37 microns.
In most instances the tetraarylboron compounds of formula (I) will be applied to human skin in conjunction with a carrier of the type hereinafter detailed. A variety of compatible and pharmaceutically acceptable carriers are suitable for this purpose. By compatible is meant that such carriers are substantially free from cations other than sodium and lithium cations and free from amines having a basic dissociation constant (K of or greater, since the compounds of formula (I) precipitate the cations of essentially all of the metals of the periodic chart, other than sodium and lithium, and
amines having K s of lO', or greater. By pharmaceutically acceptable is meant that the carriers are suitable for repeated application to human skin with little, or no, untoward physiological effects.
For example, the sodium or lithium tetrarylboron compounds of formula (I) can be applied to the skin as a solution containing an effective amount, i.e., greater than about 0.01 percent, by weight, preferably about 1 percent to about 20 percent, by weight, of said tetraarylboron compound. As is noted-hereinabove, the choice of solvent carriers for the sodium and lithium tetraarylborons is not limited other than that they be compatible and pharmaceutically acceptable, as herein defined.
There are a variety of solvents which can be used herein to prepare solutions of the compounds of formula (I) for antiperspirant use. For example, water can be used for this purpose. When water is employed as a solvent for the tetraarylboron compounds to provide aqueous antiperspirant formulations, it should first be carefully deionized by standard deionization techniques to render it substantially free of metal cations. Non-amine chelating agents can also be used to remove such interfering cations. Another procedure which can be used to advantage is to add to the solvent an excess of the sodium or lithium tetraarylboron compound over that desired in the composition, said excess being calculated to precipitate and remove the contaminating metal ions present in the water.
When organic solvents are used to prepare solutions of the compounds of formula (I) suitable for use as antiperspirants, the aforementioned problem concerning the interference by metal cations is small, since organic solvents characteristically contain little, if any, metallic cations. Organic solvents used herein can be distilled to remove substantially all such metallic residues.
As noted hereinabove, nearly all amines and aminecontaining materials precipitate the sodium and lithium tetraarylboron compounds as amine-boron complexes and are, hence, not useful herein as solvents.
Some of the solvents suitable for use with the tetraarylboron compounds of formula (I) to provide antiperspirant compositions in solution form include: alcohols, especially alcohols having from one to about 16 carbon atoms; esters, especially those liquid esters of lower organic acids and alcohols having from about one to about 16 carbon atoms; polyoxyalkylene materials, for example polyoxyethylene in the molecular weight range from about 50 to about 10,000. Non-limiting examples of compatible, pharmaceutically acceptable solvents suitable for use in preparing antiperspirant compositions containing sodium or lithium tetraarylboron compounds of formula (I) in solution include: ethyl alcohol, isopropyl alcohol, butanol, isobutanol, 2- ethyll-hexanol, hexadecanol, methyl propionate, ethyl formate, decyl formate, methyl decanoate, isopropyl myristate and the like. Especially preferred compatible, pharmaceutically acceptable carriers which are solvents for use herein in the preparation of antiperspirant compositions wherein the sodium or lithium tetraarylboron compound of formula (I) is dissolved are water, especially deionized water, ethyl alcohol, isopropyl alcohol, polyoxyethylene and mixtures thereof.
Alternatively, the sodium and lithium tetraarylboron compounds of formula (I) can be formulated in antiperspirant compositions wherein said tetraarylboron compound is not dissolved in the carrier but is merely suspended therein in particulate form. For example, a composition comprising greater than about 0.01 percent, by weight, preferably from about 1 percent to about 20 percent, by weight, of a particulate sodium or lithium tetraarylboron compound of formula (1) and a compatible, pharmaceutically acceptable solid or liquid carrier in which said boron compound is essentially insoluble provides an effective antiperspirant Composition. Suitable non-solubilizing carriers include such exemplary materials as: waxes, for instance the high molecular weight esters obtained from various plant and animal sources; oils, for example sunflower oil, turtle oil, minkoil, safflower oil, civet oil, and other oils commonly employed in cosmetic applications; high molecular weight alcoholic materials, for example sterols such as B-sitosterol and campesterol and materials such as cholesterol; lanolin and the commercially available alkylated and alkanolylated lanolins which are commonly employed in cosmetic formulations; higher molecular weight polyoxyalkylene materials which are semi-solid or waxy solids; and high molecular weight waxy hydrocarbons, e.g., petrolatum. Carboxyalkyl celluloses and high molecular weight polyoxyalkylene materials can also be used herein as gelling agents. Such materials are suitable herein, singly and in mixtures, both by virtue of their compatibility and their pharmaceutical acceptability. I
The hereinabove described non-solubilizing carrier materials useful herein fall within that class of compounds commonly referred to as skin emollients. As is "recognized in the art, such emollient materials are often employed in conjunction with many of the materials hereinabove referred to as solvents for the sodium and lithium tetraarylboron compounds. Such combinations of the solvent materials and emollient materials also provide carrier mixtures suitable for use herein in the formulation of antiperspirant compositions containing the sodium or lithium tetraarylboron compounds of formula (1).
Still another class of carriers which are suitably employed with the sodium and lithium tetraarylboron compounds include those halogenated, i.e., chlorinated, fluorinated and chloro-fluorinated, lower molecular weight hydrocarbons which are commercially used as propellants. Many of these materials have vapor pressures of 1 atmosphere, or greater, at temperatures of about 20C, and above, but ,are commonly li'quified under pressure and employed as propellants in aerosol cosmetic formulations. These liq'uified gases can be employed to propel antiperspirant solutions of the sodium or lithium tetraarylboron compound by mixing said solution with the liquified propellant gas under pressure. In an alternate mode, the undissolved, solid sodium or lithium tetraarylboron compound can be suspended in the pressurized liquified gas, itself. Commonly, antiperspirant compositions comprising liquified propellant gases and antiperspirant ingredients also contain one or more emoll'ients of the type hereinbefore noted. Such compositions comprising a dissolved or undissolved sodium or lithium tetraarylboron compound of formula (I), a liquified propellant gas and one or more of said emollient materials are also within the scope of this invention. Antiperspirant compositions comprising from about 0.1 percent to 10 percent, by weight, of an undissolved sodium or lithium tetraarylboron compound of formula (I) in combination with from about percent to percent by weight of liquified propellant gas, from about 2 percent to about 10 percent, by weight, of a compatible, pharmaceutically acceptable emollient as hereinabove disclosed and from about 0.1 percent to 2 percent, by weight, of a suspending agent capable of maintaining the particulate matter in a more-or-less stable suspension are preferred embodiments herein. Suspending agents such as fumed colloidal silica or oleophilic Bentonite clays can be employed herein in the manner well-known to those skilled in the art to help stabilize such aerosol antiperspirant compositions containing the antiperspirant compounds of formula (I).
From the foregoing, it can be seen that antiperspirant compositions comprising a sodium or lithium tetraarylboron compound of formula (I) in combination with all manner of pharmaceutically acceptable emollients, propellants, solvents and suspending agents, and mixtures thereof, which are substantially free from interfering metal cations and amines can be prepared. The sodium and lithium tetraarylboron antiperspirant compounds of formula (I) can therefore be employed in antiperspirant formulations such as sprays, sticks, rollons, aerosols and the like. All manner of additives commonly found in cosmetic formulations can be employed in the preparation of said compositions to provide more cosmetically acceptable products if such additives are substantially free from dissolved cations other than lithium or sodium cations and amines of the type hereinbefore defined.
The following examples are intended only to illustrate the preparation of the sodium and lithium tetraarylboron compounds of formula (I) which can be employed as antiperspirants in the manner'of this invention. The examples are not intended to be an ex haustive compilation of such reactions since it is wellknown to those skilled in the art that the reaction of a triarylboron compound with an appropriate aryl lithium or aryl sodium compound will provide all manner of such sodium and lithium tetraarylboron compounds. As hereinbefore noted, sodium tetraphenylboron, which is one of the most preferred compounds for use herein, is commercially available.
EXAMPLE I Preparation of Lithium tetra-(o-Tolyl)boron An ethereal solution of o-tolylmagnesium bromide is prepared from one mole of o-tolyl bromide and 1.] moles of magnesium turnings in about 1.5 liters of anhydrous diethyl ether, in the manner Slough, et al., J. Chem. Soc., (1955) 108. A solution of 0.3 moles of boron trifluoride in diethyl ether (commercially available BF 'EL O) is added to the o-tolylmagnesium bromide Grignard solution and refluxed briefly. The resulting tri-o-tolylboron compound is recovered by vacuum distillation. A solution of o-tolyl lithium is prepared from lithium shot and o-tolyl bromide in diethyl ether according to the procedure of F. Hein, et al., Z. Anorg. Chem., 141, 161 (1924). The solution of o-tolyl lithium is admixed with an ethereal solution of the tri-o-tolylboron (40C, 24 hours) and the ether removed by vacuum distillation to provide crystals of lithium tetra- (o-tolyl)boron.
In the above process, the o-tolyl lithium is replaced by four equivalents o-tolyl sodium, prepared in analogous fashion using sodium metal, and the BF Et- O is replaced by one equivalent of NaBF and the sodium tetra-(o-tolyl)boron compound is thereby secured.
In the above process, the o-tolylmagnesium bromide is replaced by an equivalent amount of p-methoxyphenyl-magnesium bromide prepared by the reaction of p-methoxyphenyl bromide with magnesium turnings in diethyl ether. The resulting tri-(p-methoxyphenyl)boron is allowed to react with p-methoxyphenyl sodium 1:1 mole basis) in diethyl ether and the resulting sodium tetra-(p-methoxy-phenyl)boron is recovered by crystallization. Sodium tetra-(p-methlbenzoate)boron is prepared in like fashion by reacting BF3-Et O with the Grignard reagent prepared from the methyl ester of p-bromobenzoic acid and subsequently reacting the triarylboron compound with the methyl ester of p-carboxyphenyl sodium.
According to the procedure of Razuvael, et al., CR. Acad. Sci. U.R.S.S., 91, 86 (1953), a-naphthyltriphenylboron is prepared by allowing a 0.321 molar mixture of boron trifluoride etherate and phenyl magnesium bromide to react and then mixing the resulting triphenylboron with a-naphthyl lithium, prepared from a-bromonaphthalene and lithium wire. In like fashion, are prepared lithium triphenyl-p-tolyboron from triphenylboron and p-tolyl lithium, and lithium phenyltri-a-naphthylboron from tri-a-naphthylmagnesium bromide, boron trifluoride etherate and phenyl lithium.
From the foregoing it can be seen that all manner of sodium and lithium tetraarylboron compounds of formula (I) can be prepared by reacting a triarylboron compound with the desired aryllithium or arylsodium compound. Of the sodium and lithium tetraarylboron compounds suitable herein, those compounds wherein the aryl group is phenyl, carboxyphenyl, i.e., benzoic acid derivatives, alkyl esters of benzoic acid, or alkoxyphenyl groups are most preferred. Substituent groups on the phenyl ring can be at any of the ortho, para or meta positions with equivalent antiperspirant results. Especially preferred are those alkoxyl and alkyl ester derivatives of the tetraphenyl boron compounds having lower alkyl groups, i.e., those containing from about one to l0, more preferably one to six, carbon atoms. When the substituent on the phenyl ring is carboxyl, i.e., benzoic acid, the sodium or lithium salt form of the acid is also suitable herein. Examples of such preferred antiperspirants include compounds of formula (I) wherein substituent R is a lower alkyl ester of benzoic acid, especially the ortho-, metaand para-methylbenzoates, and the lower alkoxyphenyl derivatives especially ortho-, paraand meta-methoxyphenyl groups; the sodium salts of these are preferred.
The following are examples of some antiperspirant compositions employing sodium or lithium tetraarylboron compounds of formula (I) as the antiperspiration ingredient in the manner of this invention.
EXAMPLE ll Antiperspirant Powder Percent By Weight Ingredient 15 Sodium tetraphenylboron (powder; having an average particle size below about 37 microns) X5 Talc Application of the above composition to the human skin in amounts of about 1.0 microgram/mm gives good antiperspirant results.
In the above composition, the sodium tetraphenyl- Dichloroditluoromethane and trifluoroethane. :20 weight mixture.
Application of about 0.001 g/mm of the above composition to the skin gives good antiperspirant results.
In the above composition the sodium tetraphenylboron is replaced by an equivalent amount of lithium tetra-(p-butoxyphenyl)boron, sodium tetra-(para-t-butoxyphenyl)boron sodium tetra-(o-tolyl)boron, sodium tetra-(p-methylbenzoate)boron, sodium tetra-(pmethoxyphenyl)boron, sodium tetra-(p-carboxy-phenyl)boron and sodium tetra-(o-decyloxyphenyl)boron, respectively, and equivalent antiperspirant compositions are secured.
EXAMPLE IV Aerosol Solution Antiperspirant Percent By Weight Ingredient 20 Sodium tetraphenylboron 20 Ethyl alcohol isopropyl alcohol (2:1 volume mixture) 0. l Hexchlorophene 0.7 Perfume Balance Propellant* Dichlorodifluoromethane and trifuloroethane, 60:40 weight mixture.
Application of about 1 g/24 cm of the above composition to the skin gives good antiperspirant results.
In the above composition the sodium tetraphenylboron is replaced by an equivalent amount of sodium tetra-(p-methylbenzoate)boron, sodium tetra-(mmethylbenzoate)boron and sodium tetra-(o-methylbenzoate)boron, respectively, and equivalent antiperspirant compositions are secured.
EXAMPLE V Antiperspirant Stick Percent By Weight Ingredient l Sodium tetraphenylboron Polyoxyethylene gel 0.2 Perfume Balance Lanolin Application of about g/24 cm of the above composition to the skin gives good antiperspirant results.
In the above composition the sodium tetraphenylboron is replaced by an equivalent amount of lithium tetra-(o-ethoxyphenyl)boron, lithium tetra-(a-carboxyl)boron, respectively, and equivalent antiperspirant compositions are secured.
EXAMPLE VI Roll-on Antiperspirant Percent By Weight Ingredient 5 Sodium tetraphenylboron 50 Ethyl alcohol 20 Lanolin 20 Isopro yl myristate 0.1 Hexch orophene 0.5 Perfume Balance lsopropyl alcohol Application of about 0.01 g/cm of the above composition to the skin gives good antiperspirant results.
In the above composition the sodium tetraphenylboron is replaced by an equivalent amount of sodium tetra-(p-carboxyphenyl)boron sodium salt form, and sodium tetra-(o-carboxyphenyl)boron, lithium salt form, and equivalent antiperspirant compositions are secured.
The following tests were used to assess the antiperspirant efficacy of sodium tetraphenylboron. In each test the sodium tetraphenylboron was used as an aqueous solution in deionized water.
TEST 1 A 5% (wt.) solution of sodium tetraphenylboron was prepared by dissolving 0.5 g. of sodium tetraphenylboron (commercial material) in 9.5 g. of deionized water. In the test procedure, 1 ml. of the above solution was applied to a l in. square cotton patch which was affixed to the inner forearm of test subjects for one hour. Following this patching procedure, the volunteers were placed in a hot room at 110F and 47 percent relative humidity for a few minutes and the perspiration inhibition on the test portion of the arm was visually estimated using a phenolphthalein test cream by comparing the patched portion with the surrounding forearm skin. The results on three test subjects were as follows:
Subject 2 Subject 3 100% inhibition 90 inhibition Aluminum chlorhydrate, the most commonly used antiperspirant compound, generally gives perspiration inhibition scores of 50 percent to percent in similar tests.
The test procedure was repeated in the same fashion using a solution com rising 1.0 g. of sodium tetraphenylboron m 9.0 g. of eionized water with the following results:
Sub'ect 1 Subject 2 inhibition Subject 3 inhibition 100% inhibition In the above tests, no evidence of skin irritation was noted.
TEST 2 In the following test, the overall antiperspirant efficacy of sodium tetraphenylboron was assessed over a five day test period and compared with the antiperspirant effectiveness of aluminum chlorhydrate, a commonly used antiperspirant, on the same test subjects and under the same test each In this test, the historical perspiration flow from three volunteers was assessed by daily perspiration collections using cotton pads at a temperature of 1 10F and 47 percent relative humidity under conditions wherein the subject exercised for five minutes and then walked for five minutes during axillary perspiration collection; the collected perspiration was weighed to establish each volunteer's normal (historical) perspiration flow under these conditions. Following the establishment of the historical average for each subject, 1 gram of a 10% (wt.) solution of sodium tetraphenylboron in deionized water (prepared fresh eacy day) was applied to the right axilla of each subject for five consecutive days. A freshly prepared 10% (wt.) solution of aluminum chlorhydrate was applied in the same fashion to the left axilla. After five days of such application the perspiration flow rate of the subjects was tested, again at F and 47 percent relative humidity using the exercise-rest procedure noted above, and the perspiration flow rate compared to the historical perspiration flow rate of the individual. On the average of the three individuals tested, the 10 percent sodium tetraphenylboron caused a 35 percent decrease in the absolute quantity of perspiration as compared to a 19 percent decrease for the 10 percent aluminum chlorhydrate.
From the foregoing, it may be seen that the tetraarylboron compounds of formula (I), especially sodium tetraphenyl boron, provide superior antiperspirant activity when applied to human skin.
What is claimed is:
l. A method for inhibiting perspiration comprising applying a perspiration inhibiting effective amount of sodium tetraphenylboron to human skin.
2. A process according to claim 1 wherein the sodium tetraphenylboron is applied to the skin in an amount of at least about 1.0 micrograms per mm of skin.
Claims (1)
- 2. A process according to claim 1 wherein the sodium tetraphenylboron is applied to the skin in an amount of at least about 1.0 micrograms per mm2 of skin.
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US12159171A | 1971-03-05 | 1971-03-05 |
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US00121591A Expired - Lifetime US3726968A (en) | 1971-03-05 | 1971-03-05 | The inhibition of perspiration with sodium tetraphenylboron |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4400543A1 (en) * | 1994-01-11 | 1995-07-13 | Hoechst Ag | Process for the isolation of tetraphenylborates |
EP0889062A1 (en) * | 1996-12-20 | 1999-01-07 | Sumitomo Chemical Company Limited | Method for feeding boron compounds, fine particles of boron compounds, catalyst components for the polymerization of olefins comprising them, and processes for the production of the particles |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2853525A (en) * | 1953-06-20 | 1958-09-23 | Wittig Georg | Process of producing sodium tetraphenylboron |
US2982785A (en) * | 1959-01-07 | 1961-05-02 | Theodore R Mckenzie | Cesium recovery |
US3062708A (en) * | 1960-01-04 | 1962-11-06 | Minnesota Mining & Mfg | Aromatic borane thallophyticides |
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1971
- 1971-03-05 US US00121591A patent/US3726968A/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2853525A (en) * | 1953-06-20 | 1958-09-23 | Wittig Georg | Process of producing sodium tetraphenylboron |
US2982785A (en) * | 1959-01-07 | 1961-05-02 | Theodore R Mckenzie | Cesium recovery |
US3062708A (en) * | 1960-01-04 | 1962-11-06 | Minnesota Mining & Mfg | Aromatic borane thallophyticides |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4400543A1 (en) * | 1994-01-11 | 1995-07-13 | Hoechst Ag | Process for the isolation of tetraphenylborates |
US5600003A (en) * | 1994-01-11 | 1997-02-04 | Hoechst Aktiengesellschaft | Process for isolating tetraphenylborates |
US5693867A (en) * | 1994-01-11 | 1997-12-02 | Hoechst Aktiengesellschaft | Process for isolating tetraphenylborates |
EP0889062A1 (en) * | 1996-12-20 | 1999-01-07 | Sumitomo Chemical Company Limited | Method for feeding boron compounds, fine particles of boron compounds, catalyst components for the polymerization of olefins comprising them, and processes for the production of the particles |
EP0889062A4 (en) * | 1996-12-20 | 2002-05-15 | Sumitomo Chemical Co | Method for feeding boron compounds, fine particles of boron compounds, catalyst components for the polymerization of olefins comprising them, and processes for the production of the particles |
US6613850B1 (en) | 1996-12-20 | 2003-09-02 | Sumitomo Chemical Comoany, Limited | Method for feeding boron compounds, fine particles of boron compounds, catalyst components for the polymerization of olefins comprising them, and processes for the production of the particles |
EP1582525A3 (en) * | 1996-12-20 | 2006-06-07 | Sumitomo Chemical Company, Limited | Boron compound in the form of fine particles, component of catalyst for olefin polymerization comprising the same and method for producing the same |
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