FR289F - Oral compositions for the prevention of cavities - Google Patents
Oral compositions for the prevention of cavities Download PDFInfo
- Publication number
- FR289F FR289F FR157012A FR157012A FR289F FR 289 F FR289 F FR 289F FR 157012 A FR157012 A FR 157012A FR 157012 A FR157012 A FR 157012A FR 289 F FR289 F FR 289F
- Authority
- FR
- France
- Prior art keywords
- acid
- stannous
- oral compositions
- hydroxy
- amino
- 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
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- 239000000203 mixture Substances 0.000 title description 17
- 230000002265 prevention Effects 0.000 title description 2
- 239000002253 acid Substances 0.000 description 18
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 14
- -1 phenyl-thenyl Chemical group 0.000 description 11
- 150000007513 acids Chemical class 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 239000001294 propane Substances 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 6
- 208000002925 dental caries Diseases 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 208000006558 Dental Calculus Diseases 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 4
- 125000004181 carboxyalkyl group Chemical group 0.000 description 4
- 150000002431 hydrogen Chemical group 0.000 description 4
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 4
- 239000002324 mouth wash Substances 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- 229940034610 toothpaste Drugs 0.000 description 4
- 239000000606 toothpaste Substances 0.000 description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229940051866 mouthwash Drugs 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000011321 prophylaxis Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NVCBLOZVMWSNST-UHFFFAOYSA-N OP(=O)OP(O)=O.CNC1=CC=CC=C1 Chemical compound OP(=O)OP(O)=O.CNC1=CC=CC=C1 NVCBLOZVMWSNST-UHFFFAOYSA-N 0.000 description 2
- DKTFTYIPPNOFQR-UHFFFAOYSA-N P(=O)(O)OP(=O)O.CNC(C)O Chemical compound P(=O)(O)OP(=O)O.CNC(C)O DKTFTYIPPNOFQR-UHFFFAOYSA-N 0.000 description 2
- 229910018828 PO3H2 Inorganic materials 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000015218 chewing gum Nutrition 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- LQONHVKOZYJEPV-UHFFFAOYSA-N cyclohexyl(phosphonooxy)phosphinic acid;methane Chemical compound C.OP(O)(=O)OP(O)(=O)C1CCCCC1 LQONHVKOZYJEPV-UHFFFAOYSA-N 0.000 description 2
- NKCWZXPMTVCPSF-UHFFFAOYSA-L difluorostannane Chemical compound F[SnH2]F NKCWZXPMTVCPSF-UHFFFAOYSA-L 0.000 description 2
- XQRLCLUYWUNEEH-UHFFFAOYSA-N diphosphonic acid Chemical compound OP(=O)OP(O)=O XQRLCLUYWUNEEH-UHFFFAOYSA-N 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000002547 new drug Substances 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- JEGNXMUWVCVSSQ-UHFFFAOYSA-N octadec-1-en-1-ol Chemical compound CCCCCCCCCCCCCCCCC=CO JEGNXMUWVCVSSQ-UHFFFAOYSA-N 0.000 description 2
- YCOZIPAWZNQLMR-UHFFFAOYSA-N pentadecane Chemical compound CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 2
- WSDQIHATCCOMLH-UHFFFAOYSA-N phenyl n-(3,5-dichlorophenyl)carbamate Chemical compound ClC1=CC(Cl)=CC(NC(=O)OC=2C=CC=CC=2)=C1 WSDQIHATCCOMLH-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000000069 prophylactic effect Effects 0.000 description 2
- 235000013024 sodium fluoride Nutrition 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229960002799 stannous fluoride Drugs 0.000 description 2
- FTLYMKDSHNWQKD-UHFFFAOYSA-N (2,4,5-trichlorophenyl)boronic acid Chemical compound OB(O)C1=CC(Cl)=C(Cl)C=C1Cl FTLYMKDSHNWQKD-UHFFFAOYSA-N 0.000 description 1
- FTZLOGYLADSPDJ-UHFFFAOYSA-N 1,1-diphosphonoethylphosphonic acid Chemical compound OP(=O)(O)C(C)(P(O)(O)=O)P(O)(O)=O FTZLOGYLADSPDJ-UHFFFAOYSA-N 0.000 description 1
- SFRLSTJPMFGBDP-UHFFFAOYSA-N 1,2-diphosphonoethylphosphonic acid Chemical compound OP(O)(=O)CC(P(O)(O)=O)P(O)(O)=O SFRLSTJPMFGBDP-UHFFFAOYSA-N 0.000 description 1
- RHWUIRMVPYNGIV-UHFFFAOYSA-N 1,3,4-triphosphonobutan-2-ylphosphonic acid Chemical compound OP(O)(=O)CC(P(O)(O)=O)C(P(O)(O)=O)CP(O)(O)=O RHWUIRMVPYNGIV-UHFFFAOYSA-N 0.000 description 1
- SXGRAKNNKBAFML-UHFFFAOYSA-N 1,3-diphosphonopropan-2-ylphosphonic acid Chemical compound OP(O)(=O)CC(P(O)(O)=O)CP(O)(O)=O SXGRAKNNKBAFML-UHFFFAOYSA-N 0.000 description 1
- XQVZPYZGUUVHEW-UHFFFAOYSA-N 16-phosphonohexadecylphosphonic acid Chemical compound OP(O)(=O)CCCCCCCCCCCCCCCCP(O)(O)=O XQVZPYZGUUVHEW-UHFFFAOYSA-N 0.000 description 1
- MPXCBQCUNKTGGN-UHFFFAOYSA-N CN(C)C.OP(=O)OP(O)=O Chemical compound CN(C)C.OP(=O)OP(O)=O MPXCBQCUNKTGGN-UHFFFAOYSA-N 0.000 description 1
- FOLKCBRADAKWQI-UHFFFAOYSA-N CNC(C)=O.OP(=O)OP(O)=O Chemical compound CNC(C)=O.OP(=O)OP(O)=O FOLKCBRADAKWQI-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- QEIOXKCYFSJIDF-UHFFFAOYSA-N P(=O)(O)OP(=O)(O)OP(=O)O.CC Chemical compound P(=O)(O)OP(=O)(O)OP(=O)O.CC QEIOXKCYFSJIDF-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910008433 SnCU Inorganic materials 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- FRCICXIVPRNPLM-UHFFFAOYSA-N [amino(phosphono)methyl]phosphonic acid Chemical compound OP(=O)(O)C(N)P(O)(O)=O FRCICXIVPRNPLM-UHFFFAOYSA-N 0.000 description 1
- BFDMEODWJJUORJ-UHFFFAOYSA-N [dimethylamino(phosphono)methyl]phosphonic acid Chemical compound CN(C)C(P(O)(O)=O)P(O)(O)=O BFDMEODWJJUORJ-UHFFFAOYSA-N 0.000 description 1
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- RZJRJXONCZWCBN-UHFFFAOYSA-N alpha-octadecene Natural products CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000000675 anti-caries Effects 0.000 description 1
- SYRIRLOOSKFSFC-UHFFFAOYSA-N butane Chemical compound CCCC.CCCC SYRIRLOOSKFSFC-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- JUNWLZAGQLJVLR-UHFFFAOYSA-J calcium diphosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])([O-])=O JUNWLZAGQLJVLR-UHFFFAOYSA-J 0.000 description 1
- 229940043256 calcium pyrophosphate Drugs 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 229940112822 chewing gum Drugs 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 239000000551 dentifrice Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 235000019821 dicalcium diphosphate Nutrition 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical group [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- MBKDYNNUVRNNRF-UHFFFAOYSA-N medronic acid Chemical compound OP(O)(=O)CP(O)(O)=O MBKDYNNUVRNNRF-UHFFFAOYSA-N 0.000 description 1
- 229940102859 methylene diphosphonate Drugs 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 239000002304 perfume 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
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229940081974 saccharin Drugs 0.000 description 1
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 1
- 235000019204 saccharin Nutrition 0.000 description 1
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 1
- 229940085605 saccharin sodium Drugs 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
-
- A—HUMAN NECESSITIES
- 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
- A61K8/55—Phosphorus compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more PâC bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3839—Polyphosphonic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Animal Behavior & Ethology (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Cosmetics (AREA)
Description
REPUBLIQUE FRANĂAISEFRENCH REPUBLIC
MINISTĂRE DD DEVELOPPEMENT INDUSTRIEL ET SCIENTIFIQUEMINISTRY DD INDUSTRIAL AND SCIENTIFIC DEVELOPMENT
SERVICE dm U PROPRIĂTĂ INDUSTRIELLESERVICE OF INDUSTRIAL PROPERTY
1" ADDITION1 "ADDITION
AU BREVET D'INVENTIONPATENT OF INVENTION
JV 7.277 MJV 7.277 M
P.V. n° 157.012 Classification internationale :P.V. 157.012 International Classification:
N° 289 CAM A 61 k // C 07 fN ° 289 CAM A 61 k // C 07 f
Compositions buccales pour la prévention de la carie. (Invention : Robert John Graben-stetter, James Stone Widder et William John Griebstein.)Oral compositions for the prevention of cavities. (Invention: Robert John Graben-stetter, James Stone Widder and William John Griebstein.)
SociĂ©tĂ© dite : THE PROCTER & GAMBLE COMPANY rĂ©sidant aux Ătats-^^j^fĂźtĂȘ<PiCCompany known as: THE PROCTER & GAMBLE COMPANY residing in the United States of America
(.Brevet principal pris le 29 décembre 1967.) ^if. IndL. Cfldo133The main claim taken on December 29, 1967. Indl. Cfldo133
DemandĂ©e le 28 juin 1968, Ă 12" 10", Ă Paris. 1 ĂKT. >371 DĂ©livrĂ©e par arrĂȘtĂ© du 8 dĂ©cembre 1969.Requested June 28, 1968, at 12:10, in Paris. 1 ĂKT. > 371 Issued by decree of December 8, 1969.
(Bulletin officiel de la Propriété industrielle [B.S.M.], n° 3 du 19 janvier 1970.)(Official Bulletin of Industrial Property [B.S.M.], No. 3 of 19 January 1970.)
La présente invention concerne des perfectionnements, changements et additions au brevet principal dans lequel on a décrit de nouveaux gem-diphosphonates distanneux, et des compositions buccales, contenant ces produits pour la prophylaxie de la carie et du tartre. En particulier, on a décrit les sels distanneux des acides gem-diphos-phoniques de formule :The present invention relates to improvements, changes and additions to the main patent in which new distanous gem-diphosphonates, and oral compositions, containing these products for the prophylaxis of caries and calculus have been disclosed. In particular, the distanous salts of gem-diphos-phonic acids of formula
Ri\r/P0>H'Ri \ r / P0> H '
R/ XP03H:R / XP03H:
dans laquelle Ri est choisi parmi l'hydrogÚne, les halogÚnes, les groupes hydroxyle, benzyle, alcoyle, hydroxyalcoyle, méthoxyalcoyle ou carboxyalcoyle contenant de 1 ù 12 atomes de carbone et R2 est choisi parmi l'hydrogÚne, les halogÚnes, les groupes hydroxyle, acétyle, phényle, benzyle et slcoyle, hydroxyalcoyle, méthoxyalcoyle ou carboxyalcoyle contenant de 1 à 12 atomes de carbone.wherein R1 is selected from hydrogen, halogen, hydroxyl, benzyl, alkyl, hydroxyalkyl, methoxyalkyl or carboxyalkyl containing from 1 to 12 carbon atoms and R2 is selected from hydrogen, halogens, hydroxyl groups, acetyl, phenyl, benzyl and alkyl, hydroxyalkyl, methoxyalkyl or carboxyalkyl containing from 1 to 12 carbon atoms.
Les compositions buccales décrites sont utilisées sous forme de : pùte dentifrice, collutoire, chewing gum, pùte prophylactique, solutions locales etc., contenant (1) un fluorure soluble en quantité suffisante pour donner de 100 à 4.000 ppm environ d'ion fluorure et (2) de 0,05 à 5,0 % en poids d'un sel distanneux d'un acide gem-diphosphonique décrit ci-dessus, le pH de la composition étant compris entre 2,5 et 7,0 environ.The oral compositions described are used in the form of: toothpaste, mouthwash, chewing gum, prophylactic paste, local solutions, etc., containing (1) a soluble fluoride in an amount sufficient to give from 100 to about 4000 ppm of fluoride ion and ( 2) from 0.05 to 5.0% by weight of a distillate salt of a gem-diphosphonic acid described above, the pH of the composition being from about 2.5 to about 7.0.
On a maintenant découvert de nouveaux polyphosphonates stanneux qui résistent à l'hydrolyse et à la transformation en espÚces inactives lorsqu'ils sont utilisés dans des compositions par voie buccale. En outre, ces polyphosphonates stanneux nouvellement découverts possÚdent aussi les propriétés 0 210030 7Novel stannous polyphosphonates have now been found which are resistant to hydrolysis and transformation into inactive species when used in oral compositions. In addition, these newly discovered stannous polyphosphonates also possess the properties 0 210030 7
anti-carie et anti-tartre des gem-diphosphonates distanneux décrits.anti-caries and anti-scale distal gem-diphosphonates described.
Les polyphosphonates stanneux conformes Ă l'invention sont les sels stanneux des acides poly-phosphoniques de formules :The stannous polyphosphonates according to the invention are the stannous salts of polyphosphonic acids of formulas:
(1) R."(1) R. "
h 1h 1
CC
POjĂźI,POjĂźI,
-r.-r.
POjHjPOjHj
(11) r3-ç-r4(11) r3-c-r4
p03h,P03H,
dans lesquelles Ri et R2 sont tous deux choisis parmi l'hydrogÚne et le groupe CH2OH; n est un entier de 2 à 10; Rj est choisi parmi les groupes phénylé-thényle, amino, amino-substitué (par exemple diméthylamino, diéthylamino, N - hydroxy - N -éthy-lamino et acétylamino),-CHj-P03H2, -CHfPOjHß) (OH), -CH2CH(P03H2)2, -CH2CH2POSH2, cyclo-alcoyle (par exemple cyclopropyle, cyclobutyle, cyclopentvle et cyclohexyle), alcoyle contenant de 13 à 20 atomes de carbone et alcényle contenant de 2 à 20 atomes de carbone; R4 est choisi parmi l'hydrogÚne, les groupes amino, hydroxyle, -CH2-PO3H2, aryle, benzyle, et alcoyle, hydroxyalcoyle, méthoxyalcoyle ou carboxyalcoyle contenant de 1 à 12 atomes de carbone.wherein R 1 and R 2 are both selected from hydrogen and CH 2 OH; n is an integer of 2 to 10; R 1 is selected from phenyl-thenyl, amino, amino-substituted (eg, dimethylamino, diethylamino, N-hydroxy-N -ethylamino and acetylamino), -CH 2 -P0 3H 2, -CH 2 PO 2 H (OH), -CH 2 CH ( P03H2) 2, -CH2CH2POSH2, cycloalkyl (for example cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl), alkyl containing from 13 to 20 carbon atoms and alkenyl containing from 2 to 20 carbon atoms; R4 is selected from hydrogen, amino, hydroxyl, -CH2-PO3H2, aryl, benzyl, and alkyl, hydroxyalkyl, methoxyalkyl or carboxyalkyl containing from 1 to 12 carbon atoms.
Parmi les acides polyphosphoniques de formule I ci-dessus utilisables pour préparer les polyphosphonates stanneux correspondants, conformes à l'invention, on peut citer les composés suivants : acide propane triphosphonique-1,2,3;Among the polyphosphonic acids of formula I above that can be used to prepare the corresponding stannous polyphosphonates, according to the invention, mention may be made of the following compounds: propane-1,2,3-triphosphonic acid;
acidc butane tétraphosphonique-1,2,3,4;butane butane 1,2,3,4-tetraphosphonic acid;
acide hexane-hexaphosphonique-1,2,3,4,5,6 ;hexane-hexaphosphonic acid-1,2,3,4,5,6;
acide hydroxv-l-hcxane pentaphosphnniqu^-2.3,4,hydroxyl-1-hexane pentaphosphinic acid -2.3.4,
5,6;5.6;
[289 CAM/7.227 M) â[289 CAM / 7.227 M) -
acide dihydroxy-1,6 - hexanetétraphosphonique-2,3,4^;2,3,4-dihydroxy-hexanetetraphosphonic acid;
acide pentane pentaphosphonique-1,2,3,4,5;pentane pentaphosphonic acid 1,2,3,4,5;
acide heptane heptaphosphonique-1,2,3,4,5,6,7 ; acide octane octaphosphonique-1,2,3,4,5,6,7,8; acide nonane nonaphosphonique-1,2,3,4,5,6,7,8,9. L'acide propane triphosphonique-l ,2,3, l'acide butane tĂ©traphosphonique-1,2,3,4 et les acides poly-phosphoniques vicinaux aliphatiques supĂ©rieurs citĂ©s ci-dessus peuvent ĂȘtre prĂ©parĂ©s en faisant rĂ©agir un aicyne de formule gĂ©nĂ©rale R'-(C » C)m â CHzX, dans laquelle R' est de l'hydrogĂšne ou un radical -CHjX, et X est un atome d'halogĂšne, ou un radical hydroxyle, m est un nombre entier de 1 Ă 4, avec un ester de phosphite dialkyie acide, le radical alkyle contenant de 1 Ă "6 atomes de carbone, en prĂ©sence de sodium, de potassium, de lithium ou de l'un de leurs hydrures, l'ester obtenu est transformĂ© ensuite en l'acide correspondant de façon connue en soi.heptane heptaphosphonic acid 1,2,3,4,5,6,7; octane octaphosphonic acid 1,2,3,4,5,6,7,8; 1,2,3,4,5,6,7,8,9 nonaphosphonic nonane acid. The propane triphosphonic acid-1,2,3, butane-1,2,3,4-tetraphosphonic acid and the higher aliphatic vicinal polyphosphonic acids mentioned above can be prepared by reacting an aicyne of general formula R In which R 'is hydrogen or a radical -CH 1 X, and X is a halogen atom, or a hydroxyl radical, m is an integer of 1 to 4, with an acid dialkyl phosphite ester, the alkyl radical containing from 1 to 6 carbon atoms, in the presence of sodium, potassium, lithium or one of their hydrides, the ester obtained is then converted into corresponding acid in a manner known per se.
Les acides polyphosphoniques vicinaux aliphatiques supĂ©rieurs indiquĂ©s ci-dessus peuvent ĂȘtre prĂ©parĂ©s par un procĂ©dĂ© dĂ©crit par D. AUan Nichol-son et Darrel Campbell dans leur demande de brevet des Ătats-Unis d'AmĂ©rique n° de sĂ©rie 693.898 dĂ©posĂ©e le 27 dĂ©cembre 1967.The higher aliphatic vicinal polyphosphonic acids listed above may be prepared by a method described by D. AUan Nichol-son and Darrel Campbell in US Patent Application Serial No. 693,898 filed December 27, 1967.
Les acides polyphosphoniques reprĂ©sentĂ©s par la formule II ci-dessus, d'oĂč dĂ©rivent les gem-poly-pbosphonates stanneux conformes Ă l'invention sont les suivants :The polyphosphonic acids represented by formula II above, from which the stannous gem-poly-phosphonates derived according to the invention are derived, are as follows:
acide Ă©thanetriphosphonique-1,1,2;1,1,2-ethanetriphosphonic acid;
acide propane tétraphosphonique-1,1,3,3;1,1,3,3-tetraphosphonic propane acid;
acide amino ⹠1 ⹠éthanediphosphonique-1,1; acide hydroxy-l-propanetriphosphonique-1,1,3 ; acide hydroxy - 2 - éthanetriphosphonique-1,1,2; acide méthane cydohexyihydroxy diphosphoni-que;amino acid ⹠1 ⹠ethanediphosphonic-1,1; hydroxy-1-propanetriphosphonic acid-1,1,3; hydroxy-2-ethanetriphosphonic acid-1,1,2; methane-cyclohexylhydroxy diphosphonic acid;
acide tétradécane diphosphonique-1,1;1,1-tetradecane diphosphonic acid;
acide hexadécane diphosphonique-1,1;hexadecane diphosphonic acid-1,1;
acide octadécane diphosphonique-1,1 ;1,1-octadecane diphosphonic acid;
acide hydroxy - 1 - pentĂšne - 4 - diphosphonique-hydroxy-1-pentene-4-diphosphonic acid
1.1; .1.1; .
acide hydroxy - 1 - octadécÚne - 9 - diphospho-nique - 1,1 phényl - 3 - diphosphono - 1,1 - pro-pÚne ⹠2;hydroxy - 1 - octadecene - 9 - diphosphonic acid - 1,1 phenyl - 3 - diphosphono - 1,1 - propene ⹠2;
acide phénylamino méthane diphosphonique ;phenylamino methane diphosphonic acid;
acide naphtyiamino méthane diphosphonique; acide N,N - diméthylamino méthane diphosphonique;naphthylamino methane diphosphonic acid; N, N-dimethylamino methane diphosphonic acid;
acide N - (hydroxy - 2 - éthyl)amino méthane diphosphonique ;N - (hydroxy - 2 - ethyl) amino methane diphosphonic acid;
acide N - acétylamino méthane diphosphonique; acide aminométhane diphosphonique.N - acetylamino methane diphosphonic acid; aminomethane diphosphonic acid.
L'acide Ă©thane triphosphonique 1,1,2 et les composĂ©s voisins de formule II peuvent ĂȘtre prĂ©parĂ©s par le procĂ©dĂ© dĂ©crit dans « Journal of the Chemical Society » (Londres) juin 1963, pages 3351 Ă 3360. L'acide propane tĂ©traphosphonique-1,1,3,3, et les composĂ©s voisins de formule II peuvent ĂȘtre prĂ©parĂ©s en faisant rĂ©agir un carbanion de mĂ©tal alcalin d'un tĂ©traalkyl mĂ©thylĂšnediphosphonate avec un dihalomĂ©thane en prĂ©sence d'un solvant organique.Ethane triphosphonic acid 1,1,2 and related compounds of formula II can be prepared by the method described in "Journal of the Chemical Society" (London) June 1963, pages 3351 to 3360. Propane tetraphosphonic acid-1 , 1,3,3, and related compounds of formula II may be prepared by reacting an alkali metal carbanion of a tetraalkyl methylenediphosphonate with a dihalomethane in the presence of an organic solvent.
D'autres composĂ©s reprĂ©sentĂ©s par la formule II peuvent ĂȘtre prĂ©parĂ©s par des procĂ©dĂ©s indiquĂ©s dans le brevet principal.Other compounds represented by Formula II may be prepared by methods set forth in the main patent.
Les sels stanneux de chacun des acides polyphosphoniques indiqués ci-dessus sont préparés en faisant réagir des solutions aqueuses des acides respectifs avec SnClß. Dans la présente invention on utilise une quantité de SnCU suffisante pour donner un rapport molaire d'étain stanneux et d'acide polyphosphonique de 2 -1 à 10 : 1, selon le nombre de groupes acides phosphoniques dans le composé. On utilise de préférence une mole d'étain stanneux pour chaque groupe acide phosphonique.The stannous salts of each of the above-mentioned polyphosphonic acids are prepared by reacting aqueous solutions of the respective acids with SnCl 3. In the present invention, a sufficient amount of SnCU is used to give a molar ratio of stannous tin and polyphosphonic acid of 2 -1 to 10: 1, depending on the number of phosphonic acid groups in the compound. One mole of stannous tin is preferably used for each phosphonic acid group.
Le polyphosphonate stanneux préféré conforme à l'invention est le propane triphosphonate-1,2,3 trh-tanneux.The preferred stannous polyphosphonate according to the invention is propane triphosphonate-1,2,3 trh-tanneux.
Du point de vue des compositions, le présente invention a pour objet des compositions buccales pour la prophylaxie du tartre et de la carie comprenant (1) un fluorure soluble dans l'eau en quantité suffisante pour donner de 100 à 4 000 ppm environ d'ion fluorure et (2) de 0,05 à 5,0 % environ d'un polyphosphonate stanneux décrit précédemment, le pH de cette solution étant compris entre 2,5 et 7,0 environ.From the viewpoint of the compositions, the present invention is directed to oral compositions for the prophylaxis of tartar and caries comprising (1) a water-soluble fluoride in an amount sufficient to provide from about 100 to about 4000 ppm of fluoride ion and (2) from about 0.05 to 5.0% of a stannous polyphosphonate described above, the pH of this solution being between about 2.5 and 7.0.
D'autres détails tels que des exemples de fluorures utilisables, la description des composants du dentifrice et les concentrations préférées de ces composants sont donnés dans le brevet principal.Other details such as examples of usable fluorides, description of dentifrice components and preferred concentrations of these components are given in the main patent.
Les exemples suivants sont représentatifs des compositions buccales conformes à l'invention.The following examples are representative of the oral compositions according to the invention.
Exemple 1.Example 1
On prépare par les procédés courants une pùte dentifrice ayant la composition suivante :A toothpaste having the following composition is prepared by common methods:
%%
âąn poid»⹠n weight
Pyrophosphate de calcium 37,80Calcium pyrophosphate 37.80
Sorbitol (solution aqueuse Ă 30 %) 19,38Sorbitol (30% aqueous solution) 19.38
Glycérine 9,69Glycerin 9.69
Carboxyméthylcellulose sodique 1,02Sodium carboxymethylcellulose 1,02
Silicate de magnésium et d'aluminium.... 0,39Silicate of magnesium and aluminum .... 0,39
Lauryl sulfate de sodium 2,35Sodium lauryl sulfate 2,35
Saccharine sodique 0,14Saccharin sodium 0.14
Parfum et colorant 1,45Fragrance and coloring 1.45
Fluorure stanneux 0,39Stannous fluoride 0.39
Ăthane triphosphonate-l,l,2-tristanneux.... 0,48Ethane triphosphonate-1,1,2-tristnose .... 0,48
Eau, pH 6,2 complémentWater, pH 6.2 supplement
La pĂąte dentifrice de cet exemple aprĂšs avoir Ă©tĂ© soumise Ă des essais dĂ©crits au brevet principal, .âąâą'esl rĂ©vĂ©lĂ©e contenir des teneurs en Ă©tain stanneux sensiblement plus Ă©levĂ©es aprĂšs vieillissementThe toothpaste of this example having been subjected to tests described in the main patent, has been shown to contain substantially higher stannous tin contents after aging.
qu'une composition tĂ©moin formulĂ©e avec des concentrations Ă©quivalentes d'Ă©tain stanneux mais sans Ă©thane triphosphonate âą 1,1,2 tiistanneux. Cette composition, appliquĂ©e Ă la brosse de la maniĂšre habituelle, retarde la formation de la carie dentaire et du tartre mĂȘme aprĂšs conservation prolongĂ©e.a control composition formulated with equivalent concentrations of stannous tin but without ethane triphosphonate âą 1,1,2 tiistanneux. This composition, applied to the brush in the usual way, delays the formation of tooth decay and tartar even after prolonged storage.
On obtient des résultats sensiblement équivalents en utilisant à la place de l'éthane triphospho-nate-1,1,2 tristanneux dans la pùte dentifrice de cet exemple, du propane triphosphonate-1,2,3-tristanneux, du butane tétraphosphonate 1,2,3,4-tétrastamieux, de l'hexane hexaphosphonate-1,2,3, 4,5,6 hexastanneux et du dihydroxy-1,6 hexane tétraphosphonate-2,3,4,5-tétrastanneux.Substantially equivalent results are obtained by using instead of ethane triphosphonate-1,1,2 tristane in the toothpaste of this example, propane triphosphonate-1,2,3-tristane, butane tétraphosphonate 1, 2,3,4-tetrastamous, hexane hexaphosphonate-1,2,3,4,5,6 hexastanneux and 1,6-dihydroxyhexane tétraphosphonate-2,3,4,5-tétrastanneux.
Exemple 2.Example 2
On prépare par les procédés habituels un collutoire ayant la formule suivante :Usual methods of preparing a mouthwash having the following formula:
%%
âąn poidsâą n weight
Ăthanol (aqueux Ă 50 %) 83,00Ethanol (50% aqueous) 83.00
Glycérine 13,76Glycerin 13,76
Parfum 0,85Perfume 0,85
Saccharine 0,12Saccharin 0.12
Fluorure de sodium 0,27Sodium fluoride 0.27
Propane tétraphosphonate-1,1,3,3- tétras-Propane tetraphosphonate-1,1,3,3-grouse
tanneux 2,00tanneux 2.00
pH 6,5pH 6.5
Utilisé de la maniÚre habituelle le collutoire de cet exemple est un prophylactique efficace de la carie et du tartre. Des teneurs notables en étain stanneux disponible ne varient pas pendant la conservation du produit.Used in the usual way the mouthwash of this example is an effective prophylactic of caries and tartar. Notable levels of available stannous tin do not vary during the storage of the product.
On obtient des résultats comparables avec des collutoires formulés comme dans l'exemple II mais en remplaçant l'éthane tétraphosphonate-1,1, 3,3-tétrastanneux par l'un des composants suivants, en quantité suffisante pour donner une concentration équivalente en étain stanneux :Comparable results are obtained with mouthwashes formulated as in Example II but replacing ethane tetraphosphonate-1,1,3,3-tetrastanneux by one of the following components, in an amount sufficient to give an equivalent concentration of tin stannous:
amino - 1 - Ă©thane diphosphonate distanneux hydroxy - 1 - propane triphosphonate-1,1,3 - tris-tanneux ;distanous amino - 1 - ethanediphosphonate hydroxy - 1 - propane triphosphonate - 1,1,3 - tris - tanneux;
hydroxy - 2 - Ă©thane triphosphonate-l,l,2-tris-tanneux;hydroxy-2-ethane triphosphonate-1,1,2-tris-tanneux;
méthane cyclohexylhvdroxydiphosphonate distanneux;distanous cyclohexylhydroxydiphosphonate methane;
hexadécanediphosphonat e-1,1 - distanneux ;hexadecanediphosphonate e-1,1-distannous;
hydroxy - 1 - octadécÚne - 9 - diphosphonate -1,1 -distanneux;hydroxy - 1 - octadecene - 9 - diphosphonate - 1, 1 - diamagnet;
phényl - 3 - diphosphono - 1,1 - propÚne - 2 distanneux.phenyl - 3 - diphosphono - 1,1 - propene - 2 distannous.
Exemple 3.Example 3
On prépare des chewing-gum de formulation conforme à celle de l'exemple XXIII du brevet principal, en remplaçant le pentadécane diphos-Chewing gums of the formulation conforming to that of Example XXIII of the main patent are prepared by replacing pentadecane diphos-
3 â [289 CAM/7.227 MJ3 - [289 CAM / 7.227 MJ
phonate-8,8 distanneux par l'un des composés suivants :a distanous 8,8-phonate by one of the following:
phénylamino méthane diphosphonate distanneux;distanous phenylamino methane diphosphonate;
N,N - diméthylamino méthane diphosphonate distanneux;Distanous N, N-dimethylamino methane diphosphonate;
N - (hydroxy - 2 - éthyl) amino méthane diphosphonate distanneux;Distanous N - (hydroxy - 2 - ethyl) amino methane diphosphonate;
N -acétylaminométhanediphosphonatedistanneux ;N-acetylaminomethanediphosphonatedistanneux;
aninométhanediphosphonate distanneux.distanous aninomethanediphosphonate.
Ces compositions retardent efficacement la carie dentaire et la formation du tartre. La teneur en étain stanneux reste sous forme stable et disponible pendant des périodes prolongées.These compositions effectively retard tooth decay and scale formation. The stannous tin content remains in stable form and is available for prolonged periods.
résuméresume
L'invention a pour objet :The subject of the invention is:
1° A titre de médicaments nouveaux les sels stanneux d'acides polyphosphonique de formules structurales :1 ° As new drugs the stannous salts of polyphosphonic acids of structural formulas:
(1) HiFi t(1) HiFi t
CC
POjH;POJH;
-R,-R,
POjH; (11) R3-Ă-R, POjH,POJH; (11) R3-C-R, POjH,
dans lesquelles Rj et Rz sont choisis parmi l'hydrogÚne et -CH2OH; n est un entier de 2 à 10; Ra est choisi parmi les groupes phényléthényie, amino, amino substitué -CH2PO3H2, -CHfPOjHß) (OH), -CH2CH (P03Hß)2, -CH2-CH2-PO3H2, cycloalcoyle, alcoyle contenant de 13 à 20 atomes de carbone et alcényle contenant de 2 à 20 atomes de carbone ; R« est choisi parmi l'hydrogÚne, les groupes amino, hydroxyle, aryße, benzyie et alcoyle, hydroxyalcoyle, méthoxyalcoyle ou carboxyalcoyle contenant de 1 à 12 atomes de carbone.wherein R 1 and R 2 are selected from hydrogen and -CH 2 OH; n is an integer of 2 to 10; Ra is selected from phenylethenyl, amino, substituted amino -CH2PO3H2, -CHfPOjH1) (OH), -CH2CH (PO3H1) 2, -CH2-CH2-PO3H2, cycloalkyl, alkyl containing from 13 to 20 carbon atoms and alkenyl containing from 2 to 20 carbon atoms; R "is selected from hydrogen, amino, hydroxyl, aryl, benzyl and alkyl, hydroxyalkyl, methoxyalkyl or carboxyalkyl containing from 1 to 12 carbon atoms.
2° A titre de médicament nouveau particulier le propane triphosphonate-1,2,3 tristanneux.(2) As a particular new drug, propane triphosphonate-1,2,3 tristane.
3° Une composition buccale pour la prophylaxie de la carie et du tartre comprenant (1) un fluorure soluble dans l'eau en quantité suffisante pour donner de 100 à 4 000 ppm d'ion fluorure et (2) de 0,05 à 5,0 % environ en poids d'un sel stanneux d'un acide polyphosphonique décrit ci-dessus, le pH de cette composition étant compris entre 2,5 et 7,0.(3) An oral composition for the prophylaxis of caries and tartar, comprising (1) water-soluble fluoride in an amount sufficient to provide from 100 to 4,000 ppm of fluoride ion and (2) from 0,05 to 5 About 0% by weight of a stannous salt of a polyphosphonic acid described above, the pH of this composition being between 2.5 and 7.0.
4° Dans une telle composition la caractéristique complémentaire suivant laquelle le fluorure est le fluorure stanneux ou le fluorure de sodium.4. In such a composition the complementary characteristic according to which the fluoride is stannous fluoride or sodium fluoride.
Société dite : THE PROCTER & GAMBLE COMPANYCompany known as: THE PROCTER & GAMBLE COMPANY
Par procuTAtion :By proxy:
Harlé & LéchopiezHarlé & Lechopiez
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US60561466A | 1966-12-29 | 1966-12-29 | |
FR134223A FR7277M (en) | 1966-12-29 | 1967-12-29 |
Publications (1)
Publication Number | Publication Date |
---|---|
FR289F true FR289F (en) | 1970-01-19 |
Family
ID=24424452
Family Applications (4)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
FR134224A Expired FR1565412A (en) | 1966-12-29 | 1967-12-29 | |
FR134223A Expired FR7277M (en) | 1966-12-29 | 1967-12-29 | |
FR157013A Expired FR95095E (en) | 1966-12-29 | 1968-06-28 | Process for the preparation of distannous compounds. |
FR157012A Expired FR289F (en) | 1966-12-29 | 1968-06-28 | Oral compositions for the prevention of cavities |
Family Applications Before (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
FR134224A Expired FR1565412A (en) | 1966-12-29 | 1967-12-29 | |
FR134223A Expired FR7277M (en) | 1966-12-29 | 1967-12-29 | |
FR157013A Expired FR95095E (en) | 1966-12-29 | 1968-06-28 | Process for the preparation of distannous compounds. |
Country Status (11)
Country | Link |
---|---|
AT (1) | AT279051B (en) |
BE (1) | BE717257A (en) |
CH (1) | CH494034A (en) |
DE (1) | DE1668572B2 (en) |
DK (1) | DK120653B (en) |
FR (4) | FR1565412A (en) |
GB (1) | GB1160640A (en) |
IT (1) | IT1003503B (en) |
NL (1) | NL162834C (en) |
NO (1) | NO125658B (en) |
SE (1) | SE348939B (en) |
Families Citing this family (5)
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JPS5846483B2 (en) | 1979-09-20 | 1983-10-17 | ă©ă€ăȘăłæ ȘćŒäŒç€Ÿ | Oral composition |
GB8419489D0 (en) * | 1984-07-31 | 1984-09-05 | Leo Pharm Prod Ltd | Chemical compounds |
US7404967B2 (en) | 1994-12-21 | 2008-07-29 | Cosmederm, Inc. | Topical product formulations containing strontium for reducing skin irritation |
WO2014100930A1 (en) | 2012-12-24 | 2014-07-03 | Colgate-Palmolive Company | Oral care composition |
US20210290765A1 (en) * | 2020-03-11 | 2021-09-23 | Advansix Resins & Chemicals Llc | Surfactants for healthcare products |
-
1967
- 1967-12-15 AT AT1135467A patent/AT279051B/en not_active IP Right Cessation
- 1967-12-16 DE DE1668572A patent/DE1668572B2/en active Granted
- 1967-12-27 IT IT41677/67A patent/IT1003503B/en active
- 1967-12-27 SE SE17824/67A patent/SE348939B/xx unknown
- 1967-12-28 NO NO171187A patent/NO125658B/no unknown
- 1967-12-28 CH CH1824167A patent/CH494034A/en not_active IP Right Cessation
- 1967-12-29 FR FR134224A patent/FR1565412A/fr not_active Expired
- 1967-12-29 DK DK666467AA patent/DK120653B/en unknown
- 1967-12-29 GB GB59117/67A patent/GB1160640A/en not_active Expired
- 1967-12-29 FR FR134223A patent/FR7277M/fr not_active Expired
-
1968
- 1968-06-27 NL NL6809107.A patent/NL162834C/en not_active IP Right Cessation
- 1968-06-27 BE BE717257A patent/BE717257A/xx not_active IP Right Cessation
- 1968-06-28 FR FR157013A patent/FR95095E/en not_active Expired
- 1968-06-28 FR FR157012A patent/FR289F/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
DE1668572B2 (en) | 1975-07-31 |
FR7277M (en) | 1969-09-22 |
FR95095E (en) | 1970-06-19 |
CH494034A (en) | 1970-07-31 |
GB1160640A (en) | 1969-08-06 |
NO125658B (en) | 1972-10-16 |
DE1668572A1 (en) | 1971-09-02 |
SE348939B (en) | 1972-09-18 |
IT1003503B (en) | 1976-06-10 |
BE717257A (en) | 1968-12-27 |
AT279051B (en) | 1970-02-25 |
NL162834B (en) | 1980-02-15 |
DK120653B (en) | 1971-06-28 |
FR1565412A (en) | 1969-05-02 |
NL162834C (en) | 1980-07-15 |
NL6809107A (en) | 1969-12-30 |
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