WO2001005797A1 - Composes de titane, leur preparation et utilisation - Google Patents

Composes de titane, leur preparation et utilisation Download PDF

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Publication number
WO2001005797A1
WO2001005797A1 PCT/FR2000/001994 FR0001994W WO0105797A1 WO 2001005797 A1 WO2001005797 A1 WO 2001005797A1 FR 0001994 W FR0001994 W FR 0001994W WO 0105797 A1 WO0105797 A1 WO 0105797A1
Authority
WO
WIPO (PCT)
Prior art keywords
agents
composition
formula
use according
oral use
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.)
Ceased
Application number
PCT/FR2000/001994
Other languages
English (en)
French (fr)
Inventor
Claudine Finidori
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sanofi Aventis France
Original Assignee
Sanofi Synthelabo SA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority to AU62968/00A priority Critical patent/AU783307B2/en
Priority to BRPI0012475 priority patent/BRPI0012475B8/pt
Priority to AT00949690T priority patent/ATE251170T1/de
Priority to IL14732000A priority patent/IL147320A0/xx
Priority to DE60005690T priority patent/DE60005690T2/de
Priority to HU0202803A priority patent/HUP0202803A2/hu
Priority to CA2378855A priority patent/CA2378855C/en
Priority to DK00949690T priority patent/DK1202996T3/da
Priority to JP2001511456A priority patent/JP5031160B2/ja
Priority to MXPA02000603A priority patent/MXPA02000603A/es
Priority to HK02107572.9A priority patent/HK1046000B/zh
Application filed by Sanofi Synthelabo SA filed Critical Sanofi Synthelabo SA
Priority to BR0012475-3A priority patent/BR0012475A/pt
Priority to NZ516454A priority patent/NZ516454A/xx
Priority to US10/031,087 priority patent/US6761879B1/en
Priority to EP00949690A priority patent/EP1202996B9/fr
Priority to SI200030264T priority patent/SI1202996T1/xx
Publication of WO2001005797A1 publication Critical patent/WO2001005797A1/fr
Priority to IL147320A priority patent/IL147320A/en
Priority to NO20020156A priority patent/NO20020156L/no
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/28—Titanium 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
    • 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
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/29—Titanium; Compounds thereof
    • 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
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/36—Carboxylic acids; Salts or anhydrides thereof
    • A61K8/368—Carboxylic acids; Salts or anhydrides thereof with carboxyl groups directly bound to carbon atoms of aromatic rings
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P1/00—Drugs for disorders of the alimentary tract or the digestive system
    • A61P1/02—Stomatological preparations, e.g. drugs for caries, aphtae, periodontitis
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • C07C51/418—Preparation of metal complexes containing carboxylic acid moieties
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages

Definitions

  • the invention relates to new compounds derived from titanium, as well as to their preparation.
  • the invention also relates to compositions for oral use comprising such compounds derived from titanium.
  • TiF 4 titanium tetrafluoride
  • Titanium tetrafluoride does however have the drawback of having a high acidity in aqueous solution (pH of the order of 1.5) which is aggressive for mineralized tissues and not compatible with physiological pH.
  • Titanium tetrafluoride also has the disadvantage of being relatively unstable, especially in aqueous solution.
  • the invention aims to remedy these drawbacks, by proposing compounds derived from titanium IV containing fluorine, capable of forming a glaze on the surface of the tooth, usable in aqueous solution and at physiological pH varying from approximately 6 , 5 to about 7.5.
  • the compounds of formula (I) may contain one or more asymmetric carbon atoms. They can therefore exist in the form of enantiomers or diastereoisomers. These enantiomers, diastereoisomers, as well as their mixtures, including racemic mixtures, form part of the invention.
  • the compounds of the present invention can exist in the form of free bases or of addition salts with pharmaceutically acceptable acids. All these forms are part of the invention.
  • compounds L which can be used are in particular the benzoic acid derivatives, in particular hydroxy-2-benzoic acid of formula:
  • the compounds derived from titanium (IV) of the invention can be prepared by reacting solid titanium IV fluoride at room temperature with a solution of benzoic acid in an anhydrous solvent such as acetonitrile, under a nitrogen atmosphere.
  • the invention also aims to protect compositions for oral use comprising at least one compound according to the invention as well as the use of the titanium derivative compounds according to the invention, as a protective agent against dental caries.
  • compositions of the invention comprise at least one compound according to the invention in an amount equivalent to from approximately 10 ppm to approximately 10,000 ppm of fluorine, calculated from the molecular weight of the compound according to the invention.
  • compositions of the invention can be in the various forms customary for compositions for buccal use and in particular in the form of toothpaste or gel, mouthwash, spray, foam, gargle, dental gel or gum chew, balm, paste, varnish, lozenge, tablet, mouthwash, powder, concentrated or non-concentrated solution, the vehicle then being chosen according to the form of use desired.
  • compositions of the invention may contain, in addition to the compound or compounds derived from titanium, as a vehicle or for their own activity, excipients or ingredients usually used in compositions for oral use.
  • compositions of the invention are prepared according to the usual methods corresponding to the vehicles chosen.
  • the physiologically acceptable vehicle can be of a different nature depending on the form chosen for the composition: aqueous solution, hydroalcoholic solution, thickened or not, gum, pasty or solid excipient, etc.
  • the compositions of the invention can also comprise at least one polishing agent in proportions of up to 80% by weight relative to the total weight of the composition.
  • the polishing agents are for example of mineral or organic origin. Their nature may differ depending on the vehicle used for the form chosen.
  • Useful polishing agents include calcium, magnesium, sodium carbonate or bicarbonate, calcium phosphates and sulfates, alumina and hydrated alumina, silicas, oxides, hydroxides, trisilicates and pyrophosphates of magnesium or calcium, or cellulosic compounds obtained by grinding cereal seeds for example.
  • compositions When the compositions are in the form of toothpaste, they may contain a polishing agent in proportions generally of between approximately 2% and approximately 70% by weight, preferably between approximately 15% and approximately 25% by weight. It is generally a mineral abrasive polishing agent consisting of one or more compounds, largely insoluble in water.
  • a polishing agent in proportions generally of between approximately 2% and approximately 70% by weight, preferably between approximately 15% and approximately 25% by weight.
  • It is generally a mineral abrasive polishing agent consisting of one or more compounds, largely insoluble in water.
  • sodium or potassium metaphosphates calcium phosphate dihydrate, dicalcium phosphate, tricalcium phosphate, calcium pyrophosphate, alumina, hydrated aluminas and in particular trihydrates, silicas, aluminum or zirconium silicates, bentonite as well as magnesium orthophosphate or trimagnesium phosphate, calcium and sodium carbonates and bicarbonates.
  • compositions of the invention in the form of toothpaste can also comprise one or more cohesion agents.
  • cohesion agents can be incorporated in proportions ranging up to approximately 10% by weight relative to the total weight of the composition, and preferably between approximately 0.5% and approximately 3% by weight.
  • the cohesion agents can be chosen in particular from natural thickeners such as alginates and pectins, natural gums such as tragacanth, xanthan, guar, carob or carrageenan gums, or synthetic thickeners such as derivatives cellulose, such as the sodium salt of carboxymethylcellulose, methylcellulose, hydroxyalkylcelluloses, crosslinked polyacrylic acids, synthetic carrageenans.
  • the compositions of the invention can comprise one or more sufficiently stable and foaming surfactants.
  • the surfactants that can be used can be anionic, amphoteric, zwitterionic, cationic or non-ionic in nature.
  • the surfactants are present in the compositions of the invention in a weight range varying from approximately 0.01% to approximately 4%, preferably from approximately 0.1% to approximately 2%, relative to the total weight of the composition.
  • compositions of the invention can comprise other active agents used in oral hygiene, in particular agents known for reducing bad breath, such as for example cyclodextrins, or zinc compounds such as for example zinc halides, zinc acetate, zinc citrate or zinc fluoride, chlorhexedine, cetylpyridinium chloride.
  • agents known for reducing bad breath such as for example cyclodextrins
  • zinc compounds such as for example zinc halides, zinc acetate, zinc citrate or zinc fluoride, chlorhexedine, cetylpyridinium chloride.
  • compositions of the invention can also comprise various cohesion agents, thickening agents, antibiotic agents, sweetening, humectant or refreshing agents, peptizing agents, preserving agents, sweetening agents, colorings, flavors, flavoring substances and agents, plasticizing agents, antibacterial agents or bactericides, vitamins, anti-tartar agents, scarring agents, vasomotors, anti-bleeding agents, active agents on the gum, anti-inflammatory agents such as enoloxone, benzydamine, allantoin, permethol, etc.
  • compositions of the invention are present in the compositions of the invention according to the form of use.
  • the vehicle when the composition for buccal use is a spray, can be a hydroalcoholic solution and the composition can also comprise flavors, peptizing agents, sweetening, humectant or refreshing agents.
  • the vehicle can be non-aqueous, aqueous or hydroalcoholic with one or more surfactants and / or one or more thickening agents, and may further comprise bactericidal agents, sweeteners and flavoring substances.
  • composition when in the form of a dental gel, it may also comprise agents active on the gum.
  • composition when in the form of a chewing gum, it comprises at least one natural or synthetic chewable gum, and may also comprise plasticizing agents, vitamins, flavoring or flavoring agents, sweetening agents, humectants, bactericides, preservatives, dyes.
  • chewable gums which can be used are in particular rubber latex, chicle gum, schlong gum, polyvinyl acetate and synthetic elastomers, in particular silicone rubber, butyl rubber and their derivatives and / or mixtures.
  • compositions for buccal use of the invention may also comprise a sweetening agent.
  • a sweetening agent which can be used, mention may be made of sucrose, lactose, fructose, xylitol, sodium cyclamate, maltose or sodium saccharinate, sodium or ammonium glycyrrhizinates, mixtures of alpha-glucosyl / steviolglucoside, D-mannitol, aspartame, Pacesulfam K, sorbitol, lycosin and their mixtures.
  • the sweetening agents are generally present in an amount ranging up to approximately 2% by weight relative to the total weight of the composition.
  • humectants mention may be made of sorbitol, glycerol or xylitol, present as such in concentrations up to 70% by weight.
  • refreshing agents such as menthol or ethylmaltol
  • preservatives chosen from in particular methyl parahydroxybenzoate, propyl parahydroxybenzoate, sodium benzoate, chlorhexedine, at concentrations generally of approximately 1% by weight or less.
  • the flavoring substances which can be used include all those authorized as such in food. For example, there may be mentioned the essences of mint, anise, eucalyptus, cinnamon, cloves, sage, licorice, or fruits such as orange, lemon, tangerine or strawberry.
  • the flavoring substances are generally present in an amount by weight of about 5% or less.
  • compositions of the invention may also comprise an antibacterial agent preferably chosen from in particular essential oils, plant extracts or substances such as cetylpyridinium chloride, alexidine, octinidine, hexetidine, phenoxyethanol, phenethyl alcohol, triclosan, chlorhexidine, cetylpyridinium chloride, delmopinol, in proportions of up to about 10% by weight relative to the total weight of the composition.
  • an antibacterial agent preferably chosen from in particular essential oils, plant extracts or substances such as cetylpyridinium chloride, alexidine, octinidine, hexetidine, phenoxyethanol, phenethyl alcohol, triclosan, chlorhexidine, cetylpyridinium chloride, delmopinol, in proportions of up to about 10% by weight relative to the total weight of the composition.
  • the compounds of the invention have been the subject of biological studies which have demonstrated their properties of forming a glaze on the surface of the tooth and their advantage as substances for the treatment or prevention of dental caries.
  • a fresh tooth sample is placed in a glass ampoule containing moistened cotton and thymol, at a temperature of + 4 ° C.
  • the sample is rid of any soft tissue present on the tooth.
  • the tooth is then polished in a rubber cup containing pumice stone free of fluoride, then rinsed in an ultrasonic bath.
  • the sample is treated with an aqueous solution at pH 5 of the compound (III) of the invention for 10 minutes at 37 ° C.
  • the sample is then washed with water for one minute and a window made on the surface of the tooth is observed by microscopy.
  • the formation of an amorphous protective layer on the surface of the tooth after treatment of the sample with the compound (III) is demonstrated.
  • Vitamin E acetate 0.5 g Sorbitol 70% 28.00 g

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • General Health & Medical Sciences (AREA)
  • Epidemiology (AREA)
  • Birds (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • Emergency Medicine (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Medicinal Chemistry (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Cosmetics (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Medicinal Preparation (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
PCT/FR2000/001994 1999-07-16 2000-07-11 Composes de titane, leur preparation et utilisation Ceased WO2001005797A1 (fr)

Priority Applications (18)

Application Number Priority Date Filing Date Title
HK02107572.9A HK1046000B (zh) 1999-07-16 2000-07-11 鈦化合物，它們的製備方法及其應用
AT00949690T ATE251170T1 (de) 1999-07-16 2000-07-11 Titanverbindungen, deren herstellung und verwendung
IL14732000A IL147320A0 (en) 1999-07-16 2000-07-11 Titanium derived compounds, preparation and use thereof
DE60005690T DE60005690T2 (de) 1999-07-16 2000-07-11 Titanverbindungen, deren herstellung und verwendung
HU0202803A HUP0202803A2 (en) 1999-07-16 2000-07-11 Titanium derived compounds, preparation and use thereof
CA2378855A CA2378855C (en) 1999-07-16 2000-07-11 Titanium derived compounds, preparation and use thereof
DK00949690T DK1202996T3 (da) 1999-07-16 2000-07-11 Titanforbindelser, fremstilling og anvendelse heraf
JP2001511456A JP5031160B2 (ja) 1999-07-16 2000-07-11 チタン誘導化合物、その製造法およびその使用
BR0012475-3A BR0012475A (pt) 1999-07-16 2000-07-11 Compostos de titânio, preparação e utilização dos mesmos
AU62968/00A AU783307B2 (en) 1999-07-16 2000-07-11 Titanium derived compounds, preparation and use thereof
BRPI0012475 BRPI0012475B8 (pt) 1999-07-16 2000-07-11 composto derivado de titânio, seu processo de preparação e utilização, bem como composição para uso oral compreendendo o mesmo.
MXPA02000603A MXPA02000603A (es) 1999-07-16 2000-07-11 Compuestos derivados de titanio, su preparacion y su utilizacion.
NZ516454A NZ516454A (en) 1999-07-16 2000-07-11 Titanium compounds, preparation and use thereof
US10/031,087 US6761879B1 (en) 1999-07-16 2000-07-11 Titanium derived compounds, preparation and use thereof
EP00949690A EP1202996B9 (fr) 1999-07-16 2000-07-11 Composes de titane, leur preparation et utilisation
SI200030264T SI1202996T1 (en) 1999-07-16 2000-07-11 Titanium derived compounds, preparation and use thereof
IL147320A IL147320A (en) 1999-07-16 2001-12-25 Compounds extracted from titanium and their preparation and use
NO20020156A NO20020156L (no) 1999-07-16 2002-01-11 Titanavledede forbindelser, fremstilling og anvendelse derav

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR99/09194 1999-07-16
FR9909194A FR2796383B1 (fr) 1999-07-16 1999-07-16 Composes derives de titane, leur preparation et leur utilisation

Publications (1)

Publication Number Publication Date
WO2001005797A1 true WO2001005797A1 (fr) 2001-01-25

Family

ID=9548142

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/FR2000/001994 Ceased WO2001005797A1 (fr) 1999-07-16 2000-07-11 Composes de titane, leur preparation et utilisation

Country Status (27)

Country Link
US (1) US6761879B1 (enExample)
EP (1) EP1202996B9 (enExample)
JP (1) JP5031160B2 (enExample)
KR (1) KR100688410B1 (enExample)
CN (1) CN1210281C (enExample)
AR (1) AR024748A1 (enExample)
AT (1) ATE251170T1 (enExample)
AU (1) AU783307B2 (enExample)
BR (2) BRPI0012475B8 (enExample)
CA (1) CA2378855C (enExample)
CZ (1) CZ2002136A3 (enExample)
DE (1) DE60005690T2 (enExample)
DK (1) DK1202996T3 (enExample)
ES (1) ES2206282T4 (enExample)
FR (1) FR2796383B1 (enExample)
HK (1) HK1046000B (enExample)
HU (1) HUP0202803A2 (enExample)
IL (2) IL147320A0 (enExample)
MX (1) MXPA02000603A (enExample)
NO (1) NO20020156L (enExample)
NZ (1) NZ516454A (enExample)
PT (1) PT1202996E (enExample)
RU (1) RU2250907C2 (enExample)
TR (1) TR200200070T2 (enExample)
WO (1) WO2001005797A1 (enExample)
YU (1) YU2502A (enExample)
ZA (1) ZA200200222B (enExample)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2844199A1 (fr) * 2002-09-06 2004-03-12 Sanofi Synthelabo Composition pour ameliorer les caracteristiques physico- chimiques de materiaux a base d'apatite, son utilisation et procede pour sa mise en oeuvre
WO2004021970A3 (fr) * 2002-09-06 2004-05-06 Sanofi Synthelabo Composition pour renforcer les materiaux a base d’apatite
FR2852511A1 (fr) * 2003-03-21 2004-09-24 Sanofi Synthelabo Utilisation de derives de titane et de fluor pour la protection contre la coloration des materiaux a base d'apatite, procede de protection contre la coloration des materiaux a base d'apatite

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060239938A1 (en) * 2005-04-25 2006-10-26 Joseph Perechocky Dental balm and method of prevention of damage to teeth
US20080112902A1 (en) * 2005-04-25 2008-05-15 Joseph Perechocky Protective Dental Balm and Method
WO2006127600A2 (en) * 2005-05-23 2006-11-30 Cadbury Adams Usa Llc Confectionery composition including an elastomeric component, a cooked saccharide component, and a flavor
US7851006B2 (en) 2005-05-23 2010-12-14 Cadbury Adams Usa Llc Taste potentiator compositions and beverages containing same
US7851005B2 (en) 2005-05-23 2010-12-14 Cadbury Adams Usa Llc Taste potentiator compositions and beverages containing same
ES2399059T3 (es) 2005-05-23 2013-03-25 Kraft Foods Global Brands Llc Composiciones potenciadoras del dulzor
KR100659139B1 (ko) * 2006-01-11 2006-12-19 (주)아모레퍼시픽 항균력이 우수한 구강용 조성물
RU2340214C2 (ru) * 2006-08-11 2008-12-10 Валерий Маркович Рудницкий Сладкая пищевая смесь
EP2155144B1 (en) * 2007-05-04 2013-11-20 Swissdent Cosmetics AG Oral composition
US10512597B2 (en) * 2007-09-06 2019-12-24 Colgate-Palmolive Company Controlled surface gelling of mucoadhesive polymers on oral mucosa
KR20130040819A (ko) 2010-04-12 2013-04-24 닛토덴코 가부시키가이샤 이온 전도성 유기 무기 복합 입자, 입자 함유 수지 조성물 및 이온 전도성 성형체
JP6058250B2 (ja) 2010-04-12 2017-01-11 日東電工株式会社 粒子分散樹脂組成物、粒子分散樹脂成形体およびそれらの製造方法
MX365710B (es) 2011-04-29 2019-06-11 Intercontinental Great Brands Llc Acido encapsulado, metodo para la preparacion del mismo y goma de mascar que comprende el mismo.
CN108324579A (zh) * 2018-02-27 2018-07-27 苏州凌科特新材料有限公司 一种牙齿修复材料及其制备方法

Non-Patent Citations (1)

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Title
DEAN, PHILIP A. W. ET AL: "Spectroscopic studies of inorganic fluoro complexes. III. fluorine-19nuclear magnetic resonance studies of silicon (IV), germanium(IV), andtitanium(IV) fluoro complexes", J. CHEM. SOC. A (1970), (15), 2569-74, XP002131802 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2844199A1 (fr) * 2002-09-06 2004-03-12 Sanofi Synthelabo Composition pour ameliorer les caracteristiques physico- chimiques de materiaux a base d'apatite, son utilisation et procede pour sa mise en oeuvre
WO2004021970A3 (fr) * 2002-09-06 2004-05-06 Sanofi Synthelabo Composition pour renforcer les materiaux a base d’apatite
FR2852511A1 (fr) * 2003-03-21 2004-09-24 Sanofi Synthelabo Utilisation de derives de titane et de fluor pour la protection contre la coloration des materiaux a base d'apatite, procede de protection contre la coloration des materiaux a base d'apatite

Also Published As

Publication number Publication date
ZA200200222B (en) 2003-04-10
ATE251170T1 (de) 2003-10-15
AR024748A1 (es) 2002-10-23
BR0012475A (pt) 2002-04-02
HUP0202803A2 (en) 2003-03-28
KR100688410B1 (ko) 2007-03-09
DE60005690T2 (de) 2004-07-22
AU783307B2 (en) 2005-10-13
TR200200070T2 (tr) 2002-06-21
CN1210281C (zh) 2005-07-13
PT1202996E (pt) 2004-02-27
FR2796383A1 (fr) 2001-01-19
ES2206282T3 (es) 2004-05-16
MXPA02000603A (es) 2002-07-30
EP1202996B9 (fr) 2004-07-14
ES2206282T4 (es) 2005-03-01
DE60005690D1 (de) 2003-11-06
DK1202996T3 (da) 2004-02-09
JP2003513011A (ja) 2003-04-08
JP5031160B2 (ja) 2012-09-19
NZ516454A (en) 2004-02-27
KR20020013959A (ko) 2002-02-21
EP1202996B1 (fr) 2003-10-01
BRPI0012475B8 (pt) 2021-07-06
YU2502A (sh) 2005-03-15
CN1361785A (zh) 2002-07-31
BRPI0012475B1 (pt) 2011-09-20
NO20020156D0 (no) 2002-01-11
CA2378855C (en) 2010-03-30
CZ2002136A3 (cs) 2002-04-17
NO20020156L (no) 2002-03-15
HK1046000A1 (en) 2002-12-20
BRPI0012475A (pt) 2002-04-02
EP1202996A1 (fr) 2002-05-08
FR2796383B1 (fr) 2002-06-14
IL147320A (en) 2007-06-17
US6761879B1 (en) 2004-07-13
RU2250907C2 (ru) 2005-04-27
HK1046000B (zh) 2004-04-08
AU6296800A (en) 2001-02-05
CA2378855A1 (en) 2001-01-25
IL147320A0 (en) 2002-08-14

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