DK157598B - Anvendelse af gem-diphosphonsyrer som tilsaetning til mund- og tandplejemidler - Google Patents
Anvendelse af gem-diphosphonsyrer som tilsaetning til mund- og tandplejemidler Download PDFInfo
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- DK157598B DK157598B DK411774A DK411774A DK157598B DK 157598 B DK157598 B DK 157598B DK 411774 A DK411774 A DK 411774A DK 411774 A DK411774 A DK 411774A DK 157598 B DK157598 B DK 157598B
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- Prior art keywords
- gem
- oral
- dental care
- water
- additives
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- 239000002253 acid Substances 0.000 title claims description 8
- 150000007513 acids Chemical class 0.000 title claims description 5
- 239000000654 additive Substances 0.000 title description 3
- 150000003839 salts Chemical class 0.000 claims description 11
- BYOBJKVGOIXVED-UHFFFAOYSA-N (2-phosphonoazepan-2-yl)phosphonic acid Chemical compound OP(O)(=O)C1(P(O)(O)=O)CCCCCN1 BYOBJKVGOIXVED-UHFFFAOYSA-N 0.000 claims description 4
- XQRLCLUYWUNEEH-UHFFFAOYSA-N diphosphonic acid Chemical compound OP(=O)OP(O)=O XQRLCLUYWUNEEH-UHFFFAOYSA-N 0.000 claims description 4
- 239000000243 solution Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000008139 complexing agent Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 208000006558 Dental Calculus Diseases 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000003951 lactams Chemical class 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 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 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 235000003599 food sweetener Nutrition 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- -1 phosphorus compound Chemical class 0.000 description 3
- IPNPIHIZVLFAFP-UHFFFAOYSA-N phosphorus tribromide Chemical compound BrP(Br)Br IPNPIHIZVLFAFP-UHFFFAOYSA-N 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 3
- 239000003765 sweetening agent Substances 0.000 description 3
- 239000000606 toothpaste Substances 0.000 description 3
- 239000000341 volatile oil Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- 229910020667 PBr3 Inorganic materials 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 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 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 235000010216 calcium carbonate Nutrition 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 235000011148 calcium chloride Nutrition 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000002324 mouth wash Substances 0.000 description 2
- 229940051866 mouthwash Drugs 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- KFZXVMNBUMVKLN-UHFFFAOYSA-N 4-chloro-5-methyl-2-propan-2-ylphenol Chemical compound CC(C)C1=CC(Cl)=C(C)C=C1O KFZXVMNBUMVKLN-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 102000005701 Calcium-Binding Proteins Human genes 0.000 description 1
- 108010045403 Calcium-Binding Proteins Proteins 0.000 description 1
- IVHVNMLJNASKHW-UHFFFAOYSA-M Chlorphonium chloride Chemical class [Cl-].CCCC[P+](CCCC)(CCCC)CC1=CC=C(Cl)C=C1Cl IVHVNMLJNASKHW-UHFFFAOYSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910018828 PO3H2 Inorganic materials 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- WXQWKYFPCLREEY-UHFFFAOYSA-N azane;ethanol Chemical class N.CCO.CCO.CCO WXQWKYFPCLREEY-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- 150000001674 calcium compounds Chemical class 0.000 description 1
- 229940031956 chlorothymol Drugs 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 208000002925 dental caries Diseases 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 239000002510 pyrogen Substances 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 229910002028 silica xerogel Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229940034610 toothpaste Drugs 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/66—Phosphorus compounds
- A61K31/675—Phosphorus compounds having nitrogen as a ring hetero atom, e.g. pyridoxal phosphate
-
- 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
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing 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
- 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 P—C 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
- C07F9/3873—Polyphosphonic acids containing nitrogen substituent, e.g. N.....H or N-hydrocarbon group which can be substituted by halogen or nitro(so), N.....O, N.....S, N.....C(=X)- (X =O, S), N.....N, N...C(=X)...N (X =O, S)
-
- 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/5532—Seven-(or more) membered rings
-
- 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/572—Five-membered rings
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- Epidemiology (AREA)
- Birds (AREA)
- Medicinal Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- General Chemical & Material Sciences (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Pharmacology & Pharmacy (AREA)
- Cosmetics (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Detergent Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Description
DK 157598 B
Den foreliggende opfindelse angår anvendelse af gem-diphos-phonsyrer som tilsætningsmidler til mund- og tandplejemidler for at hindre dannelse af tandsten.
5 Det er kendt, at 1-aminoalkan-l,1-diphosphonsyrer, der fås ved omsætning af tilsvarende nitriler med phosphortrihalogenid, kan anvendes som kompleksdannere. Således er det kendt fra schweizisk patentskrift nr. 524.371, at phosphonsyrer med formlen 10 po3h2 R3-C-R4 ! 15 PO3H2 hvor R3 f.eks. er en aminogruppe eller en substitueret ami-nogruppe, og R4 f.eks. er hydrogen eller lavere alkyl (jvf. skriftet, sp. 1), har kompleksbindende evne og kan anvendes 20 som tilsætning til mund- og tandplejemidler til hindring af tandstensdannelse.
Ifølge opfindelsen har det vist sig, at den hidtil ukendte forbindelse azacykloheptan-2,2-diphosphonsyre, som har formlen 25
H203P PO3H2 C
l\
30 CHo NH
I I
CH2 CH2
\ I
h2c-ch2 og som således adskiller sig strukturelt fra de kendte phos-phonforbindelser, har en bedre virkning til hindring af tand- 35 2
DK 157598 B
stensdannelse end ovennævnte, kendte forbindelser og desuden har cariesforebyggende virkning.
Anvendelsen ifølge opfindelsen er derfor ejendommelig ved, at 5 der som gem-diphosphonsyre anvendes azacykloheptan-2,2-diphos-phonsyre eller dens vandopløselige salte.
Den hidtil ukendte forbindelse anvendt ifølge opfindelsen kan fremstilles ved, at man omsætter en lactam med formlen 10 .....
/\ ch2 nh
I I
15 CH2 CH2
\ I
CH2-CH2 med phosphortrihalogenider eller phosphorsyrling og phosphor-20 trihalogenider, hydrolyserer reaktionsproduktet og eventuelt omdanner det til saltene.
Omsætningen udføres i almindelighed ved temperaturer mellem 40 og 150°C. Udgangsstoffet kaprolactam er et let tilgængeligt 25 teknisk produkt.
Omsætningen kan udføres således, at man f.eks. smelter lacta-men med phosphorsyrling og langsomt under omrøring tilfører PC13· Det dervecf fremkomne reaktionsprodukt hydrolyseres så.
30 Man kan dog også omsætte den smeltede lactam direkte med phosphortrihalogenider og hydrolysere trinvis. Som phosphortrihalogenider kan der især være tale om phosphortrichlorid og phosphortribromid. Sidstnævnte har vist sig særlig egnet, når lactamen anvendes uden tilsætning af phosphorsyrling. Det mo-35 lære mængdeforhold mellem lactam og phosphorforbindel se ved de beskrevne omsætninger er mellem 1:2 og 1:6, fortrinsvis 1:4.
, DK 157598 B
3
Hydrolysen sker hensigtsmæssigt ved tilsætning af vand til reaktionsblandingen. Den kan dog om ønsket udføres i nærværelse af alkali, især natronlud eller kalilud. I mange tilfælde kan den hidtil ukendte diphosphonsyre også finde anven-5 delse i form af dens vandopløselige salte, især lithium-, natrium-, kalium- og ammoniumsaltene. Syren kan let omdannes til de vandopløselige salte, især ved partiel eller fuldstændig neutralisation med de ønskede baser.
10 Saltene svarer til følgende formel 0 II ^x /· (CH 2 ) 5 p (III)
15 \ C ^OX
\Λ/0Χ
H - N P
lf"ox o 20 hvor X er et hydrogenatom, NH4- eller en metalkation, idet der højst kan være 3 hydrogenatomer til stede.
Den hidtil ukendte 2,2-diphosphonsyre-l-azacykloalkan er et 25 udmærket sekvestreringsmiddel for polyvalente metalioner, især for di- og trivalente metalioner. Den er særligt egnet som kompleksdanner for jordalkalimetalioner.
Den anvendes i mund- og tandplejemidler for at undgå dannelsen 30 af tandsten. Til forhindring af tandsten kan der foruden den frie phosphonsyre i disse midler også anvendes de farmakologisk uskadelige salte såsom natrium-, kalium-, ammonium- og substituerede ammoniumsalte såsom mono-, di- eller triethanol-ammoniumsalte. Både de partielle salte, hvori kun en del af de 35 sure protoner er erstattet med andre kationer, og de fulde salte kan anvendes.
4
DK 157598 B
Der foretrækkes imidlertid salte, som reagerer tilnærmelsesvis neutralt (pH 5-9) i vandig opløsning. Blandinger af de førnævnte salte kan ligeledes anvendes.
5 Det følgende eksempel illustrerer fremstillingen af forbindelsen anvendt ifølge opfindelsen.
Eksempel 1 10 Fremstilling af azacykloheptan-2,2-diphosphonsyre h2o3p po3h2 \/ ! Λ
CH2 NH
-------- I I
ch2 ch2 l / 20 CH2-CH2 a) 113 g kaprolactam (1,0 mol) og 164 g H3PO3 (2,0 mol) blev opvarmet til 100°C, indtil der fremkom en klar smelte. Efter afkøling til 70°C tildryppes 176 ml PC13 (2,0 mol) under om- 25 røring. Blandingen omrøres i 3 timer, og man lader den henstå natten over ved 70°C. Derefter hydrolyseres med 3 liter H20, opløsningen opkoges med aktive kul, og efter filtrering udfældes reaktionsproduktet med acetone. Det hvide stof opløses i vand og passeres over en kationbytter, opløsningen inddampes, 30 og stoffet isoleres ved tilsætning af ethanol. Udbyttet af krystallinsk, i vand tungtopløselig diphosphonsyre er 84 g = 32% af det teoretiske.
b) 56,5 g kaprolactam (0,5 mol) smeltes ved 80°C, og der til-35 sættes langsomt 190 ml PBr3 (2,0 mol). Efter 4 timer hydrolyseres ved langsom tilsætning af 100 ml vand, og til reaktionsblandingen sættes så yderligere 400 ml H20. oparbejdning sker
DK 157598 B
s analogt med punkt a). Udbyttet af krystallinsk diphosphonsyre er 33 g = 25¾ af det teoretiske.
c) 56,5 g kaprolactam (0,5 mol) opløses ved 70°C i 300 ml di-5 oxan, og der tildryppes langsomt 190 ml PBr3 (2,0 mol). Efter 4 timer hydrolyseres ved langsom tildrypning af 500 ml vand. Efter opkogning med aktivt kul og filtrering fraskilles di-oxanfasen, og den vandige fase oparbejdes som i punkt a). Udbyttet var 24 g = 18¾ af det teoretiske.
10
Stoffet udviser efter tørring ved 80°C i vakuumtørreskab en molekylvægt på 260 (titrimetisk, beregnet 259,1).
Beregnet: C 27,81¾ H 5,83¾ N 5,41¾ P 23,91¾ 15 Fundet: C 27,72¾ H 5,64¾ N 5,37¾ P 23,60¾.
I forbindelsens IR-spektrum ligger 6fjn-båndet ved 1610 cm“l. Smeltepunkt 257°C.
20 De føTgende eksempler illustrerer anvendelsen af forbindelsen anvendt ifølge opfindelsen.
Eksempel 2 25 Kompleksbindinq af calcium
Til undersøgelse af kompleksbindingen af calcium blev der anvendt den modificerede Hampshire-prøve og gået frem som beskrevet i det følgende: 30 1,0 g af kompleksdanneren opløses i 50 ml H2O, som er indstillet til pH 11 med NaOH. Til 50 ml af en Ca2+-opløsning (1470 mg CaCl2» 2 H20/1) sættes på én gang 100 ml af en sodaopløsning (7,15 g Na2C03, 10 H2O/I). Fra en burette tildryppes så 35 opløsningen af kompleksdanneren, indtil calciumcarbonatbund-faldet igen er opløst.
DK 157598B
6
Hermed blev opnået binding af 735 mg CaC03/g stof med et forbrug af kompleksdanneropløsning på 3,4 ml.
Praktisk overensstemmende resultater får man, hvis man i ste-5 det for syrerne anvender de tilsvarende natrium-, kalium- eller ammoni umsalte.
Eksempel 3 10 Tærskelværdi
Forhindringen af udfældning af tungtopløselige calciumforbindelser af understøkiometriske mængder af kompleksdanneren undersøges ved stuetemperatur med Hampshire-prøven og ved 60°C 15 samt 95°C med sodasi 1ikatprøven. Der gås frem som følger.
a) Hampshi re-prøven 200 mg af kompleksdanneren opløses i 10 ml H2O (indstillet til 20 pH 11 med NaOH), og der tilsættes 100 ml sodaopløsning (14,3 g Na2C03, 10 H20/1). Fra en burette tildryppes så en calciumopløsning (36,8 g CaCl2, 2 H20/1), indtil der netop opstår en blivende uklarhed.
25 Resultat.
Forbrug af mg CaC03
Ca-opløsning (ml) mg CaCOg_g stof 8,5 212 1060 30 b) Sodasilikatprøve
Til 25 ml 80° varmt vand (Ca:Mg = 4:1) blev der i en 100 ml målekolbe sat inhibitoropløsning (15,0 mg). Efter fortynding 35 med destilleret vand til 65-70 ml blev der tilsat 25 ml af en soda-vandglasopløsning, som gav en slutkoncentration på 4,5 g Na2C03/l og 600 mg natriumsi1ikat/1 (Si02:Na20-forhold 3,36).
DK 157598 ET
7
Efter opfyldning til mærket opvarmes prøven igen i løbet af 20 minutter til 60eC og holdes i 10 minutter ved denne temperatur (tabel II) eller i løbet af 20-30 minutter til 95 “C og holdes i 30 minutter ved 95°C (tabel IV).
5
Derefter bestemmes opløsningens ca1 c iumindho1d, den udfnug-gede mængde samt den inkrustation, der sidder fast på glasset.
Nedenfor er anført analyseresultaterne i procent, idet summen 10 af de fundne værdier blev sat til 100%.
Tabel II
150 mg/1, 60°C
15 CaO CaO CaO
opløsning udfnugget inkrusteret 79,8 " 20,1 0,1
2Q Tabel IV
150 mg/1 95eC CaO CaO CaO opl. udfnug. i nkr.
25 80,0 19,9 0,1
Eksempel 4
Tandpasta 30
Som grundrecepter til tandpastaer er følgende sammensætninger egnede: 35 8
DK 157598 B
a)
Glycerin 60,0 vægtdele
Vand 13,5 "
Natriumcarboxymethylcellulose 0,6 " 5 Kiselsyrexerogel 20,0
Natriuralaurylsulfat 2,0 " Æterisk olie 1,0 " Sødestof 0,4 " 2.2- d i phosphonsyre-l-azacykloheptan 2,5 " 10 b)
Glycerin 30,0 vægtdele
Vand 18,5 "
Natriumcarboxymethylcellulose 1,0 " 15 Aluminiumhydroxid 44,0 "
Natriumlaurylsulfat 1,0 "
Kisel syrepyrogen 1,5 " Æterisk olie 1,5 " Sødestof 0,5 " 20 2,2-diphosphonsyre-l-azacykloheptan 2,0 "
Som grundrecept til mundvand er følgende kombination egnet:
Ethylalkohol 19,5 vægtdele 25 Glycerin 7,5 “
Vand 70,0 " Æterisk olie 0,2 "
Natriumlaurylsulfat 0,1 "
Antiseptikum (chlortymol) 0,1 " 30 Sødestof 0,1 ” 2.2- diphosphonsyre-l-azacykloheptan 2,5 "
Ved regelmæssig brug af tandpastaer og/eller mundvand med et indhold af 2,2-diphosphonsyre-l-azacykloheptan kan dannelsen 35 af tandsten formindskes væsentligt. Dannelsen af hårde kompakte tandbelægninger forhindres vidtgående.
Claims (1)
- ΠΚ 1C7COOD w·' 1 \ :·.·/ OS Ο Π Patent krav. Anvendelse af gem-diphosphonsyrer som tilsætning til mund- og 5 tandplejemidler, kendetegnet ved, at der som gem-diphosphonsyre anvendes azacykloheptan-2,2-diphosphonsyre eller dens vandopløselige salte. 10 15 20 25 30 35
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DK424377A DK140342C (da) | 1973-08-27 | 1977-09-26 | Analogifremgangsmaade til fremstilling af azacykloalkan-2,2-diphosphonsyrer eller vandoploeselige salte deraf |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2343196 | 1973-08-27 | ||
| DE2343196A DE2343196C3 (de) | 1973-08-27 | 1973-08-27 | Aiacycloalkan-2^-diphosphonsäuren oder deren wasserlösliche Salze |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DK411774A DK411774A (da) | 1975-04-28 |
| DK157598B true DK157598B (da) | 1990-01-29 |
| DK157598C DK157598C (da) | 1990-06-11 |
Family
ID=5890837
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK411774A DK157598C (da) | 1973-08-27 | 1974-08-01 | Anvendelse af gem-diphosphonsyrer som tilsaetning til mund- og tandplejemidler |
Country Status (16)
| Country | Link |
|---|---|
| US (1) | US3941772A (da) |
| JP (1) | JPS5710878B2 (da) |
| AT (1) | AT326687B (da) |
| BE (1) | BE819189A (da) |
| BR (1) | BR7407080D0 (da) |
| CA (1) | CA1029020A (da) |
| CH (2) | CH613979A5 (da) |
| DE (1) | DE2343196C3 (da) |
| DK (1) | DK157598C (da) |
| ES (1) | ES429542A1 (da) |
| FR (1) | FR2245372B1 (da) |
| GB (1) | GB1451865A (da) |
| IE (1) | IE39823B1 (da) |
| IT (1) | IT1020069B (da) |
| LU (1) | LU70795A1 (da) |
| NL (1) | NL179908C (da) |
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| DE2456808A1 (de) * | 1974-11-30 | 1976-08-12 | Henkel & Cie Gmbh | Verfahren zum stabilisieren von calcium-hydrogenphosphat-anhydrid gegen die umsetzung mit fluorionen |
| DE2456666A1 (de) * | 1974-11-30 | 1976-08-12 | Henkel & Cie Gmbh | Verfahren zum stabilisieren von calcium-hydrogenphosphat-dihydrat gegen hydrolyse |
| US4118474A (en) * | 1976-08-16 | 1978-10-03 | Colgate-Palmolive Company | Antibacterial oral composition |
| US4118476A (en) * | 1976-08-16 | 1978-10-03 | Colgate-Palmolive Company | Antibacterial oral composition |
| SE431285B (sv) * | 1976-08-16 | 1984-01-30 | Colgate Palmolive Co | Munvardskomposition innehallande en fosfonforening, for minskning av missfergning bildad av ett ingaende kvevehaltigt antibakteriellt plaquehemmande medel |
| US4118475A (en) * | 1976-08-16 | 1978-10-03 | Colgate-Palmolive Company | Antibacterial oral composition |
| US4118473A (en) * | 1976-08-16 | 1978-10-03 | Colgate-Palmolive Company | Antibacterial oral composition |
| US4118472A (en) * | 1976-08-16 | 1978-10-03 | Colgate-Palmolive Company | Antibacterial oral composition |
| NL7711307A (nl) * | 1976-10-19 | 1978-04-21 | Hoechst Ag | Fosforcarbonzuurverbindingen en hun bereiding. |
| DE2745083C2 (de) * | 1977-10-07 | 1985-05-02 | Henkel KGaA, 4000 Düsseldorf | Hydroxydiphosphonsäuren und Verfahren zu deren Herstellung |
| FR2411810A1 (fr) * | 1977-12-14 | 1979-07-13 | Protex Manuf Prod Chimique | Compositions additives pour melanges a base de platre de gypse ou anhydrite |
| DE3027040A1 (de) * | 1980-07-17 | 1982-02-25 | Hoechst Ag, 6000 Frankfurt | Dimethylphosphinyl-alkanphosphonsaeuren, ein verfahren zu ihrer herstellung und ihre verwendung als gipsabbindeverzoegerer |
| US4466835A (en) * | 1983-04-18 | 1984-08-21 | The Dow Chemical Company | Cement compositions containing set retarders |
| US4466836A (en) * | 1983-04-28 | 1984-08-21 | The Dow Chemical Company | Set retarding compounds for use in cement slurries |
| US4468252A (en) * | 1983-06-01 | 1984-08-28 | The Dow Chemical Company | Set retarding additives for cement from aminomethylenephosphonic acid derivatives |
| US4569838A (en) * | 1983-12-23 | 1986-02-11 | Colgate-Palmolive Company | Dentifrice |
| GB2157279A (en) * | 1984-04-12 | 1985-10-23 | Dow Chemical Co | Well treating composition |
| US4606776A (en) * | 1984-09-28 | 1986-08-19 | Salis International, Inc. | Air brush cleaning unit |
| DE3439094A1 (de) * | 1984-10-25 | 1986-05-07 | Henkel KGaA, 4000 Düsseldorf | Mund- und zahnpflegemittel |
| US4575456A (en) * | 1984-11-30 | 1986-03-11 | Colgate-Palmolive Company | Gel dentifrice of desirable consistency |
| IL77243A (en) * | 1984-12-21 | 1996-11-14 | Procter & Gamble | Pharmaceutical compositions containing geminal diphosphonic acid compounds and certain such novel compounds |
| US4687768A (en) * | 1984-12-21 | 1987-08-18 | The Procter & Gamble Company | Certain hexahydroindan-2,2-diphosphonic acids useful in treating diseases associated with abnormal calcium and phosphate metabolism |
| US5104863A (en) * | 1984-12-21 | 1992-04-14 | The Procter & Gamble Company | Certain bicycloalkane and azabicycloalkane-1,1-diphosphonic acid derivatives useful for treating diseases associated with abnormal calcium and phosphate metabolism |
| JPS62185092A (ja) * | 1986-02-07 | 1987-08-13 | Teijin Ltd | 新規ホスホン酸誘導体および除草剤 |
| DE3627469A1 (de) * | 1986-08-13 | 1988-02-25 | Henkel Kgaa | Verfahren zur ueberfuehrung von organophosphonsaeuren in die alkali- oder ammoniumsalze |
| US4964917A (en) * | 1986-08-26 | 1990-10-23 | Sandoz Ltd. | Methods and compositions for reclaiming concrete |
| US4917837A (en) * | 1986-09-08 | 1990-04-17 | Clarke Jr John L | Gypsum-based insecticide pellets and method of manufacture |
| US4868164A (en) * | 1986-12-19 | 1989-09-19 | Norwich Eaton Pharmaceuticals, Inc. | Octahydro-pyridine diphosphonate compounds, pharmaceutical compositions, and methods for treating abnormal calcium and phosphate metabolism |
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| IL86951A (en) * | 1987-07-06 | 1996-07-23 | Procter & Gamble Pharma | Methylene phosphonoalkylphosphinates and pharmaceutical preparations containing them |
| US5203919A (en) * | 1988-01-14 | 1993-04-20 | Sandoz Ltd. | Method and compositions for stabilizing concrete residues |
| DE3808074A1 (de) * | 1988-03-11 | 1989-09-21 | Henkel Kgaa | Verfahren zur herstellung von azacycloalkan-2,2-diphosphonsaeuren |
| DE3811763C2 (de) * | 1988-04-08 | 1993-10-07 | Jungbunzlauer Ladenburg Gmbh | Wäßrige Dispersion von Gips in Form von Calciumsulfatdihydrat und deren Verwendung als Füllstoff und Streichpigment bei der Papier- und Kartonherstellung |
| DE3841775A1 (de) * | 1988-12-12 | 1990-06-13 | Henkel Kgaa | Zahnpaste |
| DE3930130A1 (de) * | 1989-09-09 | 1991-03-21 | Boehringer Mannheim Gmbh | Neue amidingruppen-haltige diphosphonsaeurederivate, verfahren zu deren herstellung und diese verbindungen enthaltende arzneimittel |
| DE4007431A1 (de) * | 1990-03-09 | 1991-09-12 | Henkel Kgaa | Den zahnschmelz schuetzende mund- und zahnpflegemittel |
| US5096699A (en) * | 1990-12-20 | 1992-03-17 | Colgate-Palmolive Company | Anticalculus oral compositions |
| US5158763A (en) * | 1990-10-09 | 1992-10-27 | Colgate-Palmolive Company | Non-staining anti-bacterial oral composition |
| US6214320B1 (en) * | 1990-10-09 | 2001-04-10 | Colgate-Palmolive Company | Oral compositions containing anticalculus and antiplaque agents |
| DE4114586A1 (de) * | 1991-05-04 | 1992-11-05 | Boehringer Mannheim Gmbh | Arzneimittel enthaltend azacyclodiphosphonsaeurederivate, neue azacyclodiphosphonsaeurederivate sowie verfahren zu deren herstellung |
| US5240697A (en) * | 1991-10-17 | 1993-08-31 | Colgate-Palmolive Company | Desensitizing anti-tartar dentifrice |
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| EP0676948B1 (en) * | 1992-12-16 | 2000-06-21 | Colgate-Palmolive Company | Antiplaque, antigingivitis, anticaries oral composition |
| US5368845A (en) * | 1993-01-07 | 1994-11-29 | Colgate Palmolive Company | Oral composition |
| US5451401A (en) * | 1993-09-29 | 1995-09-19 | The Procter & Gamble Company | Diphosphonic acid esters as tartar control agents |
| GB9325113D0 (en) * | 1993-12-08 | 1994-02-09 | Albright & Wilson | Substituted phosphonic acids |
| US5653797A (en) * | 1996-04-26 | 1997-08-05 | National Gypsum Company | Ready mixed setting-type joint compound and method of making same |
| US5753633A (en) * | 1997-04-11 | 1998-05-19 | Colgate-Palmolive Company | Method of inhibiting bone resorption |
| US6475498B1 (en) | 1999-12-08 | 2002-11-05 | The Procter & Gamble Company | Method to inhibit tartar and stain using denture adhesive compositions |
| US6677391B1 (en) | 1999-12-08 | 2004-01-13 | The Procter & Gamble Company | Tartar control denture adhesive compositions |
| US6475497B1 (en) | 1999-12-08 | 2002-11-05 | The Procter & Gamble Company | Tartar control denture adhesive compositions |
| US6905672B2 (en) * | 1999-12-08 | 2005-06-14 | The Procter & Gamble Company | Compositions and methods to inhibit tartar and microbes using denture adhesive compositions with colorants |
| US6409824B1 (en) | 2000-04-25 | 2002-06-25 | United States Gypsum Company | Gypsum compositions with enhanced resistance to permanent deformation |
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| US8450294B2 (en) * | 2004-12-16 | 2013-05-28 | Lubrizol Advanced Materials, Inc. | Shampoo compositions |
| GB0505758D0 (en) * | 2005-03-21 | 2005-04-27 | Glaxo Group Ltd | Novel compositions |
| DE102011082891A1 (de) | 2011-09-16 | 2013-03-21 | Wacker Chemie Ag | Konservierungsmittel enthaltend Glykolipide |
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| EP2981179B1 (de) | 2013-02-27 | 2020-03-04 | Symrise AG | Stoffgemische enthaltend vanillin und vanillylvanillat |
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| ES2738355T3 (es) | 2013-10-31 | 2020-01-22 | Symrise Ag | Mezcla de sustancias |
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| EP2960235B1 (de) | 2014-06-25 | 2018-09-26 | Symrise AG | Tetrahydrofuranderivate als riechstoffe |
| EP3061500B1 (de) | 2015-02-25 | 2019-07-10 | Symrise AG | Stabile Dispersion |
| EP3093002B1 (de) | 2015-05-15 | 2018-04-25 | Symrise AG | Flüssige kühlstoffzubereitungen |
| ES2770703T3 (es) | 2015-12-01 | 2020-07-02 | Symrise Ag | Composiciones de sustancias |
| CN109069378B (zh) | 2016-02-15 | 2022-10-11 | 西姆莱斯股份公司 | 含有酯和酮的香料混合物 |
| WO2017190789A1 (de) | 2016-05-05 | 2017-11-09 | Symrise Ag | Kühlstoffmischungen |
| EP3454825A1 (de) | 2016-05-14 | 2019-03-20 | Symrise AG | Menthol-haltige aromazubereitungen |
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| US11344857B2 (en) | 2016-12-22 | 2022-05-31 | Symrise Ag | Microcapsules |
| WO2018233841A1 (de) | 2017-06-22 | 2018-12-27 | Symrise Ag | Geschmacksmodulierende aromastoffe |
| EP3911296A1 (de) | 2019-01-15 | 2021-11-24 | Symrise AG | Diester von pflanzlichem 1,3-propandiol |
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| EP3864966A1 (de) | 2020-02-12 | 2021-08-18 | Savanna Ingredients GmbH | Orale zubereitungen mit kristalliner allulose |
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| WO2023143741A1 (de) | 2022-01-28 | 2023-08-03 | Symrise Ag | Neue kühlstoffe und zubereitungen, die diese enthalten |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1958123C3 (de) * | 1969-11-19 | 1978-09-28 | Henkel Kgaa, 4000 Duesseldorf | Verfahren zur Herstellung von 1 -Aminoalkan-1,1 -diphosphonsäuren oder deren Salzen |
-
1973
- 1973-08-27 DE DE2343196A patent/DE2343196C3/de not_active Expired
-
1974
- 1974-08-01 DK DK411774A patent/DK157598C/da not_active IP Right Cessation
- 1974-08-01 NL NLAANVRAGE7410369,A patent/NL179908C/xx not_active IP Right Cessation
- 1974-08-20 US US05/499,000 patent/US3941772A/en not_active Expired - Lifetime
- 1974-08-21 IT IT26461/74A patent/IT1020069B/it active
- 1974-08-23 GB GB3706674A patent/GB1451865A/en not_active Expired
- 1974-08-26 IE IE1778/74A patent/IE39823B1/xx unknown
- 1974-08-26 AT AT689574A patent/AT326687B/de active
- 1974-08-26 CA CA207,802A patent/CA1029020A/en not_active Expired
- 1974-08-26 BE BE147908A patent/BE819189A/xx not_active IP Right Cessation
- 1974-08-26 BR BR7080/74A patent/BR7407080D0/pt unknown
- 1974-08-26 ES ES429542A patent/ES429542A1/es not_active Expired
- 1974-08-26 LU LU70795A patent/LU70795A1/xx unknown
- 1974-08-26 CH CH1160374A patent/CH613979A5/xx not_active IP Right Cessation
- 1974-08-27 FR FR7429204A patent/FR2245372B1/fr not_active Expired
- 1974-08-27 JP JP9832074A patent/JPS5710878B2/ja not_active Expired
-
1979
- 1979-01-18 CH CH52779A patent/CH615097A5/de not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| DK157598C (da) | 1990-06-11 |
| IE39823B1 (en) | 1979-01-03 |
| BR7407080D0 (pt) | 1975-06-24 |
| IT1020069B (it) | 1977-12-20 |
| JPS5050366A (da) | 1975-05-06 |
| DK411774A (da) | 1975-04-28 |
| FR2245372A1 (da) | 1975-04-25 |
| AT326687B (de) | 1975-12-29 |
| US3941772A (en) | 1976-03-02 |
| DE2343196C3 (de) | 1980-01-10 |
| DE2343196B2 (de) | 1979-05-10 |
| FR2245372B1 (da) | 1978-07-21 |
| GB1451865A (en) | 1976-10-06 |
| LU70795A1 (da) | 1975-06-11 |
| CA1029020A (en) | 1978-04-04 |
| DE2343196A1 (de) | 1975-04-03 |
| CH615097A5 (da) | 1980-01-15 |
| ATA689574A (de) | 1975-03-15 |
| ES429542A1 (es) | 1976-08-16 |
| CH613979A5 (da) | 1979-10-31 |
| NL179908C (nl) | 1986-12-01 |
| IE39823L (en) | 1975-02-27 |
| NL7410369A (nl) | 1975-03-03 |
| BE819189A (fr) | 1975-02-26 |
| JPS5710878B2 (da) | 1982-03-01 |
| NL179908B (nl) | 1986-07-01 |
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