DE3232998A1 - Diphosphonic acids - Google Patents
Diphosphonic acidsInfo
- Publication number
- DE3232998A1 DE3232998A1 DE19823232998 DE3232998A DE3232998A1 DE 3232998 A1 DE3232998 A1 DE 3232998A1 DE 19823232998 DE19823232998 DE 19823232998 DE 3232998 A DE3232998 A DE 3232998A DE 3232998 A1 DE3232998 A1 DE 3232998A1
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- 239000002253 acid Substances 0.000 title description 18
- 150000007513 acids Chemical class 0.000 title description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 5
- 150000001768 cations Chemical class 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 abstract description 10
- -1 iron ions Chemical class 0.000 abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 5
- 208000006558 Dental Calculus Diseases 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 3
- 229910001424 calcium ion Inorganic materials 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 229910052742 iron Inorganic materials 0.000 abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 2
- 239000003352 sequestering agent Substances 0.000 abstract description 2
- 230000002265 prevention Effects 0.000 abstract 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 229910001431 copper ion Inorganic materials 0.000 abstract 1
- 239000011505 plaster Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 8
- ZAISDHPZTZIFQF-UHFFFAOYSA-N 2h-1,4-thiazine Chemical compound C1SC=CN=C1 ZAISDHPZTZIFQF-UHFFFAOYSA-N 0.000 description 7
- LCKXJCKRKBQVJZ-UHFFFAOYSA-N 2h-1,4-thiazine 1,1-dioxide Chemical compound O=S1(=O)CC=NC=C1 LCKXJCKRKBQVJZ-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 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
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 235000003599 food sweetener Nutrition 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000003765 sweetening agent Substances 0.000 description 3
- 239000000341 volatile oil Substances 0.000 description 3
- AGIJRRREJXSQJR-UHFFFAOYSA-N 2h-thiazine Chemical compound N1SC=CC=C1 AGIJRRREJXSQJR-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 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
- 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
- 239000012670 alkaline solution Substances 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- XQRLCLUYWUNEEH-UHFFFAOYSA-N diphosphonic acid Chemical compound OP(=O)OP(O)=O XQRLCLUYWUNEEH-UHFFFAOYSA-N 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002324 mouth wash Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000000606 toothpaste Substances 0.000 description 2
- IFJKPUUSPDSXMA-UHFFFAOYSA-N (1-amino-2-phosphonoethyl)phosphonic acid Chemical compound OP(=O)(O)C(N)CP(O)(O)=O IFJKPUUSPDSXMA-UHFFFAOYSA-N 0.000 description 1
- 125000000183 1,4-thiazinyl group Chemical group S1C(C=NC=C1)* 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- SGDYNMJTXCTTAF-UHFFFAOYSA-N 3,6-dihydro-2h-thiazine Chemical compound C1NSCC=C1 SGDYNMJTXCTTAF-UHFFFAOYSA-N 0.000 description 1
- 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
- 229910021532 Calcite Inorganic materials 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 102000005701 Calcium-Binding Proteins Human genes 0.000 description 1
- 108010045403 Calcium-Binding Proteins Proteins 0.000 description 1
- 102000008133 Iron-Binding Proteins Human genes 0.000 description 1
- 108010035210 Iron-Binding Proteins Proteins 0.000 description 1
- MXBDBLBKBBAYGD-UHFFFAOYSA-N P(O)(O)=O.C Chemical compound P(O)(O)=O.C MXBDBLBKBBAYGD-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 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
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229940031956 chlorothymol Drugs 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine hydrate Chemical class O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material 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
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-O triethanolammonium Chemical class OCC[NH+](CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-O 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/167—Phosphorus-containing compounds
- C23F11/1676—Phosphonic acids
-
- 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
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic 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
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/003—Phosphorus-containing compounds
-
- 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
- C07F9/6536—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and sulfur atoms with or without oxygen atoms, as the only ring hetero atoms
- C07F9/6544—Six-membered rings
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Animal Behavior & Ethology (AREA)
- Ceramic Engineering (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- Environmental & Geological Engineering (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Hydrology & Water Resources (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Molecular Biology (AREA)
- Water Supply & Treatment (AREA)
- Biochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Structural Engineering (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Cosmetics (AREA)
Abstract
Description
Diphosphonsäuren"Diphosphonic acids "
Gegenstand der Erfindung sind neue Diphosphonsäuren, die eine Thiazindioxid-Gruppe im Molekül enthalten.The invention relates to new diphosphonic acids which have a thiazine dioxide group contained in the molecule.
Aus der US-Patentschrift 4 264 767 ist die Umsetzung von alpha-Aminoalkanmonophosphonsäuren mit Divinylsulfon in wäßrig-alkalischen Lösungen bekannt. Dabei erhält man Monophosphonsäuren, die eine Thiazin-Gruppe im Molekül enthalten. Diese Verbindungen werden unter anderem zur Verwendung als Steinansatz- und Korrosionsschutzmittel vorgeschlagen.US Pat. No. 4,264,767 discloses the conversion of alpha-aminoalkanemonophosphonic acids known with divinyl sulfone in aqueous alkaline solutions. This gives monophosphonic acids, which contain a thiazine group in the molecule. These connections are among others proposed for use as stone deposits and anti-corrosion agents.
Es wurde nun gefunden, daß die nachstehend beschriebenen, neuen, eine 1,4-Thiazin-Gruppe im Molekül enthaltenen Diphosphonsäuren eine wesentliche Verbesserung der Eigenschaften, insbesondere bezüglich des Komplexierungsvermögens, gegehüber den bekannten Verbindungen aufweisen.It has now been found that the new, one described below 1,4-thiazine group in the molecule contained diphosphonic acids a substantial improvement the properties, especially with regard to the complexing capacity have the known compounds.
Die neuen Verbindungen entsprechen der nachstehenden Formel (I) wobei R = ein Wasserstoffatom, eine Alkyl-Gruppe mit 1 - 4 C-Atomen oder eine Phenylgruppe und Me = ein Wasserstoffatom oder ein wasserlösliches Salz bildendes Kation bedeuten.The new compounds correspond to the following formula (I) where R = a hydrogen atom, an alkyl group with 1-4 C atoms or a phenyl group and Me = a hydrogen atom or a water-soluble salt-forming cation.
Die neuen Verbindungen werden erhalten durch Umsetzung von Divinylsulfon mit alpha-Aminoalkan-alpha,alpha-diphosDhonsäuren, wobei der Alkanrest auch durch eine Phenyl-Gruppe ersetzt sein kann, beziehungsweise deren wasserlöslichen Salze, wie insbesondere Ammonium-, Kalium- und vorzugsweise Natriumsalz. Dabei werden zweckmäßigerweise die Komponenten in molaren Mengen eingesetzt und im alkalischen Medium gearbeitet.The new compounds are obtained by reacting divinyl sulfone with alpha-aminoalkane-alpha, alpha-diphosDhonsäuren, whereby the alkane residue also through a phenyl group can be replaced, or its water-soluble salts, such as in particular the ammonium, potassium and preferably sodium salt. It will be expedient the components used in molar amounts and worked in an alkaline medium.
Bei der Zugabe des Divinylsulfons erfolgt eine exotherme Reaktion. Die Umsetzung wird bei Temperaturen von etwa 25 bis SOOC vorgenommen und das Reaktionsgemisch noch eine Zeit lang bei dieser Temperatur belassen.When the divinyl sulfone is added, an exothermic reaction takes place. The reaction is carried out at temperatures from about 25 to SOOC and the reaction mixture leave it at this temperature for a while.
Das Reaktionsprodukt kann dann durch Behandlung mit Ionenaustauschern (Säureform) in die Diphosphonsäure überführt werden. Die Ausbeuten liegen dabei über 90 %.The reaction product can then be treated with ion exchangers (Acid form) can be converted into the diphosphonic acid. The yields are there over 90%.
Sofern nicht die wasserlöslichen Salze direkt, wie beispielsweise Natriumsalze, anfallen, können die neuen Diphosphonsäuren durch teilweise oder vollständige Neutralisation mit anorganischen Verbindungen, wie NaOH, KOH, Alkalicarbonate oder auch Alkanolamine, wie Monoethanolamin, Diethanolamin oder Triethanolamin, in die entsprechenden wasserlöslichen Salze überführt werden.Unless the water-soluble salts directly, such as Sodium salts, the new diphosphonic acids can be partially or completely Neutralization with inorganic compounds such as NaOH, KOH, alkali carbonates or also alkanolamines, such as monoethanolamine, diethanolamine or triethanolamine, in the corresponding water-soluble salts are transferred.
Die erhaltenen Produkte sind gute Komplexbildner für Erdalkali, vorzugsweise Calciumionen, und können daher speziell für Vorgänge der Wasserenthärtung Anwendung finden. Es ist dabei nicht notwendig, mit stöchiometrischen Mengen zu arbeiten, sondern man kann auch durch Anwendung unterstochiometrischer Mengen Calcitfällungen erheblich verzögern.The products obtained are good complexing agents for alkaline earths, preferably Calcium ions, and can therefore be used specifically for water softening processes Find. It is not necessary to work with stoichiometric quantities, but you can also use sub-stoichiometric amounts of calcite precipitations delay considerably.
Die neuen Verbindungen sind weiterhin auch als Korrosions-und Steinansatzverhinderungsniittel für Kühlwasser, insbesondere auch in Kombination mit bekannten Zusätzen, wie beispielsweise Zinksalze, Orthoshosphate oder Hydrazinhydrate, zu verwenden.The new compounds are also used to prevent corrosion and stone build-up for cooling water, especially in combination with known additives such as Zinc salts, orthoshosphates or hydrazine hydrates.
Die neuen Diphosphonsäuren der Formel I sind ausgezeichnete Sequestrierungsmittel für mehrwertige Metallionen, insbesondere für 2- und 3-wertige Metallionen, wie Kupfer und Eisen. Sie sind insbesondere geeignet als Komplexbildner für Erdalkalimetallionen, insbesondere Calciumionen, so daß sie für zahlreiche technische Anwendungen, wie beispielsweise in Wasch- und Reinigungsmitteln sowie bei der Wasserbehandlung eingesetzt werden können; auf Perverbindungen wirken sie stabilisierend.The new diphosphonic acids of formula I are excellent sequestering agents for polyvalent metal ions, especially for divalent and trivalent metal ions, such as Copper and iron. They are particularly suitable as complexing agents for alkaline earth metal ions, in particular calcium ions, so that they are used for numerous technical applications, such as used for example in detergents and cleaning agents as well as in water treatment can be; they have a stabilizing effect on per compounds.
Ebenfalls sind sie geeignet als Zusatz zur Abbindeverzögerung von Gips und als Schlickerverflüssigungsmittel. Dabei können im übrigen außer den freien Säuren auch die Natrium-, Kalium- oder Ammoniumsalze Anwendung finden.They are also suitable as additives to retard the setting of Gypsum and as a slip liquefier. Besides the free Acids also the sodium, potassium or ammonium salts are used.
Weiterhin können sie in Mund- und Zahnpflegemitteln Anwendung finden, um die Bildung von Zahnstein zu vermeiden. Zur Zahnstein-Verhinderung können außer den freien Phosphonsäuren in diesen Mitteln auch die nharmakologisch unbedenklichen Salze; wie Natrium-, Kalium-, Ammonium-und substituierten Ammoniumsalze wie Mono-, Di- oder Triethanolammoniumsalze Verwendung finden. Sowohl die partiellen Salze, in denen nur ein Teil der aciden Protonen durch andere Kationen ersetzt ist, als auch die Vollsalze können verwendet werden.They can also be used in oral and dental care products, to avoid the formation of tartar. To prevent tartar, you can also use The free phosphonic acids in these agents also contain the pharmacologically harmless ones Salts; such as sodium, potassium, ammonium and substituted ammonium salts such as mono-, Find di- or triethanolammonium salts use. Both the partial salts, in which only a part of the acidic protons is replaced by other cations than the full salts can also be used.
Vorzuziehen sind jedoch solche Salze, die in wäßriger Lösung annähernd neutral (pH 5 bis 9) reagieren. Mischungen der vorgenannten Salze können ebenfalls benutzt werden.However, preference is given to those salts which are approximately in aqueous solution react neutrally (pH 5 to 9). Mixtures of the aforementioned salts can also be used to be used.
Der Anmeldungsgegenstand wird durch die nachstehenden Beispiele näher erläutert, ohne hierauf beschränkt zu sein.The subject of the application is illustrated by the following examples explained without being limited to this.
Beispiel 1 0,1 Mol Tetranatrium-1-aminomethandiphosphonat wurde in 125 ml Wasser gelöst und bei 300C langsam mit 0,1 Mol Divinylsulfon versetzt. Dabei erfolgte ein Temperatur anstieg. Nach einstündigem Nachrühren bei 500C zeigte der chromatographische Befund einen 100%igen Umsatz. Zur Isolierung des Reaktionsproduktes wurde die Lösung mit einem Ionenaustauscher in Säureform behandelt und dann eingeengt. Aus dem Konzentrat wurden 91,6 % eines Niederschlages, der als 1 1,4-Thiazindioxid-N-methandiphosphonsäure identifiziert wurde, isoliert.Example 1 0.1 mol of tetrasodium 1-aminomethane diphosphonate was added to Dissolve 125 ml of water and slowly add 0.1 mol of divinyl sulfone at 300C. Included a temperature rise occurred. After stirring at 50 ° C. for one hour, the showed chromatographic results show a 100% conversion. To isolate the reaction product the solution was treated with an ion exchanger in acid form and then concentrated. 91.6% of a precipitate, which was 1 1,4-thiazine dioxide-N-methanediphosphonic acid, was obtained from the concentrate was identified, isolated.
Analyse gefunden: C 18,8 H 4,33 N 4,36 P 19,8 S 9,92 berechnet: 19,42 4,21 4,53 20,06 10,36 Beispiel 2 Bei gleicher Arbeitsweise wie im Beispiel 1 jedoch ausgehend von Aminoethandiphosphonsäure wurde alpha-(1 >4-Thiazindioxid3-N-ethan-alpha,alpha-diphosphonsäure erhalten. Die Ausbeute betrug 96 t.Analysis found: C 18.8 H 4.33 N 4.36 P 19.8 S 9.92 calcd: 19.42 4.21 4.53 20.06 10.36 Example 2 Using the same procedure as in Example 1, however starting from aminoethanediphosphonic acid, alpha- (1> 4-thiazine dioxide3-N-ethane-alpha, alpha-diphosphonic acid obtain. The yield was 96 t.
Analyse gefunden: C 20,9 H 5,65 N 4,31 P 18,9 S 9,06 berechnet: 22,29 4,64 4,33 19,20 9,91 Die Verbindung wurde auch in Form ihres vollneutralisierten Natriumsalzes isoliert, indem nach der Umsetzung mit Divinylsulfon das Tetranatriumsalz durch Zugabe von Ethanol ausgefällt wurde.Analysis found: C 20.9 H 5.65 N 4.31 P 18.9 S 9.06 calcd: 22.29 4.64 4.33 19.20 9.91 The connection was also in the form of its fully neutralized Sodium salt isolated by adding the tetrasodium salt after the reaction with divinyl sulfone was precipitated by adding ethanol.
Analyse gefunden: C 17,8 H 2,98 N 3,22 P 15,2 S 7,57 Na 22,0 berechnet: 17,52 2,68 3,41 15,09 7,79 22,38 Beispiel 3 0,1 Mol Tetranatrium-1-amino-1-phenylmethandiphosphonat gelöst in 100 ml Wasser, wurden bei 300C mit 0,1 Mol Divinylsulfon langsam zugesetzt und etwa 2 Stunden bei 50 0C belassen. Die klare Lösung wurde dann mit konzentrierter Salzsäure auf pH 1 gestellt. Der dabei ausgefallene Niederschlag wurde abgetrennt und als alpha-(1,4-Thi azindioxid) -N-phenylmethandiphosphons äure i denti fi -ziert.Analysis found: C 17.8 H 2.98 N 3.22 P 15.2 S 7.57 Na 22.0 calculated: 17.52 2.68 3.41 15.09 7.79 22.38 Example 3 0.1 mole of tetrasodium 1-amino-1-phenylmethane diphosphonate dissolved in 100 ml of water, 0.1 mol of divinyl sulfone were slowly added at 300 ° C. and leave at 50 ° C. for about 2 hours. The clear solution was then concentrated with Hydrochloric acid adjusted to pH 1. The resulting precipitate was separated off and as alpha- (1,4-thiazine dioxide) -N-phenylmethanediphosphonic acid i denti fi -ziert.
Analyse gefunden: C 31,7 N 3,35 P 14,6 S 7,69 berechnet: 31,01 3,29 14,56 7,51 Beispiel 4 Hampshire-Tept (Calcium-Bindevermögen) 1000 mg der in der nachstehenden Tabelle 1 angegebenen Phosphonsäure werden in 80 ml H20 gelöst (mit NaOH auf pH 11 gestellt), mit 10 ml Sodalösung versetzt (14,3 g Na2CO3 . H20 / 1). Aus einer Bürette wird dann eine Calciumsalzlösung (36,8 g CaCl2 . 2 H20 / 1) so lange zugetropft, bis gerade eine bleibende Tnibung entsteht.Analysis found: C 31.7 N 3.35 P 14.6 S 7.69 Calculated: 31.01 3.29 14.56 7.51 Example 4 Hampshire Tept (calcium binding capacity) 1000 mg of the in the The phosphonic acid given in Table 1 below is dissolved in 80 ml of H20 (with NaOH adjusted to pH 11), mixed with 10 ml soda solution (14.3 g Na2CO3. H20 / 1). A calcium salt solution (36.8 g CaCl2. 2 H20 / 1) is then obtained from a burette Dripped in for a long time, until a permanent tint is created.
Die Ergebnisse sind aus der nachstehenden Tabelle 1 ersichtlich und zeigen die Oberlegenheit der erfindunesgemen Verbindungen (c, e und e).The results are shown in Table 1 below and show the superiority of the compounds according to the invention (c, e and e).
Tabelle 1 mg CaCO3 Substanz g Substanz a) 1-Aminomethan-1,1-di- 220 Vergleichsphosphonsäure substanz b) 1,4-Thiazindioxid-N- 30 Vergleichsmethanmonophosphonsäure substanz c) 1,4-Thiazindioxid-N- 1.070 methandiphosphonsäure d) Aminoethan-1,1-diphosphon- 1.000 Vergleichssäure substanz e) 1-(1,4-Thiazindioxid)-N- 2.500 ethan-1,1,diphosphonsäure f) alnha-(1,4-Thiazindioxid)- <100 Vergleichs-N-phenylmethan-monophosnhon- substanz säure g) alpha-(1,4-Thiazindioxid)- 2.500 N-phenylmethan-diphosphonsäure Beispiel 5 In den nachstehenden Tabellen 2 und 3 sind die Ergebnisse angegeben für das Eisen- und Kuferbindunsvermögen. Es wurden die Werte in sodaalkalischer Lösung bei 1000C ermittelt. Zum Vergleich sind auch die Ergebnisse angegeben, die mit 1 ,4-Thiazindioxid-N-methanmonophosphonsäure ermittelt wurden. Dabei wird die Überlegenheit der erfindungsgemäßen Verbindungen deutlich.Table 1 mg CaCO3 substance g substance a) 1-aminomethane-1,1-di-220 Comparative phosphonic acid substance b) 1,4-thiazine dioxide-N-30 comparative methane monophosphonic acid substance c) 1,4-thiazine dioxide-N-1,070 methanediphosphonic acid d) aminoethane-1,1-diphosphonic 1,000 comparison acid substance e) 1- (1,4-thiazine dioxide) -N- 2,500 ethane-1,1, diphosphonic acid f) alnha- (1,4-thiazine dioxide) - <100 comparative N-phenylmethane-monophosnhon- substance acid g) alpha- (1,4-thiazine dioxide) - 2,500 N-phenylmethane-diphosphonic acid example 5 Tables 2 and 3 below show the results for the iron and buyer loyalty. The values were in a soda-alkaline solution at 1000C determined. For comparison, the results are also given, those with 1,4-thiazine dioxide-N-methanemonophosphonic acid were determined. This shows the superiority of the compounds according to the invention clear.
In den Tabellen bedeutet ein "+" Ausfällung als schwerlösliche Verbindung und ein "-" keine Ausfällung bei der jeweils angegebenen Konzentration.In the tables, a "+" means precipitation as a poorly soluble compound and a "-" no precipitation at the given concentration.
Tabelle 2 (Eisenbindungsvermögen) Vergleichssubstanz: alpha-(1,4-Thiazindioxid)-N-ethan- 1,4-Thiazindioxid-N- 1,4-Thiazindioxid-N-mMol alpha,alpha-diphoshonsäure methandiphosphonsäure methanmonophosphonsäure 0,010 + + 0,015 + + 0,020 + + 0,025 + -0,030 - -0,035 - -0,040 - ->0,9 Tabelle 3 (Kupferbindungsvermögen) Vergleichssubstanz: alpha-(1,4-Thiazindioxid)-N-ethan- 1,4-Thiazindioxid-N- 1,4-Thiazindioxid-N-mMol alpha,alpha-diphoshonsäure methandiphosphonsäure methanmonophosphonsäure 0,045 + 0,050 + 0,055 + 0,060 -0,065 -0,070 -0,075 + -0,080 + 0,085 + 0,090 -0,095 -0,10 ->2,0 + Beispiel 6 Als Grundrezenturen für Zahnpasten sind folgende Formulierungen geeignet: a.) Glycerin 60,0 Gew.-Teile Wasser 13,5 Gew.-Teile Natriumcarboxymethylcellulose 0,6 Gew.-Teile Kieselsäureexerogel 20,0 Gew.-Te-ile Natriumlaurylsulfat 2,0 Gew.-Teile Atherische Öle 1,0 Gew.-Teile Süßstoff 0,4 Gew.-Teile 1,4-Thiazindioxid-N-methandiphosphonsäure 2,5 Gew.-Teile b .) Glycerin 30,0 Gew.-Teile Wasser 18,5 Gew.-Teile Natriumcarboxymethylcellulose 1,0 Gew.-Teile Aluminiumhydroxid 44,0 Gew.-Teile Natriumlaurylsulfat 1,0 Gew.-Teile Kieselsäurepirogen 1,5 Gew.--Teile Ätherische Öle 1,5 Gew.-Teile Süßstoff 0,5 Gew.-Teile 1 ,4-Thiazindioxid-N- ethandiphosphonsäure 2,0 Gew.-Teile Als Grundrezeptur für Mundwässer ist folgende Kombination geeignet: Ethylalkohol 19,5 Gew.-Teile Glycerin 7,5 Gew.-Teile Wasser 70,0 Gew.-Teile ätherische Öle 0,2 Gew.-Teile Natriumlaurylsulfat 0,1 Gew.-Teile Antiseptikum (Chlorthymol) 0,1 Gew.-Teile Süßstoff 0,1 Gew.-Teile 1,4-Thiazindioxid-N-methandiphsnhonsäure 2,5 Gew.-Teile Anstelle der verwendeten Diphosphonsäuren kann auch alpha-(1 ,4-Thiazindioxid) -N-phenylmethandiphosnhonsä'ure eingesetzt werden. Table 2 (iron binding capacity) comparison substance: alpha- (1,4-thiazine dioxide) -N-ethan- 1,4-thiazine dioxide-N-1,4-thiazine dioxide-N-mmol alpha, alpha-diphosonic acid, methanediphosphonic acid methane monophosphonic acid 0.010 + + 0.015 + + 0.020 + + 0.025 + -0.030 - -0.035 - -0.040 - -> 0.9 Table 3 (copper binding capacity) Comparative substance: alpha- (1,4-thiazine dioxide) -N-ethane-1,4-thiazine dioxide-N-1,4-thiazine dioxide-N-mmol alpha, alpha-diphosphonic acid methanediphosphonic acid methane monophosphonic acid 0.045 + 0.050 + 0.055 + 0.060 -0.065 -0.070 -0.075 + -0.080 + 0.085 + 0.090 -0.095 -0.10 -> 2.0 + Example 6 The following are the basic recents for toothpastes Suitable formulations: a.) Glycerin 60.0 parts by weight water 13.5 parts by weight sodium carboxymethyl cellulose 0.6 parts by weight of silica exerogel, 20.0 parts by weight of sodium lauryl sulfate, 2.0 parts by weight Essential oils 1.0 part by weight sweetener 0.4 part by weight 1,4-thiazine dioxide-N-methanediphosphonic acid 2.5 parts by weight b.) Glycerin 30.0 parts by weight water 18.5 parts by weight sodium carboxymethyl cellulose 1.0 part by weight of aluminum hydroxide 44.0 parts by weight of sodium lauryl sulfate 1.0 part by weight Silicic acid pirogen 1.5 parts by weight essential oils 1.5 parts by weight sweetener 0.5 parts by weight 1, 4-thiazine dioxide-N-ethanediphosphonic acid 2.0 parts by weight As a basic recipe The following combination is suitable for mouthwashes: ethyl alcohol 19.5 parts by weight glycerine 7.5 parts by weight of water 70.0 parts by weight of essential oils 0.2 parts by weight of sodium lauryl sulfate 0.1 part by weight of antiseptic (chlorothymol) 0.1 part by weight of sweetener 0.1 part by weight 1,4-thiazine dioxide-N-methandiphsnhonsäure 2.5 parts by weight instead of the used Diphosphonic acids can also be alpha- (1,4-thiazine dioxide) -N-phenylmethanediphosnhonsä'ure can be used.
Durch regelmäßigen Gebrauch der Mundwässer und/oder Zahnpasten mit einem Gehalt an den oben genannten Diphosphonsäuren läßt sich die Bildung von Zahnstein wesentlich verringern. Die Ausbildung von harten, komnakten Zahnbelägen wird weitgehend verhindert. By regularly using the mouthwashes and / or toothpastes with A content of the above-mentioned diphosphonic acids can prevent the formation of tartar reduce significantly. The formation of hard, compact plaque is largely increased prevented.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19823232998 DE3232998A1 (en) | 1982-09-04 | 1982-09-04 | Diphosphonic acids |
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| DE19823232998 DE3232998A1 (en) | 1982-09-04 | 1982-09-04 | Diphosphonic acids |
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| DE19823232998 Withdrawn DE3232998A1 (en) | 1982-09-04 | 1982-09-04 | Diphosphonic acids |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1987003598A1 (en) * | 1985-12-12 | 1987-06-18 | Leo Pharmaceutical Products Ltd. A/S | Novel bisphosphonic derivatives, a method for their production and a pharmaceutical composition |
| WO1988001609A1 (en) * | 1986-08-28 | 1988-03-10 | Eberhard Christ | Use of substituted alkyl phosphonates in concrete and mortar mixes, cement slurry and latex paints |
-
1982
- 1982-09-04 DE DE19823232998 patent/DE3232998A1/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1987003598A1 (en) * | 1985-12-12 | 1987-06-18 | Leo Pharmaceutical Products Ltd. A/S | Novel bisphosphonic derivatives, a method for their production and a pharmaceutical composition |
| JPS63501956A (en) * | 1985-12-12 | 1988-08-04 | レオ・ファ−マシュ−ティカル・プロダクツ・リミテッド・エイ／エス（レ−ベンス・ケミスケ・ファブリック・プロデュクチオンスアクチ−セルスカブ） | New bisphosphonic acid derivatives, their production and uses |
| US4870063A (en) * | 1985-12-12 | 1989-09-26 | Leo Pharmaceutical Products Ltd. A/S | Bisphosphonic acid derivatives, their production and use |
| WO1988001609A1 (en) * | 1986-08-28 | 1988-03-10 | Eberhard Christ | Use of substituted alkyl phosphonates in concrete and mortar mixes, cement slurry and latex paints |
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