DE3444678A1 - 1-Phenylethane-1,2,2-triphosphonic acid, its water-soluble salts and esters, and their use - Google Patents
1-Phenylethane-1,2,2-triphosphonic acid, its water-soluble salts and esters, and their useInfo
- Publication number
- DE3444678A1 DE3444678A1 DE19843444678 DE3444678A DE3444678A1 DE 3444678 A1 DE3444678 A1 DE 3444678A1 DE 19843444678 DE19843444678 DE 19843444678 DE 3444678 A DE3444678 A DE 3444678A DE 3444678 A1 DE3444678 A1 DE 3444678A1
- Authority
- DE
- Germany
- Prior art keywords
- phenylethane
- acid
- water
- salts
- triphosphonic
- 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.)
- Withdrawn
Links
- 150000003839 salts Chemical class 0.000 title claims abstract description 20
- OWLKYBGHDRTLLD-UHFFFAOYSA-N (1-phenyl-2,2-diphosphonoethyl)phosphonic acid Chemical compound OP(=O)(O)C(P(O)(O)=O)C(P(O)(=O)O)C1=CC=CC=C1 OWLKYBGHDRTLLD-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 150000002148 esters Chemical class 0.000 title claims abstract description 15
- 239000008139 complexing agent Substances 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 5
- 239000002537 cosmetic Substances 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000003814 drug Substances 0.000 abstract description 2
- 239000002253 acid Substances 0.000 description 23
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 150000007513 acids Chemical class 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- -1 alkali metal salts Chemical class 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- SVHAMPNLOLKSFU-UHFFFAOYSA-N 1,2,2-trichloroethenylbenzene Chemical compound ClC(Cl)=C(Cl)C1=CC=CC=C1 SVHAMPNLOLKSFU-UHFFFAOYSA-N 0.000 description 5
- 229910021532 Calcite Inorganic materials 0.000 description 5
- 229960000583 acetic acid Drugs 0.000 description 5
- 230000000536 complexating effect Effects 0.000 description 5
- 230000005764 inhibitory process Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Inorganic materials [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- BYMVZHORNHZYPQ-UHFFFAOYSA-N sodium;diethyl phosphite Chemical compound [Na+].CCOP([O-])OCC BYMVZHORNHZYPQ-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- MTKUWDYQPVIKLB-UHFFFAOYSA-N sodium;dipropan-2-yl phosphite Chemical compound [Na+].CC(C)OP([O-])OC(C)C MTKUWDYQPVIKLB-UHFFFAOYSA-N 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- JSBMVKVNJQZVEF-UHFFFAOYSA-N 1,2,2-triphosphonoethylphosphonic acid Chemical compound OP(O)(=O)C(P(O)(O)=O)C(P(O)(O)=O)P(O)(O)=O JSBMVKVNJQZVEF-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 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 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000005662 Paraffin oil Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 230000037396 body weight Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 235000010216 calcium carbonate Nutrition 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 238000011081 inoculation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OAMHTTBNEJBIKA-UHFFFAOYSA-N 2,2,2-trichloro-1-phenylethanone Chemical compound ClC(Cl)(Cl)C(=O)C1=CC=CC=C1 OAMHTTBNEJBIKA-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- IQEYFLNKNLYSQO-UHFFFAOYSA-N C(C)(C)OP(OC(C)C)(=O)C(C(P(OC(C)C)(=O)OC(C)C)P(OC(C)C)(=O)OC(C)C)C1=CC=CC=C1 Chemical compound C(C)(C)OP(OC(C)C)(=O)C(C(P(OC(C)C)(=O)OC(C)C)P(OC(C)C)(=O)OC(C)C)C1=CC=CC=C1 IQEYFLNKNLYSQO-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 102000005701 Calcium-Binding Proteins Human genes 0.000 description 1
- 108010045403 Calcium-Binding Proteins Proteins 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 208000006558 Dental Calculus Diseases 0.000 description 1
- 229910001060 Gray iron Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- JETSKDPKURDVNI-UHFFFAOYSA-N [C].[Ca] Chemical compound [C].[Ca] JETSKDPKURDVNI-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 125000005131 dialkylammonium group Chemical group 0.000 description 1
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 1
- XQRLCLUYWUNEEH-UHFFFAOYSA-N diphosphonic acid Chemical compound OP(=O)OP(O)=O XQRLCLUYWUNEEH-UHFFFAOYSA-N 0.000 description 1
- NFORZJQPTUSMRL-UHFFFAOYSA-N dipropan-2-yl hydrogen phosphite Chemical compound CC(C)OP(O)OC(C)C NFORZJQPTUSMRL-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 208000035475 disorder Diseases 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000011507 gypsum plaster Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000000819 hypertonic solution Substances 0.000 description 1
- 229940021223 hypertonic solution Drugs 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000007918 intramuscular administration Methods 0.000 description 1
- 238000001990 intravenous administration Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 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
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002324 mouth wash Substances 0.000 description 1
- 229940051866 mouthwash Drugs 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000007920 subcutaneous administration Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000003826 tablet Substances 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- GKLVYJBZJHMRIY-UHFFFAOYSA-N technetium atom Chemical compound [Tc] GKLVYJBZJHMRIY-UHFFFAOYSA-N 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
- 229940034610 toothpaste Drugs 0.000 description 1
- 125000005209 triethanolammonium group Chemical class 0.000 description 1
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 description 1
- 238000001665 trituration Methods 0.000 description 1
- 239000008215 water for injection Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- 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
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/10—Organic substances
- A23K20/111—Aromatic compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/55—Phosphorus compounds
-
- 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
- C07F9/3843—Polyphosphonic acids containing no further substituents than -PO3H2 groups
-
- 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)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4025—Esters of poly(thio)phosphonic acids
- C07F9/4028—Esters of poly(thio)phosphonic acids containing no further substituents than -PO3H2 groups in free or esterified form
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/36—Organic compounds containing phosphorus
- C11D3/361—Phosphonates, phosphinates or phosphonites
-
- 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
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/51—Chelating agents
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Veterinary Medicine (AREA)
- Polymers & Plastics (AREA)
- Molecular Biology (AREA)
- Animal Behavior & Ethology (AREA)
- Biochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Public Health (AREA)
- Mechanical Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Animal Husbandry (AREA)
- Zoology (AREA)
- Metallurgy (AREA)
- Food Science & Technology (AREA)
- Materials Engineering (AREA)
- Birds (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Epidemiology (AREA)
- Oral & Maxillofacial Surgery (AREA)
Abstract
Description
1-Phenylethan-1, 2, 2-triphosphonsäure, ihre 1-phenylethane-1, 2, 2-triphosphonic acid, their
wasserlöslichen Salze und Ester, sowie ihre Verwendung Die vorliegende Erfindung betrifft l-Phenylethan-1,2,2-triphosphonsäure, ihre Salze und Ester, sowie ihre Verwendung. water-soluble salts and esters, and their use The present The invention relates to l-phenylethane-1,2,2-triphosphonic acid, its salts and esters, as well as their use.
Die DE-OS 31 11 152 beschreibt ein Verfahren zur Herstellung von Oligophosphonsäuren bzw. Oligophosphinsäuren, ihren Salzen und/oder Estern durch Umsetzung von organischen Halogenverbindungen mit Diestern der Phosphorigen Säure bzw. Estern von Alkyl- bzw. Arylphosphonigen Säuren, wobei man Olefinpolyhalogenide mit endständiger Doppelbindung unter Austausch doppelbindungsständigen Halogens und gleichzeitiger Sättigung der Doppelbindung mit Alkalimetallsalzen von Diestern der Phosphorigen Säure bzw. von Estern Alkyl-bzw. Arylphosphoniger Säuren umsetzt und die gebildeten Umsetzungsprodukte gewünschtenfalls zu den freien Phosphonsäuren bzw. Phosphinsäuren oder ihren Salzen verseift.DE-OS 31 11 152 describes a process for the production of oligophosphonic acids or oligophosphinic acids, their salts and / or esters by reaction of organic Halogen compounds with diesters of phosphorous acid or esters of alkyl or Arylphosphonous acids, being olefin polyhalides with a terminal double bond with the exchange of double bonded halogen and simultaneous saturation of the Double bond with alkali metal salts of diesters of phosphorous acid or of Esters alkyl or. Arylphosphonous acids converts and the reaction products formed if desired to the free phosphonic acids or phosphinic acids or their salts saponified.
Die Aufgabe der vorliegenden Erfindung besteht darin, neue Verbindungen zu schaffen, die verbesserte Komplexbildner-Eigenschaften aufweisen.The object of the present invention is to find new compounds to create that have improved complexing properties.
Dementsprechend betrifft die vorliegende Erfindung 1-Phenylethan-1 , 2, 2-triphosphonsäure der Formel ihre Salze sowie Verfahren zu ihrer Herstellung.The present invention accordingly relates to 1-phenylethane-1,2,2-triphosphonic acid of the formula their salts and processes for their preparation.
Die Erfindung betrifft ferner die Verwendung der 1-Phenylethan-1 , 2, 2-triphosphonsäure bzw. deren wasserlöslichen Salze und Ester zum Komplexieren insbesondere von Erdalkaliionen, vorzugsweise Calciumionen.The invention also relates to the use of 1-phenylethane-1, 2,2-triphosphonic acid or its water-soluble salts and esters for complexing in particular of alkaline earth ions, preferably calcium ions.
Die Herstellung der l-Phenylethan-1,2, 2-triphosphonsäure erfolgt nach an sich bekannten Verfahren, wie sie beispielsweise in der DE-OS 31 11 152 beschrieben sind.The production of l-phenylethane-1,2,2-triphosphonic acid takes place by methods known per se, such as those described, for example, in DE-OS 31 11 152 are described.
Beispielsweise erhält man bei der Umsetzung von Trichlorvinylbenzol bei Raumtemperatur mit Diethylphosphitnatrium in einer THF-Lösung und anschließende Neutralisation den Hexaethylester der 1-Phenylethan-1,2,2-triphosphonsäure, den man durch Acidolyse zur freien 1-Phenylethan-1 , 2, 2-triphosphonsäure umsetzt.For example, when trichlorovinylbenzene is converted, one obtains at room temperature with diethylphosphite sodium in a THF solution and then Neutralization of the hexaethyl ester of 1-phenylethane-1,2,2-triphosphonic acid, the is converted by acidolysis to the free 1-phenylethane-1, 2, 2-triphosphonic acid.
Geht man anstelle von Diethylphosphitnatrium von Diisopropylphosphitnatrium aus, so erhält man den Hexaisopropylester der 1-Phenylethan-1 , 2, 2-triphosphonsäure. Die l-Phenylethan-1,2 , 2-triphosphonsäuren bzw. deren wasserlösliche Salze besitzen ein ausgezeichnetes Komplexiervermögen gegenüber 2- und mehrwertigen Metallionen, wie beispielsweise gegenüber Ca, Cu, Fe, Cr und anderen, bei verschiedenen Temperaturen und pH-Werten.If one goes instead of sodium diethyl phosphite by sodium diisopropyl phosphite off, the hexaisopropyl ester of 1-phenylethane-1,2,2-triphosphonic acid is obtained. the Have l-phenylethane-1,2,2-triphosphonic acids or their water-soluble salts an excellent complexing ability against bivalent and polyvalent metal ions, such as against Ca, Cu, Fe, Cr and others, at different temperatures and pH values.
Insbesondere zeigen sie ein besonders gutes Calcium-Bindevermögen, das besser ist als dasjenige bekannter analoger Verbindungen, wie sich in einfacher Weise durch den "Hampshire-Test" nachweisen läßt.In particular, they show a particularly good calcium binding capacity, that is better than that of known analog connections, as in simpler Way can be proven by the "Hampshire test".
Daher sind die 1-Phenylethan-1, 2, 2-triphosphonsäuren sowie deren wasserlösliche Salze geeignet zur Verwendung als Komplexiermittel bzw. Sequestriermittel.Therefore, the 1-phenylethane-1, 2, 2-triphosphonic acids as well as their water-soluble salts suitable for use as complexing agents or sequestering agents.
Außer dem ausgezeichneten Komplexiervermögen zeichnen sich l-Phenylethan-1,2,2-triphosphonsäuren bzw. deren wasserlösliche Salze durch eine starke Threshold-Aktivität aus, d.h. sie sind in der Lage, die Ausfällung schwerlöslicher Erdalkalimetallsalze auch in Impfmengen, das sind unterstöchiometrische Mengen, zu verhindern.In addition to the excellent complexing properties, l-phenylethane-1,2,2-triphosphonic acids are also notable or their water-soluble salts are characterized by a strong threshold activity, i.e. they are able to prevent the precipitation of poorly soluble alkaline earth metal salts in Inoculation quantities, which are sub-stoichiometric quantities, must be prevented.
1-Phenylethan-1 ~2, 2-triphosphonsäuren bzw. deren wasserlösliche Salze sind als Komplexiermittel sehr vielseitig verwendbar: Beispielsweise können sie speziell für die Vorgänge der Wasserenthärtung Anwendung finden, wobei die vorstehend erwähnte Threshold-Wirkung eine wesentliche Rolle spielt. Es ist daher nich notwendig, mit stöchiometrischen Mengen zu arbeiten, sondern man kann auch mit unterstöchiometrischen Mengen Calcitfällungen erheblich verzögern.1-Phenylethane-1,2,2-triphosphonic acids or their water-soluble ones Salts are very versatile as complexing agents: For example, can they are specifically used for the processes of water softening, the above mentioned threshold effect plays an essential role. It is therefore not necessary Work with stoichiometric amounts, but you can also work with substoichiometric amounts Delay quantities of calcite precipitation considerably.
Sie sind auch als Korrosions- und Steinansatzverhütungsmittel für Kühlwässer, insbesondere in Kombination mit an sich bekannten Zusätzen, gut geeignet.They are also used as a corrosion and stone build-up preventive for Cooling water, especially in combination with additives known per se, is well suited.
Die genannten Eigenschaften bewirken, daß die l-Phenylethan-1,2,2-triphosphonsäuren bzw. deren wasserlösliche Salze beispielsweise auch für die Entkrustung von Geweben, in denen sich Erdalkalimetallsalze abgelagert haben, und zur Verminderung der Ascheanreicherung in Geweben Anwendung finden können. Sie kommen auch als Buildersubstanzen mit komplexierenden Eigenschaften in Wasch- und Reinigungsmitteln in Frage und können in Kombination mit bekannten anionenaktiven, kationenaktiven oder nichtionogenen Netzmitteln verwendet werden. Weiterhin können sie in Kombination mit Ätzalkalien, Alkalicarbonaten, Alkalisilikaten, Phosphaten oder Boraten Anwendung finden.The properties mentioned have the effect that the l-phenylethane-1,2,2-triphosphonic acids or their water-soluble salts, for example, also for de-encrusting tissues, in which alkaline earth metal salts have deposited, and to reduce the accumulation of ash can be used in tissues. They also come as builders with complexing agents Properties in detergents and cleaning agents in question and can be used in combination used with known anion-active, cation-active or non-ionic wetting agents will. They can also be used in combination with caustic alkalis, alkali carbonates, alkali silicates, Find phosphates or borates application.
Aufgrund ihres starken Komplexierungsvermögens können sie auch mit Vorteil in Systemen eingesetzt werden, in denen Schwermetallionen, beispielsweise Kupferionen, unerwünschte Effekte auslösen. Beispielhaft seien hier genannt die Zersetzung von Perverbindungen in Bleichmitteln bzw. Verfärbungen oder Ranzigwerden von Fetten und Seifen.Due to their strong ability to complex, they can also with Advantageously used in systems in which heavy metal ions, for example Copper ions, triggering undesirable effects. Examples are the Decomposition of per compounds in bleaching agents or discoloration or rancidity of fats and soaps.
Die l-Phenylethan-1,2,2-triphosphonsäuren bzw. deren wasserlösliche Salze sind ferner geeignet für Reinigungsprozesse von starren Gegenständen wie insbesondere Metall oder Glas. Hierbei kommt insbesondere die Verwendung als Zusatz zu Flaschenspülmitteln in Betracht.The l-phenylethane-1,2,2-triphosphonic acids or their water-soluble ones Salts are also suitable for cleaning processes of rigid objects such as in particular Metal or glass. In particular, it is used as an additive to bottle washing agents into consideration.
Die erfindungsgemäßen Produkte sind auch geeignet für pharmazeutische Zwecke, insbesondere zur Behandlung von Störungen des Calcium- bzw. des Phosphatstoff- wechsels und den damit verbundenen Erkrankungen. Weiterhin können die 1-Phenylethan-1,2,2-triphosphonsäuren und deren wasserlösliche Salze in kosmetischen Präparaten, wie insbesondere Zahnpasta, Mundwasser und ähnlichen Produkten, verwendet werden, da sie die Bildung von Zahnstein wesentlich reduzieren bzw. inhibieren.The products according to the invention are also suitable for pharmaceuticals Purposes, in particular for the treatment of disorders of the calcium or phosphate substance change and related diseases. Furthermore, the 1-phenylethane-1,2,2-triphosphonic acids and their water-soluble salts in cosmetic preparations, such as toothpaste in particular, Mouthwash, and similar products, can be used as they reduce the build-up of tartar significantly reduce or inhibit.
Geeignete wasserlösliche Salze der 1-Phenylethan-1,2,2-triphosphonsäuren sind Natrium-, Kalium-, Ammonium- und substituierte Ammoniumsalze, wie Mono-, Di- oder Triethanolammoniumsalze. Auch Lithiumsalze können Anwendung finden. Bevorzugt sind die Natrium-, Kalium- und Ammoniumsalze sowie Dialkylammonlumsalze und Triethanolaminsalze. Es können auch Mischungen der Salze verwendet werden.Suitable water-soluble salts of 1-phenylethane-1,2,2-triphosphonic acids are sodium, potassium, ammonium and substituted ammonium salts, such as mono-, di- or triethanolammonium salts. Lithium salts can also be used. Preferred are the sodium, potassium and ammonium salts as well as dialkylammonium salts and triethanolamine salts. Mixtures of the salts can also be used.
Bei der pharmazeutischen Anwendung ist die Dosierung der verwendeten Verbindungen variabel und hängt von den jeweiligen Konditionen, wie Art und Schwere der Erkrankung, Dauer der Behandlung und der jeweiligen Verbindung ab. Einzelne Dosierungen können von 0,05 bis 500 mg pro kg Körpergewicht und Tag betragen. Die bevorzugte Dosierung beträgt 1 bis 50 mg pro kg Körpergewicht und Tag und kann in bis zu 4 % täglich verabreicht werden. Die höheren Dosierungen sind bei oraler Applikation infolge der begrenzten Resorption erforderlich. Bei länger dauernden Behandlungen sind nach anfänglich höheren Dosierungen normalerweise geringere Dosierungen notwendig, um den gewünschten Effekt aufrechtzuerhalten.In pharmaceutical use, the dosage is that used Connections variable and depends on the respective conditions, such as type and severity the disease, duration of treatment and the particular connection. Separate Dosages can range from 0.05 to 500 mg per kg of body weight per day. the preferred dosage is 1 to 50 mg per kg of body weight and day and can be used in up to 4% can be administered daily. The higher dosages are for oral administration required due to the limited absorption. For longer treatments after initially higher doses, lower doses are usually necessary, to maintain the desired effect.
Die 1-Phenylethan-l, 2, 2-triphosphonsäuren bzw. deren Salze können sowohl oral als auch in hypertonischer Lösung subkutan, intramuskulär oder intravenös appli- ziert werden. Die bevorzugten Dosisbereiche für diese Anwendung sind (in mg/kg . Tag) oral 1 bis 50 subkutan 1 bis 50 intramuskulär 0,05 bis 10 intravenös 0,05 bis 2 Die Substanzen können zur Verabreichung in Tabletten, Pillen, Kapseln oder Injektionslösungen formuliert werden. Für Tiere können die Substanzen auch im Futter bzw. als Futterzusätze Verwendung finden.The 1-phenylethane-1,2,2-triphosphonic acids or their salts can both orally and in hypertonic solution subcutaneously, intramuscularly or intravenously appli- be adorned. The preferred dose ranges for this application are (in mg / kg. day) oral 1 to 50 subcutaneous 1 to 50 intramuscular 0.05 to 10 intravenous 0.05 to 2 The substances can be administered in tablets, pills, Capsules or injection solutions can be formulated. For animals, the substances can can also be used in feed or as feed additives.
Schließlich eignen sich l-Phenylethan-1,2,2-triphosphonsäuren und deren Salze als Zusatz zu Präparaten m für die Herstellung von 99m-Technetium-Radiodiagnostika.Finally, l-phenylethane-1,2,2-triphosphonic acids and are suitable their salts as an additive to preparations for the production of 99m technetium radiodiagnostics.
Die Erfindung wird durch die nachstehenden Beispiele und Versuche weiter erläutert.The invention is illustrated by the following examples and experiments further explained.
Die NMR-Messungen wurden mit dem HX 90 R Spektrometer, Bruker, Analytische Meßtechnik GmbH., Rheinstetten, durchgeführt. Bei den Umsetzungen mit Dialkylphosphitnatrium und Carbanionen wurden absolute Lösungsmittel verwendet und unter N2-Schutzgas gearbeitet.The NMR measurements were made with the HX 90 R spectrometer, Bruker, Analytische Meßtechnik GmbH., Rheinstetten. In the reactions with dialkyl phosphite sodium and carbanions, absolute solvents were used and the process was carried out under an N2 protective gas.
Bezugsbeispiele zur Herstellung der Ausgangsmaterialien Bezugsbeispiel 1: Diethylphosphitnatrium, 1M Lösung in THF: Zu einer Suspension von 60 g NaH-Paste (Merck, 80 % NaH, 20 % Paraffinöl, 48 g NaH, (2 Mol)) in 800 ml abs. THF tropft man innerhalb von 8 h eine Lösung von 276 g Diethylphosphit (2 Mol) in 160 ml abs. THF. Nach beendeter Wasserstoffentwicklung wird 2 h zum Rückfluß erwärmt, auf Raumtemperatur abgekühlt und zu 2 1 mit abs. THF aufgefüllt.Reference examples for the preparation of the starting materials Reference example 1: Diethylphosphite sodium, 1M solution in THF: To a suspension of 60 g NaH paste (Merck, 80% NaH, 20% paraffin oil, 48 g NaH, (2 mol)) in 800 ml Section. THF is added dropwise within 8 h a solution of 276 g of diethyl phosphite (2 mol) in 160 ml abs. THF. After the evolution of hydrogen has ceased, the mixture is refluxed for 2 h heated, cooled to room temperature and added to 2 1 with abs. THF replenished.
Bezugsbeispiel 2 Diisopropylphosphitnatrium, 0,6 M Lösung in THF: Analog zum Bezugsbeispiel 1 wird die gewünschte Verbindung aus NaH und Diisopropylphosphit hergestellt.Reference Example 2 Diisopropylphosphite sodium, 0.6 M solution in THF: Analogously to reference example 1, the desired compound is made from NaH and diisopropyl phosphite manufactured.
Bezugsbeispiel 3 Trichlorvinylbenzol: Das Trichlorvinylbenzol wird analog J.G.Aston, J.D.Reference Example 3 Trichlorovinylbenzene: The trichlorovinylbenzene will analogous to J.G. Aston, J.D.
Newkirk, J. Dorsky und D.M. Jenkins Organic Synthesis" 23, 48 (1943); S.G. Cohnen, H.T. Wolosinski und P.J.Newkirk, J. Dorsky and D.M. Jenkins Organic Synthesis "23, 48 (1943); S.G. Cohnen, H.T. Wolosinski and P.J.
Scheurer, JACS 72, 3952 /1950) und J.H. Simons und D.F. Herman, JACS 65, 2064 (1943) ausgehend von C6H5COCH3 hergestellt: C6H5COCHCl 2: J.G. Aston et al, loc cit.Scheurer, JACS 72, 3952/1950) and J.H. Simons and D.F. Herman, JACS 65, 2064 (1943) prepared starting from C6H5COCH3: C6H5COCHCl 2: J.G. Aston et al, loc cit.
C6H5COCCl3 (94 %, 83 %): S.G. Cohnen et al, loc cit.C6H5COCCl3 (94%, 83%): S.G. Cohnen et al, loc cit.
C6H5CCl2CCl3 (80 %, 75 %, 84 %) : S.G. Cohnen et al, loc cit. und J.H. Simons et al, loc cit.C6H5CCl2CCl3 (80%, 75%, 84%): S.G. Cohnen et al, loc cit. and J.H. Simons et al, loc cit.
Die in J.H. Simons et al, loc cit. angegebene Reaktionstemperatur 2200 ist irreführend. C6H5COCC13 und PCl5 müssen bei 1300C zu C6H5CCl2CCl3 umgesetzt werden.The in J.H. Simons et al, loc cit. specified reaction temperature 2200 is misleading. C6H5COCC13 and PCl5 must be converted to C6H5CCl2CCl3 at 1300C will.
Beispiel 1 1-Phenylethan-1 ~2, 2-triphosphonsäurehexaethylester: Zu 400 ml 1 M Diethylphosphitnatrium in abs. THF tropft man innerhalb von 5 h bei Raumtemperatur eine Lösung von 20 g Trichlorvinylbenzol (0,096 M) in 50 ml abs.Example 1 1-Phenylethane-1-2, 2-triphosphonic acid hexaethyl ester: To 400 ml of 1 M sodium diethylphosphite in abs. THF is added dropwise over the course of 5 h at room temperature a solution of 20 g of trichlorovinylbenzene (0.096 M) in 50 ml of abs.
THF hinzu. Anschließend erwärmt man 8 h zum Rückfluß.THF added. The mixture is then refluxed for 8 h.
Zur Vervollständigung der Reaktion werden bei Raumtemperatur noch 100 ml (0,1 M) Na(O)P(OEt)2 in abs.To complete the reaction are still at room temperature 100 ml (0.1 M) Na (O) P (OEt) 2 in abs.
THF hinzugetropft. Nach 6 h Erwärmen unter Rückfluß kühlt man auf Raumtemperatur ab, neutralisiert den Ansatz mit konz. Essigsäure und engt im Rotationsverdampfer im Wasserstrahlvakuum ein. Der ölige Rückstand wird mit 500 ml CH2Cl2 und 500 ml H2O versetzt und geschüttelt. Die wässrige Phase wird abgetrennt und wiederholt mit CH2Cl2 extrahiert. Die vereinigten CH2Cl2-Phasen werden nach Trocknen über MgSO4 sicc. im Rotationsverdampfer eingeengt.THF was added dropwise. After 6 hours of refluxing, the mixture is cooled Room temperature from, neutralizes the approach with conc. Acetic acid and concentrated in a rotary evaporator in a water jet vacuum. The oily residue is mixed with 500 ml of CH2Cl2 and 500 ml H2O added and shaken. The aqueous phase is separated off and repeated extracted with CH2Cl2. The combined CH2Cl2 phases are dried over MgSO4 sicc. concentrated in a rotary evaporator.
Der ölige Rückstand trennt sich in eine obere klare Paraffinölphase, die mit Ligroin 30/50 entfernt werden kann, und in eine viskose, untere Rohesterphase, die am Dünnschichtverdampfer bei 82°C/0,1 Torr von leichtflüchtigen Nebenprodukten befreit wird. Der nahezu farblose Ester verbleibt als unter diesen Bedingungen nicht flüchtige Flüssigkeit mit einer Ausbeute von 39,5 g (80 %). Das Produkt ist nach NMR-Spektrum rein.The oily residue separates into an upper clear paraffin oil phase, which can be removed with Ligroin 30/50, and into a viscous, lower crude ester phase, that of the thin film evaporator at 82 ° C / 0.1 Torr of volatile by-products is released. The almost colorless ester does not remain as under these conditions volatile liquid with a yield of 39.5 g (80%). The product is after Pure NMR spectrum.
C20H37OgP3 514,30 C: gef. 46,1 % ber. 46,7 % H: gef. 7,4 % ber. 7,3 % P: gef. 18,1 % ber. 18,1 % A =24,45 ppm, gB = 22,06 ppm, dC = 19,97 ppm, JAB -62,4 Hz, JAC = 5,5 Hz, JBC= 0,3 Hz (0,1 m in CDCl ) Beispiel 2 1-Phenylethan-1,2,2-triphosphonsäurehexaisopropylester Analog Beispiel 1 wird die gewünschte Verbindung aus 1543 ml 0,5 M Diisopropylphosphitnatrium und 40 g (0,096 M) Trichlorvinylbenzol erhalten. Man erhält 92 g (80 %) eines hochviskosen Öles, das aus Ligroin 30/50 verlustreich umkristallisiert werden kann. Farblose Plättchen vom Schmp. 61 - 620C, NMR-spektroskopisch sauber.C20H37OgP3 514.30 C: found. 46.1% calc. 46.7% H: found. 7.4% calc. 7.3 % P: found 18.1% calc. 18.1% A = 24.45 ppm, gB = 22.06 ppm, dC = 19.97 ppm, JAB -62.4 Hz, JAC = 5.5 Hz, JBC = 0.3 Hz (0.1 m in CDCl) Example 2 1-Phenylethane-1,2,2-triphosphonic acid hexaisopropyl ester Analogously to Example 1, the desired compound is obtained from 1543 ml of 0.5 M diisopropylphosphite sodium and 40 g (0.096 M) trichlorovinylbenzene. 92 g (80%) of a highly viscous one are obtained Oil that can be recrystallized from ligroin 30/50 with high losses. Colorless Platelets with a melting point of 61 ° -620 ° C., clean by NMR spectroscopy.
C26H49OgP3 598,40 C: gef. 51,7 % ber. 52,1 % H: gef. 8,3 % ber. 8,3 % P: gef. 15,6 % berg. 15,5 % ZA = 24,03 ppm, #B = 20,54 ppm, & = 18,54 ppm, JAB = 66,0 Hz, JAC = 2,7 Hz, JBC =° Hz (0,2 m in CDC135 3 Beispiel 3 Acidolyse des Esters nach Beispiel 1 zu l-Phenylethan-1'2,2,-triphosphonsäure mit konzentrierter HC1: 20 g 1-Phenylethan-1,2,2-triphosphonsäurehexaethylester (0,039 M) werden mit 150 ml konzentrierter Salzsäure versetzt und 6 h am Rückfluß gekocht. Nach Einengen am Rotationsverdampfer entsteht ein braungelbes Öl, welches nach einigen Stunden bei Raumtemperatur erstarrt. Durch Verreiben mit Aceton verbleibt die Säure als weißer Festkörper. Nach Aufarbeiten der Mutterlauge erhält man insgesamt 8,9 g (66 %) der Säure vom Schmp. 192 - 1980C (Zers.). Man erhält ein NMR-spektroskopisch sauberes Produkt.C26H49OgP3 598.40 C: found. 51.7% calc. 52.1% H: found. 8.3% cal. 8.3 % P: found 15.6% mountain 15.5% ZA = 24.03 ppm, #B = 20.54 ppm, & = 18.54 ppm, JAB = 66.0 Hz, JAC = 2.7 Hz, JBC = ° Hz (0.2 m in CDC135 3 example 3 acidolysis of Esters according to Example 1 to l-phenylethane-1'2,2, -triphosphonic acid with concentrated HC1: 20 g of 1-phenylethane-1,2,2-triphosphonic acid hexaethyl ester (0.039 M) are with 150 ml of concentrated hydrochloric acid are added and the mixture is refluxed for 6 h. After narrowing A brown-yellow oil is produced on the rotary evaporator, which after a few hours solidified at room temperature. By trituration with acetone, the acid remains as white solid. After working up the mother liquor, a total of 8.9 g (66 %) of the acid of m.p. 192 - 1980C (dec.). An NMR spectroscopy is obtained clean product.
Die freie Säure wird durch folgende NMR-Parameter charakterisiert (0,1 M in DMF): 24,72 ppm, #B = 18,62 ppm, #C = 18,12ppm, JAB -A B 24,72 ppm, C 51,1 Hz + 0,1 Hz, JAC = 9,8 Hz + 0,1 Hz, J = o 1 Hz+ 0,1 Hz.The free acid is characterized by the following NMR parameters (0.1 M in DMF): 24.72ppm, #B = 18.62ppm, #C = 18.12ppm, JAB -A B 24.72ppm, C 51.1 Hz + 0.1 Hz, JAC = 9.8 Hz + 0.1 Hz, J = o 1 Hz + 0.1 Hz.
Beispiel 4 Acidolyse des Esters nach Beispiel 1 zur l-Phenylethan-1,2,2-triphosphonsäure in Eisessig: 20 g des 1-Phenylethan-1,2,2-trisphosphonsäurehexaethylesters (0,039 M) werden mit 100 ml Eisessig und 1 ml H2S04 konz. versetzt und 9 h zum Rückfluß erwärmt.Example 4 Acidolysis of the ester according to Example 1 to give 1-phenylethane-1,2,2-triphosphonic acid in glacial acetic acid: 20 g of 1-phenylethane-1,2,2-trisphosphonic acid hexaethyl ester (0.039 M) are concentrated with 100 ml of glacial acetic acid and 1 ml of H2S04. added and refluxed for 9 h warmed up.
Danach kühlt man mit Eiswasser, wobei sich langsam die in Eisessig unlösliche Säure als grauer Festkörper abscheidet. Dieser kann abfiltriert und mit Aceton gewaschen werden. Nach Aufarbeiten der Mutterlauge ergibt sich insgesmat eine Ausbeute von 10,1 g (75 %).Then it is cooled with ice water, whereby slowly the in glacial acetic acid insoluble acid separates as a gray solid. This can be filtered off and with Acetone to be washed. After working up the mother liquor, the result is a total a yield of 10.1 g (75%).
Dieses Produkt enthält jedoch noch Spuren ( kleiner 1 %) von Essigsäure, die durch erneutes Auflösen der Säure in konzentrierter HC1, kurzzeitiges Erwärmen und anschließendes Einengen der Lösung vollständig beseitigt werden können. Einengen im Rotationsverdampfer und Waschen mit Aceton gibt spektroskopisch reines 1-Phenylethan-1,2,2-triphoshonsäure. Schmp. 192 bis 1980C (Zers.) 8 13 9 3 346,10 C: gef. 27,9 % ber. 27,7 % H: gef. 3,8 % ber. 3,8 % P: gef. 26,8 % ber. 26,9 %.However, this product still contains traces (less than 1%) of acetic acid, by redissolving the acid in concentrated HC1, brief heating and then concentrating the solution can be completely eliminated. Constrict in a rotary evaporator and washing with acetone gives spectroscopically pure 1-phenylethane-1,2,2-triphosonic acid. Mp. 192 to 1980 C (decomp.) 8 13 9 3 346.10 C: found. 27.9% calc. 27.7% H: found. 3.8% calc. 3.8% P: found. 26.8% cal. 26.9%.
Das erhaltene Produkt ist mit dem aus Beispiel 3 identisch.The product obtained is identical to that from Example 3.
Vergleichsbeispiel Die Threshold-Aktivität, d.h. die Fähigkeit des Komplexbildners, in unterstöchiometrischen Mengen das Scaling schwerlöslicher Calciumsalze (Gips und Calcit) zu verhindern bzw. zu verzögern, wurde in synthetischen Salzsolen, die in ihrer Zusammensetzung Lagerstätten-Injektionswässern niedriger Salinität entsprechen, getestet.Comparative example The threshold activity, i.e. the ability of the Complexing agent, the scaling of poorly soluble calcium salts in sub-stoichiometric amounts (Gypsum and calcite) to prevent or to delay, was in synthetic brine, the reservoir water for injection of low salinity in its composition correspond, tested.
Die Threshold-Aktivität der erfindungsgemäßen Diphosphonsäure wurde bei Gips im Impfbereich von 1 bis 20 ppm, bei Calcit von 5 bis 50 ppm untersucht.The threshold activity of the diphosphonic acid according to the invention was in the case of plaster of paris in the inoculation range from 1 to 20 ppm, in the case of calcite from 5 to 50 ppm.
Bei der Gips-Inhibition wurde eine Calciumsalzlösung von 2110d und bei der Calcit-Inhibition von 2820d, bestehend aus einer Mischhärte von 2310d Ca- und 510d Mg-Härte, eingesetzt. Die Testlösungen wurden 3 Tage bei 700C im Wasserbad gelagert. Anschließend wurde der in Lösung verbliebene Anteil an Erdalkalisalz bestimmt.A calcium salt solution of 2110d and with calcite inhibition of 2820d, consisting of a mixed hardness of 2310d Ca- and 510d Mg hardness. The test solutions were for 3 days at 700C in a water bath stored. The proportion of alkaline earth metal remaining in the solution was then determined.
Die Bestimmung erfolgte nach der Standard-Testmethode 03-74 der National Association of Corrosion Engineers.The determination was carried out according to the National standard test method 03-74 Association of Corrosion Engineers.
Außerdem wurde zum Vergleich noch die Threshold-Aktivität von Ethan-1,1,2, 2-tetraphosphonsäure bestimmt.In addition, the threshold activity of ethane-1,1,2, 2-tetraphosphonic acid determined.
Die Ergebnisse sind in den nachstehenden Tabellen I und II aufgeführt.The results are shown in Tables I and II below.
Tabelle 1 mq CaCO3 / g Säure Ethan-l,1,2,2-tetraphosphonsäure (1) 144 l-Phenylethan-1,2,2-triphosphonsäure (2) 850 Tabelle 2 a) Gipsinhibierung, eingesetzt 5230 mg CaSO4 /1 Verbliebener Calciumsulfatanteil in Lösung mg/l 1 ppm 3 ppm 5 ppm 10 ppm 20 ppm B1.W.Table 1 mq CaCO3 / g acid ethane-l, 1,2,2-tetraphosphonic acid (1) 144 l-phenylethane-1,2,2-triphosphonic acid (2) 850 Table 2 a) Gypsum inhibition, used 5230 mg CaSO4 / 1 Remaining calcium sulfate content in solution mg / l 1 ppm 3 ppm 5 ppm 10 ppm 20 ppm B1.W.
(1) 3247 3270 3468 4806 5036 3187 (2) 3387 4579 4908 5035 5078 3187 b) Calcitinhibierung, einsetzt 4248 mg CaCO3/l Verbliebener Calciumcarbonanteil in Lösung mg/l 5 ppm 10 ppm 20 ppm 40 ppm 50 ppm B1.W.(1) 3247 3270 3468 4806 5036 3187 (2) 3387 4579 4908 5035 5078 3187 b) Calcite inhibition, uses 4248 mg CaCO3 / l remaining calcium carbon content in solution mg / l 5 ppm 10 ppm 20 ppm 40 ppm 50 ppm B1.W.
(1) 2354 2314 2428 2289 2555 2354 (2) 3106 3368 3585 3682 3455 2354 Aus dem Vergleich der erfindungsgemässen 1-Phenvlethan-1,2,2-triphosphonsäure mit der bekannten Ethan-1,1,2,2-tetraphosphonsäure ist ersichtlich, daß die erfindungsgemässe Verbindung ein wesentliches Komplexierungsvermögen aufweist und eine wesentlich erhöhte Tresholdwirkung hat.(1) 2354 2314 2428 2289 2555 2354 (2) 3106 3368 3585 3682 3455 2354 From the comparison of the 1-phenylethane-1,2,2-triphosphonic acid according to the invention with the known ethane-1,1,2,2-tetraphosphonic acid can be seen that the invention Compound has an essential complexing capacity and an essential has increased threshold effect.
Ferner zeigte die erfindungsgemässe Verbindung im Vortest auf korrosionsschützende Eigenschaften günstige Inhibierungseffekte. Im Grauguß-Spantest, einem Vortest auf Korrosionsinhibierung, wurde bei pH 5,5 nur eine schwache und bei pH 9 eine sehr schwache bis schwache Rostbildung festgestellt.Furthermore, the compound according to the invention showed anti-corrosion properties in the preliminary test Properties favorable inhibition effects. In the gray cast iron frame test, a preliminary test Corrosion inhibition became only weak at pH 5.5 and very high at pH 9 weak to weak rust formation noted.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19843444678 DE3444678A1 (en) | 1984-12-07 | 1984-12-07 | 1-Phenylethane-1,2,2-triphosphonic acid, its water-soluble salts and esters, and their use |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19843444678 DE3444678A1 (en) | 1984-12-07 | 1984-12-07 | 1-Phenylethane-1,2,2-triphosphonic acid, its water-soluble salts and esters, and their use |
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| Publication Number | Publication Date |
|---|---|
| DE3444678A1 true DE3444678A1 (en) | 1986-06-19 |
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| Application Number | Title | Priority Date | Filing Date |
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| DE19843444678 Withdrawn DE3444678A1 (en) | 1984-12-07 | 1984-12-07 | 1-Phenylethane-1,2,2-triphosphonic acid, its water-soluble salts and esters, and their use |
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1984
- 1984-12-07 DE DE19843444678 patent/DE3444678A1/en not_active Withdrawn
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