EP0000930A1 - Acides N-carboxyalcane-aminoalcane-diphosphoniques, acides N-carboxyalcane-azacycloalcane diphosphoniques et acides N-carboxyalcane aminoaryle, alcane diphosphoniques, procédé pour leur préparation et leur utilisation comme agents complexants - Google Patents
Acides N-carboxyalcane-aminoalcane-diphosphoniques, acides N-carboxyalcane-azacycloalcane diphosphoniques et acides N-carboxyalcane aminoaryle, alcane diphosphoniques, procédé pour leur préparation et leur utilisation comme agents complexants Download PDFInfo
- Publication number
- EP0000930A1 EP0000930A1 EP78100697A EP78100697A EP0000930A1 EP 0000930 A1 EP0000930 A1 EP 0000930A1 EP 78100697 A EP78100697 A EP 78100697A EP 78100697 A EP78100697 A EP 78100697A EP 0000930 A1 EP0000930 A1 EP 0000930A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- radical
- acid
- hydrogen atom
- diphosphonic
- compound
- 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.)
- Granted
Links
- 239000002253 acid Substances 0.000 title claims abstract description 33
- 150000007513 acids Chemical class 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims description 3
- 239000003352 sequestering agent Substances 0.000 title 1
- -1 alkyl radical Chemical class 0.000 claims abstract description 48
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 17
- 150000003976 azacycloalkanes Chemical group 0.000 claims abstract description 16
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- XQRLCLUYWUNEEH-UHFFFAOYSA-N diphosphonic acid Chemical compound OP(=O)OP(O)=O XQRLCLUYWUNEEH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- 239000012736 aqueous medium Substances 0.000 claims abstract description 3
- 150000002148 esters Chemical class 0.000 claims abstract description 3
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 claims abstract 4
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims abstract 3
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052799 carbon Inorganic materials 0.000 claims abstract 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims abstract 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 34
- 150000001875 compounds Chemical class 0.000 claims description 21
- 125000001424 substituent group Chemical group 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 125000004181 carboxyalkyl group Chemical group 0.000 claims description 2
- 150000001350 alkyl halides Chemical class 0.000 claims 2
- 125000003118 aryl group Chemical group 0.000 claims 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 2
- QUPDWYMUPZLYJZ-UHFFFAOYSA-N ethyl Chemical compound C[CH2] QUPDWYMUPZLYJZ-UHFFFAOYSA-N 0.000 claims 2
- GODCLGCOHHTLHX-UHFFFAOYSA-N 3,3-diphosphonopropanoic acid Chemical compound OC(=O)CC(P(O)(O)=O)P(O)(O)=O GODCLGCOHHTLHX-UHFFFAOYSA-N 0.000 claims 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims 1
- 230000002411 adverse Effects 0.000 claims 1
- 125000004103 aminoalkyl group Chemical group 0.000 claims 1
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical group C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 claims 1
- GATNOFPXSDHULC-UHFFFAOYSA-N ethylphosphonic acid Chemical group CCP(O)(O)=O GATNOFPXSDHULC-UHFFFAOYSA-N 0.000 claims 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical group CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims 1
- 150000003254 radicals Chemical class 0.000 abstract description 3
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 150000001447 alkali salts Chemical class 0.000 abstract 2
- 229910052736 halogen Inorganic materials 0.000 abstract 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 abstract 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 abstract 1
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract 1
- 125000005001 aminoaryl group Chemical group 0.000 abstract 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 23
- 229910052698 phosphorus Inorganic materials 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 10
- 238000010992 reflux Methods 0.000 description 8
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- FRCICXIVPRNPLM-UHFFFAOYSA-N [amino(phosphono)methyl]phosphonic acid Chemical compound OP(=O)(O)C(N)P(O)(O)=O FRCICXIVPRNPLM-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- GPCTYPSWRBUGFH-UHFFFAOYSA-N (1-amino-1-phosphonoethyl)phosphonic acid Chemical compound OP(=O)(O)C(N)(C)P(O)(O)=O GPCTYPSWRBUGFH-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 150000003977 halocarboxylic acids Chemical class 0.000 description 4
- PCTMREJZUSEOQD-UHFFFAOYSA-N (1-amino-1-phosphonopropyl)phosphonic acid Chemical compound CCC(N)(P(O)(O)=O)P(O)(O)=O PCTMREJZUSEOQD-UHFFFAOYSA-N 0.000 description 3
- QEYMMOKECZBKAC-UHFFFAOYSA-N 3-chloropropanoic acid Chemical compound OC(=O)CCCl QEYMMOKECZBKAC-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- ISZIECUHZQGAPV-UHFFFAOYSA-N NP(O)(=O)OP(O)=O Chemical compound NP(O)(=O)OP(O)=O ISZIECUHZQGAPV-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- IUDGNRWYNOEIKF-UHFFFAOYSA-N 11-bromo-undecanoic acid Chemical compound OC(=O)CCCCCCCCCCBr IUDGNRWYNOEIKF-UHFFFAOYSA-N 0.000 description 2
- NVRVNSHHLPQGCU-UHFFFAOYSA-N 6-bromohexanoic acid Chemical compound OC(=O)CCCCCBr NVRVNSHHLPQGCU-UHFFFAOYSA-N 0.000 description 2
- WTCJJEJMYYASNT-UHFFFAOYSA-N 7-chloro-1-(2,4-difluorophenyl)-6-fluoro-4-oxo-1,8-naphthyridine-3-carboxylic acid Chemical compound C12=NC(Cl)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1=CC=C(F)C=C1F WTCJJEJMYYASNT-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 2
- QQWGVQWAEANRTK-UHFFFAOYSA-N bromosuccinic acid Chemical compound OC(=O)CC(Br)C(O)=O QQWGVQWAEANRTK-UHFFFAOYSA-N 0.000 description 2
- 230000021523 carboxylation Effects 0.000 description 2
- 238000006473 carboxylation reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- WBJINCZRORDGAQ-UHFFFAOYSA-N ethyl formate Chemical compound CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 150000003009 phosphonic acids Chemical class 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VMBKQCJPBAHOJQ-UHFFFAOYSA-N (1-amino-1-phosphonododecyl)phosphonic acid Chemical compound CCCCCCCCCCCC(N)(P(O)(O)=O)P(O)(O)=O VMBKQCJPBAHOJQ-UHFFFAOYSA-N 0.000 description 1
- IJCDULQTWJJMNB-UHFFFAOYSA-N (1-amino-3-hydroxy-1-phosphonopropyl)phosphonic acid Chemical compound OP(=O)(O)C(P(O)(O)=O)(N)CCO IJCDULQTWJJMNB-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- KGRYDYSUTVMJNV-UHFFFAOYSA-N 2-(1,1-diphosphonoethylimino)propanedioic acid Chemical compound OP(=O)(O)C(P(O)(O)=O)(C)N=C(C(O)=O)C(O)=O KGRYDYSUTVMJNV-UHFFFAOYSA-N 0.000 description 1
- CZHOSQVLPPLTGF-UHFFFAOYSA-N 3-amino-3,3-diphosphonopropanoic acid Chemical compound OP(=O)(O)C(P(O)(O)=O)(N)CC(O)=O CZHOSQVLPPLTGF-UHFFFAOYSA-N 0.000 description 1
- YBJGQSNSAWZZHL-UHFFFAOYSA-N 3-chloro-2,2-dimethylpropanoic acid Chemical compound ClCC(C)(C)C(O)=O YBJGQSNSAWZZHL-UHFFFAOYSA-N 0.000 description 1
- WNXNUPJZWYOKMW-UHFFFAOYSA-N 5-bromopentanoic acid Chemical compound OC(=O)CCCCBr WNXNUPJZWYOKMW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- OCRFGLXFNZWRHX-UHFFFAOYSA-N ClCC(C(=O)O)(C)C.ClCC(C(=O)O)(C)C Chemical compound ClCC(C(=O)O)(C)C.ClCC(C(=O)O)(C)C OCRFGLXFNZWRHX-UHFFFAOYSA-N 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- NVCBLOZVMWSNST-UHFFFAOYSA-N OP(=O)OP(O)=O.CNC1=CC=CC=C1 Chemical compound OP(=O)OP(O)=O.CNC1=CC=CC=C1 NVCBLOZVMWSNST-UHFFFAOYSA-N 0.000 description 1
- NFVZIERLAZUYBQ-UHFFFAOYSA-N [K].[Zn] Chemical compound [K].[Zn] NFVZIERLAZUYBQ-UHFFFAOYSA-N 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- QABLOFMHHSOFRJ-UHFFFAOYSA-N methyl 2-chloroacetate Chemical compound COC(=O)CCl QABLOFMHHSOFRJ-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 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
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 229940079864 sodium stannate Drugs 0.000 description 1
- HVTHJRMZXBWFNE-UHFFFAOYSA-J sodium zincate Chemical compound [OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Zn+2] HVTHJRMZXBWFNE-UHFFFAOYSA-J 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- 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
- 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
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/29—Development processes or agents therefor
- G03C5/305—Additives other than developers
- G03C5/3053—Tensio-active agents or sequestering agents, e.g. water-softening or wetting agents
Definitions
- the present invention relates to N-carboxyalkane-aminoalkane-diphosphonic acids, N-carboxyalkane-azacycloalkane-diphosphonic acids and N-carboxyalkane-aminoarylalkane-diphosphonic acids, and a process for their preparation.
- N-carboxymethylaminoalkane diphosphonic acids and N-carboxymethylaminoarylalkane diphosphonic acids are known, which can be obtained by reacting aminoalkane or aminoarylalkane diphosphonic acids in an alkaline medium with formaldehyde and alkali metal cyanide while heating to 70-150 ° C receives.
- R 1 is as defined above for formula II, while R 2 is a hydrogen atom, or a lower alkyl radical, or the same radical as R 3 , or R 2 together with the substituent R 1 is an alkylene group having 3 to 5 C atoms and an azacycloalkane ring with the moiety forms, and R 3 is a carboxyl-substituted unbranched or branched alkyl radical, or a dicarboxyl-substituted alkyl radical.
- New compounds of this type are N-carboxymethane-azacycloheptane-2,2-diphosphonic acid, N-carboxypentane-1-aminoethane-1,1-diphosphonic acid, N-carboxyethane-1-aminoethane-1,1-diphosphonic acid, N-carboxy -2,2-dimethylpropane-aminomethane-diphosphonic acid, N-10-carboxydecane-aminomethane-diphosphonic acid, N, N-bis-10-carboxydecane-aminomethane-diphosphonic acid and N- (1,1-diphosphonoprop-1-yl) -DL -aminosuccinic acid.
- Suitable compounds for the carboxylation of the aminoalkane, aminoarylalkane or azacycloalkane diphosphonic acids are, for example, monochloro- or bromoacetic acid, 6-bromohexanoic acid, 3-chloropropionic acid, 3-chloro 2,2-dimethylpropionic acid (ß-chloro-pivalic acid), 11-bromundecanoic acid, and as dicarboxylic acid bromosuccinic acid.
- the diphosphonic acid and halocarboxylic acid are advantageously suspended in water and completely or partially neutralized with alkali metal hydroxide.
- the reaction time and temperature are 0.5 to 3 hours and 50 - 160 ° C, advantageously 60 to 110 ° C.
- alkali hydroxide e.g. Alkali carbonate or, for special purposes, alkali and alkaline earth hydroxides together, e.g. Sodium or calcium hydroxide or alkali heavy metal hydroxides, e.g. Use sodium aluminate, sodium zincate or sodium stannate.
- Products manufactured in this way are particularly suitable for corrosion protection agents and for products in the treatment of service water.
- the solutions are used directly, the salts crystallize or, after ion exchange, the acid is obtained by methods known per se, such as evaporation concentration or precipitation or extraction with organic solvents.
- the carboxylation gives, depending on the molar ratios used and the aminodiphosphonic acid used, single or multiple carboxyalkylated products.
- a molar ratio of the reactants of 1: 1 N-carboxyalkane-aminoalkane-diphosphonic acids are preferably obtained.
- a molar ratio of the reactants of aminodiphosphonic acid: halocarboxylic acid of 1: 2 to 1: 3 preferably gives N, N-bis-carboxyalkane-aminoalkane-diphosphonic acids.
- the substances obtained according to the present invention can be used wherever a good complex binding capacity with respect to di- and polyvalent metal ions is required. They are particularly characterized by their resistance to hydrolysis at high temperatures. They can be used in all media in which the hardness constituents of the water interfere or in which all influences of polyvalent metal ions are to be eliminated.
- the treatment of hard water, textile treatment baths, paper production, photographic processing baths, electroplating baths and tanning are to be mentioned here in detail.
- These diphosphonic acids are also suitable for stabilizing the water hardness in substoichiometric amounts. They can also serve as stabilizers for dispersions and suspensions.
- the products according to the invention have the properties of phosphonic acids and aminocarboxylic acids, they offer application-related advantages over the phosphonic acids or aminocarboxylic acids alone, which are greater than the sum of their own of the individual components.
- the N, N-bis-carboxymethane-1-aminoethane-1,1-diphosphonic acid could be crystallized with methanol / ethanol in a yield of 91.3% Theory can be gained.
- the reaction product is treated with an acid exchanger (Lewatit S 100) and the solution is concentrated.
- the result is a light yellow, viscous oil which is crystallized with methanol / ethanol.
- After drying in a water jet vacuum at 80 ° C. 25.4 g of N-carboxy are obtained methane-1-aminoethane-1,1-diphosphonic acid, which corresponds to a yield of 96.6% of theory.
- a conversion of 73.4% of theory was determined by determining the free amino groups using the Van Slyke method.
- 140 g of 50% potash are added to a mixture of 51 g of 1-aminoethane-1,1-diphosphonic acid, 27.2 g of 3-chloropropionic acid and 150 ml of water with stirring at 70 ° C. in the course of one hour lye was added dropwise and the clear solution was then refluxed for two hours.
- a conversion of 73.5% of theory could be determined by determining the primary amino groups in the solution.
- the resulting solution has a content of about 20% N, N-bis-carboxymethylene-1-aminoethane-1,1-diphosphonic acid.
- the thin-layer chromatographic analysis shows a content of about 20% N-carboxyethane-3-hydroxy-1-aminopropane-1,1-diphosphonic acid and about 80% N, N-bis-carboxyethane-3-hydroxy-1-aminopropane-1 , 1-diphosphonic acid.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Water Supply & Treatment (AREA)
- General Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Detergent Compositions (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2737259 | 1977-08-18 | ||
| DE19772737259 DE2737259A1 (de) | 1977-08-18 | 1977-08-18 | N-carboxyalkan-aminoalkan-diphosphonsaeuren, n-carboxyalkan-azacycloalkan-diphosphonsaeuren und n-carboxyalkan-aminoarylalkan-diphosphonsaeuren sowie verfahren zu ihrer herstellung |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0000930A1 true EP0000930A1 (fr) | 1979-03-07 |
| EP0000930B1 EP0000930B1 (fr) | 1981-07-01 |
Family
ID=6016730
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP78100697A Expired EP0000930B1 (fr) | 1977-08-18 | 1978-08-17 | Acides N-carboxyalcane-aminoalcane-diphosphoniques, acides N-carboxyalcane-azacycloalcane diphosphoniques et acides N-carboxyalcane aminoaryle, alcane diphosphoniques, procédé pour leur préparation et leur utilisation comme agents complexants |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0000930B1 (fr) |
| JP (1) | JPS5470222A (fr) |
| AT (1) | AT369015B (fr) |
| CA (1) | CA1106843A (fr) |
| DE (2) | DE2737259A1 (fr) |
| DK (1) | DK364478A (fr) |
| IE (1) | IE47653B1 (fr) |
| IT (1) | IT1098368B (fr) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0059259A1 (fr) * | 1981-02-28 | 1982-09-08 | Benckiser-Knapsack GmbH | Procédé de préparation d'acides N-(carboxy-alkyl) amino-1 alcane diphosphoniques-1,1 et leurs sels alcalins |
| EP0118395A2 (fr) * | 1983-03-03 | 1984-09-12 | Ciba-Geigy Ag | Procédé pour inhiber la corrosion des surfaces métalliques et/ou l'entartrage de celles-ci |
| EP0286874A1 (fr) * | 1987-04-13 | 1988-10-19 | Minnesota Mining And Manufacturing Company | Compositions de développement pour matériaux photographiques à l'halogénure d'argent |
| WO2020070543A1 (fr) * | 2018-10-03 | 2020-04-09 | Italmatch Chemicals S.P.A. | Procédé de fabrication d'acides aminés de n-alkyl-diphosphonate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2318416A1 (de) * | 1973-04-12 | 1974-11-07 | Benckiser Knapsack Gmbh | N-carboxialkan-aminoalkan- bzw. n-carboxialkan-aminoarylalkan-phosphonsaeuren sowie verfahren zu ihrer herstellung |
-
1977
- 1977-08-18 DE DE19772737259 patent/DE2737259A1/de not_active Withdrawn
-
1978
- 1978-08-09 IT IT26633/78A patent/IT1098368B/it active
- 1978-08-17 CA CA309,547A patent/CA1106843A/fr not_active Expired
- 1978-08-17 DK DK364478A patent/DK364478A/da unknown
- 1978-08-17 JP JP9957578A patent/JPS5470222A/ja active Pending
- 1978-08-17 EP EP78100697A patent/EP0000930B1/fr not_active Expired
- 1978-08-17 DE DE7878100697T patent/DE2860812D1/de not_active Expired
- 1978-08-18 IE IE1681/78A patent/IE47653B1/en unknown
- 1978-08-18 AT AT0602778A patent/AT369015B/de not_active IP Right Cessation
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2318416A1 (de) * | 1973-04-12 | 1974-11-07 | Benckiser Knapsack Gmbh | N-carboxialkan-aminoalkan- bzw. n-carboxialkan-aminoarylalkan-phosphonsaeuren sowie verfahren zu ihrer herstellung |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0059259A1 (fr) * | 1981-02-28 | 1982-09-08 | Benckiser-Knapsack GmbH | Procédé de préparation d'acides N-(carboxy-alkyl) amino-1 alcane diphosphoniques-1,1 et leurs sels alcalins |
| EP0118395A2 (fr) * | 1983-03-03 | 1984-09-12 | Ciba-Geigy Ag | Procédé pour inhiber la corrosion des surfaces métalliques et/ou l'entartrage de celles-ci |
| EP0118395A3 (en) * | 1983-03-03 | 1986-05-21 | Ciba-Geigy Ag | Process for inhibiting corrosion of metallic surfaces and/or scale deposits thereon |
| EP0286874A1 (fr) * | 1987-04-13 | 1988-10-19 | Minnesota Mining And Manufacturing Company | Compositions de développement pour matériaux photographiques à l'halogénure d'argent |
| WO2020070543A1 (fr) * | 2018-10-03 | 2020-04-09 | Italmatch Chemicals S.P.A. | Procédé de fabrication d'acides aminés de n-alkyl-diphosphonate |
Also Published As
| Publication number | Publication date |
|---|---|
| CA1106843A (fr) | 1981-08-11 |
| ATA602778A (de) | 1982-04-15 |
| JPS5470222A (en) | 1979-06-05 |
| IE781681L (en) | 1979-02-18 |
| IT7826633A0 (it) | 1978-08-09 |
| DE2860812D1 (en) | 1981-10-08 |
| DE2737259A1 (de) | 1979-03-01 |
| EP0000930B1 (fr) | 1981-07-01 |
| IE47653B1 (en) | 1984-05-16 |
| DK364478A (da) | 1979-02-19 |
| AT369015B (de) | 1982-11-25 |
| IT1098368B (it) | 1985-09-07 |
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