CA1106843A - N-carboxy-alkane-aminoalkane-diphosphonic acids, n- carboxy-alkane-azacycloalkane-diphosphonic acids and n-carboxy-alkane-aminoaryl-alkane-diphosphonic acids and process for theirproduction - Google Patents
N-carboxy-alkane-aminoalkane-diphosphonic acids, n- carboxy-alkane-azacycloalkane-diphosphonic acids and n-carboxy-alkane-aminoaryl-alkane-diphosphonic acids and process for theirproductionInfo
- Publication number
- CA1106843A CA1106843A CA309,547A CA309547A CA1106843A CA 1106843 A CA1106843 A CA 1106843A CA 309547 A CA309547 A CA 309547A CA 1106843 A CA1106843 A CA 1106843A
- Authority
- CA
- Canada
- Prior art keywords
- acid
- carboxy
- alkane
- diphosphonic
- diphosphonic acid
- 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.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims description 14
- 239000002253 acid Substances 0.000 title abstract description 29
- 150000007513 acids Chemical class 0.000 title abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 229910018828 PO3H2 Inorganic materials 0.000 claims abstract description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 3
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 8
- FRCICXIVPRNPLM-UHFFFAOYSA-N [amino(phosphono)methyl]phosphonic acid Chemical compound OP(=O)(O)C(N)P(O)(O)=O FRCICXIVPRNPLM-UHFFFAOYSA-N 0.000 claims description 7
- -1 haloalkane monocarboxylic acid Chemical class 0.000 claims description 7
- 150000003977 halocarboxylic acids Chemical class 0.000 claims description 7
- 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 claims description 6
- QEYMMOKECZBKAC-UHFFFAOYSA-N 3-chloropropanoic acid Chemical compound OC(=O)CCCl QEYMMOKECZBKAC-UHFFFAOYSA-N 0.000 claims description 5
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 5
- NVRVNSHHLPQGCU-UHFFFAOYSA-N 6-bromohexanoic acid Chemical compound OC(=O)CCCCCBr NVRVNSHHLPQGCU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- QQWGVQWAEANRTK-UHFFFAOYSA-N bromosuccinic acid Chemical compound OC(=O)CC(Br)C(O)=O QQWGVQWAEANRTK-UHFFFAOYSA-N 0.000 claims description 4
- WBJINCZRORDGAQ-UHFFFAOYSA-N ethyl formate Chemical compound CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- 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 claims description 2
- BYOBJKVGOIXVED-UHFFFAOYSA-N (2-phosphonoazepan-2-yl)phosphonic acid Chemical compound OP(O)(=O)C1(P(O)(O)=O)CCCCCN1 BYOBJKVGOIXVED-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- WNXNUPJZWYOKMW-UHFFFAOYSA-N 5-bromopentanoic acid Chemical compound OC(=O)CCCCBr WNXNUPJZWYOKMW-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- XZTIUQAKASWQJM-UHFFFAOYSA-N OP(=O)OP(O)=O.NCC1=CC=CC=C1 Chemical compound OP(=O)OP(O)=O.NCC1=CC=CC=C1 XZTIUQAKASWQJM-UHFFFAOYSA-N 0.000 claims description 2
- 239000012736 aqueous medium Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- QABLOFMHHSOFRJ-UHFFFAOYSA-N methyl 2-chloroacetate Chemical compound COC(=O)CCl QABLOFMHHSOFRJ-UHFFFAOYSA-N 0.000 claims description 2
- 229940116254 phosphonic acid Drugs 0.000 claims 4
- 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 claims 2
- IUDGNRWYNOEIKF-UHFFFAOYSA-N 11-bromo-undecanoic acid Chemical compound OC(=O)CCCCCCCCCCBr IUDGNRWYNOEIKF-UHFFFAOYSA-N 0.000 claims 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 claims 1
- 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 claims 1
- YBJGQSNSAWZZHL-UHFFFAOYSA-N 3-chloro-2,2-dimethylpropanoic acid Chemical compound ClCC(C)(C)C(O)=O YBJGQSNSAWZZHL-UHFFFAOYSA-N 0.000 claims 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims 1
- 150000001350 alkyl halides Chemical class 0.000 claims 1
- XQRLCLUYWUNEEH-UHFFFAOYSA-N diphosphonic acid Chemical compound OP(=O)OP(O)=O XQRLCLUYWUNEEH-UHFFFAOYSA-N 0.000 claims 1
- 230000003472 neutralizing effect Effects 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- 239000003112 inhibitor Substances 0.000 abstract description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 48
- 235000011118 potassium hydroxide Nutrition 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000004458 analytical method Methods 0.000 description 11
- 238000010992 reflux Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical compound NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 description 3
- 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
- 230000021523 carboxylation Effects 0.000 description 2
- 238000006473 carboxylation reaction Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000003009 phosphonic acids Chemical class 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 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 1
- NGWKGSCSHDHHAJ-YPFQVHCOSA-N Liquoric acid Chemical compound C1C[C@H](O)C(C)(C)C2CC[C@@]3(C)[C@]4(C)C[C@H]5O[C@@H]([C@](C6)(C)C(O)=O)C[C@@]5(C)[C@@H]6C4=CC(=O)C3[C@]21C NGWKGSCSHDHHAJ-YPFQVHCOSA-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
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 229910001860 alkaline earth metal 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
- 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
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001627 detrimental effect Effects 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
- 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
- 239000008233 hard water Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 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
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-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
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003141 primary amines Chemical group 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
- 239000000126 substance Substances 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
Landscapes
- 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)
Abstract
ABSTRACT OF THE DISCLOSURE
An N-carboxy-alkane-aminoalkane-diphosphonic acids, N-carboxy-alkane-azacycloalkane-diphosphonic acids and N-carboxy-alkane-aminoaryl-alkane-diphosphonic acid having the general formula wherein R is H, CH3, -(CH2)10CH3, C6H5, C2H4OH or CH2COOH, R1 is PO3H2,-R'2 is H, CH3 or R3 or together with R1 forms a ring of formula -(CH2)5- and R3 is (CH2)mCOOH where m is 2 to 12, -CH2-C(CH3)2-COOH or .
The compounds are suitable particularly for corrosion inhibitors and for products used in the treatment of service water.
An N-carboxy-alkane-aminoalkane-diphosphonic acids, N-carboxy-alkane-azacycloalkane-diphosphonic acids and N-carboxy-alkane-aminoaryl-alkane-diphosphonic acid having the general formula wherein R is H, CH3, -(CH2)10CH3, C6H5, C2H4OH or CH2COOH, R1 is PO3H2,-R'2 is H, CH3 or R3 or together with R1 forms a ring of formula -(CH2)5- and R3 is (CH2)mCOOH where m is 2 to 12, -CH2-C(CH3)2-COOH or .
The compounds are suitable particularly for corrosion inhibitors and for products used in the treatment of service water.
Description
~1~6843 The present invention provides N-carboxy-alkane-amino-alkane-diphosphoric acids, N-carboxy-alkane-azacycloalkane-diphosphonic acids and N-carboxy-alkane-aminoaryl-alkane-diphos-phonic acids as well as a process for their production.
German Patent No. 23 18 416 discloses N-carboxy-methyl-aminoalkane diphosphonic acids and N-carboxy-methyl aminoaryl-alkane-diphosphonic acids. They are obtained by reacting amino-alkane or aminoaryl-alkane diphosphonic acids in an alkaline medium with formaldehyde and alkali metal cyanide while heating to temperatures of from 70 to 150C. This process has the dis-advantage that very great care must be taken when working with alkali metal cyanides and, therefore, extensive safety precautions are indispensable.
It has now been found that these compounds of German Patent No. 23 18 416 as well as novel N-carboxy-alkane-aminoalkane-diphosphonic acids, N-carboxy-alkane-azacycloalkane-diphosphonic acids and N-carboxy-alkane-aminoaryl-alkane diphosphonic acids can be produced ~nder more favourable operating conditions when aminoalkane-,azacycloalkane- or aminoaryl-alkane-diphosphonic acids having the general formula P~3H2 R - ~ - N /
Rl R2 wherein R represents H, (CH2)x-CH3, C2H4OH, CH2COOH, C6H5, (CH2)n-N(CH2COOH)~ or (CH2)n-PO3H2, wherein n is 1 or 2 and x is 0-10 or together with R2 a ring of the formula (CH2)3 5, Rl is PO3H2 and R2 is H, CH3 or together with R2 a ring of the formula (CH2)3 5 are reacted with straight-chain or branched halo-alkane monocarboxylic acids containing 2 to 12 carbon atoms or with haloalkane dicarboxylic acids or their alkali metal salts or esters at temperatures ranging from 50 to 160C in a molar ratio of 1:1 to 1:3 in an aqueous medium at a pH value between 4 and 12.
In this manner compounds having the general formula ¦ ~ R3 R - C - N
are obtained in which R and Rl have the meanings defined herein-before while R3 is -(CH2)mCOOH, where m = 2-12, straight or branched chain, -CH2-C(CH3)2-COOH or -CH - COOH and R2 is H or CH3, R3 or, together with CH2- COOH
R a ring of the formula (CH2)3 5.
Suitable novel compounds include N-carboxy-methane-azacycloheptane-2,2-diphosphonic acid, N-carboxy-pentane-l-amino-ethane-l,l-diphosphonic acid, N-carboxy-ethane-l,l-aminoethane-l,l-diphosphonic acid, N-carboxy-2,2-dimethyl-propane-aminomethane-diphosphonic acid, N-10-carboxy-decane-aminomethane-diphosphonic acid, N,N-bis~10-carboxy-decane-aminomethane-diphosphonic acid and N-(l,1-diphosphono-prop-1-yl)-DL-aminosuccinic acid.
Suitable compounds for the carboxylation of the amino-alkane-, aminoaryl-alkane- or azacycloalkane-phosphonic acids are, for example, monochloro acetic acid or bromo acetic acid, 6-bromo hexanoic acid, 3-chloro-propionic acid, 3-chloro-2,2-dimethyl propionic acid (~-chloro pivalic acid), ll-bromo-hendecanoic acid and bromo succinic acid as dicarboxylic acid.
For the production of the compounds according to the invention it is possible to dissolve the aminophosphonic acid in the alkali liquor used in excess, whereupon the halocarboxylic acid is added so that the pH does not fall below 4. The process can be carried out in a much more elegant manner if the alkali liquor is used only in amounts required for the desired pH value between 4 and 12, preferably between 7 and 9. The further dosage of alkali liquor and halocarboxylic acid is then controlled as a function of the pH value.
In many cases it is advantageous to suspend the phosphonic ~1~P6843 acid and halocarboxylic acid in water and to carry out the neutralization completely or partially with alkali metal hydroxide.
When ut:ilizing the heat of neutralization the reaction time is from 0~5 to 3 hours and the temperature from 50 to 160 C, advantageously from 80 to 120C.
In this manner completely or partially neutralized salts are obtained as reaction products, which can be converted into the face acids by means of cation exchangers.
Instead of using alkali metal hydroxide it is possible to use, for example, alkali metal carbonate directly or, for special purposes, alkali and alkaline earth metal hydroxides jointly, for example, sodium and calcium hydroxide or alkali-heavy-metal hydroxides, for example, sodium aluminate, sodium zincate or sodium stannate.
Products thus produces are suitable particularly for corrosion inhibitors and for products used in the treatment of service water.
Depending on the properties or on the intended purpose, the solutions are used directly, the salts are crystallized or, after ion exchange, the acid is obtained by means of conventional processes, such as concentration by evaporation or precipitation or extraction with organic solvents.
Singly or multiply carboxy-alkylated products are obtained in the carboxylation depending on the molar ratios used and on the aminophosphonic acid used. At a molar ratio of the reactants of 1:1 N-carboxy-alkane-aminoalkane-diphosphonic acids are preferably obtained. A molar radio of the reactants amino-phosphonic acid:
halocarboxylic acid of 1:2 to 1:3 results preferably in the production of N,N-bis-carboxy-alkane-aminoalkane-diphosphonic acids.
The substances obtained according to the present invention can be used whenever good complexing efficiency with ~(P6~343 respect to 2- and polyvalent metal ions is required. They are also distinguished particularly by their hydrolyzation stability at high temperatures. They can be used in all the media in which the hardness salts of the water have a detrimental effect or in which influences of polyvalent metal ions must be eliminated.
This relates particularly to the treatment of hard water, baths for treating textiles, paper making and tanning. Moreover, these phosphonic acids are suitable for stabilizing the hardness of water in amounts below the stoichiometric amount. They can also serve as stabilizers for dispersions and suspensions.
Since the products according to the invention have the properties of phosphonic acids and aminocarboxylic acids, they have syenergistic advantages as compared with the phosphonic acid or aminocarboxylic acids alone. These advantages exceed the sum of the individual components.
The present invention will be further illustrated by way of the following Examples.
Example 1 6.72 kg of a 50% caustic potash solution are put into a stirring apparatus fitted with thermometer and reflux condenser and 2.05 kg of 1 aminoethane-l,l-diphosphonic acid are so added that the bottom temperature does not rise above 60C. Within one hour a solution of 1.89 kg of monochloroacetic acid in 2.2 kg of water is added dropwise, followed by heating for three hours to 10 0C .
After freeing an aliquot portion of the reaction product from salt by means of an intensely acid cation exchanger and concentrating the solution the N,N-bis-carboxy-methane-l-amino-ethane-l,l-diphosphonic acid can be obtained by crystallizing with methanol/ethanol. The yield is 91.3% of the theoretical yield.
~ 6843 Analysis computed: C 22.40~ N 4.36% P 19.29%
obtained: C 22.6 % N 4.4 % P 19.3 %
molar ratio: C : P : N = 5.99 : 1.98 : 1 -Example 2 28 g of potassium hydroxide are dissolved in 100 ml of water and 20.5 g of l-aminoethane-l,l-diphosphonic acid are added.
13.9 g of bromoacetic acid are then added, whereupon the solution is boiled for 3 hours with reflux.
The reaction product is treated with an acid exchanger (e.g. supplied under the trademark ~ewatit S100) and the solution is concentrated. The result is a bright yellow viscous oil, which is crystallized with methanol/ethanol. After drying in a water-jet vacuum at 80C 25.4 g of carboxy-methane-l-aminoethane-l,l-diphosphonic acid are obtained corresponding to a yield of 96.6%
of the theoretical yield.
Analysis computed: C 18.26% N 5.32% P 23.55%
obtained: C 17.6 ~ N 5.2 % P 23.3 %
molar ratio: C : P : N = 3.95 : 2.02 : 1 Example 3 47.8 g of aminomethane-diphosphonic acid are dissolved in 148 g of a 50% caustic potash solution at 60C and a solution of 99.4 g of potassium salt of monochloroaceti~ acid in 250 ml of water is added, whereupon the solution is heated for three hours to 80-90C.
After treating the reaction solution in the manner described in the preceding Example 75.2 g of N,N-bis-carboxy-methane-aminomethane-diphosphonic acid are obtained.
Analysis computed: C 19.56% N 4.56% P 20.17%
obtained: C 20.3 ~ N 4.7 % P 20.3 %
molar ratio: C : P : N = 5.04 : 1.95 : 1 ~ ~6843 Example 4 95.5 g of aminomethane diphosphonic acid are dissolved in 224 g of a 50% caustic potash solution at 60C, whereupon 300 ml of water and 54.3 g of chloroacetic methyl ester are added.
After boiling for -three hours with reflux the solution is cooled.
After treating the solution with an acid exchanger, concentrating, crystallizing and drying, 115 g of N-carboxy-methane-aminomethane-diphosphonic acid are obtained corresponding to 92.3% of the theoretical yield.
Analysis computed: C 14.47~ N 5.62% P 24.87%
obtained: C 15.1 % N 5.7 % P 25.0 %
molar ratio: C : P : N = 3.09 : 1.98 : 1 Example 5 13.4 g of phenyl-aminomethane diphosphonic acid are dissolved in a solution of 8 g of NaOH in 100 ml of water in such a way that the temperature does not exceed 60C, whereupon 4.8 g of monochloroacetic acid are added. The reaction solution is then kept for 3 hours at 110 C. Aftercooling the solution itis treated with an intensely acid exchanger.
From the concentrated solution 15 g of crystalline N-carboxy-methane-phenyl-aminomethane-diphosphonic acid are obtained by means of methanol.
Analysis computed: C 33.233 N 4.31% P 19.05~
obtained: C 32.8 % N 4.3 % P 18.6 %
molar ratio: C : P : N = 8.9 : 1.95 : 1 Example 6 54.8 g of l-aminopropane-l,l-diphosphonic acid are stixred in 200 ml of water and 14.6 g of basic zinc carbonate are slowly added. When the generation of gas is completed 140 g of a 50% caustic potash solution is added and upon cooling to 50C 47.3 g of monochloroacetic acid are added in portions.
~6~43 After boiling for two hours with reflux a clear, faintly yellow-colored solution of the potassium zinc salt of N,N-bis-carboxy-methane-l-aminopropane-l,l-diphosphonic acid is obtained.
Thin-layer chromatographical examination show a minimum reaction rate of 90~ of the theoretical rate. A portion of the solution is further treated as described in the preceding examples.
Analysis computed: C 25.09% N 4.18~ P 18.48~
obtained: C 24.5 % N 4.2 % P 18.2 %
molar ratio: C : P : N = 6.81 : 1.96 : l Example 7 90 g of potassium hydroxide are dissolved in 250 ml of distilled water and 103.6 g of azacycloheptane-2,2-diphosphonic acid are so added to this solution that the temperature does not exceed 60C, whereupon 38 g of monochloroacetic acid are added, followed by heating for 2 l/2 hours to 110C and cooling. By means of the method described in Example l, 102.5 g of N-carboxy-methane-azacycloheptane-2,2-diphosphonic acid are obtained from the solution.
Analysis computed: C 30.49~ N 4.44% P 19.66~
obtained: C 30.0 % N 4.5 % P 20.0 %
~ molar ratio: C : P : N = 7.8 : 2 : l ; Example 8 41 g of l-aminoethane-l,l-diphosphonic acid dissolved in 187 g of a 30~ caustic potash solution while stirring and 39 g of 6-bromo hexanoic acid are added at 60C. To complete the reaction the solution is slowly heated to 100C and left at this temperature for 3 hours. After treatment as in Example l, N-carboxy-pentane-l-aminoethane-l,l-diphosphonic acid is obtained.
By determining the free amino groups according to the method of Van Slyke a reaction rate of 73.4~ of the theoretical rate is obtained.
~ 6843 Example 9 140 g of a 50~ caustic potash solution are added dropwise to a mixture of 51 g of l-aminoethane-l,1-diphosphonic acid, 27.2 g of 3-chloro propionic acid and 150 ml of water within one hour at 70C while stirring. The clear solution is then boiled for two hours with reflux.
After further treatment of the solution 57.5 g of N-carboxy-ethane-l-aminoethane-l,l-diphosphonic acid are obtained.
Analysis computed: C 21.67% N 5.05% P 22.35~
obtained: C 20.5 % N 4.8 ~ P 21.3 %
molar ratio: C : N : P = 4.98 : 2 : 1 Example 10 34.6 g of 3-chloro-2,2-dimethyl-propionic acid ~-chloro pivalic acid) are added to a solution of 47.8 g of aminomethane diphosphonic acid in 288 g of a 30% caustic potash solution while stirring. The solution is heated to the boiling point within an hour and is kept at this temperature for 2 hours. After further treatment N-2-carboxy-2,2-dimethyl ethane-aminomethane-diphos-phonic acid is obtained.
By determining the primary amine groups in the solutiona reaction rate of 73.5% of the theoretical rate was determined.
Example 11 54.7 g of l-aminopropane-l,l-diphosphonic acid are dissolved in 150 g of a 40% solution of caustic soda and 49.5 g of DL-bromo succinic acid are added at 60C. The solution is then boiled for two hours with reflux in order to complete the reaction.
By quantitative thin-layer chromatography 21 g of l-aminopropane-l,l-diphosphonic acid and 51.4 g of N-(l,l-diphos-phonoprop-l-yl)-DL-aminosuccinic acid could be detected in the solution.
Example 12 47.8 g of aminomethane diphosphonic acid are dissolved 68~3 in 150 g of a 50% caustic potash solution and 88.8 g of ll-bromo hendecanoic acid are added to this solution at 80C. After boiling the solution for two hours with reflux and cooling it approximately 30% of aminomethane diphosphonic acid, approximately 60~ of N-10-carboxy-decane-aminomethane diphosphonic acid and approximately 10% of N,N-bis-10-carboxy-decane~aminomethane-diphosphonic acid could be detected by thin-layer chromatographical examinations.
Example 13 In a 1 cu m stirring apparatus provided with reflux condenser, heating unit, built in single-rod pH-measuring chain and 2 dropping funnels 127.7 kg of l-aminoethane-l,l-diphosphonic acid are dissolved in 292.2 kg of water and 69.8 kg of a 50%
caustic potash solution. By utilizing the heat of neutralization the solution is heated to 80C and 147.7 kg of a 80% monochloro-acetic acid solution and approximately 362 kg of a 50% caustic potash solution are added from the two receivers. The addition is so controlled that the pH value in the reaction medium is between 8.0 and 8.5. The reaction mixture can be kept at a temperature of 80 to 90C by the generating reaction heat. Upon completion of the inflow the pH is adjusted to 8.5 by means of caustic potash solution, whereupon the solution is stirred for an hour at 90 to 100C.
The solution thus obtained contains approximately 20%
of N,N-bis-carboxy- methane -l-aminoethane-l,l-diphosphonic acid.
Example 14 -58.7 g of 3-hydroxy-1-aminopropane-1,1-diphosphonic acid are fed to a solution of 84 g of KOH in 300 ml of water. The solution is heated to 60C and, while stirring vigorously, 56 g of 3-chloro propionic acid are so added that the temperature slowly increases to 80C. After boiling for three hours with reflux a faintly yellow colored solution is obtained. After treating the ~1~68~3 solution with an intensely acid ion exchanger, concentrating, crystallizing and drying it 81 g of slightly yellowish hygroscopic crystals are obtained. The thin-layer chromatographical analysis shows a content of approximately 20% of N-carboxy-ethane-3-hydroxy-l-aminopropane-l,l-diphosphonic acid and approximately 80% of N,N-bis-carboxy-ethane-3-hydroxy-1-aminopropane-1,1-diphosphonic acid.
Example 15 24.9 g of 2-carboxy-1-aminoethane-1,1-diphosphonic acid are dissolved in a 30% caustic potash solutlon at 50C while stirring and at this temperature 19 g of 5-bromo valeric acid are added. The solution is then boiled for 3 1/2 hours with reflux, cooled and treated with a cation exchanger, whereupon the acid solution is concentrated almost to dryness and fractionally crystallized with mixtures of methanol, ethanol and acetone. The yield of 2-carboxy-1,1-diphosphono-ethane-5-aminopentanoic acid is 24.5 g.
Analysis computed: C 27.52% N 4.01% P 17.74%
obtained: C 27.5 % N 3.9 % P 17.8 %
molar ratio: C : P : N = 8.23 : 2.06 : 1 Example 16 6.9 g of l-amino-dodecane-l,l-diphosphonic acid are dissolved in 56 g of a 10% caustic potash solution and 2.8 g of 3-chloro-2,2-dimethyl propionic acid are added at 60C, whereupon the solution is boiled for three hours with reflux. After treating the reaction solution with an acid cation exchanger the acid solution is filtered and concentrated. By crystallizing with methanol/water 6 g of N-2-carboxy-2,2-dimethyl-ethane-1-amino-decane-l,l-diphosphonic acid are obtained.
Analysis computed: C 45.84~ N 3.14% P 13.91%
obtained: C 47.8 % N 3.2 % P 14.4 %
molar ratio: C : P : N = 17.43 : 2.03 : 1
German Patent No. 23 18 416 discloses N-carboxy-methyl-aminoalkane diphosphonic acids and N-carboxy-methyl aminoaryl-alkane-diphosphonic acids. They are obtained by reacting amino-alkane or aminoaryl-alkane diphosphonic acids in an alkaline medium with formaldehyde and alkali metal cyanide while heating to temperatures of from 70 to 150C. This process has the dis-advantage that very great care must be taken when working with alkali metal cyanides and, therefore, extensive safety precautions are indispensable.
It has now been found that these compounds of German Patent No. 23 18 416 as well as novel N-carboxy-alkane-aminoalkane-diphosphonic acids, N-carboxy-alkane-azacycloalkane-diphosphonic acids and N-carboxy-alkane-aminoaryl-alkane diphosphonic acids can be produced ~nder more favourable operating conditions when aminoalkane-,azacycloalkane- or aminoaryl-alkane-diphosphonic acids having the general formula P~3H2 R - ~ - N /
Rl R2 wherein R represents H, (CH2)x-CH3, C2H4OH, CH2COOH, C6H5, (CH2)n-N(CH2COOH)~ or (CH2)n-PO3H2, wherein n is 1 or 2 and x is 0-10 or together with R2 a ring of the formula (CH2)3 5, Rl is PO3H2 and R2 is H, CH3 or together with R2 a ring of the formula (CH2)3 5 are reacted with straight-chain or branched halo-alkane monocarboxylic acids containing 2 to 12 carbon atoms or with haloalkane dicarboxylic acids or their alkali metal salts or esters at temperatures ranging from 50 to 160C in a molar ratio of 1:1 to 1:3 in an aqueous medium at a pH value between 4 and 12.
In this manner compounds having the general formula ¦ ~ R3 R - C - N
are obtained in which R and Rl have the meanings defined herein-before while R3 is -(CH2)mCOOH, where m = 2-12, straight or branched chain, -CH2-C(CH3)2-COOH or -CH - COOH and R2 is H or CH3, R3 or, together with CH2- COOH
R a ring of the formula (CH2)3 5.
Suitable novel compounds include N-carboxy-methane-azacycloheptane-2,2-diphosphonic acid, N-carboxy-pentane-l-amino-ethane-l,l-diphosphonic acid, N-carboxy-ethane-l,l-aminoethane-l,l-diphosphonic acid, N-carboxy-2,2-dimethyl-propane-aminomethane-diphosphonic acid, N-10-carboxy-decane-aminomethane-diphosphonic acid, N,N-bis~10-carboxy-decane-aminomethane-diphosphonic acid and N-(l,1-diphosphono-prop-1-yl)-DL-aminosuccinic acid.
Suitable compounds for the carboxylation of the amino-alkane-, aminoaryl-alkane- or azacycloalkane-phosphonic acids are, for example, monochloro acetic acid or bromo acetic acid, 6-bromo hexanoic acid, 3-chloro-propionic acid, 3-chloro-2,2-dimethyl propionic acid (~-chloro pivalic acid), ll-bromo-hendecanoic acid and bromo succinic acid as dicarboxylic acid.
For the production of the compounds according to the invention it is possible to dissolve the aminophosphonic acid in the alkali liquor used in excess, whereupon the halocarboxylic acid is added so that the pH does not fall below 4. The process can be carried out in a much more elegant manner if the alkali liquor is used only in amounts required for the desired pH value between 4 and 12, preferably between 7 and 9. The further dosage of alkali liquor and halocarboxylic acid is then controlled as a function of the pH value.
In many cases it is advantageous to suspend the phosphonic ~1~P6843 acid and halocarboxylic acid in water and to carry out the neutralization completely or partially with alkali metal hydroxide.
When ut:ilizing the heat of neutralization the reaction time is from 0~5 to 3 hours and the temperature from 50 to 160 C, advantageously from 80 to 120C.
In this manner completely or partially neutralized salts are obtained as reaction products, which can be converted into the face acids by means of cation exchangers.
Instead of using alkali metal hydroxide it is possible to use, for example, alkali metal carbonate directly or, for special purposes, alkali and alkaline earth metal hydroxides jointly, for example, sodium and calcium hydroxide or alkali-heavy-metal hydroxides, for example, sodium aluminate, sodium zincate or sodium stannate.
Products thus produces are suitable particularly for corrosion inhibitors and for products used in the treatment of service water.
Depending on the properties or on the intended purpose, the solutions are used directly, the salts are crystallized or, after ion exchange, the acid is obtained by means of conventional processes, such as concentration by evaporation or precipitation or extraction with organic solvents.
Singly or multiply carboxy-alkylated products are obtained in the carboxylation depending on the molar ratios used and on the aminophosphonic acid used. At a molar ratio of the reactants of 1:1 N-carboxy-alkane-aminoalkane-diphosphonic acids are preferably obtained. A molar radio of the reactants amino-phosphonic acid:
halocarboxylic acid of 1:2 to 1:3 results preferably in the production of N,N-bis-carboxy-alkane-aminoalkane-diphosphonic acids.
The substances obtained according to the present invention can be used whenever good complexing efficiency with ~(P6~343 respect to 2- and polyvalent metal ions is required. They are also distinguished particularly by their hydrolyzation stability at high temperatures. They can be used in all the media in which the hardness salts of the water have a detrimental effect or in which influences of polyvalent metal ions must be eliminated.
This relates particularly to the treatment of hard water, baths for treating textiles, paper making and tanning. Moreover, these phosphonic acids are suitable for stabilizing the hardness of water in amounts below the stoichiometric amount. They can also serve as stabilizers for dispersions and suspensions.
Since the products according to the invention have the properties of phosphonic acids and aminocarboxylic acids, they have syenergistic advantages as compared with the phosphonic acid or aminocarboxylic acids alone. These advantages exceed the sum of the individual components.
The present invention will be further illustrated by way of the following Examples.
Example 1 6.72 kg of a 50% caustic potash solution are put into a stirring apparatus fitted with thermometer and reflux condenser and 2.05 kg of 1 aminoethane-l,l-diphosphonic acid are so added that the bottom temperature does not rise above 60C. Within one hour a solution of 1.89 kg of monochloroacetic acid in 2.2 kg of water is added dropwise, followed by heating for three hours to 10 0C .
After freeing an aliquot portion of the reaction product from salt by means of an intensely acid cation exchanger and concentrating the solution the N,N-bis-carboxy-methane-l-amino-ethane-l,l-diphosphonic acid can be obtained by crystallizing with methanol/ethanol. The yield is 91.3% of the theoretical yield.
~ 6843 Analysis computed: C 22.40~ N 4.36% P 19.29%
obtained: C 22.6 % N 4.4 % P 19.3 %
molar ratio: C : P : N = 5.99 : 1.98 : 1 -Example 2 28 g of potassium hydroxide are dissolved in 100 ml of water and 20.5 g of l-aminoethane-l,l-diphosphonic acid are added.
13.9 g of bromoacetic acid are then added, whereupon the solution is boiled for 3 hours with reflux.
The reaction product is treated with an acid exchanger (e.g. supplied under the trademark ~ewatit S100) and the solution is concentrated. The result is a bright yellow viscous oil, which is crystallized with methanol/ethanol. After drying in a water-jet vacuum at 80C 25.4 g of carboxy-methane-l-aminoethane-l,l-diphosphonic acid are obtained corresponding to a yield of 96.6%
of the theoretical yield.
Analysis computed: C 18.26% N 5.32% P 23.55%
obtained: C 17.6 ~ N 5.2 % P 23.3 %
molar ratio: C : P : N = 3.95 : 2.02 : 1 Example 3 47.8 g of aminomethane-diphosphonic acid are dissolved in 148 g of a 50% caustic potash solution at 60C and a solution of 99.4 g of potassium salt of monochloroaceti~ acid in 250 ml of water is added, whereupon the solution is heated for three hours to 80-90C.
After treating the reaction solution in the manner described in the preceding Example 75.2 g of N,N-bis-carboxy-methane-aminomethane-diphosphonic acid are obtained.
Analysis computed: C 19.56% N 4.56% P 20.17%
obtained: C 20.3 ~ N 4.7 % P 20.3 %
molar ratio: C : P : N = 5.04 : 1.95 : 1 ~ ~6843 Example 4 95.5 g of aminomethane diphosphonic acid are dissolved in 224 g of a 50% caustic potash solution at 60C, whereupon 300 ml of water and 54.3 g of chloroacetic methyl ester are added.
After boiling for -three hours with reflux the solution is cooled.
After treating the solution with an acid exchanger, concentrating, crystallizing and drying, 115 g of N-carboxy-methane-aminomethane-diphosphonic acid are obtained corresponding to 92.3% of the theoretical yield.
Analysis computed: C 14.47~ N 5.62% P 24.87%
obtained: C 15.1 % N 5.7 % P 25.0 %
molar ratio: C : P : N = 3.09 : 1.98 : 1 Example 5 13.4 g of phenyl-aminomethane diphosphonic acid are dissolved in a solution of 8 g of NaOH in 100 ml of water in such a way that the temperature does not exceed 60C, whereupon 4.8 g of monochloroacetic acid are added. The reaction solution is then kept for 3 hours at 110 C. Aftercooling the solution itis treated with an intensely acid exchanger.
From the concentrated solution 15 g of crystalline N-carboxy-methane-phenyl-aminomethane-diphosphonic acid are obtained by means of methanol.
Analysis computed: C 33.233 N 4.31% P 19.05~
obtained: C 32.8 % N 4.3 % P 18.6 %
molar ratio: C : P : N = 8.9 : 1.95 : 1 Example 6 54.8 g of l-aminopropane-l,l-diphosphonic acid are stixred in 200 ml of water and 14.6 g of basic zinc carbonate are slowly added. When the generation of gas is completed 140 g of a 50% caustic potash solution is added and upon cooling to 50C 47.3 g of monochloroacetic acid are added in portions.
~6~43 After boiling for two hours with reflux a clear, faintly yellow-colored solution of the potassium zinc salt of N,N-bis-carboxy-methane-l-aminopropane-l,l-diphosphonic acid is obtained.
Thin-layer chromatographical examination show a minimum reaction rate of 90~ of the theoretical rate. A portion of the solution is further treated as described in the preceding examples.
Analysis computed: C 25.09% N 4.18~ P 18.48~
obtained: C 24.5 % N 4.2 % P 18.2 %
molar ratio: C : P : N = 6.81 : 1.96 : l Example 7 90 g of potassium hydroxide are dissolved in 250 ml of distilled water and 103.6 g of azacycloheptane-2,2-diphosphonic acid are so added to this solution that the temperature does not exceed 60C, whereupon 38 g of monochloroacetic acid are added, followed by heating for 2 l/2 hours to 110C and cooling. By means of the method described in Example l, 102.5 g of N-carboxy-methane-azacycloheptane-2,2-diphosphonic acid are obtained from the solution.
Analysis computed: C 30.49~ N 4.44% P 19.66~
obtained: C 30.0 % N 4.5 % P 20.0 %
~ molar ratio: C : P : N = 7.8 : 2 : l ; Example 8 41 g of l-aminoethane-l,l-diphosphonic acid dissolved in 187 g of a 30~ caustic potash solution while stirring and 39 g of 6-bromo hexanoic acid are added at 60C. To complete the reaction the solution is slowly heated to 100C and left at this temperature for 3 hours. After treatment as in Example l, N-carboxy-pentane-l-aminoethane-l,l-diphosphonic acid is obtained.
By determining the free amino groups according to the method of Van Slyke a reaction rate of 73.4~ of the theoretical rate is obtained.
~ 6843 Example 9 140 g of a 50~ caustic potash solution are added dropwise to a mixture of 51 g of l-aminoethane-l,1-diphosphonic acid, 27.2 g of 3-chloro propionic acid and 150 ml of water within one hour at 70C while stirring. The clear solution is then boiled for two hours with reflux.
After further treatment of the solution 57.5 g of N-carboxy-ethane-l-aminoethane-l,l-diphosphonic acid are obtained.
Analysis computed: C 21.67% N 5.05% P 22.35~
obtained: C 20.5 % N 4.8 ~ P 21.3 %
molar ratio: C : N : P = 4.98 : 2 : 1 Example 10 34.6 g of 3-chloro-2,2-dimethyl-propionic acid ~-chloro pivalic acid) are added to a solution of 47.8 g of aminomethane diphosphonic acid in 288 g of a 30% caustic potash solution while stirring. The solution is heated to the boiling point within an hour and is kept at this temperature for 2 hours. After further treatment N-2-carboxy-2,2-dimethyl ethane-aminomethane-diphos-phonic acid is obtained.
By determining the primary amine groups in the solutiona reaction rate of 73.5% of the theoretical rate was determined.
Example 11 54.7 g of l-aminopropane-l,l-diphosphonic acid are dissolved in 150 g of a 40% solution of caustic soda and 49.5 g of DL-bromo succinic acid are added at 60C. The solution is then boiled for two hours with reflux in order to complete the reaction.
By quantitative thin-layer chromatography 21 g of l-aminopropane-l,l-diphosphonic acid and 51.4 g of N-(l,l-diphos-phonoprop-l-yl)-DL-aminosuccinic acid could be detected in the solution.
Example 12 47.8 g of aminomethane diphosphonic acid are dissolved 68~3 in 150 g of a 50% caustic potash solution and 88.8 g of ll-bromo hendecanoic acid are added to this solution at 80C. After boiling the solution for two hours with reflux and cooling it approximately 30% of aminomethane diphosphonic acid, approximately 60~ of N-10-carboxy-decane-aminomethane diphosphonic acid and approximately 10% of N,N-bis-10-carboxy-decane~aminomethane-diphosphonic acid could be detected by thin-layer chromatographical examinations.
Example 13 In a 1 cu m stirring apparatus provided with reflux condenser, heating unit, built in single-rod pH-measuring chain and 2 dropping funnels 127.7 kg of l-aminoethane-l,l-diphosphonic acid are dissolved in 292.2 kg of water and 69.8 kg of a 50%
caustic potash solution. By utilizing the heat of neutralization the solution is heated to 80C and 147.7 kg of a 80% monochloro-acetic acid solution and approximately 362 kg of a 50% caustic potash solution are added from the two receivers. The addition is so controlled that the pH value in the reaction medium is between 8.0 and 8.5. The reaction mixture can be kept at a temperature of 80 to 90C by the generating reaction heat. Upon completion of the inflow the pH is adjusted to 8.5 by means of caustic potash solution, whereupon the solution is stirred for an hour at 90 to 100C.
The solution thus obtained contains approximately 20%
of N,N-bis-carboxy- methane -l-aminoethane-l,l-diphosphonic acid.
Example 14 -58.7 g of 3-hydroxy-1-aminopropane-1,1-diphosphonic acid are fed to a solution of 84 g of KOH in 300 ml of water. The solution is heated to 60C and, while stirring vigorously, 56 g of 3-chloro propionic acid are so added that the temperature slowly increases to 80C. After boiling for three hours with reflux a faintly yellow colored solution is obtained. After treating the ~1~68~3 solution with an intensely acid ion exchanger, concentrating, crystallizing and drying it 81 g of slightly yellowish hygroscopic crystals are obtained. The thin-layer chromatographical analysis shows a content of approximately 20% of N-carboxy-ethane-3-hydroxy-l-aminopropane-l,l-diphosphonic acid and approximately 80% of N,N-bis-carboxy-ethane-3-hydroxy-1-aminopropane-1,1-diphosphonic acid.
Example 15 24.9 g of 2-carboxy-1-aminoethane-1,1-diphosphonic acid are dissolved in a 30% caustic potash solutlon at 50C while stirring and at this temperature 19 g of 5-bromo valeric acid are added. The solution is then boiled for 3 1/2 hours with reflux, cooled and treated with a cation exchanger, whereupon the acid solution is concentrated almost to dryness and fractionally crystallized with mixtures of methanol, ethanol and acetone. The yield of 2-carboxy-1,1-diphosphono-ethane-5-aminopentanoic acid is 24.5 g.
Analysis computed: C 27.52% N 4.01% P 17.74%
obtained: C 27.5 % N 3.9 % P 17.8 %
molar ratio: C : P : N = 8.23 : 2.06 : 1 Example 16 6.9 g of l-amino-dodecane-l,l-diphosphonic acid are dissolved in 56 g of a 10% caustic potash solution and 2.8 g of 3-chloro-2,2-dimethyl propionic acid are added at 60C, whereupon the solution is boiled for three hours with reflux. After treating the reaction solution with an acid cation exchanger the acid solution is filtered and concentrated. By crystallizing with methanol/water 6 g of N-2-carboxy-2,2-dimethyl-ethane-1-amino-decane-l,l-diphosphonic acid are obtained.
Analysis computed: C 45.84~ N 3.14% P 13.91%
obtained: C 47.8 % N 3.2 % P 14.4 %
molar ratio: C : P : N = 17.43 : 2.03 : 1
Claims (9)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for producing a N-carboxy-alkane-amino-alkane-,N-carboxy-alkane-azacycloalkane- and N-carboxy-alkane-aminoaryl-alkane phosphonic acid in which an aminoalkane-, aza-cycloalkane- or aminoaryl-alkane phosphonic acid having the general formula wherein R represents H, (CH2)xCH3, C2H4OH, CH2COOH, C6H5, (CH2)n-N-(CH2COOH)2 or (CH2)n-PO3H2, wherein n is 1 or 2 and x is 0-10, R1 is PO3H2 and R2 is H or CH3 or, together with R1 forms a ring of the formula (CH2)3-5, are reacted with a straight or branched chain haloalkane monocarboxylic acid or with haloalkane dicarboxylic acid or an alkali metal salt or ester thereof at a temperature from 50 to 160°C in a molar ratio of 1:1 to 1:3 in an aqueous medium at a pH value between 4 and 12.
2. A process as claimed in claim 1 in which the pH is from 7 to 9.
3. A process as claimed in claim 1 in which the phos-phonic acid and halocarboxylic acid are suspended in water and neutralizing is effected with an alkali metal hydroxide at a temperature from 80°C to 120°C.
4. A process as claimed in claim 1, 2 or 3 in which the molar ratio is 1:1.
5. A process as claimed in claim 1, 2 or 3 in which the molar ratio is from 1:2 to 1:3.
6. A process as claimed in claim 1, 2 or 3 in which the halocarboxylic acid is selected from monochloroacetic acid or bromo acetic acid, 6-bromo hexanoic acid, 3-chloro-propionic acid, 3-chloro-2,2-dimethyl propionic acid (.beta.-chloro pivalic acid), 11-bromo hendecanoic acid and bromo succinic acid.
7. A process as claimed in claim 1, 2 or 3 in which the halocarboxylic acid is selected from monochloroacetic acid, bromoacetic acid, chloroacetic methyl ester, 6-bromo hexanoic acid, 3-chloro propionic acid, 3-chloro-2,2-dimethyl-propionic acid, DL-bromo succinic acid, 11-bromo hendecanoic acid, 5-bromo-valeric acid and 3-chloro-2,2-dimethyl propionic acid and the phosphonic acid is selected from 1-aminoethane-1,1-diphosphonic acid, amino-methane diphosphonic acid, phenyl-aminomethane diphosphonic acid, 1-aminopropane-1,1-diphosphonic acid, azacycloheptane-2,2-diphosphonic acid, 3-hydroxy-1-aminopropane-1,1-diphosphonic acid, 2-carboxy-1-aminoethane-1,1-diphosphonic acid or 1-aminododecane-1,1-diphosphonic acid.
8. An N-carboxy-alkane-aminoalkane-diphosphonic acid, N-carboxy-alkane-azacycloalkane-diphosphonic acid and N-carboxy-alkane-aminoaryl-alkane-diphosphonic acid having the general formula wherein R is H, CH3, -(CH2)10CH3, C6H5, C2H4OH or CH2COOH, R1 is PO3H2, R'2 is H, CH3 or R3 or together with R1 forms a ring of formula -(CH2)5- and R3 is (CH2)mCOOH where m is from 2 to 12, -CH2-C(CH3)2-COOH or .
9. A compound as claimed in claim 8 selected from N-carboxy-methane-azacycloheptane-2,2-diphosphonic acid, N-carboxy-pentane-1-aminoethane-1,1-diphosphonic acid, N-carboxy-ethane-1,1-aminoethane-1,1-diphosphonic acid, N-carboxy-2,2-dimethyl-propane-amino-methane-diphosphonic acid, N-10-carboxy-decane-aminomethane-diphosphonic acid, N,N-bis-10-carboxy-decane-amino-methane, diphosphonic acid and N-(1,1-diphosphonic-prop-1-yl)-DL-amino-succinic acid.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19772737259 DE2737259A1 (en) | 1977-08-18 | 1977-08-18 | N-CARBOXYALKANE AMINOALKANE DIPHOSPHONIC ACIDS, N-CARBOXYALKANE-AZACYCLOALKANE DIPHOSPHONIC ACIDS AND N-CARBOXYALKANE AMINOARYLALKANE DIPHOSPHONIC ACIDS AND THE PROCESS FOR THEIR PRODUCTION |
| DEP2737259.4 | 1977-08-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1106843A true CA1106843A (en) | 1981-08-11 |
Family
ID=6016730
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA309,547A Expired CA1106843A (en) | 1977-08-18 | 1978-08-17 | N-carboxy-alkane-aminoalkane-diphosphonic acids, n- carboxy-alkane-azacycloalkane-diphosphonic acids and n-carboxy-alkane-aminoaryl-alkane-diphosphonic acids and process for theirproduction |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0000930B1 (en) |
| JP (1) | JPS5470222A (en) |
| AT (1) | AT369015B (en) |
| CA (1) | CA1106843A (en) |
| DE (2) | DE2737259A1 (en) |
| DK (1) | DK364478A (en) |
| IE (1) | IE47653B1 (en) |
| IT (1) | IT1098368B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3107673A1 (en) * | 1981-02-28 | 1982-09-16 | Benckiser-Knapsack Gmbh, 6802 Ladenburg | "METHOD FOR PRODUCING N- (CARBOXY-ALKYL) -1-AMINO-ALKAN-1,1-DIPHOSPHONIC ACIDS AND THEIR ALKALINE SALTS" |
| US4501667A (en) * | 1983-03-03 | 1985-02-26 | Ciba-Geigy Corporation | Process of inhibiting corrosion of metal surfaces and/or deposition of scale thereon |
| IT1215423B (en) * | 1987-04-13 | 1990-02-08 | Minnesota Mining & Mfg | DEVELOPMENT COMPOSITIONS FOR SILVER HALIDE PHOTOGRAPHIC MATERIALS. |
| EP3860956A1 (en) | 2018-10-03 | 2021-08-11 | Italmatch Chemicals S.p.A. | Process for manufacturing n-alkyl-diphosphonate amino aminoacids |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL7404705A (en) * | 1973-04-12 | 1974-10-15 |
-
1977
- 1977-08-18 DE DE19772737259 patent/DE2737259A1/en not_active Withdrawn
-
1978
- 1978-08-09 IT IT26633/78A patent/IT1098368B/en active
- 1978-08-17 EP EP78100697A patent/EP0000930B1/en not_active Expired
- 1978-08-17 JP JP9957578A patent/JPS5470222A/en active Pending
- 1978-08-17 DK DK364478A patent/DK364478A/en unknown
- 1978-08-17 CA CA309,547A patent/CA1106843A/en not_active Expired
- 1978-08-17 DE DE7878100697T patent/DE2860812D1/en not_active Expired
- 1978-08-18 IE IE1681/78A patent/IE47653B1/en unknown
- 1978-08-18 AT AT0602778A patent/AT369015B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| EP0000930A1 (en) | 1979-03-07 |
| DE2737259A1 (en) | 1979-03-01 |
| IE47653B1 (en) | 1984-05-16 |
| DE2860812D1 (en) | 1981-10-08 |
| IT1098368B (en) | 1985-09-07 |
| DK364478A (en) | 1979-02-19 |
| IE781681L (en) | 1979-02-18 |
| IT7826633A0 (en) | 1978-08-09 |
| ATA602778A (en) | 1982-04-15 |
| EP0000930B1 (en) | 1981-07-01 |
| JPS5470222A (en) | 1979-06-05 |
| AT369015B (en) | 1982-11-25 |
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| MKEX | Expiry |