DE3214307A1 - Process for the preparation of 1-aminoalkane-1,1-diphosphonic acids - Google Patents
Process for the preparation of 1-aminoalkane-1,1-diphosphonic acidsInfo
- Publication number
- DE3214307A1 DE3214307A1 DE19823214307 DE3214307A DE3214307A1 DE 3214307 A1 DE3214307 A1 DE 3214307A1 DE 19823214307 DE19823214307 DE 19823214307 DE 3214307 A DE3214307 A DE 3214307A DE 3214307 A1 DE3214307 A1 DE 3214307A1
- Authority
- DE
- Germany
- Prior art keywords
- ammonium
- acid
- acids
- preparation
- diphosphonic
- 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 15
- 150000007513 acids Chemical class 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 title claims description 11
- -1 ammonium carboxylates Chemical class 0.000 claims abstract description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 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 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- JDRJCBXXDRYVJC-UHFFFAOYSA-N OP(O)O.N.N.N Chemical compound OP(O)O.N.N.N JDRJCBXXDRYVJC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 3
- BVCZEBOGSOYJJT-UHFFFAOYSA-N ammonium carbamate Chemical compound [NH4+].NC([O-])=O BVCZEBOGSOYJJT-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims abstract description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 3
- 239000000010 aprotic solvent Substances 0.000 claims abstract description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 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 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 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 1
- IFJKPUUSPDSXMA-UHFFFAOYSA-N (1-amino-2-phosphonoethyl)phosphonic acid Chemical compound OP(=O)(O)C(N)CP(O)(O)=O IFJKPUUSPDSXMA-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- WLJVXDMOQOGPHL-PPJXEINESA-N 2-phenylacetic acid Chemical compound O[14C](=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-PPJXEINESA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- 229910020667 PBr3 Inorganic materials 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- XJMWHXZUIGHOBA-UHFFFAOYSA-N azane;propanoic acid Chemical compound N.CCC(O)=O XJMWHXZUIGHOBA-UHFFFAOYSA-N 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- FPIQZBQZKBKLEI-UHFFFAOYSA-N ethyl 1-[[2-chloroethyl(nitroso)carbamoyl]amino]cyclohexane-1-carboxylate Chemical compound ClCCN(N=O)C(=O)NC1(C(=O)OCC)CCCCC1 FPIQZBQZKBKLEI-UHFFFAOYSA-N 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical class NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- IPNPIHIZVLFAFP-UHFFFAOYSA-N phosphorus tribromide Chemical compound BrP(Br)Br IPNPIHIZVLFAFP-UHFFFAOYSA-N 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 229940005605 valeric acid Drugs 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)
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
Description
Gegenstand der vorliegenden Erfindung ist ein Verfahren zurThe present invention is a method for
Herstellung von 1-Aminoalkan-1, 1-diphosphonsäuren aus Ammoniumcarbox ylaten, phosphoriger Säure und Säureanhydriden.Production of 1-aminoalkane-1, 1-diphosphonic acids from ammonium carbox ylates, phosphorous acid and acid anhydrides.
Aus der DE-PS 10 02 355 ist bekannt, 1-Aminzalkan-1,1-diphosphonsäuren durch Umsetzen von Alkylnitrilen mit Phosphorhalogeniden und anschließender Hydrolyse herzustellen, wobei jedoch nur mit PBr3 zufriedenstellende Umsätze erzielt werden.DE-PS 10 02 355 discloses 1-amine alkane-1,1-diphosphonic acids by reacting alkyl nitriles with phosphorus halides and subsequent hydrolysis produce, but only with PBr3 satisfactory conversions are achieved.
Die DE-PS 26 25 767 beschreibt die Herstellung von Aminoalkandiphosphonsäuren aus Nitrilen und phosphoriger Säure bei Temperaturen zwischen 140 und 200°C, wobei die Umsetzung jedoch erst bei Temperaturen um 180-7900C mit befriedigender Geschwindigkeit abläuft, wie aus den Beispielen zu entnehmen ist.DE-PS 26 25 767 describes the production of aminoalkanediphosphonic acids of nitriles and phosphorous acid at temperatures between 140 and 200 ° C, wherein however, the reaction only takes place at a satisfactory rate at temperatures around 180-7900C runs, as can be seen from the examples.
Nach der DE-PS 22 03 340 erhält man 1-Aminoethan-1,1-diphosphonsäure und deren am Stickstoff substituierten Derivate bei der Einwirkung von phosphoriger Säure und Phorphorpentoxid auf die entsprechenden Acetamid. Des weiteren ist aus der DE-PS 20 48 913 bekannt, zur Gewinnung von Aminoalkan-diphosphonsäuren Nitrile mit phosphoriger Säure in Gegenwart von Halogenwasser stoffen umzusetzen.According to DE-PS 22 03 340, 1-aminoethane-1,1-diphosphonic acid is obtained and their derivatives substituted on nitrogen when exposed to phosphorous Acid and phosphorus pentoxide to the corresponding acetamide. Furthermore it is off from DE-PS 20 48 913 known, for the production of aminoalkanediphosphonic acids nitriles to implement with phosphorous acid in the presence of hydrogen halides.
Ein Nachteil der geschilderten Verfahren besteht darin, daß die zur Reaktion notwendigen Stickstoffverbindungen selten in der erforderlichen Menge sowie zu wirtschaftlich vertretbaren Preisen zur Verfügung stehen. Bei einigen Verfahren treten äußerst stark korrodierende Nebenprodukte auf, wie zum Beispiel Halogenwasserstoffe oder Polyphosphorsäure, so daß die Verfahren erhebliche und nur selten zu erfüllende Anforderungen an das Material der Reaktionsapparate stellen.A disadvantage of the method described is that the for Reaction necessary nitrogen compounds rarely in the required amount as well are available at economically reasonable prices. With some procedures extremely corrosive by-products occur, such as hydrogen halides or polyphosphoric acid, making the process considerable and rarely met Make demands on the material of the reaction apparatus.
Es wurde nun gefunden, daß sich 1-Aminoalkan-1,1-diphosphonsäuren durch Einwirken von organischen Säureanhvdriden auf Mischungen von phosphoriger Säure und Ammoniumcarboxylaten in recht guten Ausbeuten herstellen lassen.It has now been found that 1-aminoalkane-1,1-diphosphonic acids by the action of organic acid anhydrides on mixtures of phosphorous Make acid and ammonium carboxylates in fairly good yields.
Die Bildung von Aminoalkan-diphosphonsäuren ist insofern überraschend, als aufgrund der höheren Säurestärke der phosporigen Säure die Bildung von Ammoniumphosphit aus den Ammoniumcarboxylaten unter Freisetzung von Alkansäuren erfolgen sollte und somit die Entstehung von Aminophosphonsäuren undenkbar schien. Zum anderen wäre zu erwarten gewesen, daß sich die Säureanhydride mit phosphoriger Säure zu 1-HVdroxValkan-1,1-diphosphonsäuren umsetzen, was nach der US-PS 3.366.677 bereits bei Temperaturen zwischen 50 und 60 C erfolgt.The formation of aminoalkanediphosphonic acids is surprising in that than the formation of ammonium phosphite due to the higher acidity of the phosphoric acid should take place from the ammonium carboxylates with the release of alkanoic acids and thus the formation of aminophosphonic acids seemed unthinkable. On the other hand would be it was to be expected that the acid anhydrides would react with phosphorous acid to form 1-HVdroxValkan-1,1-diphosphonic acids implement what according to US-PS 3,366,677 already at temperatures between 50 and 60 C takes place.
Ebenso überraschend ist, daß anstelle der Ammoniumcarboxylate Carbonsäuren zusammen mit Ammoniumphosphit und phosphoriger Säure eingesetzt werden können, Es ist hierbei nicht unbedingt erforderlich, die Carbonsäuren bzw. deren Ammoniumsalze von vornherein der Reaktionsmischung zuzufügen, da sich während der Reaktion aus den Anhydriden Carbonsäuren bilden. Dies läßt sich insbesondere dann nützen, wenn Ammoniak in Form von Ammoniumphosphit eingesetzt wird. Eine weitere Variante des Verfahrens besteht darin Ammoniumsalze wie Ammoniumcarbonat, Ammoniumcarbamat oder Ammoniumchlorid als preiswerte Ammoniakspender zu verwenden.It is also surprising that, instead of the ammonium carboxylates, carboxylic acids can be used together with ammonium phosphite and phosphorous acid, It is not absolutely necessary here, the carboxylic acids or their ammonium salts to be added to the reaction mixture from the outset, as it will result during the reaction the anhydrides form carboxylic acids. This can be particularly useful when Ammonia is used in the form of ammonium phosphite. Another variant of the Method consists in ammonium salts such as ammonium carbonate, ammonium carbamate or Use ammonium chloride as an inexpensive ammonia dispenser.
Die höchsten Ausbeuten werden erzielt, wenn pro Mol Carboxylat 2-2,5 Mol H3P03 und 2 Mol Säureanhydrid eingesetzt werden.The highest yields are achieved when 2-2.5 per mole of carboxylate Moles of H3P03 and 2 moles of acid anhydride are used.
Um den Einfluß schädlicher Feuchtigkeit weitgehend zu verhindern, können die Anhydride in 5-10%igem Überschuß angewandt werden. Werden Ammoniakspender die mehr als 1 Stickstoffatom pro Mol enthalten, verwendet, so setzt man sie in solcher Menge zu, daß das Verhältnis von Ammoniak : Csrbonsäure - 1:1 eingehalten wird. Bei Verwendung von Ammoniumphosphit wird die Hälfte der erforderlichen Menge phosphoriger Säure als Ammoniumphosphit eingesetzt.In order to largely prevent the influence of harmful moisture, the anhydrides can be used in a 5-10% excess. Become an ammonia donor which contain more than 1 nitrogen atom per mole are used, they are put into in such an amount that the ratio of ammonia: carbonic acid - 1: 1 is maintained will. When using ammonium phosphite it becomes half the required amount Phosphorous acid used as ammonium phosphite.
Als Carbonsäurekomponenten eignen sich alle Ammoniumcarboxylate, deren Kohlenwasserstoffrest 1-20 Kohlenstoffatome enthält. Bei Verwendung von Ammoniumphosphiten oder anderen NH3-Spendern können die entsprechenden Carbonsäuren der allgemeinen Formel RCOOH eingesetzt werden, wobei es sich bei R um einen aliphatischen, verzweigten oder unverzweigten oder auch um einen alicyclischen Rest handeln kann. Ansonsten kennen auch Substituenten wie -OH, NH2, -COOH, -C6H11 oder -c 6H5 vorhanden sein. Als bevorzugte Carbonsäuren, die als solche oder in Form ihrer Ammoniumsalze eingesetzt werden, sind zu nennen: Essigsäure, Propionsäure, Isobuttersäure, Buttersäure, Valeriansäure,Dodecansäure, Octadecansäure, Glykolsäure, Glycin, Alanine, Asparaginsäure, Cyclohexancarbonsäure, Phenylessigsäure, Bernsteinsäure und Glutarsäure.As carboxylic acid components are all ammonium carboxylates, their Hydrocarbon radical contains 1-20 carbon atoms. When using ammonium phosphites or other NH3 donors can use the corresponding carboxylic acids of the general Formula RCOOH can be used, where R is an aliphatic, branched one or unbranched or an alicyclic radical. Otherwise also know substituents such as -OH, NH2, -COOH, -C6H11 or -c 6H5. Preferred carboxylic acids used as such or in the form of their ammonium salts should be mentioned: acetic acid, propionic acid, isobutyric acid, butyric acid, valeric acid, dodecanoic acid, Octadecanoic acid, glycolic acid, glycine, alanine, aspartic acid, cyclohexanecarboxylic acid, Phenylacetic acid, succinic acid and glutaric acid.
Die Reaktion kann sowohl in Gegenwart von LBsungsmitteln als auch ohne . Lösungsmittel durchgeführt werden. Es ist zweckmässig, die erste Reaktionsphase in Anwesenheit von Lösungsmitteln durchzuführen. Hierzu eignen sich die entsprechenden Carbonsäuren oder aber auch polare, aprotische Ldsungsmittel, wie zum Beispiel Dioxan, Glykol- oder Diglykolether, oder Sulfone. Die Lösungsmittel werden, sofern ihre Siedepunkte unter 1600C liegen, bei der Hauptreaktion zusammen mit den gebildeten Carbonsäuren abdestilliert.The reaction can be in the presence of solvents as well without . Solvent to be carried out. It is advisable to start the first reaction phase to be carried out in the presence of solvents. The appropriate ones are suitable for this Carboxylic acids or polar, aprotic solvents, such as dioxane, Glycol or diglycol ethers, or sulfones. The solvents are, provided their Boiling points below 1600C are, in the main reaction, together with those formed Carboxylic acids distilled off.
Beispiel 1 In 220 g Acetanhydrid werden unter Rühren 77 g Ammbniumacetat und 164 g H3P03 portionsweise eingetragen. Während 1,5 Stunden steigert man die Temperatur auf 16O0C, wobei Essigsäure abdestilliert. Anschließend wird noch 4 Stunden bei dieser Temperatur gehalten, unter 1000C abgekühlt und 100 ml Wasser zugegeben. Man kocht 1 Stunde unter Rückfluss, lässt abkühlen, versetzt mit 100 ml Methanol und saugt die feinkristalline 1-Aminoethan-1, 1-diphosphonaäure ab.EXAMPLE 1 77 g of ammonium acetate are added to 220 g of acetic anhydride with stirring and 164 g of H3P03 entered in portions. This is increased for 1.5 hours Temperature to 160 ° C., with acetic acid distilling off. Then another 4 hours kept at this temperature, cooled below 1000C and 100 ml of water admitted. The mixture is refluxed for 1 hour, allowed to cool, and 100 ml of methanol are added and sucks off the finely crystalline 1-aminoethane-1, 1-diphosphona acid.
Ausbeute: 151 g.Yield: 151 g.
Beispiel 2 Eine Mischung aus 41 g phosphoriger Säure und 49,5 g Ammoniumphosphit werden unter Rühren tropfenweise mit 110 g Acetanhydrid versetzt und die Mischung allmählich auf 1600C erwärmt. Es destillieren hierbei rund 95 g einer Flüssigkeit ab, die in der Hauptsache aus Essigsäure besteht. Der Rückstand wird 4 Stunden bei 1600C gehalten, nach Abkühlen mit 50 ml Wasser versetzt und anschließend 30 Min. gekocht, wobei ein GroBteil der gebildeten Aminoethandiphosphonsäure auskristallisiert. Zur Vervollständigkeit der Kirstallisstion wird unter Rühren tropfenweise mit 100 ml Methanol versetzt.Example 2 A mixture of 41 g of phosphorous acid and 49.5 g of ammonium phosphite 110 g of acetic anhydride are added dropwise with stirring and the mixture gradually heated to 1600C. Around 95 g of a liquid are distilled here which mainly consists of acetic acid. The residue is 4 hours at Maintained 1600C, after cooling mixed with 50 ml of water and then 30 min. cooked, whereby a large part of the aminoethanediphosphonic acid formed crystallizes out. To complete the Kirstallission, add 100 ml of methanol are added.
Ausbeute: 81 g.Yield: 81 g.
Beispiel 3 Zu einer Mischung aus 45,5 g Ammoniumprapionat, 82 g phosphoriger Säure und 50 ml Propionsäure tropft man unter Rühren und Kühlen mittels eines Wasserbades 145 g Propionanhydrid. Nach- beendeter Zugabe steigert man allmählich die Temperatur auf 160°C, bis alle flüchtigen Substanzen abdestilliert sind und hält 6 Stunden bei 160°C. Man kühlt abf verdünnt mit 80 ml Wasser, kocht 30 Minuten unter Rückfluss und fällt anschließend durch Zugabe von 120 ml Methanol die 1-Aminopropan-1, 1-diphosphonsäure aus.Example 3 To a mixture of 45.5 g of ammonium propionate, 82 g of phosphorous Acid and 50 ml of propionic acid are added dropwise with stirring and cooling by means of a water bath 145 g propionic anhydride. When the addition is complete, the temperature is gradually increased to 160 ° C until all volatile substances have distilled off and lasts 6 hours at 160 ° C. It is cooled, diluted with 80 ml of water, refluxed for 30 minutes and then 1-aminopropane-1,1-diphosphonic acid is precipitated by adding 120 ml of methanol the end.
Ausbeute: 76 g.Yield: 76 g.
Beispiel 4 In 160 g Acetanhydrid trägt man nacheinander unter krSftigem Rühren 50 g Bernsteinsäureanhydrid, 49,5 g Ammoniumphosphit und 41 g phosphorige Säure ein, wobei man durch Kühlen die Temperatur unter 45°C hält. Unter Abdestillieren der gebildeten Essigsäure steigert man die Reaktionstemperatur auf 165uns und hält 5 Stunden bei dieser Temperatur.Example 4 In 160 g of acetic anhydride one carries successively under strong Stir 50 g of succinic anhydride, 49.5 g of ammonium phosphite and 41 g of phosphorous Acid, keeping the temperature below 45 ° C by cooling. While distilling off of the acetic acid formed, the reaction temperature is raised to 165 us and held 5 hours at this temperature.
Nach Hydrolyse mit 60 ml Wasser wird zur vollständigen Fällung der Z-Carboxy-1-aminopropan-1,1-diphosphonsäure 100 ml Ethanol zugegeben. Die eo erhaltene Phosphonsäure enthält als Verunreinigung 1-Aminoethan-1, 1-diphosphonsäure.After hydrolysis with 60 ml of water, the Z-carboxy-1-aminopropane-1,1-diphosphonic acid was added to 100 ml of ethanol. The eo received Phosphonic acid contains 1-aminoethane-1,1-diphosphonic acid as an impurity.
In der Ldsung sind noch geringe Mengen 1-HVdroxyethan-1,1-diphosphonsäure und 2-Carboxy-1-hydroxypropan-1,1-diphosphonsäure enthalten.Small amounts of 1-hydroxyethane-1,1-diphosphonic acid are still in the solution and 2-carboxy-1-hydroxypropane-1,1-diphosphonic acid.
Claims (4)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19823214307 DE3214307A1 (en) | 1982-04-19 | 1982-04-19 | Process for the preparation of 1-aminoalkane-1,1-diphosphonic acids |
| DE19823232753 DE3232753A1 (en) | 1982-04-19 | 1982-09-03 | Process for the preparation of 1-aminoalkane-1,1-diphosphonic acids |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19823214307 DE3214307A1 (en) | 1982-04-19 | 1982-04-19 | Process for the preparation of 1-aminoalkane-1,1-diphosphonic acids |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| DE3214307A1 true DE3214307A1 (en) | 1983-11-17 |
| DE3214307C2 DE3214307C2 (en) | 1990-09-06 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19823214307 Granted DE3214307A1 (en) | 1982-04-19 | 1982-04-19 | Process for the preparation of 1-aminoalkane-1,1-diphosphonic acids |
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| DE (1) | DE3214307A1 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1002355B (en) * | 1954-05-03 | 1957-02-14 | Thomae Gmbh Dr K | Process for the production of ª ‡ -prim.-amino-diphosphonic acids and their esters |
| US3366677A (en) * | 1965-05-13 | 1968-01-30 | Procter & Gamble | Low temperature preparation of ethane-1-hydroxy-1, 1-diphosphonic acid |
| DE2048913A1 (en) * | 1970-10-06 | 1972-04-13 | Henkel & Cie GmbH, 4000 Dusseldorf | Process for the preparation of 1 ammoalkane 1,1 diphosphonic acids |
| DE2203340A1 (en) * | 1972-01-25 | 1973-08-02 | Benckiser Gmbh Joh A | 1-aminoethane-1,1-diphosphonic acid prepn - from acetamide and phosphorous acid in presence of phosphorus pentoxide |
| DE2625767A1 (en) * | 1976-06-09 | 1977-12-15 | Benckiser Knapsack Gmbh | PROCESS FOR THE PREPARATION OF 1-AMINOALKANE-1,1-DIPHOSPHONIC ACIDS |
-
1982
- 1982-04-19 DE DE19823214307 patent/DE3214307A1/en active Granted
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1002355B (en) * | 1954-05-03 | 1957-02-14 | Thomae Gmbh Dr K | Process for the production of ª ‡ -prim.-amino-diphosphonic acids and their esters |
| US3366677A (en) * | 1965-05-13 | 1968-01-30 | Procter & Gamble | Low temperature preparation of ethane-1-hydroxy-1, 1-diphosphonic acid |
| DE2048913A1 (en) * | 1970-10-06 | 1972-04-13 | Henkel & Cie GmbH, 4000 Dusseldorf | Process for the preparation of 1 ammoalkane 1,1 diphosphonic acids |
| DE2203340A1 (en) * | 1972-01-25 | 1973-08-02 | Benckiser Gmbh Joh A | 1-aminoethane-1,1-diphosphonic acid prepn - from acetamide and phosphorous acid in presence of phosphorus pentoxide |
| DE2625767A1 (en) * | 1976-06-09 | 1977-12-15 | Benckiser Knapsack Gmbh | PROCESS FOR THE PREPARATION OF 1-AMINOALKANE-1,1-DIPHOSPHONIC ACIDS |
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| Publication number | Publication date |
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| DE3214307C2 (en) | 1990-09-06 |
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