DE2658961B2 - Process for the preparation of 1-hydroxy-3-aminopropane-l, l-diphosphonic acids - Google Patents
Process for the preparation of 1-hydroxy-3-aminopropane-l, l-diphosphonic acidsInfo
- Publication number
- DE2658961B2 DE2658961B2 DE19762658961 DE2658961A DE2658961B2 DE 2658961 B2 DE2658961 B2 DE 2658961B2 DE 19762658961 DE19762658961 DE 19762658961 DE 2658961 A DE2658961 A DE 2658961A DE 2658961 B2 DE2658961 B2 DE 2658961B2
- Authority
- DE
- Germany
- Prior art keywords
- alanine
- hydroxy
- aminopropane
- phosphorus
- preparation
- 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
- 238000000034 method Methods 0.000 title claims description 6
- 238000002360 preparation method Methods 0.000 title claims description 3
- 239000002253 acid Substances 0.000 title description 3
- 150000007513 acids Chemical class 0.000 title 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical group ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 7
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 239000003085 diluting agent Substances 0.000 description 4
- -1 phosphorus halide Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910014033 C-OH Inorganic materials 0.000 description 2
- 229910014570 C—OH Inorganic materials 0.000 description 2
- 235000004279 alanine Nutrition 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-alanine Chemical compound NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 0.000 description 1
- 229940000635 beta-alanine Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 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
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229930186566 minutin Natural products 0.000 description 1
- WRUUGTRCQOWXEG-UHFFFAOYSA-N pamidronate Chemical compound NCCC(O)(P(O)(O)=O)P(O)(O)=O WRUUGTRCQOWXEG-UHFFFAOYSA-N 0.000 description 1
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 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
- C07F9/386—Polyphosphonic acids containing hydroxy substituents in the hydrocarbon radicals
-
- 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)
Description
N-CH2-CH2-C-OH
R2 PO3H2 N-CH 2 -CH 2 -C-OH
R 2 PO 3 H 2
wobei Ri und R2 ein Wasserstoffatom oder einen Alkylrest mit 1 -4 Kohlenstoffatomen bedeuten, aus jS-Alanin oder Poly-ß-alanin oder an Stickstoff alkyliertem ^-Alanin und phosphoriger Säure in Gegenwart eines Phosphorhalogenids, dadurch gekennzeichnet, daß man als Phosphorhalogenid Phosphoroxychlorid einsetztwhere Ri and R 2 denote a hydrogen atom or an alkyl radical with 1-4 carbon atoms, from jS-alanine or poly-ß-alanine or on nitrogen alkylated ^ -alanine and phosphorous acid in the presence of a phosphorus halide, characterized in that the phosphorus halide is phosphorus oxychloride begins
Gegenstand der Anmeldung ist ein Verfahren zur Herstellung von l-Hydroxy^-amino-propan-l.l-diphosphonsäure bzw. deren am Stickstoff alkylierten Derivaten sowie Salzen davon der allgemeinen Formel:The application relates to a process for the preparation of l-hydroxy ^ -amino-propane-l.l-diphosphonic acid or their derivatives alkylated on the nitrogen and salts thereof of the general formula:
R, PO3H2 R, PO 3 H 2
N-CH2-CH2-C-OHN-CH 2 -CH 2 -C-OH
/ I / I.
R2 PO3H2 R 2 PO 3 H 2
wobei Rt und R2 ein Wasserstoffatom oder einen Alkylrest mit 1-4 Kohlenstoffatomen bedeuten, durch Umsetzung von 0-Alanin oder Poly-/J-alanin oder am Stickstoff alkyliertem ^-Alanin mit phosphoriger Säure und einem Phosphorhalogenid.where Rt and R 2 denote a hydrogen atom or an alkyl radical having 1-4 carbon atoms, by reaction of 0-alanine or poly- / J-alanine or ^ -alanine alkylated on the nitrogen with phosphorous acid and a phosphorus halide.
Es ist aus der deutschen Patentschrift 2130 794 bekannt 1 - Hydroxy-3-amino-propan-1,1 -diphosphonsäure durch Umsetzung von ^-Alanin oder PoIy-jJ-alanin mit einem Gemisch aus phosphoriger Säure und Phosphortrochlorid in Gegenwart oder Abwesenheit eines organischen Verdünnungsmittels herzustellen. ^-Alanin, phosphorige Säure und das Verdünnungsmittel werden im siedenden Wasserbad erhitzt und dazu Phosphortrichlorid getropft. Der Nachteil dieser Methode besteht darin, daß sich beim Zutropfen des Phosphortrichlorids ein klebriges Reaktionsprodukt bildet, Jas sich nur schwer durchrühren läßt. Außerdem treten gelbe Nebenprodukte auf, die auf t-ilweises Zersetzen des Phosphortrichlorids bei Siedetemperatur zurückzuführen sind. Auch ist das Arbeiten mit einem organischen Verdünnungsmittel bei technischen Ansätzen schon aus preislichen Gründen nachteilig und das Abtrennen des Verdünnungsmittels erfordert einen zusätzlichen Arbeitsgang,It is from German patent specification 2130 794 known 1 - hydroxy-3-aminopropane-1,1-diphosphonic acid by converting ^ -alanine or poly-jJ-alanine with a mixture of phosphorous acid and phosphorus trochloride in the presence or absence to produce an organic diluent. ^ -Alanine, phosphorous acid and the diluent are heated in a boiling water bath and phosphorus trichloride is added dropwise. The disadvantage of this method consists in the fact that a sticky reaction product is formed when the phosphorus trichloride is added dropwise forms, Jas is difficult to stir. aside from that yellow by-products occur which result from partial decomposition of the phosphorus trichloride at the boiling point are due. Working with an organic diluent is also part of technical approaches disadvantageous for reasons of price and the separation of the diluent requires one additional work step,
Es wurde nun gefunden, daß die geschilderten Schwierigkeiten nicht auftreten, wenn man als Phosphorhalogenid Phosphoroxychlorid einsetzt.It has now been found that the difficulties outlined do not occur when using the phosphorus halide Phosphorus oxychloride is used.
Vorteilhaft arbeitet man so, daß man ^-Alanin, phosphorige Säure und Phosphoroxychlorid bei Zimmertemperatur unter Rühren zusammengibt und die Mischung anschließend bis zu einer Innentemperatur von 10O0C erhitzt oder es werden /»-Alanin und phosphorige Säure bei 90-1000C als klare Schmelze vorgelegt, dazu das Phosphoroxychlorid getropft und noch kurz bei 1000C Innentemperatur nachgerührt Nach Verdünnen mit Wasser fällt die Phosphonsäure in kristalliner Form aus.It is advantageous to work in such a way that ^ -alanine, phosphorous acid and phosphorus oxychloride are combined at room temperature with stirring and the mixture is then heated to an internal temperature of 10O 0 C or there are / »- alanine and phosphorous acid at 90-100 0 C as Submitted clear melt, added dropwise the phosphorus oxychloride and stirred briefly at 100 0 C internal temperature. After dilution with water, the phosphonic acid precipitates in crystalline form.
Man kann auch ^-Alanin und Wasser bei Zimmertemperatur vorlegen und die zur Bildung der phosphorigenYou can also use ^ -alanine and water at room temperature submit and the formation of the phosphorous
ίο Säure entsprechende Menge Phosphortrichlorid zutropfen. Anschließend gibt man Phosphoroxychlorid zu, erhitzt auf eine Innentemperatur von 1000C und verdünnt mit Wasser. Bei dieser Arbeitsmethode muß die wäßrige Endlösung zweckmäßig noch kurz aufge-ίο Add the appropriate amount of phosphorus trichloride to the acid. Phosphorus oxychloride is then added, the mixture is heated to an internal temperature of 100 ° C. and diluted with water. With this working method, the final aqueous solution must expediently be made up briefly.
kocht werden, da sonst die Phosphonsäure nur schwer kristallisiertbe boiled, otherwise the phosphonic acid will be difficult to crystallize
Im Gegensatz zu dem bisherigen Verfahren mit Phosphortrichlorid anstelle des Phosphoroxychlorids wird stets ein gut rührbarer Sirup erhalten, der -rich gutIn contrast to the previous process with phosphorus trichloride instead of phosphorus oxychloride a well-stirrable syrup is always obtained, the -rich good
in Wasser löst Gelbe Nebenprodukte treten nicht auf.Dissolves in water. Yellow by-products do not occur.
89,1 g (i,ö Moi) p-Aianin und 164,0 g (2 Mol) phosphorige Säure werden bei 90- 1000C unter Rühren als klare Schmelze vorgelegt Dazu tropft man in 30—40 Minuten 1533 g (I Mol) Phosphoroxychlorid. Durch exotherme Reaktion steigt die Innentemperatur auf etwa 115°C an und fällt dann unter schwachem POCls-Rückfluß auf etwa 85° C.89.1 g (i, ö Moi) p-Aianin and 164.0 g (2 moles) of phosphorous acid are introduced at 90- 100 0 C with stirring as a clear melt is added dropwise in 30-40 minutes 1533 g (I mol ) Phosphorus oxychloride. As a result of the exothermic reaction, the internal temperature rises to about 115 ° C and then falls to about 85 ° C under a weak POCl reflux.
jo Es wird 20-30 Minuten bis zum Rückflußende und bis zum Erreichen von etwa 1000C innen nachgerührt Dann wird mit 198 g (11 Mol) Wasser verdünnt Beim Verdünnen steigt die Innentemperatur kurzfristig bis 165°C an und fällt dann schnell unter Wasser-Rückfluß wieder ab.jo is 20-30 minutes to the Rückflußende, and to reach about 100 0 C stirred inside Then, 198 g (11 moles) of water diluted When diluting the internal temperature rises in the short term to 165 ° C and then drops rapidly under water Reflux from again.
Beim Abkühlen auf Raumtemperatur scheidet sich die Phosphonsäure als rein-weißes Kristallisat ab. Die
Ausbeute beträgt 112 " g (51,14% der Theorie).
Durch Einengen der Mutterlauge und Zugabe vonOn cooling to room temperature, the phosphonic acid separates out as pure white crystals. The yield is 112 "g (51.14% of theory).
By concentrating the mother liquor and adding
4Π Methanol fällt noch weitere Phosphonsäure aus.4Π methanol also precipitates further phosphonic acid.
89,1 g (1,0 Mol) ^-Alanin und 72 g (4,0 Mol) Wasser werden bei Raumtemperatur als Suspension unter 4-, Rühren vorgelegt In 20-30 Minuten werden dann 274,7 g (2,0 Mol) Phosphortrichlorid zugetropft. Die Temperatur wird dabei durch Kühlen unteir 35° C gehalten.89.1 grams (1.0 moles) of ^ -alanine and 72 grams (4.0 moles) of water are presented at room temperature as a suspension with 4-, stirring. In 20-30 minutes are then 274.7 g (2.0 mol) of phosphorus trichloride were added dropwise. The temperature is reduced to below 35 ° C. by cooling held.
ίο Innentemperatur auf 90- 1000C gesteigert. Dann tropft man 122,7 g (0,8 Mol) Phosphoroxychkvid in 20-30increased ίο internal temperature of 90- 100 0 C. 122.7 g (0.8 mol) of phosphorus oxychloride in 20-30 are then added dropwise
auf.on.
Nach Abkühlen und Absaugen erhält man 99,0 g (45,2% der Theorie) Phosphonsäure.After cooling and filtering off with suction, 99.0 g (45.2% of theory) of phosphonic acid are obtained.
B e i s ρ i e 1 3B e i s ρ i e 1 3
Zu einem Gasgemisch aus 89,1 g (1 Mol)/?-Alanin und 221,4 g (2,7 Mol) phosphorigi; Säure gießt man 222,3 g (1,45 Mol) Phosphoroxychlorid. Es bildet sich für wenige Sekunden unter HCI-Entwicklung ein dünner, weißer Schaum und die Innentemperatur steigt durch die exotherme Reaktion auf45-:5O°Can.To a gas mixture of 89.1 g (1 mol) /? - alanine and 221.4 g (2.7 moles) phosphorigi; Acid is poured into 222.3 g (1.45 moles) phosphorus oxychloride. A thin, white layer forms for a few seconds with the development of HCI Foam and the internal temperature rises to 45-50 ° Can due to the exothermic reaction.
Danach wird unter Rühren aufgeheizt. Sind innen 95— 100°C erreicht, so rührt man noch 30 Minuten beiThen the mixture is heated while stirring. When 95-100 ° C have been reached inside, stir for a further 30 minutes
3 43 4
dieser Temperatur nach. Dann tropft man in 2-3 Durch Einengen der Mutterlauge und Zugabe vonaccording to this temperature. Then one drips in 2-3 by concentrating the mother liquor and adding
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19762658961 DE2658961C3 (en) | 1976-12-24 | 1976-12-24 | Process for the preparation of 1-hydroxy-3-aminopropane-1,1-diphosphonic acids |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19762658961 DE2658961C3 (en) | 1976-12-24 | 1976-12-24 | Process for the preparation of 1-hydroxy-3-aminopropane-1,1-diphosphonic acids |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DE2658961A1 DE2658961A1 (en) | 1978-06-29 |
| DE2658961B2 true DE2658961B2 (en) | 1980-09-25 |
| DE2658961C3 DE2658961C3 (en) | 1981-09-24 |
Family
ID=5996718
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19762658961 Expired DE2658961C3 (en) | 1976-12-24 | 1976-12-24 | Process for the preparation of 1-hydroxy-3-aminopropane-1,1-diphosphonic acids |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE2658961C3 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2943498C2 (en) * | 1979-10-27 | 1983-01-27 | Henkel KGaA, 4000 Düsseldorf | Process for the preparation of 3-amino-1-hydroxypropane-1,1-diphosphonic acid |
| DE3016289A1 (en) | 1980-04-28 | 1981-10-29 | Henkel KGaA, 4000 Düsseldorf | METHOD FOR PRODUCING OMEGA-AMINO-1-HYDROXYALKYLIDEN-1,1-BIS-PHOSPHONIC ACIDS |
| DE3425812A1 (en) * | 1984-07-13 | 1986-01-16 | Deutsches Krebsforschungszentrum, 6900 Heidelberg | NEW 1-HYDROXY-1,1-DIPHOSPHONIC ACID COMPOUNDS, PROCESS FOR THEIR PRODUCTION AND PHARMACOLOGICAL PREPARATIONS, IN PARTICULAR FOR THE TREATMENT OF BONE TUMORS |
| GB8616447D0 (en) * | 1986-07-05 | 1986-08-13 | Ciba Geigy Ag | Compounds |
| PE20011065A1 (en) * | 2000-02-01 | 2001-11-21 | Procter & Gamble | PROCESS FOR MANUFACTURING GEMINAL BISPHOSPHONATES |
| US7723542B2 (en) | 2003-12-23 | 2010-05-25 | Trifarma S.P.A. | Process for the preparation of alkyl- and aryl-diphosphonic acids and salts thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2130794C3 (en) * | 1971-06-22 | 1974-07-11 | Joh. A. Benckiser Gmbh, 6700 Ludwigshafen | Process for the preparation of l-hydroxy-S-aminopropane-ljl-diphosphonic acid |
-
1976
- 1976-12-24 DE DE19762658961 patent/DE2658961C3/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE2658961A1 (en) | 1978-06-29 |
| DE2658961C3 (en) | 1981-09-24 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| OAP | Request for examination filed | ||
| OD | Request for examination | ||
| C3 | Grant after two publication steps (3rd publication) | ||
| 8339 | Ceased/non-payment of the annual fee |