DE2166577C3 - Process for the preparation of a, w-alkanediphosphonic acids - Google Patents
Process for the preparation of a, w-alkanediphosphonic acidsInfo
- Publication number
- DE2166577C3 DE2166577C3 DE19712166577 DE2166577A DE2166577C3 DE 2166577 C3 DE2166577 C3 DE 2166577C3 DE 19712166577 DE19712166577 DE 19712166577 DE 2166577 A DE2166577 A DE 2166577A DE 2166577 C3 DE2166577 C3 DE 2166577C3
- Authority
- DE
- Germany
- Prior art keywords
- preparation
- acids
- alkane
- diphosphonic
- cyclic carbonates
- 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 5
- 238000002360 preparation method Methods 0.000 title claims description 4
- 239000002253 acid Substances 0.000 title description 9
- 150000007513 acids Chemical class 0.000 title description 8
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 4
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 239000012454 non-polar solvent Substances 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000007014 Michaelis-Becker reaction Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- UDPGUMQDCGORJQ-UHFFFAOYSA-M 2-chloroethyl(hydroxy)phosphinate Chemical compound OP([O-])(=O)CCCl UDPGUMQDCGORJQ-UHFFFAOYSA-M 0.000 description 1
- XYJLPCAKKYOLGU-UHFFFAOYSA-N 2-phosphonoethylphosphonic acid Chemical compound OP(O)(=O)CCP(O)(O)=O XYJLPCAKKYOLGU-UHFFFAOYSA-N 0.000 description 1
- IOWJYMAPHQYKSB-UHFFFAOYSA-N 3-hydroxypropyl hydrogen carbonate Chemical compound OCCCOC(O)=O IOWJYMAPHQYKSB-UHFFFAOYSA-N 0.000 description 1
- KYTWUFXLRDBYGE-UHFFFAOYSA-N CC.OP(=O)OP(O)=O Chemical class CC.OP(=O)OP(O)=O KYTWUFXLRDBYGE-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- VYHCCEKWJYJGHE-UHFFFAOYSA-N P(O)(OCCl)=O Chemical compound P(O)(OCCl)=O VYHCCEKWJYJGHE-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000004965 chloroalkyl group Chemical group 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- MBKDYNNUVRNNRF-UHFFFAOYSA-N medronic acid Chemical compound OP(O)(=O)CP(O)(O)=O MBKDYNNUVRNNRF-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C07F9/3843—Polyphosphonic acids containing no further substituents than -PO3H2 groups
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)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
1515th
Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung von cwJ-Alkan-diphosphonsäuren. The present invention relates to a process for the preparation of cwJ-alkane-diphosphonic acids.
Üblicherweise werden die Alkan-diphosphonsäuren aus den Tetraäthylestern der entsprechenden Säuren gewonnen. Zur Darstellung dieser Ester werden hauptsächlich 2 Methoden angewandt, indem man einmal nach der (viichaelis-Arbusow-Reaktion «/D-Dihalogenalkane mit Trialkylphosph'it bzw. nach der Michaelis-Becker-Reaktion Dihalogen-aikane mit Alkalidialkyiphosphiten umsetzt Beide Reaktionen eignen sich nur zur Darstellung von Alkandiphosphonsäuren, die sich von Kohlenwasserstoffen mit mindestens 3 »1 C-Atomen ableiten. Äthan-diphosphonsäure entsteht nur in mittleren Ausbeuten, während die Methan-diphosphonsäure nach der Michaelis-Becker-Reaktion überhaupt nicht herzustellen ist.The alkane-diphosphonic acids are usually used obtained from the tetraethyl esters of the corresponding acids. To represent these esters are mainly two methods are used, one after the (viichaelis-Arbusow reaction) / D-dihaloalkanes with trialkylphosphite or, according to the Michaelis-Becker reaction, dihalo-alkanes with alkali dialkyiphosphites converts Both reactions are only suitable for the preparation of alkanediphosphonic acids, which are derived from hydrocarbons with at least 3 »1 carbon atoms. Ethane-diphosphonic acid is formed only in medium yields, while methane-diphosphonic acid according to the Michaelis-Becker reaction cannot be produced at all.
Zur Herstellung von Methan- bzw. Äthan-diphosphonsäuren kann man Chlormethylphosphonat ClCH2P (O) (OR)2 bzw. 2-Chloräthylphosphonat CIC2H4P(OXOR)2 mit Alkalidialkylphosphit in Äiher oder Tetrahydrofuran umsetzen.To prepare methane or ethane diphosphonic acids, chloromethyl phosphonate ClCH 2 P (O) (OR) 2 or 2-chloroethyl phosphonate CIC 2 H 4 P (OXOR) 2 can be reacted with alkali dialkyl phosphite in ether or tetrahydrofuran.
All diesen Umsetzungen haften die Nachteile an, daß sie entweder umständlich durchzuführen sind oder daß Nebenprodukte durch Isomerisierung nicht zu vermeiden sind und somit keine reinen Substanzen in guter Ausbeute erhalten werden.All of these reactions have the disadvantage that they are either cumbersome to carry out or that By-products by isomerization cannot be avoided and thus no pure substances in good Yield can be obtained.
Es wurde gleichzeitig vorgeschlagen, o^u-Alkan-diphosphonsäuren dadurch herzustellen, daß man Triphenylphosphit und Tris-(chloralkyl)-phosphit im Molverhältnis 2:1 auf Temperaturen von 210 bis 3000C erhitzt und den erhaltenen Ester in üblicher Weise verseiftIt has been suggested at the same time, o ^ u-alkane-diphosphonic acids thereby to produce in that triphenyl phosphite and tris (chloroalkyl) phosphite in a molar ratio 2: 1 is heated to temperatures of 210-300 0 C and hydrolyzed the ester obtained in the usual manner
In ebenso einfacher Weise kann man a^u-Aikan-diphosphonsäuren herstellen, wenn man Triphenylphosphit mit cyklischen Carbonaten, insbesondere Äthylenglykol-, Propylenglykol- und Trimethylenglykol-Carbonat im Molverhältnis von 2 :1 in Gegenwart eines Katalysators, insbesondere Alkalijodid oder höhersiedenden tertiären Aminen, wie Dimethylanilin bei Temperaturen von 210 bis 3000C, vorzugsweise 220 bis 2400C umsetzt, die Nebenprodukte durch Auswaschen mit unpolaren Lösungsmitteln entfernt und den erhaltenen Ester in üblicher Weise verseiftA ^ u-Aikan diphosphonic acids can be prepared in an equally simple manner if triphenyl phosphite is used with cyclic carbonates, in particular ethylene glycol, propylene glycol and trimethylene glycol carbonate in a molar ratio of 2: 1 in the presence of a catalyst, in particular alkali iodide or higher-boiling tertiary amines, how dimethylaniline is converted at temperatures of 210 to 300 ° C., preferably 220 to 240 ° C., the by-products are removed by washing with non-polar solvents and the ester obtained is saponified in the customary manner
Dabei bilden sich α,ω-Alkan-diphosphonsäure-tetrapenylester der allgemeinen FormelIn the process, α, ω-alkane-diphosphonic acid tetrapenyl esters are formed the general formula
P-CnH2n-PPC n H 2n -P
Q7H5OQ 7 H 5 O
OQ1H5 OQ 1 H 5
wobei η = 2 bis 6 sein kann, je nachdem von welchen cyklischen Carbonaten man ausgeht, in 60- bis 85%iger Ausbeute.where η = 2 to 6, depending on which cyclic carbonates are used, in 60 to 85% yield.
Darstellung der Alkan-diphosphonsäuren über cyklische Carbonate: 62 g (0,2 Mol) Triphenylphosphit 0,1 Mol Carbonat und 0,2 g NaJ werden 2 Stunden auf 220 bis 24O0C erhitzt Nach Abkühlen wird das Produkt mit Petroläther ausgewaschen. Ausbeute 60—85% je nach Art des Carbonates.Representation of the alkane-diphosphonic acids via cyclic carbonates: 62 g (0.2 mol) of triphenyl phosphite 0.1 mole carbonate and 0.2 g of NaI are heated to 24O 0 C. After cooling, the product is washed with petroleum ether for 2 hours at 220th Yield 60-85% depending on the type of carbonate.
1 Mol des Tetraphenylesters wird mit 200 g NaOH gelöst in 1 Ltr. Wasser unter Rühren und Erwärmen verseift. Man neutralisiert mit Salzsäure, trennt die Phenolschicht schüttelt die wäßrige Phase zur Entfernung des restlichen Phenols mit Benzol und geht über einen sauren Ionenaustauscher. Die Lösung der freien Säure wird eingeengt, der Rückstand aus Äthanol-Wasser umkristallisiert.1 mol of the tetraphenyl ester is dissolved with 200 g of NaOH in 1 liter of water while stirring and heating saponified. It is neutralized with hydrochloric acid, the phenol layer is separated and the aqueous phase is shaken to remove it of the remaining phenol with benzene and goes through an acidic ion exchanger. The solution to the free The acid is concentrated and the residue is recrystallized from ethanol-water.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19712166577 DE2166577C3 (en) | 1971-11-26 | 1971-11-26 | Process for the preparation of a, w-alkanediphosphonic acids |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19712166577 DE2166577C3 (en) | 1971-11-26 | 1971-11-26 | Process for the preparation of a, w-alkanediphosphonic acids |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DE2166577A1 DE2166577A1 (en) | 1974-09-05 |
| DE2166577B2 DE2166577B2 (en) | 1978-09-14 |
| DE2166577C3 true DE2166577C3 (en) | 1979-05-03 |
Family
ID=5830154
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19712166577 Expired DE2166577C3 (en) | 1971-11-26 | 1971-11-26 | Process for the preparation of a, w-alkanediphosphonic acids |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE2166577C3 (en) |
-
1971
- 1971-11-26 DE DE19712166577 patent/DE2166577C3/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE2166577A1 (en) | 1974-09-05 |
| DE2166577B2 (en) | 1978-09-14 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| OI | Miscellaneous see part 1 | ||
| OI | Miscellaneous see part 1 | ||
| C3 | Grant after two publication steps (3rd publication) | ||
| 8339 | Ceased/non-payment of the annual fee |