DE1010965B - Process for the preparation of acidic esters of acylphosphonic acids or their salts - Google Patents
Process for the preparation of acidic esters of acylphosphonic acids or their saltsInfo
- Publication number
- DE1010965B DE1010965B DEH26995A DEH0026995A DE1010965B DE 1010965 B DE1010965 B DE 1010965B DE H26995 A DEH26995 A DE H26995A DE H0026995 A DEH0026995 A DE H0026995A DE 1010965 B DE1010965 B DE 1010965B
- Authority
- DE
- Germany
- Prior art keywords
- acid
- acids
- salts
- acylphosphonic
- acidic esters
- 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.)
- Pending
Links
- 239000002253 acid Substances 0.000 title claims description 16
- 150000002148 esters Chemical class 0.000 title claims description 12
- 230000002378 acidificating effect Effects 0.000 title claims description 11
- 150000007513 acids Chemical class 0.000 title claims description 9
- 150000003839 salts Chemical class 0.000 title claims description 7
- 238000000034 method Methods 0.000 title claims description 5
- -1 carboxylic acid halides Chemical class 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 5
- 235000002639 sodium chloride Nutrition 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 4
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 4
- 229960003750 ethyl chloride Drugs 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 3
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- BVXOPEOQUQWRHQ-UHFFFAOYSA-N dibutyl phosphite Chemical compound CCCCOP([O-])OCCCC BVXOPEOQUQWRHQ-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- NQGIJDNPUZEBRU-UHFFFAOYSA-N dodecanoyl chloride Chemical compound CCCCCCCCCCCC(Cl)=O NQGIJDNPUZEBRU-UHFFFAOYSA-N 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WZHHYIOUKQNLQM-UHFFFAOYSA-N 3,4,5,6-tetrachlorophthalic acid Chemical compound OC(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C(O)=O WZHHYIOUKQNLQM-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000251730 Chondrichthyes Species 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- PWAXUOGZOSVGBO-UHFFFAOYSA-N adipoyl chloride Chemical compound ClC(=O)CCCCC(Cl)=O PWAXUOGZOSVGBO-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 208000027697 autoimmune lymphoproliferative syndrome due to CTLA4 haploinsuffiency Diseases 0.000 description 1
- XEDLVIBRXVIWLS-UHFFFAOYSA-N benzoylphosphonic acid Chemical compound OP(O)(=O)C(=O)C1=CC=CC=C1 XEDLVIBRXVIWLS-UHFFFAOYSA-N 0.000 description 1
- GGCXLVWDCPTFMN-UHFFFAOYSA-N bis(2-chloroethyl) hydrogen phosphite Chemical compound ClCCOP(O)OCCCl GGCXLVWDCPTFMN-UHFFFAOYSA-N 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- IPIVAXLHTVNRBS-UHFFFAOYSA-N decanoyl chloride Chemical compound CCCCCCCCCC(Cl)=O IPIVAXLHTVNRBS-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- XMQYIPNJVLNWOE-UHFFFAOYSA-N dioctyl hydrogen phosphite Chemical compound CCCCCCCCOP(O)OCCCCCCCC XMQYIPNJVLNWOE-UHFFFAOYSA-N 0.000 description 1
- NFORZJQPTUSMRL-UHFFFAOYSA-N dipropan-2-yl hydrogen phosphite Chemical compound CC(C)OP(O)OC(C)C NFORZJQPTUSMRL-UHFFFAOYSA-N 0.000 description 1
- OFNNRXJYHHERJS-UHFFFAOYSA-N dodecanoylphosphonic acid Chemical compound CCCCCCCCCCCC(=O)P(O)(O)=O OFNNRXJYHHERJS-UHFFFAOYSA-N 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 150000003977 halocarboxylic acids Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 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 1
- 238000009988 textile finishing Methods 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 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)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4062—Esters of acids containing the structure -C(=X)-P(=X)(XR)2 or NC-P(=X)(XR)2, (X = O, S, Se)
- C07F9/4065—Esters of acids containing the structure -C(=X)-P(=X)(XR)2, (X = O, S, Se)
Landscapes
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Description
Es ist bekannt, daß man durch Umsetzung von Acetyl- oder Benzoylchlorid mit Triäthylphosphit den Diäthylester der Acetyl- bzw. Benzoylphosphonsäure erhalten kann. Die so gewonnenen neutralen Ester zerfallen bei der Verseifung entweder in die entsprechende Carbonsäure und phosphorige Säure oder in den betreffenden Aldehyd und Phosphorsäure. Es ist daher nicht möglich, auf diesem Wege saure Ester von Acylphosphonsäuren oder deren Salze herzustellen.It is known that the diethyl ester can be obtained by reacting acetyl or benzoyl chloride with triethyl phosphite the acetyl or benzoyl phosphonic acid can be obtained. The neutral esters obtained in this way disintegrate the saponification either in the corresponding carboxylic acid and phosphorous acid or in the relevant Aldehyde and phosphoric acid. It is therefore not possible to use acidic esters of acylphosphonic acids in this way or to produce their salts.
Es wurde nun gefunden, daß man saure Ester von Acylphosphonsäuren in einfacher Weise dadurch herstellen kann, daß man Säurehalogenide von ein- oder mehrbasischen Carbonsäuren mit Dialkylphosphiten bei erhöhter Temperatur zur Reaktion bringt. Die erfindungsgemäße Umsetzung verläuft bei Verwendung eines Monocarbonsäurehalogenids wahrscheinlich nach folgender allgemeiner Formel:It has now been found that acidic esters of acylphosphonic acids can be produced in a simple manner in this way can that one acid halides of mono- or polybasic carboxylic acids with dialkyl phosphites brings about increased temperature to the reaction. The inventive implementation proceeds when using a Monocarboxylic acid halide probably according to the following general formula:
Verfahren zur HerstellungMethod of manufacture
von sauren Estern der
Acylphosphonsäuren bzw. ihrer Salzeof acid esters of the
Acylphosphonic acids or their salts
Anmelder:Applicant:
Henkel & Cie. G.m.b.H.,
Düsseldorf-Holthausen, Henkelstr. 67Henkel & Cie. GmbH,
Düsseldorf-Holthausen, Henkelstr. 67
Dr. Bruno Blaser, Düsseldorf-Urdenbach,
und Dr. Wilhelm Jakob Kaiser, Düsseldorf-Holthausen, sind als Erfinder genannt wordenDr. Bruno Blaser, Düsseldorf-Urdenbach,
and Dr. Wilhelm Jakob Kaiser, Düsseldorf-Holthausen, have been named as the inventor
— RO,- RO,
R'O/ R'O /
+ R" — C — Hai+ R "- C - shark
wasserstoffreste mit vorzugsweise weniger als acht Kohlenstoffatomen und R" einen aliphatischen, cycloaliphatischen oder aromatischen Kohlenwasserstoff rest. Die Reste R, R' und R" können geradkettig oder ver-25 zweigt sein. Sie können auch substituiert sein, z. B. durch R' Hai. Halogenatome. Der Rest R" kann außerdem durch Heteroatome unterbrachen sein. Verwendet man als Ausgangsmaterial für das erfindungsgemäße Verfahren das Säurehalogenid einer zwei- oder mehrbasischen In dieser Formel bedeuten R und R' gleiche oder ver- 30 Carbonsäure, so entstehen in analoger Weise zwei- oder schiedene aliphatische oder cycloaliphatische Kohlen- mehrbasische saure Ester, z, B. nach folgender Formel:hydrogen radicals with preferably fewer than eight carbon atoms and R ″ an aliphatic, cycloaliphatic or aromatic hydrocarbon rest. The radicals R, R 'and R "can be straight-chain or ver-25 be branches. They can also be substituted, e.g. B. by R 'Hai. Halogen atoms. The remainder R ″ can also pass through Heteroatoms be interrupted. Is used as the starting material for the process according to the invention the acid halide of a di- or polybasic. In this formula, R and R 'denote the same or different carboxylic acid, so in an analogous manner two- or different aliphatic or cycloaliphatic carbon polybasic acidic esters, e.g. according to the following formula:
" —c —p:"—C —p:
OHOH
OROR
RO, ,0RO,, 0
CHaICHaI
Il ,OR
r ρ y Il, OR
r ρ y
\s JL \ s JL
Λ + 2R'HalΛ + 2R'Hal
0 OR
C-P' 0 OR
C-P '
Als Ausgangsmaterial für das erfindungsgemäße Verfahren kommen demnach die Säurehalogenide, vorzugsweise die Chloride oder Bromide von aliphatischen, cycloaliphatischen oder aromatischen Mono-; Di- oder Polycarbonsäuren in Frage, deren Kohlenwasserstoffreste die verschiedensten Substituenten tragen oder auch durch Heteroatome oder Heteroatomgruppen unterbrochen sein können, z. B. Essigsäure, Buttersäure, Isobuttersäure, Laurinsäure und höhere Fettsäuren, Mono-, Di- und Trichloressigsäure sowie andere Halogencarbonsäuren, ferner Äthercarbonsäuren, Thioäthercarbonsäuren, Aminocarbonsäuren, weiterhin Cyclohexancarbonsäure, Benzoe-O O The starting material for the process according to the invention is accordingly the acid halides, preferably the chlorides or bromides of aliphatic, cycloaliphatic or aromatic mono-; Di- or polycarboxylic acids in question whose hydrocarbon radicals carry a wide variety of substituents or can be interrupted by heteroatoms or heteroatom groups, e.g. B. acetic acid, butyric acid, isobutyric acid, lauric acid and higher fatty acids, mono-, di- and trichloroacetic acid and other halocarboxylic acids, also ether carboxylic acids, thioether carboxylic acids, aminocarboxylic acids, furthermore cyclohexanecarboxylic acid, benzoic OO
säure und andere, auch substituierte, aromatische Carbon säuren, schließlich auch Di- und Polycarbonsäuren, ζ. B-Adipinsäure, Sebacinsäure, Tricarballysäure, Phthalsäure, Tetrachlorphthalsäure, Terephthalsäure und Trimesinsäure. acid and other, also substituted, aromatic carboxylic acids, finally also di- and polycarboxylic acids, ζ. B-adipic acid, Sebacic acid, tricarballyic acid, phthalic acid, tetrachlorophthalic acid, terephthalic acid and trimesic acid.
Dialkylphosphite, welche erfindungsgemäß mit Carbonsäurehalogeniden zur Umsetzung gelangen, sind beispielsweise Diäthylphosphit, Diisopropylphosphit, Dibutylphosphit, Dioctylphosphit und Di-(2-chlor-äthyl)-phosphit. Dialkyl phosphites, which according to the invention with carboxylic acid halides come to implementation are, for example, diethyl phosphite, diisopropyl phosphite, dibutyl phosphite, Dioctyl phosphite and di- (2-chloro-ethyl) -phosphite.
Die beiden Reaktionspartner werden vorzugsweise in einem solchen Mengenverhältnis eingesetzt, daß auf eineThe two reactants are preferably used in such a quantitative ratio that on one
709 550/439709 550/439
— CO — Hai-Gruppe etwa 1 Mol Dialkylphosphit trifft. Ein Überschuß der einen oder anderen Komponente ist jedoch nicht schädlich.- CO - Hai group meets about 1 mole of dialkyl phosphite. However, an excess of one or the other component is not harmful.
Die Umsetzung erfolgt bei erhöhten Temperaturen, vorzugsweise zwischen 50 und 150°. In manchen Fällen, vor allem wenn ein besonders reaktionsfähiges Carbonsäurehalogenid zur Anwendung gelangt, ist es zweckmäßig, die Reaktion in Gegenwart eines organischen Lösungsoder Verdünnungsmittels, z. B. Tetrachlorkohlenstoff oder Benzol, durchzuführen.The reaction takes place at elevated temperatures, preferably between 50 and 150 °. In some cases, especially when a particularly reactive carboxylic acid halide is used, it is advisable to the reaction in the presence of an organic solvent or diluent, e.g. B. Carbon tetrachloride or benzene.
Die erfindungsgemäße Umsetzung erfolgt, wie aus den obenstehenden Formen zu entnehmen ist, unter Abspaltung von Alkylhalogenid. Dieses destilliert, falls zur Herstellung des Dialkylphosphits ein niedermolekularer Alkohol verwendet wird, während der Umsetzung laufend aus dem Reaktionsgemisch ab. Wird zur Darstellung des Dialkylphosphits ein höhermolekularer Alkohol verwendet, so kann das Alkylhalogenid während oder nach der Reaktion im Vakuum abdestilliert werden.As can be seen from the above forms, the reaction according to the invention takes place with cleavage of alkyl halide. This distilled, if a low molecular weight to produce the dialkyl phosphite Alcohol is used, continuously from the reaction mixture during the reaction. Used to represent the Dialkyl phosphite uses a higher molecular weight alcohol, the alkyl halide can be used during or after the reaction are distilled off in vacuo.
Die nach der erfindungsgemäßen Reaktion erhaltenen sauren Ester von Acylphosphonsäuren lassen sich in einfacher Weise in ihre Salze, z. B. die Alkalisalze, überführen. Diese Salze können bei geeigneter Molekülgröße als kapillaraktive Mittel für die verschiedensten Zwecke, z. B. als Reinigungsmittel oder zur Textilveredelung, Verwendung finden.The acidic esters of acylphosphonic acids obtained after the reaction according to the invention can be easily processed Way into their salts, e.g. B. the alkali salts, transfer. These salts can with a suitable molecular size as capillary-active agents for various purposes, e.g. B. as a cleaning agent or for textile finishing, Find use.
Die sauren Ester können auch durch Erhitzen mit vorzugsweise höhermolekularen Alkoholen, gegebenenfalls in Anwesenheit geeigneter Veresterungskatalysatoren, umgeestert oder auch in neutrale Ester übergeführt werden.The acidic esters can also be prepared by heating with preferably higher molecular weight alcohols, optionally in Presence of suitable esterification catalysts, transesterified or converted into neutral esters.
Die aus den Halogeniden von Di- und Polycarbonsäuren hergestellten mehrbasischen sauren Ester von Acylphosphonsäuren können auch mit mehrwertigen Alkoholen zu sauren oder auch neutralen Polyestern verschiedener Molekülgrößen umgesetzt werden.The polybasic acidic esters of Acylphosphonic acids can also be mixed with polyhydric alcohols to form acidic or neutral polyesters different molecular sizes are implemented.
das reine Natriumsalz des Monoäthylesters der Lauroylphosphonsäure in fester Form erhalten.the pure sodium salt of the monoethyl ester of lauroylphosphonic acid received in solid form.
61 g Adipinsäuredichlorid und 92 g Diäthylphosphit wurden 8 Stunden bei 90 bis 95° gerührt, wobei 40 g Äthylchlorid abdestillierten. Das Umsetzungsprodukt stellt eine farblose, viskose, in Wasser mit saurer Reaktion klar lösliche Flüssigkeit dar.61 g of adipic acid dichloride and 92 g of diethyl phosphite were stirred for 8 hours at 90 to 95 °, with 40 g of ethyl chloride distilled off. The reaction product turns a colorless, viscous, in water with an acidic reaction clear soluble liquid.
55,2 g Diäthylphosphit und 87,4 g Lauroylchlorid wurden bei einer Temperatur von 85 bis 95° 8 Stunden gerührt, wobei etwa 16 g Äthylchlorid abdestülierten. Der Rückstand stellte eine wasserhelle, mäßig viskose Flüssigkeit dar.55.2 g of diethyl phosphite and 87.4 g of lauroyl chloride were stirred at a temperature of 85 to 95 ° for 8 hours, with about 16 g of ethyl chloride distilled off. The residue was a water-white, moderately viscous liquid represent.
29,2 g des Reaktionsproduktes wurden mit 4 g NaOH, gelöst in 1,4 1 Wasser, verrührt. Es entstand eine einer Seifenlösung ähnliche, stark schäumende, trübe Lösung. Aus dieser Lösung wurde durch Aussalzen mit Kochsalz 55,2 g Diäthylphosphit wurden mit 56,2 g Benzoylchlorid 20 Stunden unter Rühren auf 85 bis 95° erwärmt, wobei 25 g Äthylchlorid abdestillierten. Das Reaktionsprodukt stellte eine viskose, wasserhelle Flüssigkeit dar, die sich beim Schütteln mit verdünnter Natronlauge leicht löste.29.2 g of the reaction product were stirred up with 4 g of NaOH dissolved in 1.4 l of water. There was a one Soap solution-like, strongly foaming, cloudy solution. This solution was made by salting out with common salt 55.2 g of diethyl phosphite were heated with 56.2 g of benzoyl chloride for 20 hours with stirring to 85 to 95 °, 25 g of ethyl chloride distilled off. The reaction product was a viscous, water-white liquid, which easily dissolved when shaken with dilute sodium hydroxide solution.
19 g Caprinsäurechlorid wurden mit 14,5 g Diäthylphosphit 8 Stunden bei 85 bis 95° gerührt, wobei 6 g Äthylchlorid abdestülierten. Der Rückstand stellte ein wasserhelles mäßig viskoses Öl dar und war in verdünnter Natronlauge leicht löslich.19 g of capric acid chloride were stirred with 14.5 g of diethyl phosphite for 8 hours at 85 to 95 °, with 6 g of ethyl chloride distilled off. The residue was a water-white, moderately viscous oil and was in dilute sodium hydroxide solution easily soluble.
109,3 g Lauroylchlorid und 97 g Dibutylphosphit wurden unter Durchleiten von Stickstoff auf 95° erhitzt, wobei das gebüdete Butylchlorid in einer gekühlten Vorlage aufgefangen wurde. Nach etwa 20 Stunden fand keine weitere Abspaltung von Butylchlorid mehr statt. Die Gewichtsabnahme des Ansatzes betrug 43,5 g. Der Rückstand stellte ein viskoses, fast farbloses Ol dar. Der Phosphor- und Kohlenstoffgehalt des Reaktionsproduktes entsprach der Formel109.3 g of lauroyl chloride and 97 g of dibutyl phosphite were heated to 95 ° while nitrogen was passed through, the butyl chloride formed was collected in a cooled receiver. Found after about 20 hours no further elimination of butyl chloride takes place. The weight loss of the batch was 43.5 g. Of the The residue was a viscous, almost colorless oil. The phosphorus and carbon content of the reaction product corresponded to the formula
CuH23 — CO — PO(OH) — OC4H9.CuH 23 - CO - PO (OH) - OC 4 H 9 .
Der Chlorgehalt war kleiner als 0,1 0J0, die Säurezahl betrug 182 bzw. 186 (berechnet 175), die Verseifungszahl 355 bzw. 363 (berechnet 350).The chlorine content was less than 0.1 0 I 0 , the acid number was 182 or 186 (calculated 175), the saponification number 355 or 363 (calculated 350).
Claims (1)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEH26995A DE1010965B (en) | 1956-05-08 | 1956-05-08 | Process for the preparation of acidic esters of acylphosphonic acids or their salts |
| GB14121/57A GB810642A (en) | 1956-05-08 | 1957-05-03 | A process for the preparation of esters of acylphosphorous acids |
| US657496A US2900408A (en) | 1956-05-08 | 1957-05-07 | Acid esters of acyl-phosphorous acids and method of making the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEH26995A DE1010965B (en) | 1956-05-08 | 1956-05-08 | Process for the preparation of acidic esters of acylphosphonic acids or their salts |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1010965B true DE1010965B (en) | 1957-06-27 |
Family
ID=7150451
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEH26995A Pending DE1010965B (en) | 1956-05-08 | 1956-05-08 | Process for the preparation of acidic esters of acylphosphonic acids or their salts |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US2900408A (en) |
| DE (1) | DE1010965B (en) |
| GB (1) | GB810642A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1148552B (en) | 1961-07-03 | 1963-05-16 | Henkel & Cie Gmbh | Process for the production of phosphonic acids with at least 2 phosphorus atoms in the molecule |
| US3159581A (en) * | 1962-04-13 | 1964-12-01 | Procter & Gamble | Detergency composition |
| US3940436A (en) * | 1970-04-13 | 1976-02-24 | Monsanto Company | Substituted ethane diphosphonic acids and salts and esters thereof |
| US3944599A (en) * | 1970-04-13 | 1976-03-16 | Monsanto Company | Substituted ethane diphosphonic acids and salts |
| US3957858A (en) * | 1970-04-13 | 1976-05-18 | Monsanto Company | Substituted ethane diphosphonic acids and salts and esters thereof |
| EP0007508A3 (en) * | 1978-07-14 | 1980-10-29 | Basf Aktiengesellschaft | Acylphosphinoxide compounds, their preparation, their use, photopolymerisable printing compositions and process for the preparation of relief forms |
| US5196409A (en) * | 1989-08-20 | 1993-03-23 | Yissum, Research Development Company Of The Hebrew University Of Jerusalem | Bisphosphonates, pharmaceutical compositions, and process for the treatment of irregularities in calcium metabolism |
| US5312954A (en) * | 1989-08-20 | 1994-05-17 | Yissum, Research Development Company Of The Hebrew University Of Jerusalem | Bis- and tetrakis-phosphonates useful for treating calcium related disorders |
| EP0601413A1 (en) * | 1992-12-05 | 1994-06-15 | BASF Aktiengesellschaft | Arene bisphosphinoxides |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3118876A (en) * | 1958-07-26 | 1964-01-21 | Takeda Pharmaceutical | Process for preparing glycoside phosphates |
| NL242785A (en) * | 1958-09-06 | 1900-01-01 | ||
| US3012054A (en) * | 1960-03-18 | 1961-12-05 | Dow Chemical Co | Tetraalkyl esters of diphosphonates |
| US3324202A (en) * | 1963-07-09 | 1967-06-06 | Fmc Corp | Phosphorus-containing polyols |
| US3382060A (en) * | 1964-11-18 | 1968-05-07 | Chemagro Corp | Dialkyl and diphenyl esters of aryloxyacetyl-phosphonic acid as herbicides |
| US3400148A (en) * | 1965-09-23 | 1968-09-03 | Procter & Gamble | Phosphonate compounds |
| US3676532A (en) * | 1969-11-21 | 1972-07-11 | Olin Corp | Alpha-(dialkoxyphosphinyl)aryl methyl dialkyl phosphates |
| US3899496A (en) * | 1970-10-06 | 1975-08-12 | Henkel & Cie Gmbh | Production of 1-aminoalkane-1,1-diphosphonic acids |
| US4339443A (en) * | 1978-09-22 | 1982-07-13 | Fbc Limited | Compounds and compositions |
| FR2489711A1 (en) * | 1980-04-21 | 1982-03-12 | Minemet Rech Sa | EXCHANGE COMPOSITIONS OF METAL CATIONS |
| DE3039998A1 (en) * | 1980-10-23 | 1982-06-03 | Bayer Ag, 5090 Leverkusen | PHOSPHONOFORMALDEHYDE, A METHOD FOR THE PRODUCTION THEREOF AND ITS USE AS AN INTERMEDIATE PRODUCT FOR THE PRODUCTION OF MEDICINAL PRODUCTS |
| US5017306A (en) * | 1988-11-09 | 1991-05-21 | W. R. Grace & Co.-Conn. | Corrosion inhibitor |
| US4911887A (en) * | 1988-11-09 | 1990-03-27 | W. R. Grace & Co.-Conn. | Phosphonic acid compounds and the preparation and use thereof |
| US4981648A (en) * | 1988-11-09 | 1991-01-01 | W. R. Grace & Co.-Conn. | Inhibiting corrosion in aqueous systems |
| US5266722A (en) * | 1988-11-09 | 1993-11-30 | W. R. Grace & Co.-Conn. | Polyether bis-phosphonic acid compounds |
| DE4033215A1 (en) * | 1990-10-19 | 1992-04-23 | Hoechst Ag | Novel photoinitiator cpds. - comprise acyl-(2'-hydroxybiphenyl-2-yl)- phosphinic acid salts |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2491920A (en) * | 1946-05-16 | 1949-12-20 | Du Pont | Diesters of 1-ketophosphonic acids |
| US2629731A (en) * | 1951-03-07 | 1953-02-24 | Shell Dev | Esters of phosphonoformic acids and polyhydric alcohols |
| US2719167A (en) * | 1953-04-13 | 1955-09-27 | Ciba Ltd | Compounds containing phosphorus and process therefor |
-
1956
- 1956-05-08 DE DEH26995A patent/DE1010965B/en active Pending
-
1957
- 1957-05-03 GB GB14121/57A patent/GB810642A/en not_active Expired
- 1957-05-07 US US657496A patent/US2900408A/en not_active Expired - Lifetime
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1148552B (en) | 1961-07-03 | 1963-05-16 | Henkel & Cie Gmbh | Process for the production of phosphonic acids with at least 2 phosphorus atoms in the molecule |
| US3159581A (en) * | 1962-04-13 | 1964-12-01 | Procter & Gamble | Detergency composition |
| US3940436A (en) * | 1970-04-13 | 1976-02-24 | Monsanto Company | Substituted ethane diphosphonic acids and salts and esters thereof |
| US3944599A (en) * | 1970-04-13 | 1976-03-16 | Monsanto Company | Substituted ethane diphosphonic acids and salts |
| US3957858A (en) * | 1970-04-13 | 1976-05-18 | Monsanto Company | Substituted ethane diphosphonic acids and salts and esters thereof |
| EP0007508A3 (en) * | 1978-07-14 | 1980-10-29 | Basf Aktiengesellschaft | Acylphosphinoxide compounds, their preparation, their use, photopolymerisable printing compositions and process for the preparation of relief forms |
| US5196409A (en) * | 1989-08-20 | 1993-03-23 | Yissum, Research Development Company Of The Hebrew University Of Jerusalem | Bisphosphonates, pharmaceutical compositions, and process for the treatment of irregularities in calcium metabolism |
| US5312954A (en) * | 1989-08-20 | 1994-05-17 | Yissum, Research Development Company Of The Hebrew University Of Jerusalem | Bis- and tetrakis-phosphonates useful for treating calcium related disorders |
| US5338731A (en) * | 1989-08-20 | 1994-08-16 | Yissum, Research Development Company Of The Hebrew University Of Jerusalem | Bisphosphonates, processes for preparation and pharmaceutical compositions containing the same |
| EP0601413A1 (en) * | 1992-12-05 | 1994-06-15 | BASF Aktiengesellschaft | Arene bisphosphinoxides |
| US5410060A (en) * | 1992-12-05 | 1995-04-25 | Basf Aktiengesellschaft | Process for preparation of arenebisphosphine oxides |
Also Published As
| Publication number | Publication date |
|---|---|
| GB810642A (en) | 1959-03-18 |
| US2900408A (en) | 1959-08-18 |
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