DE1817682A1 - Production of urethane-phosphonic esters - Google Patents
Production of urethane-phosphonic estersInfo
- Publication number
- DE1817682A1 DE1817682A1 DE19681817682 DE1817682A DE1817682A1 DE 1817682 A1 DE1817682 A1 DE 1817682A1 DE 19681817682 DE19681817682 DE 19681817682 DE 1817682 A DE1817682 A DE 1817682A DE 1817682 A1 DE1817682 A1 DE 1817682A1
- Authority
- DE
- Germany
- Prior art keywords
- urethane
- formula
- esters
- lower alkyl
- phosphonic 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
- 150000002148 esters Chemical class 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 4
- 150000001340 alkali metals Chemical group 0.000 claims abstract description 4
- 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 4
- 125000005843 halogen group Chemical group 0.000 claims abstract description 3
- -1 haloalkyl urethanes Chemical class 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000000543 intermediate Substances 0.000 abstract description 2
- 239000003879 lubricant additive Substances 0.000 abstract description 2
- 239000000575 pesticide Substances 0.000 abstract description 2
- 125000002947 alkylene group Chemical group 0.000 abstract 1
- 239000003063 flame retardant Substances 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001350 alkyl halides Chemical class 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- QHSHDVYEJKLXLB-UHFFFAOYSA-N ethyl n-(2-chloroethyl)carbamate Chemical compound CCOC(=O)NCCCl QHSHDVYEJKLXLB-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 238000007014 Michaelis-Becker reaction Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- SYDYRFPJJJPJFE-UHFFFAOYSA-N [[4,6-bis[bis(hydroxymethyl)amino]-1,3,5-triazin-2-yl]amino]methanol Chemical compound OCNC1=NC(N(CO)CO)=NC(N(CO)CO)=N1 SYDYRFPJJJPJFE-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- VXIVSQZSERGHQP-UHFFFAOYSA-N chloroacetamide Chemical compound NC(=O)CCl VXIVSQZSERGHQP-UHFFFAOYSA-N 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- BESCFIAGVMCBAI-UHFFFAOYSA-N ethyl n-(2-bromoethyl)carbamate Chemical compound CCOC(=O)NCCBr BESCFIAGVMCBAI-UHFFFAOYSA-N 0.000 description 1
- KKPJZAUJVRPXCW-UHFFFAOYSA-N ethyl n-(4-bromobutyl)carbamate Chemical compound CCOC(=O)NCCCCBr KKPJZAUJVRPXCW-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical class NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 239000007966 viscous suspension Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
- C08K5/5353—Esters of phosphonic acids containing also nitrogen
-
- 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
- C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
Description
Urethan-phosphonester und Verfahren zu ihror Herstellung Die Herstellung von Alkylphosphonestern aus Alkylhalogeniden und niederen Di- oder Trialkylestern der phosphorigen Säure ist bekannt (Michaolis-Arbuzow- und Michaelis-Becker-Reaktion ; Houben-Weyl, 4. Auflage, Band 12/I, Seite 433 und 446). Diese Reaktionen wurden auch für das Chloracetamid beschrieben (J. org. Chem. 24 (1959) 434).Urethane phosphonic ester and process for its manufacture The manufacture of alkylphosphonic esters from alkyl halides and lower di- or trialkyl esters phosphorous acid is known (Michaolis-Arbuzow and Michaelis-Becker reaction ; Houben-Weyl, 4th edition, Volume 12 / I, pages 433 and 446). These reactions were also described for chloroacetamide (J. org. Chem. 24 (1959) 434).
Gegenstand der Erfindung sind Urethanalkyl-phosphonester der Formol I in welcher A für einen niederon Alkylenrest und R für eine niedere Alkylgruppe steht, sowie ein Verfahren zu ihror Herstellung, das dadurch gekennzeichnet ist, daß man Halogemalkylurothane der Formel II H2N-CO-O-A-X II in welcher A die vorstchend genannte Bedeutung hat und X für ein Halogematem stcht, mit Esterm der phosphorigen Säuro der Formol III in welcher E die vorstchend genannte Bedoutung hat und Y ein Alkalimstallatem eder eine niedere Alkylgruppe bedeutet, bei Temperaturen von etwa 0 bis etwa 140°C umsetzt.The invention relates to urethane alkyl phosphonic esters of the formula I. in which A stands for a lower alkylene radical and R stands for a lower alkyl group, as well as a process for their preparation, which is characterized in that one Halogemalkylurothane of the formula II H2N-CO-OAX II in which A has the meaning mentioned above and X is a Halogematem stcht, with ester of the phosphorous acid of the formula III in which E has the abovementioned meaning and Y is an alkali metal stable or a lower alkyl group, and is reacted at temperatures from about 0 to about 140.degree.
Als Ausgangsstoffe kommen durch Halogenatome, wie Jod und Brom, substituierte Alkylurethane, wie beispielsweise 2-Bromäthyl-urethan, 3-Brospropyl-urethan oder 4-Brombutyl-urethan, in Betracht. Überraschenderweise verlaufen die Reaktionen auch mit den entsprechenden Chlorverbindungen glatt, deren Einsatz aus wirtschaftlichen Gründen vorteilhafter ist.The starting materials are substituted by halogen atoms such as iodine and bromine Alkyl urethanes, such as, for example, 2-bromoethyl urethane, 3-brospropyl urethane or 4-bromobutyl urethane, into consideration. Surprisingly, the reactions also work with the corresponding chlorine compounds smooth, their use from economic Reasons is more advantageous.
Beim Einsatz vn Dialkylphosphiten, wie beispielsweise Diäthylphosphit und insbesondere Dimethylphosphit, wird zunächst in bekannter Weise deren Alkaliverbindung hergestellt, z. B. durch Umsetzung mit einem Alkalimetall, vorzugsweise Natrium oder mit Alkalialkoholat, vorzugsweise Natriumalkoholat. Die Alkaliverbindung wird anschließend mit der Halogenverbindung bei etwa 0 bis etwa 100°C, vorzugsweise bei Normaltemperatur, unter Abscheidung von Alkalihalogenid in bekannter Weise umgesetzt, an dessen Bildung die Reaktion erkennbar ist.When using dialkyl phosphites such as diethyl phosphite and in particular dimethyl phosphite, their alkali compound is first used in a known manner manufactured, e.g. B. by reaction with an alkali metal, preferably sodium or with alkali alcoholate, preferably sodium alcoholate. The alkali compound will then with the halogen compound at about 0 to about 100 ° C, preferably at Normal temperature, converted in a known manner with the deposition of alkali halide, the formation of which the reaction can be recognized.
Beim Einsatz von Trialkylphosphiten, wie Triäthylphosphit und insbesondere Trimthylphosphit, sind Temperaturen von etwa 90 bis etwa 140°C erforderlich. Hier ist die Reaktion am Abdestillieren des als Nebenprodukt anfallenden Alkylhalogenids, das aus einer Estergruppe stammt, erkennbar.When using trialkyl phosphites such as triethyl phosphite and in particular Trimthyl phosphite, temperatures of about 90 to about 140 ° C are required. here is the reaction to the distillation of the by-product alkyl halide, which originates from an ester group, recognizable.
Gegebenenfalls können Verdünnungsmittel zugesetzt werden, von denen Dimethylformamid besonders giinstig ist. Die Phosphonester fallen- gegebenenfalls nach Abtrennung des Alkylhalogenids beim Einsatz von Dielkylphosphiten und eines evtl. verwendeten Verdünnungsmittets durch Destillation be vermindertem Druck e als dickflüssige Öle an, die in Wasser, Methanol, Chloroferm und Dimethylformamid leicht löslich, in Aceton und T@@@@@l schwerlöslich sind. Die neuen Phosphonester können als Zwischenprodukte für die Herstellung von Schädlingsbekämpfungsmitteln und als Schmiermittelzusätze Verwendung finden. Insbesondere eignen sie ich in Kombination mit Vernetzungsmitteln, wie Formaldehyd und/oder organischen N-Methylolamiden, wie Pentamethylolmelamin, zur Herstellung von unbrennbaren oder selbstverlöschenden Kunststoffen und Überzügen.If necessary, diluents can be added, of which Dimethylformamide is particularly favorable. The phosphonic esters fall - if necessary after separation of the alkyl halide when using Dielkylphosphiten and one any diluents used by distillation under reduced pressure e as viscous oils in water, methanol, chloroferm and dimethylformamide Easily soluble, sparingly soluble in acetone and T @@@@@ l. The new Phosphonic esters can be used as intermediates in the manufacture of pesticides and are used as lubricant additives. I especially like them in combination with crosslinking agents such as formaldehyde and / or organic N-methylolamides, such as Pentamethylolmelamine, for the manufacture of non-combustible or self-extinguishing Plastics and coatings.
Beispiel 1 124 g (1 Mol) 2-Chloräthyl-urethan werden in 60 g Dimethylformamid angerührt und bei 140°C gelöst. Sodann werden bei 140°C 137 g (1,1 Mol) Trimethylphosphit in 2 Stunden in kleinen Portionen zugegeben, wobei reichlich Methylchlorid abdestilliert, das nach Passieren einer Eisfalle in einer Kältefalle von -75°C kondensiert wird (Ausbeute 49 g = 97 % d. Th.). Aus dem öligen Reaktionsprodukt wird bei 80°C/5 Torr das Dimethylformamid und restliches Trimethylphosphit abgezogen. Als Rückstand hinterbleiben 171 g (87 % d. Th.) eines farblosen dicken, bei -40°C glasig erstarrenden Öles, das in Wasser, Methanol und Chloroform leicht, und in Aceton schwer löslich ist.Example 1 124 g (1 mol) of 2-chloroethyl urethane are dissolved in 60 g of dimethylformamide stirred and dissolved at 140 ° C. 137 g (1.1 mol) of trimethyl phosphite are then obtained at 140.degree added in small portions in 2 hours, with plenty of methyl chloride distilling off, which is condensed after passing through an ice trap in a cold trap of -75 ° C (Yield 49 g = 97% of theory). From the oily reaction product is at 80 ° C / 5 Torr the dimethylformamide and remaining trimethyl phosphite are removed. Left behind as residue 171 g (87% of theory) of a colorless thick oil that solidifies glassy at -40 ° C, which is easily soluble in water, methanol and chloroform and sparingly soluble in acetone.
Elementargnalyset C5H12O5NP (Molgewicht 197) ber. : 30,0 % C ; 6,0 % H ; 7,0 % N ; 15,7 % P gef. : 30,9 % C ; 6,4 % H ; 7,6 % N ; 14,8 % P Im IR-Spektrum erkennt man die aus anderen Alkylphosphonestern bekannte P-O-C-Schwingung bei einer Wellenzahl von 1040 cm-¹, die P=O-Schwingung bei 1220 cm-¹, die C=O-Schwingung der Urethane bei 1700 cm , die NH-Schwingungen der Urethan bei 1330, 1400, 1600 und 3300 cm-¹ sowie die C-O-C-Schwingung der Urethane bei 1080 cm-¹. Im Phosphor-Kernresonanzspektrum erschsint in starkem Umfange eine für Alkyl-phosphonsäure-dimethylester charakteristische Phosphor-Kernresonanz mit einer Verschiebung von -31 ppm gegen H3PO4-Standard.Elementary analysis set C5H12O5NP (molecular weight 197) calc .: 30.0% C; 6.0 % H ; 7.0% N; 15.7% P found. : 30.9% C; 6.4% H; 7.6% N; 14.8% P in the IR spectrum the P-O-C oscillation known from other alkylphosphonic esters can be seen in a Wavenumber of 1040 cm-¹, the P = O vibration at 1220 cm-¹, the C = O vibration of the Urethane at 1700 cm, the NH vibrations of urethane at 1330, 1400, 1600 and 3300 cm-¹ and the C-O-C vibration of the urethanes at 1080 cm-¹. In the phosphorus nuclear magnetic resonance spectrum A characteristic of dimethyl alkyl phosphonate appears to a large extent Nuclear magnetic resonance with a shift of -31 ppm against the H3PO4 standard.
Löst man 99 g (0,5 Mol) des Phosphonesters bei gewöhnlicher Temperatur in 20 ml Wasser, stellt mit wenig NaOH auf pH 8 und gibt 0,5 Mol 40 %iges Formalin hinzu, so bildet sich bei 50°C die sehr leicht wasserlösliche, ölige N-Nethylolverbindung. Sie bildet sich auch beim mehrstündigen Verrühren des Phosphonesters mit 1 Mol Paraformaldehyd bei 800C bis zur Auflösung des letzteren.Dissolve 99 g (0.5 mol) of the phosphonic ester at ordinary temperature in 20 ml of water, adjusts to pH 8 with a little NaOH and gives 0.5 mol of 40% formalin added, the very easily water-soluble, oily N-methylol compound is formed at 50.degree. It is also formed when the phosphonic ester is stirred with 1 mol of paraformaldehyde for several hours at 800C until the latter dissolves.
Beispiel 2 Zu 110 g (1 Mol) Dimethylphosphit wird bei gewöhnlicher Temperatur unter Rühren 1 Mol 2 N Natriummethylatlösung zugetropft und das Methanol bei 400C/180 Torr abdestilliert. Man erhält 133 g der honigartigen Natriumverbindungl die sofort in 50 g Dimethylformamid gelöst wird.Example 2 To 110 g (1 mole) of dimethyl phosphite is added to ordinary Temperature with stirring 1 mol of 2 N sodium methylate solution was added dropwise and the methanol distilled off at 400C / 180 torr. 133 g of the honey-like sodium compound are obtained which is immediately dissolved in 50 g of dimethylformamide.
Hierzu werden portionsweise 124 g (i Mol) 2-Chloräthylurethan zugegeben und die so erhaltene Suspension 12 Stunden bei 70°C verrührt, wobei sich NaCl ausscheidet.To this end, 124 g (1 mol) of 2-chloroethyl urethane are added in portions and the suspension obtained in this way is stirred for 12 hours at 70 ° C., NaCl separating out.
Die Titration einer Proba der Suspension mit Silbernitrat ergibt 8,9 % Chlorionen (80 % d. Th.).The titration of a sample of the suspension with silver nitrate gives 8.9 % Chlorine ions (80% of theory).
Zur dickflüssigen Suspension werden 300 g Methanol zugesetzt und aus der dünnen Suspension das NaCl abgesaugt (nach Waschen mit Methanol und Trocknen 48 g (80 % d. Th.)).300 g of methanol are added to the viscous suspension and removed the NaCl sucked off the thin suspension (after washing with methanol and drying 48 g (80% of theory)).
Das methanolische Filtrat liefert beim Abziehen des Methanols bei 50°C/170 Torr 162 g des im Beispiel 1 charakterisierten Phosphonesters.The methanolic filtrate supplies when the methanol is drawn off 50 ° C / 170 Torr 162 g of the phosphonic ester characterized in Example 1.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19681817682 DE1817682A1 (en) | 1968-12-30 | 1968-12-30 | Production of urethane-phosphonic esters |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19681817682 DE1817682A1 (en) | 1968-12-30 | 1968-12-30 | Production of urethane-phosphonic esters |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1817682A1 true DE1817682A1 (en) | 1970-07-16 |
Family
ID=5717702
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19681817682 Pending DE1817682A1 (en) | 1968-12-30 | 1968-12-30 | Production of urethane-phosphonic esters |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1817682A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1211023B (en) * | 1963-03-16 | 1966-02-17 | Kloeckner Humboldt Deutz Ag | Valve control for internal combustion engines |
| US3758554A (en) * | 1971-06-18 | 1973-09-11 | Stevens & Co Inc J P | Phosphorus-containing carbamates |
| US3835204A (en) * | 1971-06-28 | 1974-09-10 | Stauffer Chemical Co | Hydroxyalkylphosphonate carbamates |
-
1968
- 1968-12-30 DE DE19681817682 patent/DE1817682A1/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1211023B (en) * | 1963-03-16 | 1966-02-17 | Kloeckner Humboldt Deutz Ag | Valve control for internal combustion engines |
| US3758554A (en) * | 1971-06-18 | 1973-09-11 | Stevens & Co Inc J P | Phosphorus-containing carbamates |
| US3835204A (en) * | 1971-06-28 | 1974-09-10 | Stauffer Chemical Co | Hydroxyalkylphosphonate carbamates |
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