DD242810A1 - PROCESS FOR THE PREPARATION OF N-PHOSPHINOFOMYL AMINOSAURES AND THEIR DERIVATIVES - Google Patents

PROCESS FOR THE PREPARATION OF N-PHOSPHINOFOMYL AMINOSAURES AND THEIR DERIVATIVES Download PDF

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DD242810A1
DD242810A1 DD28305085A DD28305085A DD242810A1 DD 242810 A1 DD242810 A1 DD 242810A1 DD 28305085 A DD28305085 A DD 28305085A DD 28305085 A DD28305085 A DD 28305085A DD 242810 A1 DD242810 A1 DD 242810A1
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Prior art keywords
phosphinoformyl
formula
alkyl
aryl
alkali metal
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DD28305085A
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German (de)
Inventor
Kurt Issleib
Arno Balszuweit
Beate Stiebitz
Werner Moegelin
Juergen Reefschlaeger
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Univ Halle Wittenberg
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Abstract

Die Erfindung betrifft ein Verfahren zur Herstellung von N-(Phosphinoformyl)-aminosaeuren und deren Derivaten der Formel I, durch Umsetzung von Phosphonigsaeure-trimethylsilylestern mit Isocyanatocarbonsaeureestern bei erhoehter Temperatur zu N-(Phosphinoformyl)-aminosaeureestern, die mittels alkalischer Solvolyse in Verbindungen der Formel I ueberfuehrt werden koennen, wobei R Alkyl, Cycloalkyl, Aryl, subst. Aryl; R1 Trimethylsilyl, Waserstoff, ein Alkalimetall, Ammonium, ein substituierter Ammoniumrest; R2 Alkyl von C1 bis C4, Wasserstoff oder ein Alkalimetall; A verzweigte oder unverzweigte, substituierte bzw. unsubstituierte Alkylen von C1 bis C9, Cycloalkylen oder heterocyclischen Rest bedeuten. N-(Phosphinoformyl)-aminosaeuren besitzen antivirale Eigenschaften. FormelThe invention relates to a process for the preparation of N- (phosphinoformyl) -amino acids and their derivatives of the formula I, by reaction of phosphonous trimethylsilyl esters with Isocyanatocarbonsaeureestern at elevated temperature to N- (phosphinoformyl) amino acid esters by alkaline solvolysis in compounds of the formula I can be converted, where R is alkyl, cycloalkyl, aryl, subst. aryl; R1 is trimethylsilyl, hydrogen, an alkali metal, ammonium, a substituted ammonium radical; R2 is alkyl of C1 to C4, hydrogen or an alkali metal; A is branched or unbranched, substituted or unsubstituted alkylene of C1 to C9, cycloalkylene or heterocyclic radical. N- (phosphinoformyl) amino acids have antiviral properties. formula

Description

Anwendungsgebiet der ErfindungField of application of the invention

Die Erfindung betrifft ein Verfahren zur Herstellung von N-Phosphinoformyl-aminosäuren und deren Derivaten der allgemeinen Formel IThe invention relates to a process for the preparation of N-phosphinoformyl-amino acids and their derivatives of general formula I.

OO . OO .

(I » 2(I »2

K-P-C-NH-A-COORK-P-C-NH-A-COOR

OR1 OR 1

in derin the

R Alkyl, Cycloalkyl, Aryl, subst. ArylR is alkyl, cycloalkyl, aryl, subst. aryl

R1 Trimethylsilyl, Wasserstoff, einen Alkalimetall, Ammonium, ein substituierter Ammoniumrest R2 Alkyl von Ci bis C4, Wasserstoff oder ein AlkalimetallR 1 is trimethylsilyl, hydrogen, an alkali metal, ammonium, a substituted ammonium radical R 2 is alkyl of C 1 to C 4 , hydrogen or an alkali metal

A verzweigte oder unverzweigte, substituierte bzw. unsubstituierte Alkylen von C1 bis Cg, Cycloalkylen oder heterocyclischenA branched or unbranched, substituted or unsubstituted alkylene of C 1 to Cg, cycloalkylene or heterocyclic

Rest bedeutenMean rest

N-Phosphinoformyl-aminosäuren besitzen antivirale Eigenschaften. N-phosphinoformyl-amino acids have antiviral properties.

Charakteristik der bekannten technischen LösungenCharacteristic of the known technical solutions

N-Phosphinoformyl-aminosäuren der allgemeinen Formel I sind bisher nicht bekannt.N-phosphinoformyl-amino acids of general formula I are not yet known.

Ziel der ErfindungObject of the invention

Das Ziel der Erfindung ist eine einfache Herstellung von Verbindungen der allgemeinen Formel I, welche in wenigen Verfahrensschritten nahezu quantitative Ausbeuten liefert.The object of the invention is a simple preparation of compounds of general formula I, which yields almost quantitative yields in a few process steps.

Darlegung des Wesens der ErfindungExplanation of the essence of the invention

Die Aufgabe der Erfindung ist ein Verfahren zur Herstellung von N-Phosphinoformyl-aminosäuren und deren Derivaten der Formel I unter Verwendung leicht zugänglicher stabiler Ausgangsstoffe. Es wurde gefunden, daß durch Umsetzung von Phosphonigsäure-trimethylsilylestem der Fyormel Il mit Isocyanatocarbonsäureestern der allgemeinen Formel II, bei erhöhter Temperatur, in sehr guten Ausbeuten Verbindungen der Formel IV resultieren, die durch partielle oder vollständige alkalische Solvolyse in Verbindungen entsprechend der Formel I überführt werden können.The object of the invention is a process for the preparation of N-phosphinoformyl-amino acids and their derivatives of the formula I using readily available stable starting materials. It has been found that result by reacting phosphonous trimethylsilylestem of F y Ormel Il with Isocyanatocarbonsäureestern of the general formula II, at elevated temperature, in very good yields compounds of formula IV obtained by partial or complete alkaline solvolysis in compounds according to formula I can be transferred.

R-P-H + O=C=N-A-COO1T OöiMe,-RPH + O = C = NA-COO 1 T OöiMe, -

II IIIII III

OOOO

if ii 3if ii 3

-> R-P-C-NH-A-COOR-> R-P-C-NH-A-COOR

Oo iMe.-Oo iMe.-

IV IV

In den Formeln Il bis IV bedeutenIn the formulas II to IV mean

R3 Alkyl von C1 bis C4 und A bedeutet die gleichen Reste wie in Formel I.R 3 is alkyl of C 1 to C 4 and A is the same radicals as in formula I.

Die Umsetzungen gemäß Gleichung 1 können in polaren oder unpolaren aprotischen Lösungsmitteln, wie Benzen, Toluen oder 1,4-Dioxan, vorzugsweise aber ohne diese durchgeführt werden.The reactions according to equation 1 can be carried out in polar or nonpolar aprotic solvents, such as benzene, toluene or 1,4-dioxane, but preferably without them.

Die Reaktionen verlaufen exotherm, wobei die Verbindungen der allgemeinen Formel IV aquantitativ in hoher Reinheit anfallen.The reactions are exothermic, the compounds of the general formula IV being obtained quantitatively in high purity.

Die selektive Solvolyse der PhosDhinesteraruDDe aelinat mittels änuivalpnter Mennen Δΐι<·ηΗηΐ Aikaiiaii^hnidt WaooarThe selective solvolysis of PhosDhinesteraruDDe aelinate by means of similar groups Δΐι <· ηΗηΐ Aikaiiaii ^ hnidt Waooar

Die vollständige Hydrolyse der Carbon- und Phosphinestergruppen wird durch Umsetzung mit stöchiometrischen Mengen wäßriger Alkalihydroxide erreicht. Die Solvolyseprodukte bzw. deren Salze sind nach Abdestillieren des Lösungsmittels in reiner Form isolierbar.Complete hydrolysis of the carboxylic and phosphine ester groups is achieved by reaction with stoichiometric amounts of aqueous alkali metal hydroxides. The solvolysis products or their salts can be isolated in pure form after distilling off the solvent.

Ausführungsbeispieleembodiments Beispiel 1example 1

N-fTrimethylsiloxy-phenylphosphinoformyOglycinethylesterN-fTrimethylsiloxy-phenylphosphinoformyOglycinethylester

Zu 0,053 Mol (11,3g) Benzenphosphonigsäuretrimethylsilylester tropft man unter Rühren bei Raumtemperatur, in einer Schutzgasatmosphäre, die äquimolare Menge Isocyanatessigsäureethylester (0,053 Mol entspricht 6,8g). Anschließend wird bei einer Badtemperatur von 850C 4 Stunden gerührt. Die Vollständigkeit der Addition wird mittels ^-NMR-Spektroskopie überprüft.To 0.053 mol (11.3 g) Benzenphosphonigsäuretrimethylsilylester is added dropwise with stirring at room temperature, in an inert gas atmosphere, the equimolar amount of ethyl isocyanate (0.053 mol equivalent to 6.8 g). The mixture is then stirred at a bath temperature of 85 0 C for 4 hours. The completeness of the addition is checked by ^ -NMR spectroscopy.

Der Ester fällt in nahezu quantitativer Ausbeute analysen rein an.The ester is almost pure in almost quantitative yield.

ο οο o

» u Ph-P-C-NH-CHxCOOEt»U Ph-PC-NH-CH x COOEt

OSiMe,OSiMe,

MQMQ

1H-NMR(CDCI3) ppm; SiMe3O,29; OCH2CH31,22 (t,JHccH7Hz);NCH24,05(d,J7Hz); OCH2CH34,18(q,JHccH7Hz); Ph7,36-8,02(m); NH 8,18 1 H-NMR (CDCl 3 ) ppm; SiMe 3 O, 29; OCH 2 CH 3 1.22 (t, J H ccH7Hz); NCH 2 4.05 (d, J7Hz); OCH 2 CH 3 4.18 (q, J H ccH7Hz); Ph7,36-8,02 (m); NH 8,18

Beispiele 2-14: N-(Trimethylsiloxyphosphinoformyl)aminosäureesterExamples 2-14: N- (trimethylsiloxyphosphinoformyl) amino acid ester

Analog Beispiel 1 werden Phosphonigsäuretrimethylsilylestermitderäquimolaren Menge Isocyanato-carbonsäureester versetzt. Tritt dabei eine Wärmetönung auf, muß die Zugabe langsam erfolgen. Bei einer Badtemperatur von 80-95°C wird bis zur Vollständigkeit der Addition gerührt, was durch 31P- oder 1H-NMR kontrolliert wird. Die Verbindungen werden in hoher Reinheit und in nahezu quantitativen Ausbeuten erhalten, siehe Tabelle 1Analogously to Example 1 Phosphonigsäuretrimethylsilylestermitderäquimolaren amount of isocyanato-carboxylic acid ester are added. If a heat of reaction occurs, the addition must be slow. At a bath temperature of 80-95 ° C is stirred until the addition is complete, which is controlled by 31 P or 1 H-NMR. The compounds are obtained in high purity and in almost quantitative yields, see Table 1

Tabelle 1Table 1

O OO O

Il IlIl

R-P-C-NH-A-COOR3I OSiMe,RPC-NH-A-COOR 3 I OSiMe,

Bsp.Ex. RR AA R°R ° Formel MolmasseFormula molecular mass °'P(ppm)° 'P (ppm) 22 Meme -CH2--CH 2 - Etet C9H20NO6SiPC 9 H 20 NO 6 SiP 281,32281.32 33 Meme -B-CH3 -B-CH 3 Etet Ci0H22No6SiPCi 0 H 22 No 6 SiP 21,621.6 295,35295.35 44 PhPh -B-CH3 -B-CH 3 Etet C15H24NO5SiPC 15 H 24 NO 5 SiP 7,27.2 357,42357.42 55 Meme -CH2-CH2 -CH 2 -CH 2 Etet C10H22NO6SiPC 10 H 22 NO 6 SiP 22,022.0 295,35295.35 66 PhPh -CH2-CH2 -CH 2 -CH 2 Etet Ci5H24NO5SiPCi 5 H 24 NO 5 SiP 7,27.2 357,42357.42 77 Meme -B-CH2Ph-B-CH 2 Ph Etet C16H26NO5SiPC 16 H 26 NO 5 SiP 21,621.6 371,45371.45 88th Meme -B-CH2CH2SMe-B-CH 2 CH 2 SMe Meme Ci1H24NSO6SiPCi 1 H 24 NSO 6 SiP 21,3 ·21.3 · 341,38341.38 99 PhPh -B-CH2CH2SME-B-CH 2 CH 2 SME Meme Ci6H26NSO6SiPCi 6 H 26 NSO 6 SiP 7,57.5 403,45403.45 1010 Meme -B-CH2CH2CH3 -B-CH 2 CH 2 CH 3 Etet Ci2H26NO5SiPCi 2 H 26 NO 5 SiP 20,720.7 323,41323.41 1111 Meme -B-CH2CH2COOEt-B-CH 2 CH 2 COOEt Etet C14H28NO7SiPC 14 H 28 NO 7 SiP 21,321.3 381,45381.45 1212 PhPh -B-CH2CH2COOEt-B-CH 2 CH 2 COOEt Etet C16H30NO7SiPC 16 H 30 NO 7 SiP 7,47.4 443,52443.52 1313 Meme -B-CH2COOEt-B-CH 2 COOEt Etet C13H26NO7SiPC 13 H 26 NO 7 SiP 21,721.7 367,42367.42 1414 PhPh -B-CH2COOEt-B-CH 2 COOEt Etet C18H28NO7SiPC 18 H 28 NO 7 SiP 7,57.5 429,49429.49

Beispiel 15: N-iPhenyl-phosphinoformyDglycin-dinatriumsalzdihydratExample 15: N-iPhenyl phosphinoformylglycine disodium salt dihydrate

Der nach Addition von Benzenphosphonigsäure-trimethylester an Isocyanatoessigsäureethylester erhaltene N-(Trimethylsiloxyphenylphosphinoformyl)glycinethylester (0,053 Mol) wird in wenig Ether aufgenommen und unter Rühren in der Weise zu einer wäßrigen Lösung von 0,106 Mol NaOH getropft, daß die Innentemperatur 2O0C nicht überschreitet. Die Mischung wird 2 Stunden bei Raumtemperatur gerührt. Nach Entfernen aller flüchtigen Bestandteile im Vakuum fällt das Dihydrat des N-(Phenylphosphinoformyl)glycindinatriumsalzes als kristalliner Feststoff an.The N- (trimethylsiloxyphenylphosphinoformyl) glycine ethyl ester obtained after addition of benzenephosphonic acid trimethyl ester to isocyanatoacetate (0.053 mol) is taken up in a little ether and added dropwise with stirring in the manner to an aqueous solution of 0.106 moles of NaOH that the internal temperature does not exceed 2O 0 C. The mixture is stirred for 2 hours at room temperature. After removal of all volatiles in vacuo, the dihydrate of N- (phenylphosphinoformyl) glycine disodium salt precipitates as a crystalline solid.

Ausbeute: 84,8% Mg 323,24Yield: 84.8% Mg 323.24

O 0O 0

ι) uι) u

pn -P-C -NH-CH2COONa ONapn -PC-NH -CH 2 COONa ONa

ΖΗ,ΟΖΗ, Ο

31P-NMR 11,8ppm (D2O); 1H-NMR (CD3OD) ppm; CH23,66; Ph 7,12-7,92 Bsp. 16-28: N-[Alkyl(aryl)phosphinoformyl]-aminosäure-dinatrium-undtrinatriumsalze Analog Beispiel 12 werden die in Tabelle 2 erfaßten Natriumsalze der N-(Phosphinformyl)-aminosäuren in Form ihrer Dihydrate oder Trihydrate nach Verseifen der entsprechenden N-(Trimethylsiloxyphosphinoformyl)-aminosäureester mit wäßriger . Natriumhydroxidlösung gewonnen, wobei pro Phosphinsäureestergruppe und pro Carbonsäureestergruppe jeweils 1 Äquivalent NaOH zu verwenden sind. Pro Natriumatom ist ein Kristallwasser im Molekül gebunden, (s. Tab.2) 31 P NMR 11.8 ppm (D 2 O); 1 H-NMR (CD 3 OD) ppm; CH 2 3.66; Ph. 7.12-7.92 Ex. 16-28: N- [alkyl (aryl) phosphinoformyl] -amino acid-disodium and trisodium salts. Analogously to Example 12, the sodium salts of N- (phosphinoformyl) -amino acids recorded in Table 2 are in the form of their Dihydrate or trihydrate after saponification of the corresponding N- (trimethylsiloxyphosphinoformyl) -amino acid esters with aqueous. Sodium hydroxide solution is obtained, wherein each per equivalents of NaOH are to be used per phosphinic ester group and per carboxylic acid ester group. For each sodium atom, a water of crystallization is bound in the molecule (see Table 2)

Tabelle 2 O OTable 2 O O

Il Il R_p_C-NH-A-COONa · 2H2O/3H2OIl II R_p_C-NH-A-COONa · 2H 2 O / 3H 2 O

ONaONa

Bsp.Ex. RR AFormel/Molm.AFormel / Molm. 1H-NMR(PPm) 1 H-NMR (PPm) 31P(ppm)** 31 P (ppm) ** CC HH NN Ausb.*Y. * H2OH 2 O ber./gef.ber./gef. %% 1616 Meme -CH2--CH 2 - (CD3OD)(CD 3 OD) 18,3918.39 3,863.86 5,375.37 80,580.5 C4H10NO7PNa2 C 4 H 10 NO 7 PNa 2 MeP 1,51 (d,J 15 Hz)MeP 1.51 (d, J 15 Hz) 23,623.6 18,4918,49 3,743.74 5,195.19 261,17261.17 CH2 3,93 (d,J 7 Hz)CH 2 3.93 (d, J 7 Hz) 1717 PhPh -B-CH3 -B-CH 3 (D2O) CHCH31,68(D 2 O) CHCH 3 1.68 12,512.5 82,682.6 Ci0H14NO7PNa2 Ci 0 H 14 NO 7 PNa 2 (d,J7Hz) ' (d, J7Hz) ' 337,27337.27 CH 4,52 (q,J 7 Hz)CH 4.52 (q, J 7 Hz) Ph 7,68-8,24 (m)Ph 7,68-8,24 (m) 1818 Meme -B-CH3 -B-CH 3 (D2O) MeP 1,73(D 2 O) MeP 1.73 21,9821.98 4,44.4 5,115.11 84,184.1 C5H12NO7PNa2 C 5 H 12 NO 7 PNa 2 (d,J15Hz)(D, J15Hz) 24,324.3 21,7521.75 4,244.24 5,285.28 275,2275.2 CHCH31,71 (d,J 7 Hz)CHCH 3 1.71 (d, J 7 Hz) CH 4,56 (q,J 7 Hz)CH 4.56 (q, J 7 Hz) 1919 PhPh —CH2CH2""-CH2CH2 "" (D2O) CH2COO 2,74(D 2 O) CH 2 COO 2.74 12,3  12.3 79,179.1 Ci0Hi4NO7PNa2 Ci 0 Hi 4 NO 7 PNa 2 (t,J7Hz)(T, J 7 Hz) 337,27337.27 NCH2 3,79 (t,J 7 Hz)NCH 2 3.79 (t, J 7 Hz) Ph 7,7-8,22 (m)Ph 7,7-8,22 (m) 2020 Meme -CH2CH2--CH 2 CH 2 - (D2O) MeP 1,74 (d,J 15HZ)(D 2 O) MeP 1.74 (d, J 15HZ) 24,124.1 21,9821.98 4,44.4 5,115.11 15 Hz) CH2COO 2,79 (t,15 Hz) CH 2 COO 2.79 (t, 21,7721.77 4,184.18 5,245.24 76,776.7 J 7 Hz) NCH2 3,82 (t,J 7 Hz)J 7 Hz) NCH 2 3.82 (t, J 7 Hz) 2121 Meme -B-CH2Ph-B-CH 2 Ph (D2O) MeP 1,58 (d,J 15 Hz)(D 2 O) MeP 1.58 (d, J 15 Hz) 41,941.9 3,843.84 4,454.45 93,093.0 C11H16No7-C 11 H 16 No 7 - 2323 41,5841.58 4,04.0 4,194.19 PNa2 PNa 2 CH2Ph 3,44 (m)CH 2 Ph 3.44 (m) 351,3351.3 CH 4,84 (t,J 7 Hz) Ph 7,65CH 4.84 (t, J 7 Hz) Ph 7.65 2222 PhPh -B-CH2-CH2SCH3 -B-CH 2 -CH 2 SCH 3 (d2O)(d 2 O) 11,311.3 C12H18NSO7PNa2 C 12 H 18 NSO 7 PNa 2 SMe 2,34SMe 2.34 397,33397.33 CH2CH2 2,76 (m)CH 2 CH 2 2.76 (m) 86,286.2 CH 4,7 (t,J 7 Hz)CH 4.7 (t, J 7 Hz) Ph 7,64-8,26 (m)Ph 7,64-8,26 (m) 2323 Meme -BCH2CH2SMe-BCH 2 CH 2 SMe (D2O)(D 2 O) 23,723.7 25,0825.08 4,824.82 4,194.19 78,478.4 C7H16NSO7PNa2 C 7 H 16 NSO 7 PNa 2 MeP 1,78 (d,J 15 Hz)MeP 1.78 (d, J 15 Hz) 335,26335.26 SMe 2,51SMe 2.51 25,1325.13 4,674.67 3,983.98 CH2CH2 2,95 (m)CH 2 CH 2 2.95 (m) CH 4,75 (t,J 7 Hz)CH 4.75 (t, J 7 Hz) 2424 Meme -BCH2CH2CH3 -BCH 2 CH 2 CH 3 (D2O)(D 2 O) 23,823.8 27,7227.72 5,325.32 4,634.63 82,482.4 C7H16NO7PNa2 C 7 H 16 NO 7 PNa 2 CH2CH31,23 (t,J 7 Hz)CH 2 CH 3 1.23 (t, J 7 Hz) 27,6027.60 5,245.24 4,324.32 303,26303.26 MeP 1,72 (d,J 15 Hz)MeP 1.72 (d, J 15 Hz) CH2CH31,53 (m)CH 2 CH 3 1.53 (m) CHCH2 2,08 (q,J 7 Hz)CHCH 2 2.08 (q, J 7 Hz) CH 4,57 (t,J 7 Hz)CH 4.57 (t, J 7 Hz)

3sp.3sp. ** RR AFormel/Molm.AFormel / Molm. 1H-NMR(PPm) 1 H-NMR (PPm) 31P(ppm)** 31 P (ppm) ** CC HH NN Ausb.*Y. * **** H2OH 2 O ber./gef.ber./gef. %% 2525 ****** PhPh -BCH2CH2COONa-BCH 2 CH 2 COONa CH2CH2 2,44 (m)CH 2 CH 2 2.44 (m) 84,884.8 C12H17NO10PNa3 C 12 H 17 NO 10 PNa 3 CH 4,58 (t,J 7 Hz)CH 4.58 (t, J 7 Hz) 12,412.4 435,32435.32 Ph 7,7-8,3 (m)Ph 7,7-8,3 (m) 2626 Meme -BCH2CH2COONa-BCH 2 CH 2 COONa MeP 1,75 (d,J 15 Hz)MeP 1.75 (d, J 15 Hz) 23,723.7 90,590.5 C7^sNO10PNa3 C 7 ^ sNO 10 PNa 3 CH2CH22,5(m)CH 2 CH 2 2.5 (m) 22,5222.52 4,064.06 3,763.76 373,25373.25 CH 4,6 (t,J 7 Hz)CH 4,6 (t, J 7 Hz) 22,7122.71 3,943.94 3,533.53 2727 PhPh -B-CH2COONa-B-CH 2 COONa CH2 3,0 (d,J 7 Hz)CH 2 3.0 (d, J 7 Hz) 12,712.7 83,583.5 C11H15NO10PNa3 C 11 H 15 NO 10 PNa 3 Ch4,8(t,J7Hz)Ch4,8 (t, J 7 Hz) 421,29421.29 Ph 7,68-8,36 (m)Ph 7,68-8,36 (m) 2828 Meme -BCH2COONa-BCH 2 COONa CH2 2,98 (d,J 7 Hz)CH 2 2.98 (d, J 7 Hz) 24,224.2 85,585.5 C6H13NO10PNa3 C 6 H 13 NO 10 PNa 3 MeP 1,72 (d,J 15 Hz)MeP 1.72 (d, J 15 Hz) 20,620.6 3,653.65 3,913.91 359,22359.22 CH 4,82 (t,J 7 Hz)CH 4.82 (t, J 7 Hz) 20,0920.09 3,533.53 3,733.73 alle Ausbeuten beziehen sich auf das im Additionsschritt eingesetzteall yields are based on that used in the addition step Phosphonitphosphonite H3Po4 als e>H 3 Po 4 as e> (. Standard(. Default nach Entfernen des Kristal !wassers im Vakuumafter removal of the crystal water in vacuo

Claims (1)

Erfindungsanspruch:Invention claim: Verfahren zur Herstellung von N-(Phosphinoformyl)-aminosäuren und deren Derivaten der allgemeinen Formel IProcess for the preparation of N- (phosphinoformyl) -amino acids and their derivatives of general formula I. OO
- R_p-C-NH-A-COOR jOO
- R _p-C-NH-A-COOR j OR1 OR 1 in derin the R Alkyl, Cycloalkyl, Aryl, subst. Aryl . ·R is alkyl, cycloalkyl, aryl, subst. Aryl. · R1 Trimethylsilyl, Wasserstoff, ein Alkalimetall, Ammonium, einen substituierten Ammoniumrest R2 Alkyl von C1 bis C4, Wasserstoff oder ein AlkalimetallR 1 is trimethylsilyl, hydrogen, an alkali metal, ammonium, a substituted ammonium radical R 2 is alkyl of C 1 to C 4 , hydrogen or an alkali metal A verzweigte oder unverzweigte, substituierte bzw. unsbubstituierte Alkylen von Ci bis C9, Cycloalkylen oder heterocyclischen Rest bedeuten,A is branched or unbranched, substituted or unsubstituted alkylene of C 1 to C 9 , cycloalkylene or heterocyclic radical, gekennzeichnet dadurch, daß Phosphonigsäure-trimethylsilylester mit Isocyanatocarbonsäureestern, bei erhöhter Temperatur zu N-(Phosphinoformyl)-aminosäureestern umgesetzt werden, die durch partielle oder vollständige alkalische Solvolyse in Verbindungen der Formel I überführt werden.characterized in that phosphonous trimethylsilyl esters with isocyanato carboxylic acid esters are reacted at elevated temperature to N- (phosphinoformyl) -amino acid esters, which are converted by partial or complete alkaline solvolysis in compounds of formula I.
DD28305085A 1985-11-21 1985-11-21 PROCESS FOR THE PREPARATION OF N-PHOSPHINOFOMYL AMINOSAURES AND THEIR DERIVATIVES DD242810A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018054919A1 (en) * 2016-09-21 2018-03-29 Basf Se Silyl ester phosphinates as electrolyte additives

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018054919A1 (en) * 2016-09-21 2018-03-29 Basf Se Silyl ester phosphinates as electrolyte additives
CN109792084A (en) * 2016-09-21 2019-05-21 巴斯夫欧洲公司 Phosphinic acids silyl ester as electrolyte additive

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