THE CHEMISTRY AND STRUCTURE OF THE P(O)NC(O) SYSTEM. PART 1. TRIMETHYLSILYLATION OF O,O-DIETHYL-<i>N</i>-FORMYLPHOSPHORAMIDATE AND THE HEXAMETHYLDISILAZANE-PROMOTED CONVERSION TO THE<i>N</i>-PHOSPHORYLATED FORMAMIDINE

Bauermeister, S.; Modro, Tomasz A.

doi:10.1080/10426509208031552

Cited by 12 publications

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References 14 publications

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“…Organic & Biomolecular Chemistry reaction is initiated by a nucleophilic attack of the oxygen atom of FMD on the phosphorus atom of DEDNPP displacing DNP and forming an activated amide as the intermediate. Since no signal was observed near −15.6 ppm in the 31 P NMR spectra, which could be assigned to the activated amide formed in the first step, 24 we assumed that the reaction proceeds via two competitive pathways: (i) the desired nucleophilic attack of the oxygen atom of water on the phosphorus atom of the activated amide regenerates FMD and forms the non-toxic diester and (ii) nucleophilic addition of water to the iminic carbon leads to a tetrahedral intermediate. This step is followed by elimination of ammonia, which in turn acts as a nucleophile displacing formic acid.…”

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confidence: 99%

Mechanistic insights into the amidolysis of a phosphate triester: the antagonistic role of water

et al. 2022

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Section: Papermentioning

confidence: 99%

Mechanistic insights into the amidolysis of a phosphate triester: the antagonistic role of water

et al. 2022

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“…C 3 ³ 0.3268(3) ³ 0.30726(16)³ 0.59451(9) ³0.0424 C 4 ³ 0.4246(3) ³ 0.3079(2) ³ 0.5648(1) ³0.0611 C 5 ³ 0.3913(4) ³ 0.3153(2) ³ 0.52222(11)³0.0766 C 6 ³ 0.2633(4) ³ 0.3232(2) ³ 0.50977(11)³0.0767C 7 ³ 0.1671(4) ³ 0.3228(2) ³ 0.54013(12)³0.0750 C 8 ³ 0.1971(3) ³ 0.3147(2) ³ 0.58277(11)³0.0603 C 9 ³ 0.5394(2) ³ 0.13053(15)³ 0.61966(8) ³0.0368 C 10 ³ 0.5828(2) ³!0.00572(15)³ 0.58786(8) ³0.0381 C 11 ³ 0.6038(3) ³ 0.01334(18)³ 0.54603(9) ³0.0515 C 12 ³ 0.6775(3) ³!0.0429(2) ³ 0.5216(1) ³0.0673 C 13 ³ 0.7264(3) ³!0.1174(2) ³ 0.53966(12)³0.0697 C 14 ³ 0.7014(3) ³!0.1364(2) ³ 0.58163(12)³0.0674 C 15 ³ 0.6290(3) ³!0.07970(18)³ 0.60656(9) ³0.0523 C 16 ³ 0.4081(2) ³ 0.01820(15)³ 0.69536(8) ³0.0372 C 17 ³ 0.5323(3) ³ 0.01679(18)³ 0.71452(9) ³0.0473 C 18 ³ 0.5853(3) ³!0.0612(2) ³ 0.72691(9) ³0.0532 C 19 ³ 0.5153(3) ³!0.13726(18)³ 0.72206(9) ³0.0528 C 20 ³ 0.3924(3) ³!0.13560(16)³ 0.70383(9) ³0.0470 C 21 ³ 0.3394(2) ³!0.05826(16)³ 0.69025(8) ³0.0412 C 22 ³ 0.1926(2) ³ 0.10455(17)³ 0.6494(1) ³0.0475 C 23 ³ 0.1922(3) ³ 0.0684(2) ³ 0.60936(11)³0.0690 C 24 ³ 0.0766(4) ³ 0.0610(3) ³ 0.58584(13)³0.0848 C 25 ³!0.0380(4) ³ 0.0905(3) ³ 0.60254(17)³0.0882 C 26 ³!0.0406(3) ³ 0.1258(2) ³ 0.64233(18)³0.0855 C 27 ³ 0.0747(3) ³ 0.13349(19)³ 0.66651(13)³0.0684 ÄÄÄÄÁÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄ phite was carried out similarly. 31 P NMR spectrum of the reaction mixture, d P , ppm (relative intensities of the signals are given in parentheses after the chemical shifts): 35.3 (1.0) (IV), 32.3 (0.4) (V), 34.5 (0.2), mixture was evaporated and washed with petroleum ether.…”

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Reactions of N-aroxycarbonyltrichloroacetimidates with nucleophilic phosphorus derivatives

et al. 2004

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Aryl N-aroxycarbonyltrichloroacetimidates (Ar = Ph, 4-FC 6 H 4 ) react with diphenylphosphinite according to the scheme of the aza-Perkow reaction to give the corresponding aryl N-(1-aroxy-2,2-dichlorovinyl)-N-diphenylphosphinoylcarbamates. The structure of one of these compounds was confirmed by single crystal X-ray diffraction analysis. In the case of electron-accepting substituents (Ar = 4-O 2 N 6 H 4 ), the primary product undergoes mild >-elimination to give nitrophenyl diphenylphosphinate and 1-nitrophenoxy-2,2-dichlorovinyl isocyanate. The reaction of trichloroacetimidates with triethyl phosphite yields a mixture of O-and N-phosphorylation products.Reactions of N-carbonyltrichloroethanimines with nucleophilic derivatives of trivalent phosphorus are an important synthetic route to functionalized C-, N-, and O-phosphorylated imines and enamides. It was shown previously that the direction of the reaction of trichloroacetimidoyl chlorides CCl 3 C(Cl)=NX with phosphites significantly depends on the nature of substituent at the nitrogen atom. With X = COPh, the chlorine atom of the CCl 3 group takes part in the reaction (aza-Perkow reaction) [1,2]. With X = COCCl 3 , the imidoyl chlorine atom is substituted (Arbuzov reaction) [3], and with X = COOMe the reaction follows ÄÄÄÄÄÄÄÄÄÄÄÄ both competing pathways [4]. In this work we studied the phosphorylation of N-aroxycarbonyltrichloroacetimidates Ia3Ic and imidoyl chloride Id. These compounds are convenient models for revealing the electronic effect of substituents at the nitrogen (COOR) and imine carbon (ArO and Cl) atoms on the reactivity of imines and the structure of the products of the reactions with nucleophilic P(III) derivatives. Synthetically accessible [5] imidates Ia3Ic and imidoyl chloride Id [6] were prepared by the reaction of pentachloroethyl isocyanate with the corresponding phenols in the presence of triethylamine. Scheme 1. CCl 3 CCl 2 NCO % ' ' ' ' 2ArOH, 2Et 3 N %%%%%$ %%%%%$ 4-O 2 NC 6 H 4 OH Et 3 N S [ g CCl 3 OAr S Q N OAr o O Ia!Ic S [ g CCl 3 Cl S Q N OC 6 H 4 NO 2 -p o O Id Ar = Ph (a) [5], 4-O 2 NC 6 H 4 (b), 4-FC 6 H 4 (c). ÄÄÄÄÄÄÄÄÄÄÄÄImidates Ia3Ic appeared to be less reactive toward P(III) derivatives than N-acyltrichloroacetimidoyl chlorides [234]. Contrary to the latter, they do not react with triphenyl phosphite or diethyl hydrogen phosphite (20oC or refluxing in benzene), but under mild conditions (5oC, benzene) they react with more nucleophilic triethyl phosphite. In this case, mainly the aza-Perkow reaction takes place, yielding O-phosphorylated dichloroazadienes II and isomeric dichlorovinylamides III.The ratio of isomers II and III is determined by the aryl substituent in the substrate. With Ar = Ph, mainly N-phosphorylated vinyl carbamate IIIa is formed (d P

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ChemInform Abstract: Chemistry and Structure of the P(O)NC(O) System. Part 1. Trimethylsilylation of O,O‐Diethyl‐N‐formylphosphoramidate and the Hexamethyldisilazane‐Promoted Conversion to the N‐Phosphorylated Formamidine.

Bauermeister

Modro

1993

ChemInform

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THE CHEMISTRY AND STRUCTURE OF THE P(O)NC(O) SYSTEM. PART 1. TRIMETHYLSILYLATION OF O,O-DIETHYL-N-FORMYLPHOSPHORAMIDATE AND THE HEXAMETHYLDISILAZANE-PROMOTED CONVERSION TO THEN-PHOSPHORYLATED FORMAMIDINE

Cited by 12 publications

References 14 publications

Mechanistic insights into the amidolysis of a phosphate triester: the antagonistic role of water

Mechanistic insights into the amidolysis of a phosphate triester: the antagonistic role of water

Reactions of N-aroxycarbonyltrichloroacetimidates with nucleophilic phosphorus derivatives

ChemInform Abstract: Chemistry and Structure of the P(O)NC(O) System. Part 1. Trimethylsilylation of O,O‐Diethyl‐N‐formylphosphoramidate and the Hexamethyldisilazane‐Promoted Conversion to the N‐Phosphorylated Formamidine.

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