ChemInform Abstract: Oxidative Amination of P4.

Dorfman, Ya. A.; Abdreimova, R. R.; Akbaeva, D. N.

doi:10.1002/chin.199422185

Cited by 1 publication

(9 citation statements)

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“…Depending on the reactions conditions, four types of organophosphorus derivatives bearing P-O bonds are formed and identified by chromatography and NMR: trialkyl(aryl) phosphate PO(OR) 3 1, dialkyl phosphite P(O)H(OR) 2 2, dialkyl phosphate P(O)(OH)(RO) 2 3, and trialkyl(aryl)phosphite P(OR) 3 4 (see Scheme 1). It has been shown by the volumometry method [2][3][4][5] that the experimental O 2 /P 4 ratio between amounts of oxygen and phosphorus consumed is around 3-5, i.e. close to the stoichiometry of the above reactions.…”

Section: Introductionmentioning

confidence: 91%

“…A round three-neck flask (with volume about 250 cm 3 ) fitted with a refluxing condenser and a gas-inlet tube for air barbotage was used for catalytic synthesis of organophosphorus products. The constant reaction temperature (65-90°C) was supported with an oil bath, under vigorous magnetic stirring.…”

Section: Typical Proceduresmentioning

confidence: 99%

“…130-132°C (2 mm Hg); 31 P{ 1 H}NMR (CDCl 3 ): δ -0.51 ppm. 31 P NMR (CDCl 3 ): δ -0.50 (sept., 3 J P-O-CH2 = 6.8 Hz) ppm. 1 H NMR (CDCL 3 ): δ 3.92 (m, 6H, CH 2 α), 1.56 (m, 6H, CH 2 β), 1.30 (m, 6H, CH 2 γ), 0.83 (m, 9H, CH 3 ) ppm.…”

Section: Physical and Spectroscopic Datamentioning

confidence: 99%

“…1 H NMR (CDCL 3 ): δ 3.92 (m, 6H, CH 2 α), 1.56 (m, 6H, CH 2 β), 1.30 (m, 6H, CH 2 γ), 0.83 (m, 9H, CH 3 ) ppm. 13 C{ 1 H}NMR (CDCl 3 ): δ 67.24 (d, 2 J CP = 5.9 Hz, CH 2 α), 32.12 (d, 3…”

Section: Physical and Spectroscopic Datamentioning

confidence: 99%

“…We have first proposed an original "chlorine-free" method of the oxidative alko(aro)xylation of white phosphorus under mild reaction conditions in the presence of CuX 2 or FeX 3 salts (X = Cl, Br, NO 3 , CH 3 CO 2 , C 3 H 7 CO 2 , C 17 H 35 CO 2 ) which uses dioxygen as a cheap and efficient oxidant [2][3][4][5]. The new catalytic protocol allows to remove both Cl 2 and HCl from the productive cycle and to incorporate into the catalytic cycle all the advantages of a homogeneous catalytic reac-tion as both P 4 and catalyst are taken in the reaction in the dissolved forms.…”

Section: Introductionmentioning

confidence: 99%

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Catalytic Synthesis of the Esters of Phosphorus Acids from White Phosphorus and Aliphatic or Aromatic Alcohols

Abdreimova¹,

Faizova²,

Akbayeva³

et al. 2017

Eurasian Chem. Tech. J.

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The various esters of the phosphoric and phosphorous acids have been obtained directly from white phosphorus and aliphatic (or aromatic) alcohols under aerobic atmosphere in the presence of the CuX2 or FeX3 (X = Cl, NO3, C3H7CO2) salts. Irrespective of the variable nature of the used alcohols and catalysts, trialkyl(aryl) phosphates and dialkyl phosphites are a major products, whereas trialkyl(aryl) phosphites and dialkyl phosphates are a minor products of the phosphorylation process. Thanks to the presence of catalysts, the possible side reaction route of the radical chain oxidation of white phosphorus by oxygen to phosphorus oxides has been precluded. A comparison between the catalytic properties of CuX2 and FeX3 has been done. Although both of them have been found an efficient catalysts for the syntheses, the Cu(II) salts are active at 50-65 °C, whereas the Fe(III) based catalytic systems become competitive in terms of catalytic efficiency when reaction is carried out at 70-90 °C. Aromatic alcohols are characterised by less reactivity in this catalytic reaction as compared with an aliphatic ones. The same coordinative redox mechanism of the oxidative P-O coupling of P4 to ROH in the presence of both Cu(II) and Fe(III) catalysts has been proposed. Relevant steps of the catalytic cycle including the complexation of both white phosphorus and alcohol molecules to metal ion, the reduction of catalyst by white phosphorus, and the oxidation of reduced form of catalyst by oxygen have been also considered.

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Section: Introductionmentioning

confidence: 91%

Section: Typical Proceduresmentioning

confidence: 99%

Section: Physical and Spectroscopic Datamentioning

confidence: 99%

Section: Physical and Spectroscopic Datamentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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