Get 20M+ Full-Text Papers For Less Than $1.50/day. Start a 14-Day Trial for You or Your Team.

Learn More →

Reaktive E=C(p—p)π-Systeme, XVI [1] Trimethylstannvlphosphane des Typs Me3SnP(R)CF3 (R = Me, Et) als Phosphaalken-Vorstufen / Reactive E=C(p-p)π-Systeme, XVI [1] Trimethylstannylphosphanes of the Type Me3SnP(R)CF3 (R = Me, Et) as Phosphaalkene Precursors

Reaktive E=C(p—p)π-Systeme, XVI [1] Trimethylstannvlphosphane des Typs Me3SnP(R)CF3 (R = Me, Et)... AbstractStannylphosphanes of the type Me3SnP(R)CF3 [R = Me (1), Et (2)] have been prepared by a multistep synthesis (Fig. 1) starting either with F3CPI2 or with P(NEt2)3. Due to the alkyl sub­stituents, 1 and 2 show a higher thermal stability than the analogous perfluoroalkyl compounds Me3SnP(RF)2 (RF = CF3, C2F5). Pyrolysis of 1 and 2 at 380 °C/10-3 Torr gives the new phosphaalkenes RP=CF2 (R = Me, Et) as reactive intermediates collected at -196 °C. They polymerize on the attempt to prepare diluted solutions even at very low temperatures. In case of the ethyl derivative the product (EtPCF2)x is a colourless polymer which on heating (500-600 °C) yields a mixture of dimers (EtPCF2)2 (trans-, cis-1,3- and trans-1,2-diphosphetane; ratio 73:13,5:13,5). 1 and 2 have been used as equivalents of the phosphaalkenes RP=CF2 in one-pot reactions with 2,3-dimethylbutadiene and 1,3-cyclohexadiene, respectively. The labile P=C intermediates pro­duced at 120 °C are captured by the dienes affording the [2+4]-cycloadducts 3-6 in good yields. Oxidation with sulfur gives the corresponding phosphane sulfides 7-10 in almost quantitative yields. New compounds were characterized by spectroscopic (NMR, MS, IR) and analytical methods. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Zeitschrift für Naturforschung B de Gruyter

Reaktive E=C(p—p)π-Systeme, XVI [1] Trimethylstannvlphosphane des Typs Me3SnP(R)CF3 (R = Me, Et) als Phosphaalken-Vorstufen / Reactive E=C(p-p)π-Systeme, XVI [1] Trimethylstannylphosphanes of the Type Me3SnP(R)CF3 (R = Me, Et) as Phosphaalkene Precursors

Download PDF
11 pages

Loading next page...
 
/lp/de-gruyter/reaktive-e-c-p-p-systeme-xvi-1-trimethylstannvlphosphane-des-typs-XdlTLNrK4B

References

References for this paper are not available at this time. We will be adding them shortly, thank you for your patience.

Publisher
de Gruyter
Copyright
© 1946 – 2014: Verlag der Zeitschrift für Naturforschung
ISSN
0932-0776
eISSN
1865-7117
DOI
10.1515/znb-1988-0408
Publisher site
See Article on Publisher Site

Abstract

AbstractStannylphosphanes of the type Me3SnP(R)CF3 [R = Me (1), Et (2)] have been prepared by a multistep synthesis (Fig. 1) starting either with F3CPI2 or with P(NEt2)3. Due to the alkyl sub­stituents, 1 and 2 show a higher thermal stability than the analogous perfluoroalkyl compounds Me3SnP(RF)2 (RF = CF3, C2F5). Pyrolysis of 1 and 2 at 380 °C/10-3 Torr gives the new phosphaalkenes RP=CF2 (R = Me, Et) as reactive intermediates collected at -196 °C. They polymerize on the attempt to prepare diluted solutions even at very low temperatures. In case of the ethyl derivative the product (EtPCF2)x is a colourless polymer which on heating (500-600 °C) yields a mixture of dimers (EtPCF2)2 (trans-, cis-1,3- and trans-1,2-diphosphetane; ratio 73:13,5:13,5). 1 and 2 have been used as equivalents of the phosphaalkenes RP=CF2 in one-pot reactions with 2,3-dimethylbutadiene and 1,3-cyclohexadiene, respectively. The labile P=C intermediates pro­duced at 120 °C are captured by the dienes affording the [2+4]-cycloadducts 3-6 in good yields. Oxidation with sulfur gives the corresponding phosphane sulfides 7-10 in almost quantitative yields. New compounds were characterized by spectroscopic (NMR, MS, IR) and analytical methods.

Journal

Zeitschrift für Naturforschung B – de Gruyter

Published: Apr 1, 1988

There are no references for this article.