ISSN:
0009-2940
Keywords:
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Synthesis of 3,5-Disubstituted and 3,4,5-Trisubstituted λ3-Phosphorins from 1-tert-Butyl-1,6-dihydro-3(2H)-phosphorinones5-Aryl-1-tert-butyl-1,6-dihydro-3(2H)-phosphorinones 13 - easily available by reduction of the phosphane oxides 1 with phenylsilane - react with 1 mol of RMgX (RLi) exclusively by formation of the enolates, however with 6 mol of RMgX (RLi), after reaction times of several days, immediately the 3-aryl-1-tert-butyl-1,2-dihydro-5-R-phosphorins 10 are formed, which can be thermolyzed to give the 3-aryl-5-R-λ3-phosphorins 11 (R = aryl, alkyl, heteroaryl). - 5-Aryl-1-tert-butyl-1,6-dihydro-4-methyl-3(2H)-phosphorinones 19 react with 5 - 6 mol of RMgX (RLi) similar by formation of the 3-aryl-1-tert-butyl-1,2-dihydro-4-methyl-5-R-phosphorins 20, whose thermolysis yields the 3-aryl-4-methyl-5-R-λ3-phosphorins 21. The 1H, 13C, 31P NMR and UV spectra of the synthesized λ3-phosphorins are discussed. - 1,1-Dimethoxy-3,5-diphenyl-λ5-phosphorin (22a), available from 3,5-diphenyl-λ3-phosphorin (11e), undergoes coupling reaction with diazonium salts to give the 2,4,6-tris(arylazo)-1,1-dimethoxy-3,5-diphenyl-λ5-phosphorins 23.
Notes:
5-Aryl-1-tert-butyl-1,6-dihydro-3(2H)-phosphorinone 13 - durch Reduktion der Phosphanoxide 1 mit Phenylsilan glatt zugänglich - reagieren mit 1 mol RMgX (RLi) ausschließlich unter Bildung der Enolate, mit 6 mol RMgX (RLi) hingegen werden nach mehrtägigen Reaktionszeiten direkt die 3-Aryl-3-tert-butyl-1,2-dihydro-5-R-phosphorine 10 erhalten, die bei der Thermolyse zu den 3-Aryl-5-R-λ3-phosphorinen 11 (R = Aryl, Alkyl, Heteroaryl) zerfallen. - 5-Aryl-1-tert-butyl-1,6-dihydro-4-methyl-3(2H)-phosphorinone 19 reagieren mit 5 - 6 mol RMgX (RLi) entsprechend zu den 3-Aryl-1-tert-butyl-1,2-dihydro-4-methyl-5-R-phosphorinen 20, deren Thermolyse die 3-Aryl-4-methyl-5-R-λ3-phosphorine 21 liefert. - Die 1H-, 13H-, 13C-, 31P-NMR- und UV-Spektren der dargestellten λ3-Phosphorine werden diskutiert. - Das aus 3,5-Diphenyl-λ3-phosphorin (11e) zugängliche 1,1-Dimethoxy-3,5-diphenyl-λ5-phosphorin (22a) kuppelt mit Diazoniumsalzen zu den 2,4,6-Tris(arylazo)-1,1-dimethoxy-3,5-diphenyl-λ5-phosphorinen 23.
Additional Material:
4 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19841170229
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