ISSN:
0018-019X
Keywords:
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Bis-chloromethyl-alkyl-and - aryl-phosphine oxides, (CICH2)2P(O)R, which are obtained by reaction of (CICH2)2P(O)Cl with GRIGNARD reagents, undergo a MICHAELIS-ARBUSOV reaction when heated for several hours with trivalent phosphorus esters (phosphites, phosphonites, or phosphinites) at 170-180°C. The reaction affords bis-(dialkyloxyphosphonyl-methyl)-, bis (alkyloxyphosphinyl-methyl)-, and bis-(oxophosphoranyl-methyl)-, -alkyl- or -aryl-phosphine oxides, R(O)P[CH2P(O)R′R″]2 R = CH3, C2H5, n-C8H17, n-C12H25, C6H5; R′ and R″ = C2H5O, C4H9O, C6H5, CH3 in good yields.Conversion of the compounds containing alkyloxy groups to the free acids is achieved by refluxing with conc. HCl. Bis-(dihydroxyphosphonyl-methyl)-dodecylphosphine oxide, n-C12H25(O)P[CH2P(O) (OH)2]2, obtained by hydrolysis of the all-ethyl ester, titrates in aqueous solution as a tetrabasic acid with breaks at pH = 4 (two equivalents), pH = 6,9 (one equivalent) and pH = 9,6 (one equivalent). This acid, its disodium salt (m. p. 405-410°) and its tetrasodium salt (m.p. 〉 460°) are surface active and are excellent chelating agents.The 1H- and 31P-NMR. spectra of all the compounds prepared are discussed.
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/hlca.19690520336