Infrared Studies of Sulphur-Containing Organic Derivatives of Phosphorus Pyroacids

Abstract

The assignments of several infrared bands of aliphatic phosphor~~s co~npounds have been reviewed and extended on the basis of new or improved data. These bands include POP, P -+ S, PSH, PSR, PH, and PCI. Several new assignments are proposed, mainly in the 12-24 p region. ' I' xvo esarnplcs are given of the applicatio~l of these assignments to the determination of the s t r u c t~~r e of the thiopyrophosphates. I t is shown that all procedures used for preparing monothiopyrophosphates yield exclusively the thiono isomer.

Infrared Spectra of Organo-Phosphorus Compounds: Iii. Phosphoramidates, Phosphoramidothionates, and Related Compounds

“…llkyl) anti C-C (.llkyl) Bands Examination of more than a doze11 nenr compouncls has confirmed the earlier assignments for P-methyl ancl 1'-ethyl bands (7). I n addition, all compounds containing isopropyl groups (either P-0-i-PIor P-N-i-Pr) also have a medium intensity band near 893 cm-I for 0-i-Pr and near 877 cm-I for P-N-i-Pr compouncls.…”

“…Phosphonothionic acids and phosphorothionic acids also absorb in this region but with son~ewhat lesser intensity. As these compounds probably have the P(S)OH structure primarily, this band (which occurs near 606 c r n -I in the phosphonothioic acids) is probably of this type rather than a P-S-(H) stretching as suggested previously (7). T w o compounds which possibly contain P-S-P groupings have a doublet at 658 c r n -I and 630 c n l -I , the compo~zents of which retain the same relative intensities during purification procedures.…”

“…A number of compounds of types I and I1 have been examined both here and in other laboratories (5,6,7). I call be converted to I1 by heating, and the progress of the isomerization can be followecl in the infrared.…”

Solvent-free synthesis of novel 2,10-dichoro-12-trichloromethyl-6-substituted xanthato-12H-dibenzo[d,g] [1,3,2] dioxaphosphocin-6-sulfides

“…The IR spectra of 2a Á l showed characteristic absorption bands at 1262Á1237 (CÁS) (12), 1240Á 1175 (C 0S) (13), 761Á741 (P 0S) (14,15), and 660Á 625 cm…”

“…(1 (PÁS) (12). In the 1 H-NMR spectra, the six aromatic protons of the dibenzodioxaphosphocin moiety in all compounds (2a Á l) showed only three sets of signals, each signal accounting for two protons, because of their symmetrical disposition in dibenzodioxaphosphocin ring (16) General procedure for the synthesis of 2,10-dichloro-…”