Reaction of the sodium salts of RC(S) NHP(S)(O‐i‐Pr)2 (R = Ph, HLI; PhNH, HLII; 2‐MeC6H4NH, HLIII; 2,6‐Me2C6H3NH, HLIV; 2,4,6‐Me3C6H2NH, HLV) or Z[NHC(S)NHP(S)(O‐i‐Pr)2]2 (Z = o‐C6H4, H2LVI; 1,2‐CH2CH2, H2LVII) with PPh4Br in 96% aqueous EtOH leads to the compounds of formulae PPh4LI–V and (PPh4)2LVI,VII. Compounds obtained were investigated by 1H and 31P{1H} NMR spectroscopy, ES mass spectrometry, and microanalysis. Recrystallization of PPh4LI from an aqueous EtOH solution (1:1, v/v) leads to the formation of PhC(S)NHP(O)(O‐i‐Pr)2 (HQ). The crystal structure of HQ reveals to be a polymorph to the previously reported structure. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:343–350, 2010; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20607