-Substituted benzophenones, 2-benzoylthiophene, 3-benzoylpyridine, dicyclopropyl ketone, and camphor are converted into the corresponding thioketones after reaction with the dimer of p-methoxyphenylthionophosphine sulfide, ' . Except for the pyridine derivatives (2-and k-benzoylpyridines, respectively, gave no thioketones) very high yields are found. Under the same conditions dibenzylketone gave 7,3-diphenylpropene-2-thiol and 1,9-benzanthr-10-one yielded the dimer of 1,9-benzanthr-lO-thione. Aromatic thioketones are also obtained by reacting gem-dichlorides with 2-methyl-2-propanethiol in the presence of catalytic amounts of CF,COOH (or ALCL,). A mechanism is suggested based on kinetic measurements. I3C NMR data of the thiocarbonyls of all thioketones are recorded and a function describing the relation between the chemical shifts of C=S and C=O is found: bC=S = 1 -5 7 b,=, -77.45

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The thiation properties of the dimer of p-methoxyphenylthionophosphine sulfide, A, has been investigated by performing reactions with a representative series of aliphatic and aromatic primary, secondary, and tertiary carboxamides in the temperature range 80-100 "c using HMPA as solvent. This new method seems to be superior to all others as in most cases quantitative yields are found. Salicylanilide, when reacted with in HMPA. yields salicylthioanilide and a new type of phosphorus heterocycle, 1,whose structure has been determined by NMR-and X-ray analyses. 1 3 C NMR data are tabulated for a series of thioamide carbons.

Die 3‐Oxo‐ester (I) reagieren mit dem Dimeren (II) und elementarem S zu den 3H‐1,2‐Dithiol‐3‐thionen (III).

Simple alifatic and aromatic esters, such as ethyl, iso-propyl, and benzyl benzoates, benzyl butanoate, ethyl heptanoate, and ethyl 1 -and 2-naphthoate, respectively, react with the dimer of p-methoxyphenylthionophosphine sulfide 1 in anhydrous xylene at 140 "C to give the corresponding 0-substituted thioesters in nearly quantitative yields. Also simple alifatic and aromatic S-substituted thioesters, such as S-phenyl, S-benzyl and S-tert-butyl thiobenzoates, S-phenyl and S-benzyl thioacetates, and S-ethyl thiobutanoate, produced the corresponding dithioesters in nearly quantitative yields upon treatment with 1 in anhydrous toluene at 1 1 0 "C. 13C NMR data for the carbonyl-and corresponding thiocarbonyl carbons, have been recorded and a linear relation between the chemical shifts of C=S and C=O is found: 6(C=S) = 1.75.6(C=O) -79.6 for 0-substituted thioesters and 6(C=S) = 1.31.6(C=O) -22.1 for dithioesters. An anomalous reaction has been observed: Thiobenzoic acid, S,S'-methylene ester 2 reacted with 1 to give 4,5-diphenyl-1,3-dithiol-2-thion 3 .