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Piperidinecarbodithioate (Pipdtc), thiomorpholine-4- (Timdtc) and N-methylpiperazine-4- carbodithioate (CH 3 Pzdtc) complexes of iron(III), cobalt(II), nickel(II), copper(II), zinc(II), cadmium(II) and mercury(II) have been prepared and characterized by magnetic and spectroscopic techniques. Structures are proposed based upon the spectra of these new dithiocarbamate complexes.

A comparative study has been made of the donor ability of the nitrogen, oxygen and sulphur atoms in 1,4-diheterocyclohexanes with respect to divalent zinc. Complexes of zinc halides with thiomorpholine, morpholine and thioxan have been used to assign the stereochemistry and to determine the mode of co-ordination. Tetrahedral compounds of the type Zn X 2 L 2 , X = halide, L = thiomorpholine, morpholine or thioxan have been isolated. Results suggest that for the ligands under consideration the order of co-ordinating ability for the donor atoms is N > S > O.

Die Einwirkung von Schwefelwasserstoff auf 2.3-disubstituierte (1 a-f) und 2.2.3-trisubstituierte 5.6-Dihydro-1.4-thiazine (3a,b) fuhrt in guten Ausbeuten zu 2.2-disubstituierten Thiazolidinen (2a-h), die ihre Entstehung einer hydrierenden Ringverengung verdanken (Tab. 1, S. 35). - In Umkehrung der Ringverengung lassen sich 2.2-disubstituierte Thiazolidine (2a-h) durch Reaktion mit Schwefel in masigen Ausbeuten dehydrierend in substituierte 5.6-Dihydro-1.4-thiazine (1a-h; 3a,b) umlagern, die mit Ameisensaure in die entsprechenden Thiomorpholine (4a-j) ubergefuhrt werden konnen (Tab. 2, S. 39). Die dehydrierende Ringerweiterung yon Thiazolidinen, die in 2-Stellung zwei verschiedene Alkylreste tragen (2c,g), fuhrt zu strukturisomeren 5.6-Dihydro-1.4-thiazinen ( 1c,g bzw. 3a, 1h). On the Joint Action of Elementary Sulfur and Gaseous Ammonia on Ketones, LXXIII1). Rearrangements between 5,6-Dihydro-1,4-thiazines and Thiazolidines The action of hydrogen sulfide on 2,3-disubstituted (1a-f) and 2,2,3-trisubstituted 5,6-di-hydro-1,4-thiazines (3a, b) affords in good yields 2,2-disubstituted thiazolidines (2a-h), which are formed by a hydrogenating ring contraction (table 1, p. 35). - In reversal of the ring contraction 2,2-disubstituted thiazolidines (2a-h) can be rearranged in a dehydrogenating reaction with sulfur in moderate yields to substituted 5,6-dihydro-1,4-thiazines (1a-h; 3a, b) which can be converted with formic acid into the corresponding thiomorpholines (4a-j; table 2, p. 39). The dehydrogenating ring enlargement of thiazolidines which possess in the 2-position two different alkyl groups (2c, g), leads to structurally isomeric 5,6-dihydro-1,4-thiazines (1c, g, and 3a, 1h, respectively).

The chloro groups in the bis-9(10)-[alkyl-10 (9)-chlorooetadecanoate]-sulfides described previously (9) underwent reaction with water, alcohols, ammonia, amines, cyanides, cyanates, thiocyanates, and azides. The rates of these reactions were such that the chloro groups were completely replaced before significant attack on the ester group occurred. Without exception, the products of these reactions were the open-chain disubstituted-sulfide diesters, e.g. bis-9(10)-[ethyl-10 (9)-aminooctadecanoate]-sulfide, and no evidence was found for cyclic,e.g. thiomorpholine, structures. The sulfur dichloride diadducts fromcis-2-butene andtrans- 2- butene were also subjected to hydrolysis and ammonolysis and again, only the open-chain sulfides, e.g. bis-2-[3-amino-butyl]-sulfide, were formed. The diol-sulfides from m-olefins differed from the diol-sulfides oftrans- olefins in both physical and special properties. A similar difference was noted in the diamino-sulfides. Several of the fatty products were oxidized to the corresponding disubstituted sulfone diesters.

An intermediate obtained by Lowe and Ramsay in the synthesis of a homopenicillin has been shown by X-ray analysis to have a structure including a β-lactam ring fused to a thiomorpholine ring carrying 2,2-dimethyl and 3-benzyloxycarbonyl substituents. The compound crystallises in the space group P21/c, with Z= 4 in the unit cell of dimensions a= 19·160, b= 6·369, c= 19·052 A, β= 111·59°. The crystal structure was solved from diffractometer data by the symbolic addition method and refined to an R value of 5·16% for 2697 independent reflections by iterative block-diagonal least-squares procedures. The central six-membered ring exists in a distorted chair form and is oriented at 140·8° to the fused β-lactam ring.

Heteroalicyclic analogs of 2- and 3-aminoalkanethiols were synthesized from the alkanols Ia--Va via the corresponding halogenoalkylamine hydrohalides for evaluation as antiradiation drugs. The analogs described have mercapto (or potential mercapto) groups on a side chain two or three carbon atoms removed from the secondary amino groups of pyrrolidine, piperidine, thiomorpholine, and piperazine. The bicyclic dithiocarbamates VIII and IX resulted from the reaction of carbon disulfide with 2-(chloromethyl) pyrrolidine hydrochloride (Ib) and 2-(2- chloroethyl)piperidine hydrochloride (IIIc), respectively. The synthesis of VIII elucidated the structure of the water-insoluble product formed concurrently with 2-pyrrolidinylmethyl dimethyldithiocarbamate hydrochloride (Id) from Ib and sodium dimethyldithiocarbamate.

Gardner and Haenni1 described a series of compounds containing the morpholine rings, which they claimed exhibited some local anesthetic activity. The general structure of their compounds is expressed by the formula, Burrows,2 under the direction of Professor E. Emmet Reid in the Laboratory for Organic Chemistry, Johns Hopkins University, prepared 2 series of analogous compounds, which the writer had the privilege of investigating pharmacologically. One series was composed of thiomorpholines. The first of these, labelled No. 0, is thiomorpholine ethanol and has the following structure, In addition, 7 esters were prepared from this alcohol, namely, the acetate, propionate, butyrate, valerate, caproate, heptoate and ben-zoate. In this paper these are labelled Nos. 1 to 7, respectively. A second series of compounds, analogous to the thiomorpholines and containing 2 oxygen atoms attached to the sulphur, was also prepared. These may be termed sulphoxy-thiomorpholines, the first member of the series, sulphoxy-th...

The preparation and spectral and magnetic properties are reported for complexes of cobalt(II) with thiomorpholine. A comparative study has been made of the donor ability of nitrogen and sulphur atoms in the complexes. In an attempt to correlate the behaviour of thiomorpholine and morpholine with respect to divalent cobalt, work on cobalt(II)–morpholine complexes has been extended. The compounds CoX2L2, X = halide, L = thiomorpholine or morpholine, have been shown to be pseudo-tetrahedral, whereas when X = thiocyanate the compounds can be regarded as pseudo-octahedral involving thiocyanate bridging. I.r. results suggest that thiomorpholine is coordinated to cobalt through the nitrogen rather than the sulphur atom.

Complexes of palladium(II) and platinum(II) halides with thiomorpholine and thiomorpholin-3-one have been prepared and characterised. A comparative study has been made of the donor ability of the nitrogen and sulphur atoms in the complexes. I.r., Raman, and 1H n.m.r. spectroscopic measurements were used to assign the stereochemistry and to determine the mode of co-ordination. Two types of complexes have been isolated, MX2L2(M = Pd or Pt, X = halide, and L = thiomorpholin-3-one; or M = Pd, X = Cl, or Br, and L = thiomorpholine) and MX2L (M = Pd, X = I; or M = Pt, X = halide, and L = thiomorpholine). Results suggest that the former can be formulated as monomeric, trans-square-planar complexes with co-ordination through nitrogen rather than sulphur. The latter are considered to be polymeric with the ligand acting as a bridging group.