V-Trithiane

Reagents i, Bu OK Bu OH MeOCH Cl ii, NBS PhCO ) iii, MeCOSK-CH,Cl, iv, HCI-MeOH v, trithian derivative of p-MeOCsH CHO-BFj-CH, Clj vi, CK-aq. MeOH-R.T. vii, Mel-NaH xylene-heat viii, —78 °C Bu jAlH-EtjO ix, (COClij-EtjO x, nO C-GHjClj xi, I mol BuLi 110°C xii, cone. HC1-70°C xiii, separate isomers xiv, -78 "C-Bu jAlH-THF xv, AcjO-pyridine xvi, iodosobenzene diacetate-MeCN MejS xvii, aq. NaOH-MeOH-R.T. xviii, w-ClCgH COjH xix, BFj-EtjO-CHjCL-R.T. 

The second method of synthesis was to allow sodium tetra-sulfide to react with glycerol-a,a -dichlorohydrin in a water-ethanol-chloroform solvent mixture, and introduce three sulfur atoms at once to form v-trithiane ring. In order to synthesize the brugierols from the v-trithiane, it was allowed to act with excess m-chloroperbenzoic acid in chloroform. By doing so, Brugierol and Isobrugierol were obtained in a ratio of 5 to 1. 

A possible mechanism of this oxidative desulfurization is shown in as Fig. 6, namely, the central sulfur atom in the v-trithiane ring is oxidized to form sulfone, in which an intramolecular nucleophillic rearrangement takes place to give the 1,2-dithiolane ring and SO2. The intermediate, 5-hydroxy-l,2,3-trithiane in this reaction is a new v-trithiane compound. And, as we will mention later, it is a compound of importance as the base of insecticidal active derivatives. As there was no report on the crystal structure of v-trithiane, the stereochemical structure was investigated by X-ray analysis. ... 

As the crystals of (1) were unsuitable for X-ray work, the structure analysis was carried out on the crystals of 1,2,3-trithian-5-yl N-methylcarbamate(2) to elucidate the stereochemistry of the v-trithiane ring. 

The various stereochemical informations were supplied by the investigation of the X-ray analysis. For example, the molecule has an approximate mirror plane containing S(2), C(5), and nonhydrogen atoms of planar side-chain. The v-trithiane ring, having almost strict m(Cg) symmetry, assumes a chair form. The side chain at C(5) is equatorial. The interplanar angle of 64 between the... 

Aldehyde synthesis. The synthesis of -pentadecanal from s-trithiane and 1-bromo-tetradecane (3, 329) has been published.1 Purification is accomplished by extraction of 30 g. of commercial. v-tnthiane with 300 ml. of toluene. 

Pyrazine 93 was prepared by reductive cyclodimerization of 2-nitro-methylenehexahydroazocine.125 o-( 1 -Perhydroazocinyl)acetophenone was ring opened by Hg(II)fEDTA) to the aminoaldehyde 94.126 The reaction probably proceeds via JV-aryliminium ions in a manner similar to that of photocyclization of 64. Mercuric acetate oxidation of /V-methylperhydro-azocine, followed by HC1 and H2S, afforded trithiane (95).127 This was... 

C3HgBr3S3Sb, 1,3,5-Trithian antimony III) bromide, 43B, 426 C3H6Cl3S3Sb, 1,3,5-Trithian antimony III) chloride, 43B, 426 C3H7Cl5NOSb, Dimethylformamide-antimony(V) chloride complex, 31B,... 

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