The First Isolable Dithiirane by Oxidation of a Dithietane

Abstract

COMMUNICATIONScation. Elemental analysis and FAB mass spectrometry established the composition as C,oH5,0,,, consistent with a peroxide. The structure of 7 b was determined by 'HNMR spectroscopy. Para attachment is indicated by the presence of the methine and olefinic protons giving the pattern characteristic of an AABB'C spin system. This spectrum, in contrast to that of 6b, results from a symmetric or Heintschel peroxide; the radical l c undoubtedly forms a compound in which the dioxygen bridge joins para positions.Like the Jacobson dimer of triarylmethyl radicals, Jacobson and Heintschel peroxides, the common oxidation products in a variety of triarylmethyl radical studies, have escaped the attention of chemists for generations. These structures raise a concern : Why are not all bis(triarylmethy1)peroxides methyl-paracoupled in a Jacobson configuration? It previously has been shown that large radicals such as the tert-butoxy radical prefer to attach to para positions of triarylmethyls.[221 Such behavior has not been observed for oxygen. But since the first formed peroxy radical (a large radical by most standards) must attach to the second triarylmethyl radical we always might expect attack at the less hindered para site. Experiments are in progress to determine the first position bound in the formation of 6b. Experimental ProcedureBis(2,6-dimethoxyphenyl)phenylniethanol (1 b-OH): A solution of 1.3-dimethoxyphenyllithium was prepared by addition of 2.5 M nBuLi (34.8 mL, 86.9 mmol) in n-hexane to a solution of 1,3-dimethoxybenrene (10 g, 72.4 mmol) in anhydrous diethyl ether at -78 'C. The mixture was stirred at room temperature under argon for 48 h. Methylbenroate (3.13 g. 23.0 mmol) in benzene (20 mL) was added. and the reaction solution was heated at reflux for 3 days under argon. The reaction mixture was poured into 200 mL of water, and the organic layer was dried and concentrated to yield the methanol as an oil. The oil was crystallized in CH,CI, and hexane.Mp104"C,46%yield. 'HNMR(CDC1,,299.95 MHz):b = 3.38(s,12H), 6.43 (s. 1 H), 6.54(d. J = 8 Hr,4H), 7.11 (t. J = 8 Hz, 2H), 7.13 (m. 1H). 7.21 (m. 2H), 7.46 (m. Telefax: Int. code + (48)858-3698 Dr. M. Shiro Rigaku Corporation (Japan) Angeii-. Chem. h t . Ed. EngI. 1994. 33, No. 7 g ; VCH Verlugsgesrlkhafi mhH. 0-69451 Weinheim, f994 0570-0833/94/0707-0777 i % 10.00t .25/0 $: ' VCH Verlaggerellschufi mbH.

Reactions of 1,2,4‐Trithiolane, 1,2,5‐Trithiepane, 1,2,5‐Trithiocane and 1,2,6‐Trithionane with Nonacarbonyldiiron: Structural Determination and Electrochemical Investigation

“…+ ion at m/z = 432 and a stepwise fragmentation of five CO groups. These results indicate the formation of a diiron complex with both Fe(CO) 2 and Fe(CO) 3 moieties.…”

“…The isostructural ruthenium cluster was synthesised by the reaction of Ru 3 (CO) 12 and 1,4,7-trithiacyclononane (9S3) in thf. [11] Alternatively, when the complex Ru 3 (CO) 7 (µ-CO) 2 (1,1,1-η 3 -9S3) is heated at reflux for 16 h, an analogous ruthenium cluster is obtained. [12] FULL PAPER Scheme 5.…”

“…[1] In 1993, Nakayama and Ishii et al reported the first synthesis of stable dithiirane. [2] We have shown that platinum(0) complexes, for instance Pt(η 2 -C 2 H 4 )(Ph 3 P) 2 , react with 1,2,4-trithiolane (1) by insertion along the S-S bond. When two equivalents of the platinum(0) complex were used, dithiolatoplatinum(II) C was obtained (Scheme 2).…”

New developments of thiocarbonyl compounds and sulfines in organic synthesis

“…The following mechanism is proposed to explain this reaction, for which some precedents or analogues can be found in the literature (24)(25)(26). Rearrangement of the sulfoxide to a sulfenate (27) would be followed by migration of the alkylthio group towards the electrophilic sulfur of the sulfenate.…”

Metallkomplexe mit funktionalisierten Schwefelliganden, XV [1]. Reaktionen von Platin(0)-Komplexen mit 1,2,4-Trithiolanen, 1,2,4,5-Tetrathianen, 1,2,3,5,6-Pentathiepanen sowie Thioketonen. Kristallstrukturanalyse von (Ph3P)2Pt(η2-Ph2C=S) / Metal Complexes of Functionalized Sulfur Containing Ligands, XV [1]. Reactions of Platinum(O) Complexes with 1,2,4-Trithiolanes, 1,2,4,5-Tetrathianes, 1,2,3,5,6-Pentathiepanes as well as Thioketones. X-Ray Structure Analysis of

“…Vor kurzem konnten erstm als stabile D ithiirane hergestellt und isoliert werden; einige wurden auch röntgenographisch charakterisiert [6] …”