Teil‐ und perfluorierte Thioketone und Thioaldehyde Chemische Speicherung, in‐situ‐Freisetzung und ungewöhnliche 1,3‐dipolarophile Reaktivität gegenüber Bis(trimethylstannyl)diazomethan (BTSD) und C,N‐Bis(triisopropylsilyl)nitrilimin (NI)

Abstract

Partially and Perfluorinated Thioketones and Thioaldehydes: Chemical Storage, In Situ Generation and Surprising Reactivity towards Bis(trimethylstanny1)-diazomethane (BTSD) and C,N-Bis(triisopropylsily1)nitrilimine (NI)The hetero-Diels-Alder anthracene adducts la-d are synthesized in a one-pot reaction from the corresponding partially and perfluorinated carbonyl compounds in good yields. By their thermolysis in solution in presence of BTSD or NI the 1,3-dipolar 1:l cycloadducts 12a, d, 14a, b, d are obtained without any detectable by-products. The method can be of wide applicability predominantly for any aliphatic CS-unsaturated species, which are not accessible in substance due to tendency towards polymerisation, but can be stabilized as anthracene adducts. Other 1,3-dipolar cycloaddition products of BTSD and NI are obtained from reaction with isolable hexafluorothioacetone (6f) or bis(trifluoromethy1)sulfine (7f). Comparative studies were carried out with hexafluoroacetone (8). 12a, d, e, 13 are consecutive products from a 1,2-metallotropic migration of the primary addition compounds. 14a, b, d, 15, 16 are useful thiadiazolines with respect to the synthesis of active substances because of their seldom found peripheral functionality. Desilylation was achieved by fluoride support. An X-ray structure determination of 12a and 14d was carried out. In addition trifluoromethylsulfine (7c) was trapped at low temperatures. It dimerizes at ambient temperature to unsymmetrical 1,2-dithietane 11.

An Unprecedented [2+3] Cycloadditive Dimerization of a Transient Thiocarbonyl S‐Ylide

“…The CI, MALDI, and FAB ϩ mass spectra also failed to produce a molecular ion signal for 6. Fluorinated thioketones have been found to react with diazobis(trimethylstannyl)methane to form unsymmetrical azines [11] in a manner unrelated to our present observations. Huisgen et al [12] have reported the two-step, head-to-head symmetrical dimerization of diphenylmethanethione Smethylide 7 Ǟ 8 (Scheme 4), but this still means that our unsymmetrical dimerization of 5, with one molecule acting as a 1,3-dipole and the other as a 1,3-dipolarophile (Scheme 2), is unprecedented.…”

AlliumChemistry: Microwave Spectroscopic Identification, Mechanism of Formation, Synthesis, and Reactions of (E,Z)-PropanethialS-Oxide, the Lachrymatory Factor of the Onion (Allium cepa)

“…Compound 12b affords d,l -1,2-bis(trimethylsilyl)-1,2-ethanedithiol on reduction and trans -2,3-bis(trimethylsilyl)thiirane and trans -1,2-bis(trimethylsilyl)ethene on photolysis . Other sulfines have recently been reported to dimerize to 1,2-dithietane 1,1- dioxides …”