Synthesis from thiocyanogen

From a synthetic point of view, the above studies have stimulated the synthesis of new types of /3-diketonato complexes. Thus, reactions at position 4 of the l-metalla-2,6-diox-acyclohexane rings, usually denominated the y-position (equation 2), such as halogen-ation , thiocyanogenation, chlorosulfenylation , arylsulfenylation, acylation, nitration, formylation , chloromethylation and dimethylaminomethylation (equation 2) ° have been performed as well as Suzuki coupling reactions (equation 3) , or an aldol reaction with p-nitrobenzaldehyde under Lewis acidic conditions (equation 4f. ... 

Olefin synthesis. This reagent has an advantage over trialkyl phosphites (see Trimethyl phosphite, 1, 1233, and this volume) for stereospecific generation of olefins from trithio- and thionocarbonates in that the conditions are mild (30°)-s Thus optically active /rans-cyclooctene (6) has been prepared from cis-cyclooctene in the following way.3 Addition of thiocyanogen to cis-cyclooctene (3) affords trans-, 2-dithiocyanocyclooctane (4), which when refluxed with 47% hydrobromic acid affords the iminodithiocarbonate (5). This was resolved via the salt with (—)-l-phenyl-ethanesulfonic acid by thirteen recrystallizations from 2-butanone. The (+)-(5) was... 

A series of papers detailing a continuation of the study of the synthesis and reactions of uic-iodothiocyanates and -iodoisothiocyanates has been published.Similarly, the treatment of alkenes with thiocyanogen bromide [from equimolar quantitites of bromine and thallium(i) thiocyanate] gives moder-ate-to-high yields of uic-bromothiocyanates. " Unlike the analogous vic-iodothiocyanates, the bromo-compounds are not readily isomerized to the corresponding isothiocyanates. 

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