Thiocarbonyl compounds amines

The reaction of a series of thiocarbonyl compounds with primary amines has given isocyanide complexes via the intermediate carbene (13) (100). 

Photochemical reactions of nitrogen-containing thiocarbonyl compounds ([2 + 2] cycloaddition to alkenes with formation of thietanes, transformations of thioimides to lactams and cyclic amines, cyclizations of thioamides) 03H(59)399. 

Bis(trifluoromethyl)diazomethane is a reactive, electrophilic compound. It forms adducts with nucleophiles such as amines and phosphines and adds to olefins, acetylenes, and thiocarbonyl compounds to form heterocycles. It has been used as a source of bis(trifluoromethyl) carbene in reactions with benzene, saturated hydrocarbons, carbon disulfld< , and transition metal (iompounds, and it nndergoe.s a uni< im radicuil chain n aidion with saturat d hydrocarbons l.o form addiict.s that are hydrazonc.s and azines. ... 

Copolymers with hexafluorocyclobutanone have been made in ether at low temperatures using cesium fluoride as an initiator. They are of low molecylar weight and are more resistant to amine degradation than the homopolymer. Copolymerization of perfluoroacetahlehyde and perfluoropropionaldehyde with thiocarbonyl fluoride has been accomplished by initiation with complex compounds of the type Me(PR3)BB (67) in which Me is a group VIII metal and B is P(C6Hs)3 or a halogen. The products have excellent resistance to acids. 

Structures bearing carbonyl groups are generally more sensitive to base-catalyzed hydrolysis this is particularly true of the sulfones (73) which are readily ring opened to arene acids (74), aldehydes and ammonia. 2,4-Dioxo and thionyl derivatives behave similarly. Where both carbonyl and thiocarbonyl groups are present primary amines form imino derivatives by selective attack at the thiocarbonyl site in the dithioxo compound (75 X = S) reaction takes place at position 2 (Scheme 27) (79KGS291). 

Makino et al.35 developed a solid-phase synthesis of 1,3-disubstituted 2-thioxoquinazoline-4-ones using HMP Lanterns that were derivatized with a 4-aminobenzoate ester. Following the assembly of amide 25 (Scheme 9), SnAt reaction with alkyl amines gave support-bound products 26 with high conversion. The key thiocarbonylation step was achieved with thiocarbo-nyldiimidazole in decalin at 95° for 16 h in the presence of DMAP to afford 1,3-disubstituted 2-thioxoquinazoline-4-ones 27. The target compounds 28... 

In general, thiocarbonyl halides (59) function as thioacylation reagents with a variety of nucleophiles to yield the appropriate thio derivatives (60) (Scheme 31). For example, (59) on condensation with thiols, amines, potassium cyanide or potassium thiocyanide yields the corresponding thio compounds (60). Thiolocarboxylic acids (50) characteristically acylate alcohols and amines with desulfuration (Scheme 32). Dithiocarboxylic acid esters (54b) react with organolithium or Grignard reagents to give the dithioketals (61) after treatment with an alkyl halide (Scheme 33). 

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