Syntheses with ketones, sulfur, and ammonia or amines at room temperature

Abstract

A large number oj' preparatively interesting compounds have become readily available by the simultaneous action of sulfur and amnror?ia or amines on ketones. Direct syntheses of A3-thiazolines, d3-irnidazoline-5-thiones, 5,6-dihydro-4H-1,4-thiazines, and the 1,2,3,4,5,6-hexathiocane system from ketones, sulfur, and ammonia or amines, and further possibilities for rfze synthesis of these heterocyclic systems have been proposed. Other heterocycles containing N or N and S (thiazoles, thiophenes, thiazolidines, tetrahydro-thiazol0[2,3-~]-1,4-thiazines, thiomorpholines, 4-arniizo-2H-imidazoles, etc.) are readily obtainable by further reactions of these compounds. Hydrolysis of the A3-thiazolines yieIds a-mercapto ketones, which are the starting materials for other syntheses. Most of the syntheses described proceed ut room temperature and at noririni pressure.

Reactions of Benzylamine with Sulfur

“…Combination of [4] and [6] (three times [4] added to [6]) gives the stoichiometric eq. 20 where the hydrogen sulfide produced is removed by the lead oxide to give lead sulfide and water rather than reacting as per [5]. When sulfur and benzylamine were allowed to react in triethylamine in the molar ratio of 7 to 2 (i.e., b = 4), the yield of benzylidenimine polysulfides isolated was 90 f 2 % based on [20].…”

“…[4][5][6][7][8] at this time but an early step is probably ionic since the rate of formation of benzylidenimine tetrasulfide from benzylamine and sulfur in the presence of the sulfide scavenger was considerably faster in polar solvents than in non-polar solvents.…”

“…Thus, acetophenone at elevated temperatures gives thioamides (1, 2) but at room temperature (in the presence of 0.25 g atoms of sulfur per mol of ketone) gives a Schiff's base (3). When the quantity of sulfur is increased, the yield of Schiff's base decreases, and at a sulfur to ketone ratio of 8 :1 the heterocyclic compound 8-alkylamino -8 -phenyl-l,2,3,4,5,6-hexathiocane-7-thione (1) results (4,5). Primary amines are RHN to be followed by migration of the functional group or groups along the carbon chain with eventual irreversible oxidation at the end of the chain giving the final product.…”

“…It should be emphasized, however, that eqs. 9-12 offer an equally good alternative to [4] and [5] (see also reference 31). In eq.…”

Solid State and Solution Structure of an Unusual Compound Containing a CS7 Ring

“…In the Asinger reaction of acetophenone with excess sulfur and primary amines sulfur-rich thiocanes are formed in high yields [1][2][3][4]. Using 1-aminobutane as the amino component, the product of the reaction is an intensely yellow crystalline solid with a melting point of 109-110°C and a sumformula of C 12 H 15 S 7 .…”