John J. D'Amico

NOVEL SYNTHESIS OF DISUBSTITUTED THIOLCARBAMATES VIA A SULFUR TRANSFER AGENT-POTASSIUM ALKYL OR BENZYL DITHIOCARBONATES

Abstract The reaction of N,N-disubstituted carbamoyl chlorides with potassium alkyl or benzyl dithiocarbonates afforded a novel synthesis of disubstituted thiolcarbamates.

SYNTHESIS OF HETEROCYCLIC COMPOUNDS AND NEW ROUTES FOR THE PREPARATION OF CERTAIN DITHIOCARBONATES AND SULFIDES FROM POTASSIUM CYANODITHIOIMIDOCARBONATE1,2

Abstract The reaction of potassium cyanodithioimidocarbonate with 3-chloro-2,4-pentanedione, ethyl α-chloroacetoacetate, chloroacetone, or 2,3-dichloro 1,4-napthoquinone afforded novel heterocyclic compounds (2), (3), and (4) and (6). The reaction of the potassium salt with p-chlorophenyl chlorothioformate, 4-chloro-3-nitro or 3,5-dinitrobenzotrifluoride or dimethylthiocarbamoyl chloride furnished new routes for the synthesis of S,S′-bis-p-chlorophenyl dithiocarbonate (7) and the sulfides (8), (9) and (10). Possible mechanisms and supporting NMR and mass spectra are discussed.

DERIVATIVES OF 4-CHLORO-3,5-DINITROBENZO-TRIFLUORIDE. IV. SYNTHESIS OF BIS [6-(ETHYLTHIO)-5-NITRO-α,α,α-TRIFLUORO-m-TOLYL] DISULFIDE (1) AND ETHYL 2,6-DINITRO-α,α,α-TRIFLUORO-p-TOLYL SULFIDE (2)

Abstract The reaction of potassium ethyl dithiocarbonate with 4-chloro-3,5-dinitrobenzotrifluoride in dimethylformamide at 25–30°C afforded the titled disulfide (1) and sulfide (2). Possible mechanism and supporting NMR, ir, Raman and mass spectral data are discussed. The assigned structure for 1 was verified by X-ray crystal structure analysis.

A NEW ROUTE TO 2H-(1,2,4) TRIAZINO(3,4b) BENZOTHIAZOLE-3(4H)-ONE1 (4)

Abstract The reaction of 3-(carbethoxymethyl) benzothiazoline-2-thione (1) with excess hydrazine in an aqueous medium at 25–30° or 95–100°C afforded the hydrazide (3) in 99% yield and the titled heterocyclic compound (4) in 63% yield, respectively. Under the same reaction conditions and replacing the above electrophile with 3-(carbethoxymethyl)-2-benzothiazoline furnished the hydrazide (5) in 45% yield and a 6% yield of 5 plus a high yield of a resinous mixture, respectively. Possible mechanism and supporting NMR and mass spectral data are discussed.

SYNTHESIS OF ALKYL N-CYANO-N-SUBSTITUTED THIOLCARBAMATES

Abstract The reaction of S,S′ alkyl and benzyl cyanodithioimidocarbonate (1–5) with potassium hydroxide in an acetone medium afforded the O-potassium S-alkyl and benzyl cyanothioimidocarbonates (6–10). The reaction of the potassium salts with alkyl, allyl or benzyl halides furnished the titled compounds (11–29). Possible mechanisms and supporting NMR, Ir and mass spectra data are discussed.

SYNTHESIS OF HETEROCYCLIC COMPOUNDS FROM DIPOTASSIUM 1,1-DIMERCAPTO-2,2-DICYANOETHYLENE

Abstract The reaction of dipotassium 1,1-dimercapto-2,2-dicyanoethylene with 3-bromo-1-propyne, 3-chloro-3-methyl-1-propyne, 3-chloro-2,4-pentanedione, ethyl α-chloroacetoacetate or chloroacetone afforded novel heterocyclic compounds (1–5). Possible mechanisms and supporting NMR and mass spectra are discussed.

Synthesis of Mixed Thiuram Disulfides

Abstract Carbon disulfide is known to undergo “insertion reactions” with various nitrogen-carbon bonds,1 nitrogentrivalent phosphorus bonds,2 nitrogen-trivalent arsenic bonds,1,3 nitrogen-silicon bonds,1,4 nitrogen-transition metal bonds and nitrogen-sulfur bonds.6,7,8 The reaction of carbon disulfide with secondary amine sulfides or alkyl sulfenamides furnished tetralkyl thiuram disulfides6 and trithiopercarbamates,7,8 respectively (Eq. I and II).

SYNTHESIS OF 2-(2,6-DINITRO-a,a,a-TRIFLUORO-p-TOLYLIMINO)-3-(2,6-DINITRO-a,a-a-TRIFLUORO-p-TOLYL)BENZOTHIAZOLINE (1) AND 2-(METHYLIMINO)-3-(2,6-DINITRO-a,a,a-TRIFLUORO-p-TOLYL)BENZOTHIAZOLINE (2)

Abstract The reaction of 2-amino or 2-methylaminobenzothiazole with 4-chloro-3,5-dinitrobenzotrifluoride in dimethylformamide afforded the titled benzothiazolines (1) and (2), respectively. Possible mechanism and supporting nmr, ir and mass spectral data are discussed.

HETEROCYCLIC AND RELATED COMPOUNDS DERIVED FROM DIPOTASSIUM 1,1-DIMERCAPTO-2,2-DICYANOETHYLENE AND SODIUM 2-MERCAPTOPYRIDINE N-OXIDE

Abstract The reaction of dipotassium 1,1-dimercapto-2,2-dicyanoethylene with certain halogen compounds furnished the expected dialkylation products (1)-(4). Replacing the halogen compound with 4-chloro-3,5-dinitrobenzotrifluoride afforded a novel heterocycle (5). The reaction of the potassium salt with phenyl or p-chlorophenylchlorothioformate gave 2,2-diphenyl or di-p-chlorophenylthio-2,2-dicyanoethylene (6) and (7). The reaction of 1 or 2 with excess hydrogen peroxide afforded substituted oxiranes (8) and (9). Depending on reaction conditions, the reaction of sodium 2-mercaptopyridine N-oxide with 4-chloro-3,5-dinitrobenzotrifluoride afforded either the expected sulfide (11) or the unexpected heterocycle (12). Possible mechanisms and supporting NMR, Ir and mass spectral data are discussed.