W. E. Dahl

DERIVATIVES OF 4-CHLORO-3,5-DINITROBENZOTRIFLUORIDE V. SYNTHESIS OF 4,6-DINITRO-2,8-BIS(TRIFLUOROMETHYL) PHENOTHIAZINE (1), ISOPROPYL 2,6-DINITRO-4-TRIFLUOROMETHYLPHENYL SULFIDE (2) AND BIS(2,6-DINITRO-4-TRIFLUOROMETHYLPHENYL) DISULFIDE (3)

Abstract The reaction of potassium isopropyl dithiocarbonate with 4-chloro-3,5-dinitrobenzotrifluoride in dimethylformamide at 25–30°C afforded the titled phenothiazine (1) and sulfide (2). The reaction of bis(2,6-dinitro-4-trifluoromethylphenyl)-sulfide or the above halogen compound with sodium hydrosulfide in the same solvent at 80–90°C furnished 1. At 25–30°C the latter reaction afforded the titled disulfide (3). Possible mechanisms and supporting nmr, ir and mass spectral data 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 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.