Organic Polysulfides.¹ IV. Synthesis of Bis(triphenylmethyl) Polysulfides

Abstract

mole) was heated in a solution of sodium carbonate (10.6 g., 0.01 mole) in 150 ml. of 33%, ethanol until it dissolved. The solution was refluxed for 2 hr. with stirring and, after storage overnight in the cold (0°), sodium carbonate was filtered off and the filtrate was evaporated to dryness under reduced pressure. The solid residue was taken into hot benzene, and the benzene solution was concentrated to a semisolid. Petroleum ether was added, and the precipitate, obtained after storage in the cold (0°) overnight, was recrystallized from benzene-petroleum ether. The 7-hydroxybutyranilide thus obtained, 0.6 g. ( 17%), melted at 74-75°;3.0, 3.1, 3.15 (OH, NH-secondary amide); 6.0, 6.5 (CO-NH); 13.0-13.7, 14.4 µ (monosubstituted aromatic).Anal. Caled, for C10H13NO2: N, 7.8. Found: N, 7.6. Evaporation of the petroleum ether precipitation solvent left l. 1 g. (34%) of 1 -phenylpyrrolidin-2-one, identified by mixture melting point and infrared spectrum.a-Benzamido-7-chlorobutyr-N-benzylamide (V).-a-Benzamido-7-hydroxybutyr-N-benzylamide (3.2 g., 0.01 mole) was dissolved with cooling (ice-salt bath) in 10 ml. of thionyl chloride. The reaction mixture was stirred, brought to room temperature, and then heated to boiling. After cooling, ether and petroleum ether were added. The separated oil was washed with water and dissolved in ethanol. The product was precipitated by addition of water and crystallized from ethanol, yielding 2.8 g. (85%), m. p. 168°.

Nucleophilic Substitution on S4N4. Reactions with Benzylamines

“…showed only two obvious maxima at 242 (E = 1.3 x lo4) and 309 mp (E = 2.4 x lo4) while the disulfide had maxima at 294 (E = 2.8 x lo4) and 304 mp (E = 2.9 x lo4). These spectra do not closely resemble those of either typical alkyl polysulfides (32,33) or typical Schiff's bases (34). Judging from the increase in extinction coefficients in the 300 mp region for the Can.…”

Sulfuration and reversion reactions of brominated poly(isobutylene‐co‐isoprene)

“…Note that these exchange reactions may serve not only to generate crosslinks but also to alter the rank of bis‐PMN‐allylic polysulfides. A third possible crosslinking mechanism involves the oxidation of hydropersulfides by persulfenyl bromides to generate 4 and HBr 28, 29. The latter would be subsequently scavenged by epoxide.…”

A Review of Heterolytic Synthesis Methodologies for Organotri- and Organotetrasulfane Synthesis

“…32 Later, in 1964, Takeshiga Nakabayashi demonstrated that triphenylmethanethiol (TrSH) could be used for both bis(triphenylmethyl)tri-and tetrasulfane synthesis using SCl 2 and S 2 Cl 2 , respectively. 33 Also, in the 1920s, a variety of thiocarbonates were used as non-thiol, sulfur nucleophiles such as potassium thiobenzoate, 34 Bender's salt (EtOCO(SK) = potassium O-ethylthiocarbonate), 35 potassium O-ethyldithiocarbonate (EtOCS(SK)), and potassium ethyl trithiocarbonate (EtSCS(SK)), which gave rise to end-substituted trisulfides. 35 The trend in using non-thiol nucleophiles continued with Franz Fehér's contributions in 1958 36 using mercuric thiocyanate for accessing NC-(S) n -CN polysulfanes, covering both tri (n = 3, from SCl 2 ) and tetra…”