Ethyl phenyl disulfide

Ethyl phenyl disulfide 256a Ethanesulfenyl chloride (9.6 g) is dropped into a stirred solution of thiophenol (11 g) in ether (50 ml) at 0°. The mixture is warmed gently on the water-bath, the solvent is removed, and the residue is distilled in a vacuum. The product boils at 126°/ 15 mm. 

By applying a similar approach, Wu and coworkers [135] observed a highly double-stereoselective hetero Diels-Alder addition between diene 245 and ethyl glyoxylate. This reaction was catalyzed by the (salen)Co° complex 246 (Scheme 13.75). The major adduct 247 is hydroborated to give alcohol 248. Stereochemical inversion is achieved via oxidation and subsequent reduction to 249. Acid methanolysis followed by diol protection furnishes 250. Quenching of the lithium enolate of 250 with phenyl disulfide and subsequent oxidation with A-bromosuccinimide forms, after deprotection, (-f)-KDO (3-deoxy-D-mann6>-oct-2-ulosonic acid) [136a]. 

Walling and Rabinowitz observed (299,300) that, in the presence of appropriate initiators, trialkyl phosphites can undergo a free radical chain reaction with alkyl disulfides to yield an 0,0,0-trialkyl phosphorothioate and an alkyl sulfide (eq. 11a). Because of the strength of the aryl-sulfur bond in phenyl disulfide, an ethyl rather than an aryl radical would be eliminated from the radical intermediate (eq. 11b) in this instance. 

Disulfide dibenzyl. See Benzyl disulfide Disulfide, diphenyl. See Phenyl disulfide Disulfide, di-2-propenyl. SeeAllyl disulfide Disulfide, ethyl methyl. See Diisopropyl disulfide... 

Although not fully characterized, 2-carbethoxy-4-hydroxythiazole (230a), R, = C02Et, R2 = H, apparently results from the reaction of chloroacetonitrile with ethyl thiooxamate (2), Ri = C02Et (417). a-Chlorothioacids (232) condensed with thiobenzamide in the presence of carbon disulfide (542) yield the corresponding 2-phenyl-4-hydroxy-thiazole (234). The same product was obtained from 233 (Scheme 121). 

Preparative Photolysis. The preparative photolysis of an aqueous solution (pH=8.5) of AETSAPPE (2.5 M) was conducted in a 1-inch diameter quartz test tube in a Rayonet Reactor (Southern New England Radiation Co.) fitted with 254 nm lamps. Within two hours the solution gelled and the reaction was terminated. Upon acidification the solution cleared, and the product could be re-precipitated by addition of base. This indicates loss of the thiosulfate functionality. The product was dissolved in dilute HC1, precipitated with acetone, and filtered. This process was repeated three times, and the final precipitate was washed with water. The product (20 to 30 mg) was dried in vacuo for 24 hours and stored in a dessicator until use. Comparison of the13 C NMR spectrum of the product with the starting AETSAPPE 13C NMR spectrum clearly shows that the thiosulfate methylene peak shifted upfield, from 39 ppm to 35 ppm. The complete 13 C NMR and IR analysis of the product were consistent with the disulfide product. Further, elemental analysis of the product confirmed that the product was the desired disulfide product 2-amino (2-hydroxy 3-(phenyl ether) propyl) ethyl disulfide (AHPEPED) Expected C 58.39, H 7.08, N 6.20, S 14.18 actual C 58.26, H 7.22, N 6.06, S 14.28. 

A method used to prepare four of six possible thienopyridines (1992S528, 1997S949, 1998S1095) holds considerable promise. In particular, the synthesis of thieno[2,3-6]pyridine derivatives 31 and 32 involves the reaction of 2-chloro-3-(cyanomethyl)pyridine (33) and ethyl 2-chloro-3-pyridylacetate (34) with hetero-cumulenes, such as carbon disulfide and phenyl isothiocyanate. The reaction proceeds through the formation of the corresponding dianions 35 and 36 followed by cyclization through intramolecular nucleophilic substitution of the chlorine atom. 

Elution of the silica gel column with additional hexane afforded thiophenol (5,0 g), diphenyl disulfide (0.2 g), and BHT (0.1 g, stabilizer from the THF). Continued elution with increasing amounts of ethyl acetate (hexane EtOAc from 100 to 80 20) afforded dlnonyl ketone (2.4 g. 10%), S-phenyl decanoate (0.8 g, 2%), and the enol of 2-methyl-3,5-diketotetradecane (2.4 g, 6% the amount is probably greater). 

Bohme and Zinner (34), who prepared the methyl, ethyl, and benzyl derivatives. With iodine, the trisulfides give symmetrical liexasulfides. Feh6r and Kruse (66) prepared phenyl-hydrogen tri- and tetrasulfide and n-butyl-hydrogen tetrasulfide and studied their Raman spectra. The compounds are sensitive to bases, and salts are apparently unstable, although White (226) in 1918 reported a stable sodium salt of 2-naphthyl-hydrogen disulfide. 

Interaction of triethyl phosphite and phenyl benzenethiosulfonate is complicated, according to Michalski et al. (223), by concurrent reduction of the sulfonate ester. Thus, in addition to ethyl benzenesulfinate and 0,0-diethyl 8-phenyl phosphorothioate (eq. 8), there is obtained diphenyl disulfide and triethyl phosphate V... 

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