Potassium thiophenoxide

EtSNa, DMF, reflux, 3 h, 94-98% yield.Potassium thiophenoxide has been used to cleave an aryl methyl ether without causing migration of a double bond. odium benzylselenide (PhCH2SeNa) and sodium thiocre-solate (p-CH3C6H4SNa) cleave a dimethoxyaryl compound regioselec-tively, reportedly as a result of steric factors in the former case and electronic factors in the latter case. ... 

The softer, less basic potassium bromide and iodide did not react with the thiirene dioxide 19b. The latter was also inert towards potassium thiocyanate, selenocyanate or nitrile. It did react, however, with potassium thiophenoxide in DMF at room temperature to yield, most probably, the vinyl sulfmate 138 isolated as the corresponding sulfone39 (equation 56). 

Treatment of potassium thiophenoxide with dichlorodifluoromethane in dimethylformamide (DMF) affords three products, Y, Y, and Y". What are compounds Y, Y, and Y", and how are they formed ... 

Potassium thiophenoxide, or Sodium polysulfide See DIAZONIUM suleides and derivatives (reference 9) See other diazonium SALTS... 

Thiolates are powerful nucleophilic reagents. However, we observed no reaction when trifluoromethyl bromide is bubbled through a potassium thiophenoxide solution in DMF at room temperature. This failure was in agreement with the inertness reputation of this halide. Assuming that a mechanism involving radical anions (Fig. 4, X = Br) could occur, a minimal concentration of the halide should be necessary to maintain the chain process. In order to increase the amount of trifluoromethyl bromide in solution, we performed the reaction under pressure. Indeed, condensation occurred at room temperature in a glass apparatus under 2-3 bars (Fig. 5) (refs. 16,17). Inhibition of this condensation by nitrobenzene was clearly observed, in agreement with the SET process (Fig 4, X = Br). A similar trifluoromethylation of thiols by trifluoromethyl bromide in liquid ammonia under UV irradiation has also been described (ref. 18). 

Chemists at the Sagami Research Centre constructed the bicyclic compound (139) by thermolysis of (138) in benzene in the presence of copper acetoacetate. Ring opening of (139) with potassium thiophenoxide in r-butanol led to (140) which was elaborated to ( )-ll-deoxy-PGEi via alkylation with methyl 7-iodoheptanoate and decarboxylation to provide the a-chain, and then successive treatment with m-chloroperbenzoic acid and trimethyl phosphite [143]. 9-Deoxyprostagjandins have also been synthesized [144-146]. 

Treatment of 3-chlorothietan with potassium thiophenoxide or potassium thiobutoxide gave phenyl or n-butyl allyl disulphide. The thietan ring in a tricyclic system is opened in various reactions. While most cyclic sulphides give ylides on treatment with dimethyl diazomalonate, thietan gave 26% of ring-expanded product (165). In the absence of copper sulphate a polymer was obtained. "... 

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