Sodium phenylthiolate

The chlorodifluoromethylated ketone 130 proved to be a valuable substrate for promoting SrnI subtitution reaction with sodium phenylthiolate and to generate a new a-(phenylthio)-a,a-difluoroacetophenone derivative 131 (Equation 57) <2001TL3459>. Upon treatment with nitronate anions under classical SrnI reaction conditions or MW irradiation, 6-chloromethyl-5-nitro-imidazo[2,l- ]thiazole 132 yielded 5-nitroimidazothiazoles bearing a trisubstituted ethylenic double bond at the 6-position (Equation 58) <2001SC1257>. 

Methyl-3-nitro-l-nonene (427) and sodium phenylthiolate show different modes of behaviour under different conditions in HMPA the product 428 of attack at the less hindered carbon atom is obtained, whereas in the presence of Pd(PPh3)4 the isomer 429 is produced457. 

Interest in the use of reducing agents to activate C-F bonds was revived when systems that enabled selective removal of fluoride from perfluorocarbons were discovered in contrast to the complete (destructive) removal of halides as in sodium fusion reactions employed in methods for halogen analysis [31]. (Interest in this latter area has also had resurgence in the search for methods capable of destroying chlorofluorocarbons [32].) The key breakthrough was the report by MacNicol and Robertson that hexakis(thiophenoxy)napthalene can be prepared by treatment of perfluorodecalin with excess sodium phenylthiolate for 10 days at 70°C in DMF [33]. 

Thiol 237 has been prepared from bromide 228 by treatment with sodium trithiocarbonate (89JHC1205). Sulfides 221 and 224 required for the [2,3]sigmatropic rearrangements in Section V,A,3 are formed by substitution with sodium phenylthiolate from the corresponding bromides such as... 

Benzenethiol, sodium salt EINECS 213-224-0 HSDB 5771 Sodium benzenethiolate Sodium phenylmercap-tide Sodium phenylsulfide Sodium phenylthiolate Sodium thiophenate Sodium thiophenolate Sodium thio-phenoxide Sodium thiophenylate Thiophenyl sodium salt. 

Thus, treatment of easily prepared 1,1,3,3,3-penalluoro-2-phenylpropene 56 with sodium phenylthiolate in THF at... 

Knochel and co-workers have carried out a series of nucleophilic substitution reacion on ( )-allyl bromide using thiolate ions. The reaction between bromide 326 and lithium phenylthiolate yielded the ( )-sulfide 327 exclusively. However, treatment of ( )-sulfide 327 with the more nucleophilic reagent sodium methyl thiolate led to a 20 80 mixture of 327 and ( )-methyl sulfide 328. They proposed that either a S- 2 mechanism is operative, or two S- 2 substitutions eventually resulted in the thermodynamically more stable sulfide (ii)-methyl sulfide 328. A similar reaction of 326 with aniline in excess or its chloromagnesium amide gave a mixture of 5 n2 and 5 n2 products 329 and 330 which slowly equilibrate to give S-f 2 product 329 in 78% yield (Scheme 3.143). 

Nucleophilic Substitutions.— The rates of nucleophilic substitution of bromine in 3-bromo>2-nitrothiophen with o-, m-, and p-substituted thiophenoxide ions in methanol are faster than those of 2-bromo-3-nitro-thiophen with the same nucleophiles." Somewhat unexpectedly, 2,3-di-bromo-4-methyl-5-nitrothiophen reacts faster with nucleophiles such as piperidine and phenylthiolate at position 2 than does 2,3-dibromo-S-nitro-thiophen." 4-Cyano-2-nitrothiophen reacts with sodium methoxide in methanol to give the Meisenheimer adduct (107), whereas 2-cyano-4-nitro-thiophen gives the sodium salt of the carboxyimidate (108), from which methyl 4-nitrothiophen-2-carboxyiimdate can be isolated upon acidification."" If, however, 2-cyano-4-nitrothiophCT is treated with sodium methoxide in [ He]DMSO, formation of the Meisenheimer complex (109) is... 

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