Sodium thiolacetate

Attempted selective displacement (96) of the primary tosylate function in 34 with sodium iodide in refluxing 2-butanone led to the 6-deoxy-6-iodo derivative 35 in 32% yield only, while the di-iodo derivative 36 was formed in 45% yield. These results are to be compared with those reported by Owen and Ragg (85) who observed no reaction with either potassium thiolacetate or potassium thiocyanate in the corresponding / -series. 

THIOL ESTERS Chlorodiphenylphosphine. Diphenylphosphinyl azide. Polyphosphate ester. Sodium borohydride. 2,4,6-Trichlorobenzyl chloride. Triphenylphosphine-Diisopropyl azodicarboxylate-Thiolacetic acid. 

The reaction mixture is transferred to a 250-ml. Claisen flask (Note 2) and distilled rapidly at 200 mm. in order to separate the sodium salts (Note 3). The distillate of thiolacetic acid and acetic acid, b.p. 35-82°/200 mm., amounts to 120-124 g. It is fractionally distilled at atmospheric pressure through an effi-... 

Potassium nitronates, 950 Potassium nitrosodisulfonate, 940-942 Potassium permanganate, 713, 942-952 Potassium peroxymonosulfate. 952 Potassium persulfate, 952-954 silver-catalyzed, 954 Potassium phenoxide, 300 Potassium-sodium tartrate, 36 Potassium thiocyanate, 199, 378, 954 Potassium thiolacetate, 356,955-956 Potassium triacetylosmate, 955 Potassium triphenylmethide, see Triphenyl-methyl potassium Prednisolone, 997 21-acetate, 604... 

S-Acetylation. Thiolacetic acid, or an aqueous solution of the sodium salt, has been used for S-acetylation of coenzyme A = and of pantetheine. A Merck group ... 

Nucleophilic substitution of the halo sugars occurs with such strong nucleophiles as potassium hydrogen sulfide, potassium hydrogen sele-nide, sodium thiosulfate, potassium thiolacetate, potassium methane-thioxide, and sodium azide. If internal attack is not possible, and in favorable cases, substitution occurs with such weaker nucleophiles as ammonia, hydrazine, nitrate ion, and fluoride ion. ... 

The endo-methylsulfonyloxy groups of l,4 3,6-dianhydro-2,5-di-0-(methylsulfonyl)-D-mannitol (18, R = R = OMs) are readily displaced by sodium benzoate in N,N-dimethylformamide to give an L-iditol derivative,280 and by potassium thiolacetate in ethanol307 at 115°. As suggested by Cope and Shen,300 the thiolacetate formed very probably has L-ido stereochemistry (20, R = R = SAc), and is not the D-manno isomer originally proposed. 

A general procedure for synthesis of terminal episulfides of hexoses or hexitols consists in the action of potassium thiolacetate on an appropriately substituted 5,6-di-O-p-tolylsulfonyl derivative, followed by treatment of the resultant 6-(S-acetyl-6-thio-5-0-p-tolylsulfonyl derivative with cold, methanolic, sodium methoxide the reaction involves rearside attack on C-5 by the sulfur atom at C-6, to displace the p-tolylsulfonyloxy group with inversion.This procedure was used for the synthesis of 5,6-dideoxy-5,6-epithio-l,3 2,4-di-0-ethylidene-L-iditol (82), 5,6-dideoxy-5,6-epithio-l,2 3,4-di-0-isopropylidene-L-guUtol (83), and 5,6-dideoxy-5,6-epithio-1,2-0-isopropylidene-/3-L-idofuranose (84), from 1,3 2,4-di-0-ethylidene-... 

The S-alkylation of the sodium salt (72) of thiosaccharin is the basis of a new route to thiols from alkyl halides (Scheme 51). The conversion of alkyl halides (RX) to thiolacetates (RSCOMe), and hence to thiols by saponification, has been shown to be effected by a quaternary ammonium resin with thiolacetate as counterion. Thiolacetates are also available in one step from alcohols in... 

---