Thiols sulfide preparation from

Benzothiazolyl alkyl sulfides, prepared from the corresponding alcohols, are easily desulfurized (87-99%) by TBTH-AIBN. This reaction constitutes a good indirect deoxygenation of alcohols. Desulfurization of dithioketals may be controlled. Thus 1,3-dithiolanes with 1 mol equiv. of TBTH lead to 3-alkyl (or 3-aryl) thiols (64-82%), while 4 mol equiv. of TBTH leads to the completely desulfurized derivative. Desulfurization of heterocyclic thiones is also performed with this reagent. In passing, it should be noted that generation of radicals from C—S bonds and tin hydrides in the presence of radical initiators is of large synthetic interest. ... 

We have noted that this derivative is readily oxidized (either by air or iodine) to disulfide 36 which can be converted back to 35 by reduction with LiAlH4. Sucrose mono-thiol 37, prepared from the monosilylated at the C6 ( fructose end ) derivative 24, was used for construction of C2-symmetrical disulfide 38. It could be readily oxidized to di-sulfide 38 (Scheme 8). °... 

Various S-nucleophiles are allylated. Allylic acetates or carbonates react with thiols or trimethylsilyl sulfide (353) to give the allylic sulfide 354[222], Allyl sulfides are prepared by Pd-catalyzed allylic rearrangement of the dithio-carbonate 355 with elimination of COS under mild conditions. The benzyl alkyl sulfide 357 can be prepared from the dithiocarbonate 356 at 65 C[223,224], The allyl aryl sufide 359 is prepared by the reaction of an allylic carbonate with the aromatic thiol 358 by use of dppb under neutral condi-tions[225]. The O-allyl phosphoro- or phosphonothionate 360 undergoes the thiono thiolo allylic rearrangement (from 0-allyl to S -allyl rearrangement) to afford 361 and 362 at 130 C[226],... 

These sulfides are prepared from other sulfur protective groups by reaction with the sulfenyl chloride. The Npys group can also be introduced directly by treatment of the thiol with NpysCl. ... 

For example, polymers having hydroxyl end groups can be prepared by reaction of polymer lithium with epoxides, aldehydes, and ketones III-113). Carboxylated polymers result when living polymers are treated with carbon dioxide (///) or anhydrides (114). When sulfur (115, 116), cyclic sulfides (117), or disulfides (118) are added to lithium macromolecules, thiol-substituted polymers are produced. Chlorine-terminus polymers have reportedly been prepared from polymer lithium and chlorine (1/9). Although lithium polymers react with primary and secondary amines to produce unsubstituted polymers (120), tertiary amines can be introduced by use of p-(dimethylamino)benzaldehyde (121). 

Thiols have also been prepared from alcohols. One method involves treatment with H2S and a catalyst, such as Al203, but this is limited to primary alcohols. Another method involves treatment with Lawesson s reagent (see 16-10). When epoxides are substrates, the products are (3-hydroxy thiols. Tertiary nitro compounds give thiols (RNO2 —> RSH) when treated with sulfur and sodium sulfide, followed by amalgamated aluminum. ... 

The architecturally novel macrolide (+)-zampanolide was synthesized in the laboratory of A.B. Smith. The C8-C9 ( )-olefin moiety was constructed using the Kocienski-modified Julia oleHnation. The required PT-sulfone was prepared from the corresponding primary alcohol via a two-step protocol employing sequential Mitsunobu reaction and sulfide-sulfone oxidation. The primary alcohol and two equivalents of 1-phenyl-1 H-tetrazolo-5-thiol was dissolved in anhydrous THF at 0 °C and treated sequentially with triphenylphosphine and DEAD. The desired tetrazolo sulfide was isolated in nearly quantitative yield. 

Several thiols occur naturally for example, skunk secretion contains 3-methyll-butanethiol and cut onions evolve 1-propanethiol, and the thiol group of the natural amino acid cysteine plays a vital role in the biochemistry of proteins and enzymes (see Introduction, p. 2). Primary and secondary thiols may be prepared from alkyl halides (RX) by reaction with excess sodium thiolate (SN2 nucleophilic substitution by HST) or via the Grignard reagent and reaction with sulfur. Tertiary thiols can be obtained in good yields by addition of hydrogen sulfide to a suitable alkene. Thiols can also be prepared by reduction of sulfonyl chlorides (Scheme l).la,2a... 

Sulfides, or thioethers, are sulfur analogues of ethers, and like ethers they can be either symmetrical (R2S) or unsymmetrical (RSR1, where R and R are different). Sulfides can be prepared from alkyl halides by a Williamson-type synthesis with sodium hydrogen sulfide, sodium thiolate or sodium sulfide from alkyl or aryl halides via the Grignard reagent (11) from alkenes by radical-catalysed addition of thiols or by reduction of sulfoxides (Scheme 9).2b... 

The reaction has also been realized in the gas phase with sulfur being generated by mixing sulfur dioxide with hydrogen sulfide.27,28 This method seems to be very efficient for the preparation of aromatic and aliphatic compounds as well as the unsubstituted l,2-dithiole-3-thione. More complex l,2-dithiole-3-thiones such as 17 have also been prepared.28 4-Neopentyl-5-t-butyl-l,2-dithiole-3-thione has been prepared from triisobutylene and sulfur.29 1-Phenyl-1-propene does not give a simple thione in the reaction with sulfur, but thiol 18. The yield was raised by the presence of hydrogen sulfide and benzoyl peroxide.30... 

In the Massachusetts marsh, only inorganic sulfide and thiosulfate occur as the major reduced forms of sulfur over the depth profile. Although this could be related to a lack of sulfide oxidation, sulfate depletion is not very high in this core. Therefore, neither process is the more dominant biogeochemical process. Previous studies(ip, ) have not found evidence for thiols in this marsh even when sulfide oxidation was prevalent, addition, cores were prepared from this marsh for controlled microcosm experiments. In cores in which oxidation was Induced, thiols were not detected in the porewaters. 

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... 

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