Thiols, allyl

Methanethiol and other, lighter alkyl thiols are fairly common air pollutants that have ultragarlic odors both 1- and 2-butanethiol are associated with skunk odor. Gaseous methanethiol is used as an odorant leak-detecting additive for natural gas, propane, and butane it is also employed as an intermediate in pesticide synthesis. A toxic, irritating volatile liquid with a strong garlic odor, 2-propene-l-thiol (allyl mercaptan) is a typical alkenyl mercaptan. Benzenethiol (phenyl mercaptan) is the simplest of the aryl thiols. It is a toxic liquid with a severely repulsive odor. 

Methy. I -propane-thiol (Isobutyl mercaptan) 2-Propene-l-thiol (Allyl mercaptan)... 

Fouassier J P, Allonas X, Burget D, (2003) Photopolymerization of thiol-allyl ether and thiol acrylate coatings with visible light photosensitive systems. Progress in Organic Coatings 47 16-36... 

TEP involves a stoichiometric reaction of a multifunctional olefin and a multifunctional thiol (e.g. thiol-vinyl ether, thiol-allyl ether, thiol-acrylate and thiol-yne). The reaction is a step-growth addition of the thiol to the double bond [1.46a]-[ 1.46c] formation of a thiyl radical, addition of the thiyl to the ene structure, regeneration of a thiyl, etc. termination occurs through recombination and disproportionation reactions. 

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],... 

Quinoline 2-thiols are excellent precursors for construction of this ring system. Thus, allylation or vinylation of quinoline thiol 640 gave 2-vinylthioquinolines 641 or 2-allylthioquinolines 642 which were... 

Synthesis of thiopheno[3,4-c isoxa2olide is shown in Eq. 4.4, in which the Michael addidon of allyl thiol to fi-nitro enones and subsequent nitnle oxide cyclizadon are involved. ... 

Some typical transfer constants for allyl sulfides are given in Table 6.7. The values of Clt for these reagents are less dependent on the particular monomer than those for halocarbons (Table 6.2) or thiol transfer agents (Table 6.4). The low transfer constant of 32 demonstrates the importance of the activating group Z (cf. 11). 

A small library of highly functionalized pyrrolines 95 was synthesized by reaction of allylic and propargylic isocyanides 94 with thiols followed by radical cyclization (Scheme 33). The radical reaction was carried out using a radical initiator (AIBN) under flash heating microwave irradiation [67]. 

---