1- Allyl-2-mercapto

Known active constituents of garlic (there are at least 35 other constituents whose actions are unknown) ajoene, allicin, aliin, allixin, allyl mercaptan, allyl methyl thiosulfmate, allyl methyl trisulfide, allyl propyl disulfide, diallyl disulfide, diallyl hepta sulfide, diallyl hexa sulfide, diallyl penta sulfide, diallyl sulfide, diallyl tetra sulfide, diallyl tri sulfide, dimethyl disulfide, dimethyl trisulfide, dirpopyl disulfide, methyl ajoene, methyl allyl thiosulfmate, propyline sulfide, 2-vinyl-4H-l, 3-tithiin, 3-vinyl-4H-1, 2dithiin, S-allyl cysteine sulfoxide, S-allyl mercapto, cysteine. 

Cycloalliin Cysteine -S-allylcysteine -S-allyl-mercapto cysteine Cysteine sulfoxides 5-glutamyl cysteines Cystine... 

Aqueous extracts of raw garlic also inhibited cyclooxygenase activity in rabbit platelets, again contributing to an antithrombotic effect. In addition, AGE and S-allyl cysteine and S-allyl mercapto-cysteine have antiplatelet adhesion effects. Platelet adhesion to the endothelial surface is involved in atherosclerosis initiation. Furthermore, S-allyl mercaptocysteine inhibits the proliferation of rat aortal smooth muscle cells, another important... 

Alkyl-(2-mercapto-athyl)-benzyl- 247 Alkyl-phenyl- 259 Allyl- 118, 579 Allyl-benzyl- 350 Allyl-butyl-(3-oxo-butyl)- 659 Aryl- 498, 536, 568... 

The supported aqueous phase methodology was applied to the system Pd(OAc)2/5 TPPTS, a catalytic precursor for the Trost-Tsuji reaction. The characterization of the solid by 31P MAS NMR confirms the presence of Pd°(TPPTS)3 as the main surface species. The catalytic properties of the solid were tested for the allylic substitution of E-cinnamylethylcarbonate by different nucleophiles such as ethyl acetoacetate, dimethyl malonate, morpholine, phenol, and 2-mercapto-pyridine. The absence of palladium leaching was demonstrated, and having solved the problem of water leaching from the solid to the organic phase, the SAP-Pd catalyst was successfully recycled several times without loss in its activity. It was used in a continuous flow experiment which... 

Fused heterocyclic systems derived from 3-mercapto-l,2,4-triazole can be obtained by heterocyclization of 4-allyl-l,2,4-triazole-3-thione derivatives by treatment with halogens or mineral acids <1996T791>. Compounds 342 react with bromine yielding thiazolium halides 28 in good yield (Equation 64) <2000RJOC1033>. 

Ohne Kondensationshilfsmittel cyclisieren l-(2-Acetamino-phenyl)-3-allyl-thioharnstoffe ther-misch beim Erhitzen iiber den Schmelzpunkt zu 2-Mercapto-benzimidazolen91. 

Mercapto-benzimidazol (und ahnliche ambidente Nukleophile) werden mit Kohlensaure-al-lylestern thermodynamisch kontrolliert am S-Atom angegriffen, wenn man das thiophile Palladium ) als Katalysator einsetzt. Mit 3-Ethoxycarbonyloxy-l-phenyl-propen II erhalt man 2-(3-Phenyl-allylthio)-benzimidazol (III 36%), mit 2 Aquivalenten an II l-(3-Phenyl-allyl)-2-(3-phenyl-allyIthio)-benzimidazol (IV 52%) neben einer geringen Menge l,3-Bis-[3-phenyl-allyl)-2-thiono-2,3-dihydro-benzimidazol (V 7%)378. 

Mercapto-benzimidazol wird von Allyl-bromid in Gegenwart von Natriumhydrogencarbonat zunachst am S-Atom zu 2-Allylthio-benzimidazol (60%) alkyliert. Beim Erwarmen wandert der Allyl-Rest (Claisen-Umlagerung) vom S- zum N-Atom, und man erhiilt l-Allyl-2-mer-capto-benzimidazol (50% Schmp. 115—117°)372. 

Thiazolidine-2-thione, 3-allyl-, 56, 79 2-Thiazohne, 2-allylthio-, 56, 77 2-Thiazoline, 2-benzylthio-, 56, 82 2-Thiazoline, 2-cmnamylthio-, 56, 82 2 Thiazoline, 2 ethylthio, 56, 82 2-Thiazohne 2-mercapto-, 56, 77 2-Thiazoline, 2-methylthio-, 56, 82 2-Thiazohne, 2-(4-phenyl-l-buten-3-yl)-thio-, 56, 78... 

Alkenylthiophenes and alkenylbenzo[6]thiophenes are most readily obtained by dehydration of the corresponding alkanols, obtained by reduction of the appropriate acyl derivatives (equation 12 Sections 3.14.2.4, 3.15.9.2.3). Allyl derivatives can be obtained by coupling a suitable allyl halide with the appropriate thienyllithium derivatives (Section 3.14.2.4). An unusual direct synthesis of 3-vinylthiophenes by ring closure of a-mercapto-aldehydes or -ketones with 1,3-butadienyl-l-triphenylphosphonium salts (386) gives satisfactory yields (equation 13) (75CJC3526). 

An interesting cleavage of a carbon-sulfur bond in benzylic and allylic sulfides derived from 5-mercapto-l -phenyl-1 //-tetrazole has been reported [326]. The overall reaction is an alkylation a to a carbonyl group. 

The 1,1-dioxide of 3-halomethyl-2,3-dihydropyrido[l,2,3-de]-l,4-benzo-thiazinium triiodide and bromide were prepared by cyclization of 8-allyl-sulfonylquinoline with I2 in 2-PrOH, and with Br2 in CHCI3 (93MI9). When 8-[(l-chloro-2-mercapto-2-propyl)thio]quinoline HC1 was left to stand in EtOH at 20°C 2-mercapto-2-methyl-2,3-dihydropyrido[l,2,3-de]-l,4-benzothiazinium chloride was obtained (94ZOR636). 8-[2-Chloro-l-(un)-substituted ethylthio]quinolines could easily cyclized to 2,3-dihydropyrido-... 

In the morphinan series, the preparation of 3-alkyl-morphinans222 and 3-mercapto-morphinans223 has been described. In the benzomorphan series, a novel cleavage of aryl benzyl ethers and of aryl allyl ethers has been described and used in an improved synthesis of pentazocine. The lactam (162), on hydrogenolysis, gives the benzomorphan (163 R1 = R2 = H). Treatment of this with dimethylallyl... 

Mercapto-pyridine Allyl bromide Cationic effect... 

Testosterone. A 4-Chloro 17-acetate (S-114), 4-bromo (S-8), 4-methyl (S-11), 4-chloro 11/3-hydroxy 17-acetate (S-7), 4-fluoro 17-acetate (S-9), 4-hydroxy 17-acetate (S-10), la-methyl 4-chloro 17-acetate (S-79), 4-chloro 17-propionate (S-6), 4-hydroxy 17a-methyl (S-16), 4-chloro Ha-methyl (S-17), 4-mercapto 17a-methyl (S-49), 4-methylthio 17a-methyl (S-50), 4-ethylthio 17a-methyl (S-51), 4-acetylthio 17a-methyl (S-52), and 4-chloro 11/3-hydroxy 17a-methyl (S-102) substitutions all decrease the androgenic property. However, the anabolic potency is only slightly decreased and in a few cases increased, such as S-114, S-11, S-16, S-6. Substitution at the 4-position by bulky substituents i.e., 4-ethyl (S-13) and 4-allyl (S-14), abolishes both activities. 

Related reactions involve the alkylation, allylation or tenzylation of (i) a,a-di(Aio)alkylmagnesium halides, resulting from the thiophilic addition of Grignard reagents on dithioesters (Scheme 55, entry 5).259.260 (li) 2-lithio-l,3-benzodithioles (Scheme 55, entry d) " (iii) 2-aryl-2-lithio-l,3-dithiolanes and 2-lithio-l,3-dithianes derived from die l,2-dimethyl-4,5-di(mercapto)methylbenzene (Scheme 55, entry c) ( 3,264... 

Trost and coworkers developed a chiral zinc phenoxide for the asymmetric aldol reaction of acetophenone or hydroxyacetophenone with aldehydes (equations 62 and 63) . This method does not involve the prior activation of the carbonyls to silyl enol ethers as in the Mukaiyama aldol reactions. Shibasaki and coworkers employed titanium phenoxide derived from a phenoxy sugar for the asymmetric cyanosilylation of ketones (equation 64). 2-Hydroxy-2 -amino-l,l -binaphthyl was employed in the asymmetric carbonyl addition of diethylzinc , and a 2 -mercapto derivative in the asymmetric reduction of ketones and carbonyl allylation using allyltin ° . ... 

Alkylation of the sodium salt of 152 with allyl bromide in DMSO afforded the 3-S-allyl 160 (R = H), which underwent a thio-Claisen rearrangement in the presence of p-toluenesulfonic acid to give 2-allyl-3-mercapto 161 (R = H) that cyclized partially during purification to hexahydrothiophene 162 (R = H). Alternatively, acetylation of 161 (R = H) gave 163, which cyclized on heating in quinoline to afford 162 (R = H). Similarly, 2-butenyl 160 (R = Me) gave 161 (R = Me) but the... 

However, the addition occurs contrary to the Markovnikov rule under irradiation by ultraviolet light or in the presence of peroxides 1 for instance, allyl-amine hydrochloride or a derivative thereof in alcoholic solution is thiolated by an excess of hydrogen sulfide under UV-irradiation, exclusively (yields up to 57%), to give 3-aminoalkanethiols.2 Addition of hydrogen sulfide is of use in the laboratory only when the reaction can be carried out in the liquid phase and is then preferably effected under the influence of a basic catalyst Dahl-bom,3 for instance, obtained 3-mefcapto-butyric acid from crotonic acid hydrogen sulfide in the presence of diethylamine in a closed vessel at 70° and 4-mercapto-4-methyl-2-pentanone is obtained in 80% yield from mesityl oxide and hydrogen sulfide with triethylamine as catalyst.4... 

Mercapto-3-pentanone and other thiols have also been added to styrene, 2-methyl-2-butene, 1-methyl-1-cyclohexene, and olefins containing functional groups38 such as vinyl chloride, 1-chlorocyclohexene, 2-chlorocrotonaldehyde, allylamine, allyl alcohol, bromide and chloride, and cinnamyl alcohol. 

Pyrimidine-fused Systems. - Starting from 5-allyl-6-mercapto-... 

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