Thiolysis

The thiolysis of halogenopyrimidines is a valuable route to pyrimidine-2(and 4/6)-thiones and to extranuclear thiols but it fails with 5-halogenopyrimidines. The process may be... 

Pyrimidin-4-amine, N-butyI-2,6-dimethyI-synthesis, 3, 130 Pyrimidin-4-amine, 6-chloro-thiolysis, 3, 101... 

Pyrimidine, 4-efaloro-2-metfayltfaio-thiolysis, 3, 102 Pyrimidine, 5-cyano-synthesis, 3, 129 Pyrimidine, 4,6-dibenzyloxy-hydrolysis, 3, 91 Pyrimidine, diefaloro-aminolysis, 3, 99 Pyrimidine, 2,4-diefaloro-aminolysis, 3, 99 Pyrimidine, 4,6-diefaloro-aleofaolysis, 3, 100 aminolysis, 3, 99... 

Thiolysis, Alkanethiolysis, Arenethiolysis, or Arenesulfinolysis of Nuclear Halogenoquinoxalines... 

Of these processes, thiolysis appears to have been unused in recent years perhaps because the resulting mercaptoalkyl products are very prone to aerial oxidation. The following examples illustrate procedures that afford sulfides or sulfones. 

Most tautomeric quinoxalinethiones hae been made by primary synthesis (see Chapter 1), by thiolysis of halogenoquinoxalines (see Section 3.2.3), or by thiation of quinoxalinones (see Section 4.1.2.1) most nontautomeric quinoxalinethiones by primary synthesis (see Chapter 1) or by thiation of the corresponding quinoxalinones (see Section 4.5.2) and an occasional extranuclear quinoxalinethiol by... 

Crude 2,3(1//, 4//)-Quinoxalinedithione [prepared by thiolysis of 2,3-dichloro-quinoxaline (see Section 3.2.3)] gave 2,3-bismethylthioquinoxaline (10)... 

A direct conversion of the oxazoline (44) to the thiazoline (45) can be achieved by the thiolysis of the oxazoline (44) with H2S in methanol in the presence of triethylamine followed by cyclodehydration with Burgess reagent. This method is essentially free from racemisation and has been used in the transformation of peptide substrates <95TL6395>. 

Thiolysis by NaSR under the same conditions gave N3P3F5SR (R = Me or Ph). Ligand-exchange reactions between a series of organo-substi-tuted cyclotriphosphazatrienes have been studied and their synthetic potential demonstrated. Typical of these reactions is ... 

Reactions Where the DNA Base Serves as a Leaving Group Thiolysis,... 

Shaltiel, S. (1967) Thiolysis of some dinitrophenyl derivatives of amino acids. Biochem. Biophys. Res. Comm. 29, 178. 

Fatty acids are degraded by two-carbon units in a reverse manner analogous to their biosynthesis. The acyl-CoAs are first dehydrogenated to a,(3-unsaturated acyl-CoA, and then hydrated to (3-hydroxyacyl-CoA, followed by oxidation to (3-ketoacyl-CoA. The C-C bond between C-2 and C-3 of the latter compound is broken by a free CoA molecule via thiolysis to form an acyl-CoA that is two carbons shorter and acetyl-CoA. Unlike fatty acid biosynthesis, each step of the (3 oxidation of fatty acids is... 

Thiolysis of p-nitrophenyl acetate Synthetic vesicles prepared by injection. Rates compared with those in aq.CTABr Cuccovia et al., 1979... 

Thiolysis ofp-nitrophenyl octanoate Synthetic vesicles of DODAC1. Very large rate enhancements due to increased reactant concentration in the vesicles Cuccovia et al., 1982... 

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