16103-56-3

Upstream product

• 75-62-7 Bromotrichloromethane 
• 529477-74-5 N-(1-pentoxy)-5-(p-methoxyphenyl)-4-(methyl)thiazole-2(3H)-thione 
• 195213-54-8 4-(p-chlorophenyl)-N-(1-pentyloxy)thiazole-2(3H)-thione 
• 1215314-43-4 4-methyl-3-(pentyloxy)-5-phenylthiazole-2(3H)-thione 

Downstream Products

• 96-47-9 2-methyltetrahydrofuran 
• 59353-62-7 4-bromo-1-phthalimidopentane 

Relevant academic research and scientific papers

Efficiency of alkoxyl radical product formation from 5-substituted 3-alkoxy-4-methylthiazole-2(3H)-thiones

In a comparative study, reactions between 5-(p-methoxyphenyl)-substituted 3-alkoxy-4-methylthiazole-2(3H)-thiones and appropriate mediators (BrCCl3, Bu3SnH) provided higher yields of alkoxyl radical products (δ-bromohydrins, cyclic ethers, carbonyl compounds) than respective transformations of 5-phenyl- and 5-methyl-substituted derivatives. The unusual selectivity of applied thiohydroxamates to furnish products of O-alkylation, even upon treatment with soft carbon electrophiles, and the marked propensity of 3-alkoxy-5-(p-methoxyphenyl)-4-methylthiazole-2(3H)-thiones to crystallize, facilitated preparation and purification of the new family of alkoxyl radical precursors in a noteworthy manner.

Microwave-assisted generation of alkoxyl radicals and their use in additions, β-fragmentations, and remote functionalizations

Microwave irradiation (2.45 GHz, 300-500 W) of N-(alkoxy)thiazole-2(3H)- thiones in low-absorbing solvents affords alkoxyl radicals, which were identified by (i) spin adduct formation (EPR-spectroscopy) and (ii) fingerprint-type selectivities in intramolecular additions (stereoselective synthesis of disubstituted tetrahydrofurans), β-fragmentations (formation of carbonyl compounds), and C,H-activation of aliphatic subunits, by δ-selective hydrogen atom transfer. C-Radicals formed from oxygen-centered intermediates were trapped either by Bu3SnH, l-cysteine ethyl ester, the reduced form of glutathione (reductive trapping), or by bromine atom donor BrCCl3 (heteroatom functionalization) The results suggest that microwave activation is superior to UV/Vis-photolysis and conductive heating for alkoxyl radical generation from N-(alkoxy)thiazolethiones. It offers by far the shortest reaction times along with the option to reduce the amount of trapping reagent significantly. The Royal Society of Chemistry 2006.