4636-73-1Relevant articles and documents
Boule
, p. 517 (1968)
Cyclic amidine hydroiodide for the synthesis of cyclic carbonates and cyclic dithiocarbonates from carbon dioxide or carbon disulfide under mild conditions
Aoyagi, Naoto,Furusho, Yoshio,Endo, Takeshi
supporting information, (2019/12/09)
Hydroiodides of amidines can catalyze the reaction of carbon dioxide and epoxides under mild conditions such as ordinary pressure and ambient temperature, and the corresponding five-membered cyclic carbonates were obtained in high yields. The reaction of epoxide with carbon disulfide was also examined under the same conditions. Detailed investigation showed that the catalytic activity was highly affected by the counter anions of the amidine salts; the iodides were effective catalysts for both of the reaction of epoxide with carbon dioxide and carbon disulfide, whereas the bromide, chloride and fluoride counterparts exhibited almost no catalysis.
Deciphering a 20-Year-Old Conundrum: The Mechanisms of Reduction by the Water/Amine/SmI2 Mixture
Maity, Sandeepan,Hoz, Shmaryahu
, p. 18394 - 18400 (2015/12/24)
The reaction of SmI2 with the substrates 3-methyl-2-butanone, benzyl chloride, p-cyanobenzyl chloride, and anthracene were studied in the presence of water and an amine. In all cases, the water content versus rate profile shows a maximum at around 0.2 M H2O. The rate versus amine content profile shows in all cases, except for benzyl chloride, saturation behavior, which is typical of a change in the identity of the rate-determining step. The mechanism that is in agreement with the observed data is that electron transfer occurs in the first step. With substrates that are not very electrophilic, the intermediate radical anions lose the added electron back to samarium(III) relatively quickly and the reaction cannot progress efficiently. However, in a mixture of water/amine, the amine deprotonates a molecule of water coordinated to samarium(III). The negatively charged hydroxide, which is coordinated to samarium(III), reduces its electrophilicity, and therefore, lowers the rate of back electron transfer, which allows the reaction to progress. In the case of benzyl chloride, in which electron transfer is rate determining, deprotonation by the amine is coupled to the electron-transfer step.