7500-76-7Relevant articles and documents
Niobium Pentachloride Mediated (Hetero)aromatic Aldehyde Friedel-Crafts Hydroxyalkylation with Arenes: An Efficient Strategy to Synthesize Triarylmethanes
Baviera, Giovanni S.,Donate, Paulo M.,Matias, Alexandre A.,Previdi, Daniel,Rodrigues, Shirley M. M.
, p. 4498 - 4506 (2019/11/21)
Niobium pentachloride is an efficient and useful Lewis acid to conduct Friedel-Crafts hydroxyalkylation between arenes and (hetero)aromatic aldehydes, to generate triarylmethanes. This practical methodology offers several advantages, such as short reaction time, mild experimental conditions, and excellent yields.
Solventless triarylmethane synthesis via hydroxyalkylation of anisole with benzaldehyde by modified heteropoly acid on mesocellular foam silica (MCF)
Bhadra, Kalpesh H.,Yadav, Ganapati D.
, p. 150 - 158 (2018/06/18)
Triarylmethane (TRAM) compounds have wide applications such as leuco dyes for sensing tumors and other biological activities. Hydroxyalkylation of arenes with benzaldehyde results in formation of triarylmethane compounds. In the present study, 20 (wt.%) Cs2.5H0.5PW12O40 (Cs-DTP) supported on mesocellular foam (MCF) silica was prepared, characterized and tested for its activity in hydroxyalkylation reaction of anisole with benzaldehyde. Its activity was compared with commercial catalysts like Amberlyst-15, montmorillonite clay K-10, H3PW12O40 and unsupported Cs2.5H0.5PW12O40.The prepared catalyst showed the best activity compared to others with advantage of separation of catalyst and reusability. Reaction parameters were studied in detail and kinetic study was carried out for the said reaction. 20 (wt. %) Cs-DTP/MCF was found to be the best, robust and reusable catalyst. Reaction mechanism and kinetics were also studied. The results are new.
Triggering the approach of an arene or heteroarene towards an aldehyde via Lewis acid-aldehyde communication
Pratihar, Sanjay
, p. 2854 - 2865 (2016/03/12)
The present work reports a combined experimental/computational study of the Lewis acid promoted hydroxyalkylation reaction involving aldehyde and arene/heteroarene and reveals a mechanism in which the rate determining aldehyde to alcohol formation via a four-member cyclic transition state (TS) involves a transfer of hydrogen from arene/heteroarene C-H to aldehyde oxygen with the breaking of the C-H bond and formation of C-C and O-H bonds. The effect of different Sn(iv) derivatives on the hydroxyalkylation reaction from different in situ NMR and computational studies reveals that although the exergonic formation of the intermediate and its gained electrophilicity at the carbonyl carbon drive the reaction in SnCl4 compared to other Sn(iv) derivatives, the overall reaction is low yielding because of its stable intermediate. With respect to different aldehydes, LA promoted hydroxylation was found to be more feasible for an electron withdrawing aldehyde compared to electron rich aldehyde because of lower stability, enhanced electrophilicity gained at the aldehyde center, and a lower activation barrier between its intermediate and TS in the former as compared to the latter. The relative stability of the LA-aldehyde adduct decreases in the order SnCl4 > AlCl3 > InCl3 > BF3 > ZnCl2 > TiCl4 > SiCl4, while the activation barrier (ΔG#) between intermediate and transition states increases in the order AlCl3 4 3 3 4 2 4. On the other hand, the activation barriers in the case of different arenes/heteroarenes are in the order of indole 3, InCl3 and SnCl4 because they have negative free energy of formation (ΔG) for alcohol to the corresponding diaryl methyl carbocation.