3722-88-1Relevant academic research and scientific papers
Facile ring-closure cyclization of arenes by nucleophilic C-alkylation reaction in ionic liquid
Hong, Dong Jin,Kim, Dong Wook,Chi, Dae Yoon
scheme or table, p. 54 - 56 (2010/03/24)
A novel synthetic method using an ionic liquid (IL) for a six-membered ring-closure cyclization is described. The ring-closure cyclization by nucleophilic C-alkylation was achieved with various halo- and alkanesulfonyloxyalkyl aromatic compounds in high yields with minimal byproducts using ILs as the reaction media in the absence of any catalyst. For example, the cyclization of 2-(3-methanesulfonyloxy-propoxy)naphthalene (1a) to 2,3-dihydro-1H-naphtho[2,1-b]pyran (2) in IL [bmim][PF6] proceeded selectively at 150 °C for 24 h in 85% yield.
Photolyses of (3-Naphthoxypropyl)-, (4-Naphthylbutyl)-, and (4-Naphthyl-4-oxobutyl)cobaloxime
Tada, Masaru,Hiratsuka, Mitsunori,Goto, Hiroyuki
, p. 4364 - 4370 (2007/10/02)
The cobalt-carbon bond of the titled compounds is photochemically cleaved to generate an organoradical and a cobaloxime(II) radical pair. 3-(1- or 2-naphtoxy)propyl, 4-(1- or 2-naphthyl)butyl, and 4-(1-or 2-napthyl)-4-oxobutyl radicals thus formed undergo three types of reactions: (a) hydrogen abstraction to give a saturated terminal, (b) hydrogen elimination to give a terminal olefin, and (c) substitution on the naphthalene ring.In benzene and radicals follow process b exclusively (the radicals from (3-(2-napthoxy)propyl)cobaloxime (1a), (3-(1-napthoxy)propyl)cobaloxime (2a), and (4-(1-napthyl)butyl)cobaloxime (2 b)) or preferentially (the radicals from (4-(2-napthyl)butyl)cobaloxime (1 b), (4-(2-napthyl)-4-oxobutyl)cobaloxime (1c), and 4-(1-napthyl)-4-oxobutyl)cobaloxime (2c)).In chloroform, process a becomes important to the extent as the sum of the other two processes.In water-acetonitril (4:1), process c becomes important and even takes precedence of others for the radicals from 1b and 1c.This feature is accounted for by the folding of the side chain of hydrophobic radicals.Encapsulation of the radicals in β-cyclodextrin stimulates process c except for the case of the radical from 2c.In the case of cobaloxime 2c, α-cyclodextrin does not effect the partition process of the intermediate radical.This feature is accounted for by the shallow inclusion of the radical due to the hydrogen bonding as depicted in Figure 1d.
Mechanistic Studies of Photocyclizations of Vicinal Allylnaphthols: The Duality of Excited-State Proton-Transfer Complexes
Chow, Yuan L.,Zhou, Xue-Min,Gaitan, Tanis J.,Wu, Zheng-Zhi
, p. 3813 - 3818 (2007/10/02)
Photoexcitations of 2-allyl-1-naphthol and 1-allyl-2-naphthol caused cyclization, forming dihydrofuranyl and pyranyl ethers and the secondary photodehydrogenation of the dihydrofuranyl ethers.The quenching experiments of the product formations as well as fluorescence intensities of allylnaphthols by methanol, triethylamine, N-nitrosodimethylamine, and 1,3-dienes confirmed that the cyclization occurred from the singlet excited-state proton transfer (ESPT) of the phenolic group; i.e., kinetic acidity initiated photocyclization.The primary photoprocess is quenched mainly by a static quenching process arising from the ground-state hydrogen-bonding association between allylnaphthols and a quencher, as supported by IR spectroscopy, and to a minor extent by a dynamic quenching of the singlet excited state of the allylnaphthol intramolecular proton-transfer complexes.Kinetic analyses also reveal the presence of two identifiable intramolecular ESPT intermediates, probably conformers of the proton-transfer species; one is the precursor of the furanyl ethers and not quenchable in the dynamic process by Et3N, and the other that of the pyranyl ethers and quenchable in the dynamic process by Et3N.The IR absorption of intramolecular hydrogen bonds between the OH and olefin groups began to be replaced by that of intermolecular hydrogen bonds at tetrahydrofuran concentrations above 10-2 M; methanol, at about this concentration and above, also quenches the photocyclization.
