40650-73-5Relevant academic research and scientific papers
Gold(I)-Catalyzed Intramolecular C(sp3)?H Insertion by Decarbenation of Cycloheptatrienes
Yin, Xiang,Zuccarello, Giuseppe,García-Morales, Cristina,Echavarren, Antonio M.
supporting information, (2019/05/29)
A novel synthesis of indanes and dihydronaphtalenes based on the intramolecular insertion into C(sp3)?H bonds of gold(I) carbenes generated by retro-Buchner reaction (decarbenation) has been developed. Deuterium-labeling and kinetic isotope effect experiments, DFT calculations, and generation of the proposed carbene intermediate from a well-characterized gold(I) carbenoid support the involvement of a three-center concerted mechanism for the C(sp3)?H functionalization process.
The photochemical rearrangement of 1,2-dihydronaphthalenes into 1,4-dihydronaphthalenes induced by amines
Cuppen, Th. J. H. M.,Berendsen, N.,Laarhoven, W. H.
, p. 168 - 171 (2007/10/02)
The synthetic usefulness of the deprotonation/protonation reaction of excited 1,2-dihydronaphthalenes into 1,4-dihydronaphthalenes induced by amines has been investigated using 13 different substituted 1,2-dihydronaphthalenes and related compounds.The yield of the rearrangement ranges from 5 to 96percent.The formation of side-products depends on the position of protons in the substrate, which can be abstracted by the amine, and on competitive photoreactions.
The Metal-Ammonia Reduction of Mono- and Dinaphtylbenzenes
Marcinow, Zbigniew,Rabideau, Peter W.
, p. 3812 - 3816 (2007/10/02)
The metal-ammonia reduction of 1- and 2-phenylnaphthalene (9 and 10, respectively), 1,3-bis(1-naphthyl)benzene (5), 1,3-bis(2-naphthyl)benzene (6), 1,4-bis(1-naphthyl)benzene (7), and m-quinquephenyl (8) has been investigated. 9 affords a mixture of isomeric dihydro products together with 1-phenyl-1,2,3,4-tetrahydronaphthalene, and the effect of metal, temperature, and quenching methods on the product distribution is reported. 10 provided only a single dihydro (1,4-)isomer plus a tetrahydro product. both 5 and 7 provided a number of dihydro, tetrahydro, hexahydro, and octahydro products.On the other hand, 6 afforded high yields of a single tetrahydro product with lithium, and exclusively an octahydro product when 5-7 mol of sodium was used.In contrast to the terphenyls, which seem to have a propensity for inner-ring reduction, none of the naphthyl benzenes showed any tendency to reduce in the central benzene ring. m-Quinquephenyl reduced in two rings with no evidence for reduction in the central or outer rings.
Thermolysis of Phenyl-substituted 1,2-Dihydronaphthalenes. Evidence for Diphenylbutadienes as Intermediates
Lamberts, Joseph J. M.,Cuppen, Theo J. H. M.,Laarhoven, Wim H.
, p. 1819 - 1828 (2007/10/02)
The thermal rearrangement of the four phenyl-substituted 1,2-dihydronaphthalenes (15), (16), (19), and (20) have been studied by flash vacuum pyrolysis (FVP).By using the deuteriated starting compounds -(15) and -(16), it has been established that 1- and 4-phenyl-1,2-dihydronaphthalene (15) and (19) and 2- and 3-phenyl-1,2-dihydronaphthalene (16) and (20) are interconverted via the intermediates 1- and 2-phenyl-2,3-dihydronaphthalene (17) and (18), respectively, through two consecutive, sigmatropic 1,5-hydrogen shifts.In both processes partial oxidation to the corresponding phenylnaphthalenes (21) and (22) takes place.The deuterium distribution in the pyrolysis products suggests that in the hot zone diphenylbutadienes are formed, which are reconverted into phenyldihydronaphthalenes upon reaching the cold receiving flask.By FVP of 4-(p-tolyl)-1,2-dihydronaphthalene (34), 1-phenyl-1-(p-tolyl)butadiene (39), and 1-phenyl-4-(p-tolyl)butadiene (45) the latter type of interconversion could be confirmed.
Thermochemistry of Phenyl-Substituted Benzobicyclohex-2-enes
Lamberts, Joseph J.,Laarhoven, Wim H.
, p. 100 - 106 (2007/10/02)
The thermal rearrangements of benzobicyclohex-2-ene (21) and its phenyl-substituted analogues 22-25 (Scheme V) as models of sterically constrained phenylcyclopropanes have been studied by means of flash vacuum pyrolysis.In most cases the major pathway was cleavage of the "internal" C(1)-C(5) cyclopropane bond followed by a 1,2-hydrogen or a 1,2-phenylshift in the resulting biradical.For 6-phenylbenzobicyclohex-2-ene (25), substantial cleavage of the "external" C(1)-C(6) cyclopropane bond was observed, the phenyl substitution pattern being favorable for stabilization of the resulting biradical 62.Phenyl-substituted 1,2-dihydronaphthalenes 44, 47, 51, and 55 are among the major products.Comparison of the plots of the pyrolysis product composition of the 1,2-dihydronaphthalenes vs. pyrolysis temperature with similar plots of the title compounds (22-25) suggested that some of the minor products, viz., the 1,2-divinylbenzenes 31, 42, and 49, are formed via carbenes 30, 41, 50, 57, and 61 rather than via biradicals.Especially at higher pyrolysis temperatures, a large amount of an oxidation product, viz., 1- or 2-phenylnaphthalene (48 or 54), is formed.
Photochemistry of Phenyl-Substituted Benzobicyclohex-2-enes. A Reverse Di-?-methane Rearrangement
Lamberts, Joseph J. M.,Laarhoven, Wim H.
, p. 2202 - 2206 (2007/10/02)
The photochemical rearrangements of phenyl-substituted benzobicyclohex-2-enes can generally be explained by assuming that homolytic fission of that cyclopropane bond which leads to the most stable diradical is the primary step.The final products are formed by 1,2 hydrogen shifts in the intermediate.An exception to this general pattern was observed with 5-phenylbenzobicyclohex-2-ene (5).The photoproducts of 5 could only be explained by assuming reverse di-?-methane rearrangements followed by 1,3 hydrogen shifts.It is argued that this reaction path is followed because of the high rate to the back-reaction of the homolytic bond fission of 5.
