69278-45-1Relevant articles and documents
ANODIC FUNCTIONALIZATION OF OLEFINS IN ALCOHOLS IN THE PRESENCE OF HALIDE SALTS
Elinson, M. N.,Makhova, I. V.,Nikishin, G. I.
, p. 112 - 118 (2007/10/02)
Electrolysis of conjugated, unbranched arylolefins in the presence of alkali metal halides in alcohols affords 1-aryl-2-bromoketals in 60-90percent yields.Under these conditions, 2-methyl-1-phenylprop-1-ene is converted into 1-bromo-2-methyl-1-phenylprop-1-ene in 80percent yield, and arylolefins with no benzylidene hydrogens give 1-aryl-1-alkoxy-2-bromoalkanes.
Borderline between E1 and E2 Mechanisms. Bimolecular Base-Promoted Elimination via Ion Pairs Competing with Concerted E2 Elimination
Thibblin, Alf
, p. 5412 - 5416 (2007/10/02)
The solvolysis of 2-chloro-2-methyl-1-phenylpropane (1) in methanol or in 25 vol percent acetonitrile in water at 25 deg C yields substitution product 2 (ether or alcohol) and the two elimination products 3 and 4.The olefin fraction in the aqueous solution does not increase significantly in the presence of 0.75 M sodium hydroxide.In methanol, on the other hand, the fraction of 3 and 4, the ratio /, and the rate of disappearance of 1 increase with methoxide ion concentration.The kinetic isotope effects (k12H + k13H + k14H)/(k12d2 + k13d2 +k14d2) = 1.41 and 1.42, measured for the solvolysis of the dideuterated analogue d2-1 in water/acetonitrile and in methanol, respectively, are too large to be secondary effects on a rate-limiting ionization step, but they suggest reaction via a reversibly formed carbocationic intermediate.The solvolysis of the hexadeuterated analogue d6-1 exhibits "normal" secondary kinetic isotope effects, (k12H + k13H + k14H)/(k12d6 + k13d6 + k14d6) = 1.79 and 1.81 in water/acetonitrile and methanol, respectively.The presence of 2 M NaOMe increases the isotope effect for d2-1 to 2.4 but decreases the effect for d6-1 to 1.35.These results indicate that 3 is formed by a parallel methoxide-promoted one-step concerted rout (E2) and that such a route is not significant for the formation of 4.The isotope effect for the E2 reaction is estimated as kH/kd2 = 4.9 (on the basis of the assumption that the elimination product ratio / for the carbocationic route is not affected by MeO(1-)).
The Anomalous Reaction of p-Methoxy-β,β-dimethylstyrene with Mercury(II) Acetate in Methanol
Norris, Robert K.,Wright, Timothy A.
, p. 2161 - 2167 (2007/10/02)
The methoxymercurations of β,β-dimethylstyrene (7) and its p-nitro (12) and p-methoxy (13) derivatives with mercury(II) acetate in methanol are regiospecific and give methoxymercuration products in which the methoxy group is on the β-carbon.Demercuration of the adducts from (12) and (13) with alkaline borohydride proceeds normally, but the demercuration of the adduct from (7) gives considerable formation of the diastereoisomeric dimeric products (9a,b).The methoxymercuration product from (13) is surprisingly reactive and gives mercury(I) acetate and the vicinal diether 1,2-dimethoxy-1-(p-methoxyphenyl)-2-methylpropane (17)