37480-21-0Relevant articles and documents
Acid-catalyzed solvolysis of allylic ethers and alcohols. Competing elimination and substitution via a thermodynamically 'stable' carbocation
Pirinccioglu, Necmettin,Thibblin, Alf
, p. 6512 - 6517 (1998)
Specific acid-catalyzed solvolysis of 1-methoxy-1,4-dihydronaphthalene (1-OMe) or 2-methoxy-1,2-dihydronaphthalene (2-OMe) in 25 vol % acetonitrile in water yields mainly the elimination product naphthalene, which is accompanied by a trace of 2-hydroxy-1,2-dihydronaphthalene (2-OH). No intramolecular rearrangement or formation of the alcohol 1-OH from 1-OMe was found. The nucleophilic selectivity between added azide ion and solvent water was measured as k(N3)/k(HOH) = 2.1 x 104 (ratio of second-order rate constants). The results indicate a relatively stable benzallylic carbocation toward trapping by nucleophiles (k(w) = 1 x 107 s-1). However, the elimination-to-substitution ratio with solvent water as base/nucleophile is large. Thus, in contrast to other carbocations of similar reactivity toward nucleophiles, the barrier to dehydronation is very low, k(e)= 1.6 x 1010 s-1, and accordingly, this step does not show any catalysis from added general bases. The heats of reaction of the solvolytic eliminations of 1-OH and 2-OH are ΔH = -23.7 and -18.4 kcal mol-1, respectively, as measured by microcalorimetry.
REACTION OF EPOXYTETRALENES WITH n-PROPYLLITHIUM
Marks, Krystyna,Prajer-Janczewska, Lidia
, p. 1037 - 1042 (2007/10/02)
Reactions of 1,2- and 2,3-epoxytetralenes with n-propyllithium were investigated.After isomerization of 2,3-epoxy compound an unsaturated alcohol, 1,2-dihydro-2-hydroxynaphthalene was obtained. 1,2-Epoxytetralene yielded a hydrocarbon, 1-n-propyl-1,4-dihydroxynaphthalene.The structures of the obtained compounds were determined by the chemical methods and by IR and 1H NMR spectroscopies.
