Ring Contraction Reaction

Section III contains a discussion of the electrolytic reactions in which a heterocyclic system is formed the reactions will be treated under the following headings ring formation reactions, ring contractions, and ring expansions. 

Ring Closure Reactions Ring Contractions Ring Expansions... 

When aromatic hydrocarbons are treated with aluminum chloride the autocondensation is accompanied by side reactions (ring contraction, partial hydrogenation, etc.) reactions of phenyl and naphthyl ethers are, however, smoother, and Scholl and Seer278 obtained good yields of 4,4 -diethoxy-l,l -binaphthalene from 1-ethoxynaphthalene and aluminum chloride in nitrobenzene. 

The reaction sequence is successful because reverse, ring-contraction reactions are unlikely and because only the final product contains a secondary lactam group, which is depro-tonated under the reaction conditions. 

Oxidative rearrangement takes place in the oxidation of the 1-vinyl-l-cyclo-butanol 31, yielding the cyclopentenone derivative 32[84], Ring contraction to cyclopropyl methyl ketone (34) is observed by the oxidation of 1-methylcyclo-butene (33)[85], and ring expansion to cyclopentanone takes place by the reaction of the methylenecyclobutane 35. [86,87]... 

Pyridazinones may undergo ring contraction to pyrroles, pyrazoles and indoles, the process being induced either by an acid or base. The structure of the final product is strongly dependent on the reaction conditions. For example, 4,5-dichloro-l-phenylpyridazin-6(lFT)-one rearranges thermally to 4-chloro-l-phenylpyrazole-5-carboxylic acid (12S), while in aqueous base the corresponding 4-hydroxy acid (126) is formed (Scheme 40). 

In a series of reactions with potassium amide in liquid ammonia, 6-chloropyrido[2,3-f)]pyrazine gave reduction and ring contraction (Section 2.15.13.3), the 6-bromo analogue underwent only reduction, whilst the 6-fluoro derivative gave only the 6-amino substitution product (79JHC305). 

The base-promoted ring contraction of 3-bromo-2-pyrones to 2-furoic acids cf. Scheme llOd) is a well exemplified reaction 01CB1992,69JCS(C)1950,73JCS(P1)1130> which has also been applied to the obtention of benzofuran-2-carboxylic acids frorn 3-bromocoumarins 08CB830,70KGS(S2)166), Similar base treatment of 3-amino-2-pyrones provides pyrrole-2-carboxylic acids (Scheme IlOe) 75JHC129). 

Schmidt reaction of ketones, 7, 530 from thienylnitrenes, 4, 820 tautomers, 7, 492 thermal reactions, 7, 503 transition metal complexes reactivity, 7, 28 tungsten complexes, 7, 523 UV spectra, 7, 501 X-ray analysis, 7, 494 1 H-Azepines conformation, 7, 492 cycloaddition reactions, 7, 520, 522 dimerization, 7, 508 H NMR, 7, 495 isomerization, 7, 519 metal complexes, 7, 512 photoaddition reactions with oxygen, 7, 523 protonation, 7, 509 ring contractions, 7, 506 sigmatropic rearrangements, 7, 506 stability, 7, 492 N-substituted mass spectra, 7, 501 rearrangements, 7, 504 synthesis, 7, 536-537... 

Oxadiazines herbicidal activity, 3, 1085 reactions with bases, 3, 1060 ring contraction, 3, 1065 ring opening, 3, 1061... 

Mannich reactions, 3, 21 polymers, 1, 288 ring contraction, 3, 29 Pyridazinones, amino-diazotization, 3, 35 reaction... 

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