79977-63-2Relevant academic research and scientific papers
Polyhalogenated Bicycloocta-1,5,7-trienes, XI. - Preparation and Reactions of Bicycloocta-1,3,5-trien-7,8-diyl Sulfates
Roedig, Alfred,Ganns, Eva Maria,Ganns, Rainer
, p. 1982 - 1994 (2007/10/02)
The cyclic sulfates 4a, d and e were prepared from 1a, d and e with sulfuric acid at room temperature.At a higher temperature the diketones 3a or b are produced.Thermolysis of the sulfates at 180-200 deg C as well as acidic hydrolysis lead likewise to 3a or b.Alkaline hydrolysis, however, yields the phthalides 5a or b.Analogous reaction courses are observed with alkoholates yielding 5c, d, f, methanethiolate giving 5e, and secondary amines 8a-f.Contrary, with ammonia and primary amines the phenylglyoxylic amides 13a-f are formed.The other ring opening products 9a, b, 10, and 11 are obtained from 4a with phenolates under different conditions.In the reactions 4 -> 8 the intermediates 6 and 7 can be isolated, so that some general mechanistic interpretations are possible.
Polyhalogenated Bicycloocta-1,5,7-trienes, X. - Aromatizing Nucleophilic Substitutions and Rearrangements of Polyhalogenated 2,5-Diphenylbicycloocta-1,5,7-trienes
Roedig, Alfred,Ganns, Eva Maria
, p. 406 - 419 (2007/10/02)
Nucleophilic reagents attack 1b-d on the four-membered ring with aromatization of the six-membered ring by elimination of chlorine.With methoxide di- and tetrasubstituted products 4a,b and 5b are formed, with thiolates however compounds 8, 9, 10, and 11 with 1, 2, and 4 substituents can be obtained.The reaction of 1b-d with primary amines leads to the diimines 12 or monoimines 13, while secondary amines cause ring opening to 16 or formation of the aminophthalides 20. - Cyclooctatetraene rearrangement of 1b and c in formic acid or in the presence of Ag+ -ions is complicated by the competing thermal rearrangement 1b,c -> 2b,c and numerous by-products. 3b and c were isolated only in 15 and 10percent yield, respectively.The mechanism of the nucleophilic substitutions is discussed.
Polyhalogenated Bicycloocta-1,5,7-trienes, VIII Synthesis and Cyclodimerization of Polyhalogenated 2-Phenyl- and 2-Pentachlorophenyl Substituted Butenynes
Roedig, Alfred,Ganns, Eva Maria,Henrich, Christian,Schnutenhaus, Horst
, p. 1674 - 1684 (2007/10/02)
Starting material for the synthesis of the butenynes 1c-e is the aldehyde 4 which can be converted into 1c via 9 or 5 and 10 as well as into 1d via 8.In the four-step synthesis of 1e the decisive reaction is the perchlorination of the phenyl group in 6 to
