REACTIONS OF CYCLO-OCTATETRAENE AND ITS DERIVATIVES .I. CYCLOOCTATETRAENE AS A DIENOPHILE

被引:13
作者
FRAY, GI
SMITH, DPS
机构
[1] Department of Organic Chemistry, The University
来源
JOURNAL OF THE CHEMICAL SOCIETY C-ORGANIC | 1969年 / 19期
关键词
D O I
10.1039/j39690002710
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Cyclo-octatetraene behaves as a dienophile towards tetrachlorocyclopentadienone acetals to form 1:2-adducts having the hexacyclo[12,2,1,15,8,02,13,03,10,0 4,9]octadeca-6,11,15-triene skeleton (V), probably via its valence tautomer, bicyclo[4,2,0]octa-2,4,7-triene, and intermediate 1:1-adducts thereof having the tetracyclo-[8,2,1,02,9,03,8]trideca-4,6,11- triene structure (VII). The 1:1-adduct (IIIa) of 1,2,3,4-tetrachloro-5,5- dimethoxycyclopentadiene and the dibromo-derivative of cyclo-octatetraene, when treated with concentrated sulphuric acid, yields the corresponding carbonyl-bridged compound (IIId) which then undergoes skeletal rearrangement to the αβ-unsaturated ketone (VIIIa); the transformation may be reversed by u.v. irradiation. Similarly, acid hydrolysis of the 2:1-adduct (Va) from the same tetrachlorocyclopentadienone acetal and cyclo-octatetraene is accompanied by rearrangement to the hexacyclo[8,5,2,14,7,02,9,0 3,8,011,15]octadeca-5,12,16-triene system (XVI).
引用
收藏
页码:2710 / &
相关论文
共 26 条
[1]   DIHYDROPYRIDAZINE AUS OLEFINEN UND 3.6-DICARBOMETHOXY-1.2.4.5-TETRAZIN [J].
AVRAM, M ;
NENITZESCO, CD ;
MARICA, E ;
DINULESCU, IG .
CHEMISCHE BERICHTE-RECUEIL, 1962, 95 (09) :2248-&
[2]   INTERCONVERSION OF 5-ARYLBICYCLO[2,2,1]HEPT-2-EN-7-ONES AND 6-ARYLBICYCLO[3,2,0]HEPT-3-EN-2-ONES BY ACID AND BY LIGHT [J].
BESFORD, LS ;
COOKSON, RC ;
COOPER, J .
JOURNAL OF THE CHEMICAL SOCIETY C-ORGANIC, 1967, (15) :1385-&
[3]  
BIANCHI G, 1967, CHIM IND-MILAN, V49, P757
[4]  
BROWN P, 1964, P CHEM SOC LONDON, P185
[5]  
BRUCK P, 1960, CHEM IND-LONDON, P405
[6]   CONDENSED CYCLOBUTANE AROMATIC SYSTEMS .2. DIHALO DERIVATIVES OF BENZOCYCLOBUTENE AND BENZOCYCLOBUTADIENE DIMER [J].
CAVA, MP ;
NAPIER, DR .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1957, 79 (07) :1701-1705
[7]   REACTIONS OF HEXACHLOROCYCLOPENTADIENE .3. 2'3'4'5'-TETRACHLORO-1,3-DIOXOLAN-2-SPIROCYCLOPENTA-2',4'-DIENES AND THEIR ADDUCTS [J].
CHANG, WH .
JOURNAL OF THE CHEMICAL SOCIETY, 1965, (APR) :2305-&
[8]  
CHRISTL M, 1968, TETRAHEDRON LETT, P5209
[9]   REARRANGEMENTS OF OXO-DICYCLOPENTADIENES [J].
COOKSON, RC ;
HUDEC, J ;
WILLIAMS, RO .
JOURNAL OF THE CHEMICAL SOCIETY C-ORGANIC, 1967, (15) :1382-&
[10]   REARRANGEMENT OF POLYARYL-BICYCLO[2,2,1]HEPT-2-EN-7-ONES AND BICYCLO[3,2,0]HEPT-3-EN-2-ONES [J].
COOKSON, RC ;
WARRELL, DC .
JOURNAL OF THE CHEMICAL SOCIETY C-ORGANIC, 1967, (15) :1391-&