F Cycloheptene

Cyclobutyl 4-methylbenzenesulfonate, 3398a Cyclobutylmethyl methanesulfonate, 2510 c/.v-Cyclododecene, 3345 f Cycloheptane, 2845 f 1,3,5-Cycloheptatriene, 2786 f Cycloheptene, 2833 f 1,3-Cyclohexadiene, 2354 f 1,4-Cyclohexadiene, 2355... 

Classical resolutions are not restricted to racemic compounds containing tetrahedral chiral centres, a point exemplified by Phillips et al. [18] in work directed at clozapine analogues as potential neuroleptic agents. The 5//-di-benzo[a, f]cycloheptene (7), which exists as configurational enantiomers by virtue of planar chirality [19], was resolved using (215,35)- and (2/ ,3/ )-di-p-toluoyltartaric acids (Scheme 5.5)... 

In an initial step, dibenzo[a,d] cyclohepten-5-one is reacted with the Grignard reagent of 3-di-methylaminopropyl chloride and hydrolyzed to give 5-(3-dimethylaminopropyl)-dibenzo[a,d] -[1,4] cycloheptatriene-5-ol. Then 13 g of that material, 40 ml of hydrochloric acid, and 135 ml of glacial acetic acid is refluxed for 314 hours. The solution is then evaporated to dryness in vacuo and added to ice water which is then rendered basic by addition of ammonium hydroxide solution. Extraction of the basic solution with chloroform and removal of the solvent from the dried chloroform extracts yields the crude product which when distilled in vacuo yields essentially pure 5-(3-dimethylaminopropylidene)-dibenzo[a/f ] [ 1,4] cycloheptatriene, BP 173°C to 177°C at 1.0 mm. 

Kiyama, R., Honma, T., Hayashi, K., Ogawa, M., Hara, M., Fujimoto, M., and Fujishita, T. Angiotensin II receptor antagonists. Design, synthesis, and in vitro evaluation of dibenzo[a,d]cycloheptene and dibenzo[b,f oxepin derivatives. 

Although the catalytic reactions described above involve mononuclear Rh and Rh complexes, dinuclear Rh compoimds have also been studied as catalyst precursors in oxygenation reactions. The system [Rh2(p.-OAc)4]/ f-BuOOH is effective in the oxidation of cyclic alkenes such as cyclopentene, cyclohexene and cycloheptene, mainly to o, /i-unsaturated ketones and allylic acetates, but with poor yields (Eq. 4) [30,31]. 

Photocycloadditions of naphthalene derivatives to alkcnes have been recently reviewed.60 Examples of such reactions are the photocycloaddition of naphthalene to 2,3-dihy-drofuran,61 of 4-methoxy-l-naphthonitrile to acrylonitrile62 and of 2-trimethylsiloxynaph-thalene to methyl acrylate.63 2-Naphthols undergo cycloaddition with ethene in the presence of aluminum trihalides only.64 Other bicyclic aromatic compounds, e.g. A-acylindoles65-67 and /V-methylphenanthrene-9,10-dicarboximide,68 have also been studied in detail. Irradiation of 5/f-dibenzo[u,i7]cyclohepten-5-one (21) and dimethyl 2-methylfumarate (22) in dioxane gives the cyclobutane adduct 23 in 73% yield.69... 

Cycloheptene oxide has long been known to undergo amd-catalysed hydration to traw-l, 2-dicloheptancdirf.1M> 840 More recent work by f opo and oo-workers, 4 however, has unoovered in addition the presence of cia-1. d-oyotohcptanediol (Eq. 036). The latter eau be... 

S-diethylaminophenyl)-l-phenyl-3-(i>-diethylaminostyryl)pyrazoline) (d) 4-(5H-dibezo[i , J]cyclohepten-5-ylidenemethyl) benzenamine [119544-18-2] (e) 4,4 -cyclohexylidenebis [N,IV-bis(4-methylphenyl)]benzenamine [58475-78-2] (l,l-bis(di-4-tolyl-aminophenyl)cyclohexane) (f)... 

The efficiency of a new chiral non-racemic and C2-symmetric 2,2-bipyridyl ligand (6) in copper(I)-catalysed asymmetric allylic oxidation reactions of the cyclic alkenes with f-butyl peroxybenzoate has been evaluated. On performing the reaction of cyclopentene, cyclohexene, and cycloheptene in acetonitrile the corresponding product, (lS)-cycloalk-2-enyl benzoate, was isolated in up to 69% yield and in 91% ee 29... 

Scheme 8 5/f-Dibenzo[a,d]cycloheptene-Derived N -Protection of Argininel l... 

The results of the reactions involving these carbenes are compiled in Table 14. Irradiation of 5-diazo-10,l l-dihydrodibenzo[a,c/]cycloheptene with a high-pressure mercury lamp gives 10,11-dihydrodibenzo[a,rf]cyclohepten-5-ylidene, which can be trapped under the right conditions. When the photolysis was carried out in the presence of ( )-l-phenylprop-l-ene, stereospecific cycloaddition took place to give rra i-3-methyl-l-phenylspiro[cyclopropane-2,5 -10, lT-dihydro-5 //-dibenzo[a,cf]cycloheptene in 19% yield.Efficient trapping even on a synthetic scale is experienced when the diazo compound is irradiated in various styrenes. Thus, when 4-methoxystyrene was used as solvent l-(4-methoxyphenyl)spiro[cyclopropane-2,5 -10, lT-dihydro-5 7/-dibenzo[a,ii]cycloheptene (1) was isolated in 81% yield in addition 5,5 -bi(10,ll-dihydro-5//-dibenzo[u, f]cycloheptyl) (2) was obtained in 11% yield. 

A solution of 5/f-dibenzo[a,c]cycloheptene-5-one tosylhydrazone sodium salt (200 mg, 0.50 mmol) was photolyzed for 40 min at — 60 °C in dry THF (20 mL) containing freshly prepared cyclopentadiene monomer (5mL, 75 mmol). The mixture was allowed to warm to 5°C and the solvent was removed under reduced pressure. (The last trace of dicyclopentadiene was removed in vacuo). The residue was taken up in cyclohexane and column chromatographed on silica gel (cyclohexane) to give the product yield 94 mg (73%). Molecular distillation at 110°C/0.2 Torr yielded the product as a pure (GC) colorless liquid. 

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