Hexahydroanthracene

When zinc and a,a -dibromo-o-xylene are irradiated with ultrasonic waves at room temperature, synthetically useful quantities of the reactive intermediate, o xylylene, are generated which can be treated in situ with activated olefins to give good yields of cycloaddition products(30). Chew and Ferrier used this methodolgy to generate a-xylylene for the synthesis of optically pure functionalized hexahydroanthracenes(31). The reaction with lithium takes a different course(19). Rather than generate the -xylylene intermediate, ionic species are produced. The two fates of a, a -dibromo-o-xylene are presented in the scheme below ... 

An application to the asymmetric synthesis of enantiomer-ically pure tram-hexahydroanthracen-9-ones is shown in Scheme 6. It should be possible to carry out a second stereoselective reductive alkylation of the benzoyl group in 22 as was demonstrated in the related hydrofluoren-9-one and... 

Hexahydroanthracene (455) is quantitatively converted to anthracene (457) by milling with three equivalents of dichlorodicyano-parabenzoquinone (DDQ, 456) (Scheme 73). The intermediate products cannot be quantitatively obtained at 1 1 or 1 2 ratios of the reagents, as product mixtures occur [22]. Importantly,... 

Hexahydroanthracene (120) on treatment with perbenzoic acid produces the isomeric diepoxides 121 and 122. The syn-diepoxide 121 with bromine, followed by potassium t-butoxide treatment, produces the annulene 123, whereas similar reactions with the anfi-diepoxide 122 give the arene oxide 124,8... 

Keywords solid-solid reaction, hexahydroanthracene, anthracene, DDQ, DDQH... 

Treatment of 1,4,5,8,9,10-hexahydroanthracene (10) with 2 equivalents of peracetic acid gives the diepoxide (11) in almost quantitative yield isyn and anti iso-mers).36b The diepoxide (11) is treated with 2 equivalents of NBS in CCL, and the crude bromination product is dehydrohalogenated by potassium /-butoxide in THF to give carmine-red crystals of (13), l,6 8,13-diepoxy[14]annulene (syn or anti) in 5% yield. 

Hexadiene-l-ol, 465 Hexaethylphosphorous triamide, 207 Hexafluoroacetone, 119 Hexafiuoro-2-bulyne, 207 Hexafluorophosphoric acid, 402 1,4,5,8,9,10-Hexahydroanthracene, 338... 

The IBX oxidation of diol 836 has been utilized in the synthesis of the functionalized hexahydroanthracene dione 837 (Scheme 3.331), a model for the D ring of taxoids [1136]. 

Tietze, L.F., Stewart, S.G. and Polomska, M.E. (2005) Intramolecular Heck reactions for the S5mthesis of novel antibiotic mensacarcin investigation of catalytic, electronic and conjugative effects in the preparation of the hexahydroanthracene core. Eur. J. Org. Chem., 1752-9. 

Dimethyl-l,4-epoxy-l,4-dihydronaphthalene, 2,3-dimethylbutadiene, and a little hydroquinone as polymerization inhibitor dissolved in a small amount of xylene, and refluxed overnight 2,3,6,7-tetramethyl-9,10-epoxy-l,4,4a,9,9a,10-hexahydroanthracene. Y 85%. F. e., also without solvent in a sealed tube, s. E. Wolthuis, J. Org. Ghem. 26, 2215 (1961) diene synthesis with sulfoxides and sulfones s. E. G. Kataev and F. P. Tantasheva, Dokl. Akad. Nauk SSSR HI, 1101 (1961) G. A. 56, 15383h with vinylsulfonyl fluoride s. H. U. Daeniker and J.Druey, Helv. 45, 1972 (1962). 

The reaction of enantiomerically pure sulfinyl dienes with Fe(GO)s yields ( 7" -(lZ)-sulfinyl diene)iron(O) tricarbonyl complexes.Planar and axial chirality are introduced upon complexation of similar ligands with (dba)Fe(GO)3 (dba = dibenzylideneacetone). Gomplexation of sorbic acid with Fe(GO)s in acetone upon irradiation with UV light produced the ( 7" -2,4-hexadienoic acid)Fe(GO)3 complex in good yields.Stobart efal. reported the reaction of 1,4,5,8,9,10-hexahydroanthracene with Fe(GO)s under UV irradiation to form a complex in which two tricarbonyliron moieties are bound in an 77 -fashion to the ends of the isolated conjugated diene units (Equation (8)). 

A soln. of 10-oxo-5-benzyloxy-4j -acetoxy-9/ -hydroxy-9a-methyl-l,4,4aa,9,9aa,10-hexahydroanthracene in abs. ethanol treated at 20° with ethanolic 1 N Na-ethoxide, and the product isolated after 15 min. 10-oxo-5-benzyloxy-9) -hydroxy-9a-methyl-l,9,9aa,10-tetrahydroanthracene. Y 94%. M. N. Kolosov, S. A. Popravko, and M. M. Shemyakin, A. 668, 86 (1963). 

A soln. of 9,10-dikelo-l,4,4a,9,9a,-10-hexahydroanthracene in 10-15 times the amount of anhydrous benzene cooled to 5-7°, treated gradually with 1.3 moles ethereal methylmagnesium iodide, and stirred for a further 2-3 hrs. 10-keto -9 - hydroxy-9-methyl-l,4,-4a, 9,9a, 10 - hexahydroanthracene (Y 70%)... 

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