Tetracyclo octanes

Erwahnt sei femer die photochemische Isomerisierung des exo-Tricyclo-[3,2,l,08 4]octen-Derivates 48 zum Tetracyclo[3,3,0,02 8,04>8]octan-Deri-vat 49 (216), obwohl diese Reaktionen im strengen Sinne keine Cyclo-merisation darstellt. Auf analoge Weise ist auch das unsubstituierte Tetracyclo-octan sowohl aus exo- als auch aus endo-Tricyclo [3,2,1,02.4]-octen-(6) zuganglich (125). 

See Poly([7,8-bis(trifluoromethyl)tetracyclo[4.2.0.02 8.05 7]octane-3,4-diyl]-l,2-ethenediyl)... 

Before the explanation of ladder poly silanes is started, ladder compounds of other Group 14 elements are briefly mentioned. Hydrocarbons with a ladder-shaped carbon framework are known as ladderanes. The study on ladderanes goes back to 1927, when bicyclo[2.2.0]hexane ([2]ladderane) was synthesized by the reduction of dy-l,4-dibromocyclohexane with sodium.19 Ladderanes so far reported are tricyclo[4.2.0.02,5]octane ([3]ladderane),20 tetracyclo[4.4.0.02,507,1°]decane21 ([4]ladderane), and a number of their derivatives (Fig. 3). 

Poly([7,8-bis(trifluoromethyl)tetracyclo [4.2.0.02 8.05 7]octane-3,4-diyl]-1,2-ethenediyl), 3457 Poly[borane(l)], 0134 crs-Poly (butadiene), 1480 Poly(l,3-butadiene peroxide), 1528 Poly(butadiyne), 1382 Poly(carbon monofluoride), 0336 Poly(chlorotrifluoroethylene), 0589 Poly(l,3-cyclohexadiene peroxide), 2380 Poly(cyclopentadienyltitanium dichloride), 1837 Poly(diazidophosphazene), 4781 Poly(dibromosilylene), 0282 Poly(difluorosilylene), 4324 Poly(dihydroxydioxodisilane), 4474 Poly(dimercuryimmonium acetylide), 0665 Poly(dimercuryimmonium azide), 4606 Poly(dimercuryimmonium bromate), 0253 Poly (dimercury immonium iodide hydrate), 4449 Poly (dimercury immonium perchlorate), 4006 Poly(dimercuryimmonium permanganate), 4603 Poly (dime thylketene peroxide), see Poly(peroxyisobutyrolactone), 1531 Poly(dimethylsiloxane), 0918 Poly(disilicon nitride), 4752 Poly(ethenyl nitrate), see Poly(vinyl nitrate), 0760 Poly(ethylene), 0778 Poly(ethylene terephthalate), 3256 Poly(ethylidene peroxide), 0831 Poly(furan-2,5-diyl), 1398 Poly(germanium dihydride), 4409 Poly(germanium monohydride), 4407 Poly(isobutene), 1578 Poly(methyl methacrylate peroxide), 1913... 

Three tetracyclo[5.5.1.02,6.010,13]tridecanes are known at present. The reaction of glyoxal with dimethyl 3-ketoglutarate in aqueous solution at room temperature and pH 5 to give after treatment with acid c/,s-bicyclo[3.3.0]octane-3,7-dione has been discussed previously. More careful study of this condesation has led to the discovery that the two tetracyclic triketones 486 and 487 are also formed in low... 

Methyl-1-phenyl- E19a, 169 (2-Desoxygenierung) 2-Methyl-2-phenyl- V/la, 522 Tetracyclo 5.2.1.02[Pg.769]

Penten-l-in 5-Cyclohexyl-V/ld, 669 Propan 2,2-Dimethyl-l-phenyl-V/la, 479, 492, 496 Spiro 2,4 hepta-4,6-dien, 1,2-Diethyl-E19b, 797 (Carben + En) Tetracyclo 4.2.0.02,8.04, octan 1.5,5-Trimethyl- E19b, 438 (a-Eliminierung//Mnsertion) Tetracyclo[3.2.1.02-7.03,6 octan ... 

Rearrangements of strained o-bonds (see Silver fluoroborate, 3,250). Paquette et al have now examined the Ag+-catalyzed rearrangement of the less strained reco-cubane derivatives. Treatment of the endo,endo-diesttr (1) with a solution of anhydrous silver perchlorate resulted in quantitative and stereospecific conversion to the endo,endo-tetracyclo[3.3.0.02 8.04 6]octane derivative (2). In like manner, the endo,exo-isomer (3)... 

It also proved possible to modify the structures of the diphenyldiazomethane adducts 11 and 13 in the syntheses shown of ex o-3,3-diphenyl-8-methylenetricyclo[3.2.1.0 ]octane (12) and 9,9-diphenyl-cxo-tetracyclo[4.2.1 .0 ]decan-aMn -10-ol (14) (in this special case the Grignard reagent was used for solvolysis). 

Solvolysis of 7-(4-bromobenzylsulfonyloxymethyl)norboraa-2,5-diene in the presence of one equivalent of sodium acetate in acetic acid at 118°C for 48 hours gave a 53 47 mixture of 7-acetoxymethylnorborna-2,5-diene (unrearranged product) and of 3-acetoxytetracyclo-[3.3.0.0. 0 ]octane (4) in 38% yield. ° Oxidation of the mixture of products with chro-mium(VI) oxide in acetone gave the norborna-2,5-diene-7-carboxylic acid and tetracyclo-[3.3.0.02. 0 ]octan-3-one(5). ... 

Two transition metal catalyzed [27t + 2strained hydrocarbons, reacts with exo-tricyclo[3.2.1.0 " ]oct-6-ene (5) to give tetracyclo[3.3.0.0 .0 ]octane (6) in quantitative yield. The endo-isomer is unreactive. ... 

Similarly, chlorination of tetracyclo[3.3.0.0 .0 - ]octane (63) with ter/-butyl hypochlorite gave a mixture of two chlorides 64 and 65 containing intact cyclopropane rings. ... 

Thermal, or photochemical, decomposition of certain polycyclic diazines yields seven-membered rings. Thus, enr/o-10,ll-diazatetracyclo[4.3.2.0 .0 ]undec-10-ene rearranges to bicy-clo[5.2.0]nona-2,5-diene at 180°C (Section 2.4.1.5.2.8.). Substituted 9,10-diazatetracyclo-[3.3.2.0. 0 - ]dec-9-enes, e.g. 3, rearrange to give mixtures of bicyclo[5.1.0]octa-2,5-dienes and tetracyclo[3.3.0.0 . 0 ]octanes when photolyzed in methanol or benzene. ... 

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