Derivatives of exo-5-Aminomethyl-endo-5-methylbicyclo[2.2.1]hept-2-ene and exo-5-Aminomethyl-endo-5-methyl-exo-2,3-epoxybicyclo[2.2.1]heptane

exo-5-Aminomethyl-endo-5-methylbicyclo[2.2.1]hept-2-ene and its 2,3-epoxy derivative were synthesized, and their geometric parameters and conformational properties, in particular the barriers to rotation of the aminomethyl fragment about the exocyclic C⁵ÄC bond, were studied by the molecular-mechanics method (MMX) and compared with those found for structurally related exo-5-aminomethylbicyclo[2.2.1]hept-2-ene. The title compounds were brought into reactions with electrophilic reagents: arenesulfonyl chlorides, isocyanates, and isothiocyanates.     

Synthesis and Stereochemistry of exo-4-Aminomethyltetracyclo[6.2.1.13 , 6.02 , 7]dodec-9-ene

Tetracyclo[6.2.1.1^{3 , 6}.0^{2 , 7}]dodec-9-ene-4-carbonitrile was synthesized by reaction of cyclopentadi- ene with stereochemically pure bicyclo[2.2.1]hept-2-ene-exo-4-carbonitrile. The preferential configuration of the adduct was proposed on the basis of the results of MMX calculations of four possible stereoisomers. Tetra- cyclo[6.2.1.1^{3 , 6}.0^{2 , 7}]dodec-9-ene-4-carbonitrile was reduced with lithium aluminum hydride to the corre- sponding aminomethyl derivative, and the latter was brought into reactions with p-toluene-, p-chlorobenzene-, and p-nitrobenzenesulfonyl chlorides, phenyl-, mesityl-, and p-tolylsulfonyl isocyanates, o-tolyl, p-tolyl- sulfonyl, and benzoyl isothiocyanates, and p-nitrophenyloxirane. The reaction with p-nitrophenyloxirane occurred in a regioselective fashion, in keeping with the Krasusky rule. N-Mesityl- and N-(p-tolylsulfonyl)- N'-(tetracyclo[6.2.1.1^{3 , 6}.0^{2 , 7}]dodec-9-en-4-exo-ylmethyl)ureas were oxidized with peroxyphthalic acid to obtain the corresponding epoxy derivatives. The structure of the products was confirmed by their IR and ¹H, ^{1 3}C, and two-dimensional NMR spectra. The structure of N-benzoyl-N'-(tetracyclo[6.2.1.1^{3 , 6}.0^{2 , 7}]dodec-9-en- 4-exo-ylmethyl)thiourea was proved by the X-ray diffraction data.     

Esters Synthesis by Addition of Monocarboxylic Acids to exo-5-Substituted Bicyclo[2.2.1]hept-2-ene Hydrocarbons

New alicyclic esters were synthesized by addition at heating of aliphatic monocarboxylic saturated acids C₁-C₄ to exo-5-phenyl-, exo-5-cyclohexyl-, and exo-5-(cyclohex-3-enyl)bicyclo[2.2.1]hept-2-enes. Among the esters obtained the acetates has more pleasant odor with fruit tint, and they may be used as a component of synthetic perfumes.     

Thermal isomerizations of cis,anti,cis-tricyclo[7.4.0.0(2,8)]tridec-10-ene

cis,anti,cis-Tricyclo[7.4.0.0(2,8)]tridec-10-ene (13TCT) undergoes [1,3] sigmatropic rearrangements at 315 °C in the gas phase to the si product 1 and to the sr product 2 with si/sr = 2.1. The dominant thermal isomerization process, however, is epimerization at C8 to afford product 3. That stereomutation at C8 occurs 50% faster than the si and sr shifts combined.     

Die Solvolyse von exo- und endo-3-Chlor-bicyclo[3.2.1]octan

The rates of solvolysis of exo and endo 3-chloro bicyclo[3.2.1]octane 1a and 2a have been measured in 80 vol.% aqueous ethanol. The axial endo chloride reacts 263 times as fast as the equatorial exo epimer. This remarkably large rate difference is ascribed to sterically accelerated ionisation of the axial endo epimer due to the ethano bridge.     

Synthesis of 2,7-Diazabicyclo[3.2.1]oct-3-ene Derivatives

Russian Journal of Organic Chemistry - Tetracyanoethylene adducts with ketones, 4-oxoalkane-1,1,2,2-tetracarbonitriles reacted with hydrogen chloride or phosphorus(III) chloride in 1,4-dioxane to...     

Mannich Condensation of exo-2,exo-6-Tricyclo[5.2.1.02,6]decan-8-one

Mannich condensation of exo-2,exo-6-tricyclo[5.2.1.02,6]decan-8-one with paraformaldehyde and dimethylamine hydrochloride results in the addition of dimethylaminomethyl fragment at the C⁹ atom to give the exo-9-isomer. The reaction of exo-9-dimethylaminomethyl-exo-2,exo-6-tricyclo[5.2.1.02,6]decan-8-one with hydroxylamine hydrochloride in alcoholic alkali yields the corresponding Z-oxime which undergoes selective rearrangement into exo-10-dimethylaminomethyl-9-aza-exo-2,exo-6-tricyclo[5.3.1.02,6]undecan-8-one by the action of sulfuric acid in acetonitrile.     

Bicyclo[3.1.0]hex-(1,5)-ene and bicyclo[4.1.0]hept-(1,6)-ene

The formation and trapping of bicyclo[3.1.0]hex-(1,5)-ene and bicyclo[4.1.0]hept-(1,6)-ene from the corresponding vicinal dibromides is described.     

The Synthesis and Cycloaddition Reactions of 3-Azabicyclo[3.1.0]hex-2-ene 3-oxide and 3-Azabicyclo[3.2.0]hept-2-ene 3-oxide. Highly Strained Bicyclic Nitrones

The synthesis of two strained bicyclic nitrones is described. Subsequent cycloadditions demonstrated a high degree of regiochemical and stereochemical control.     

The Non-planarity of the Bicyclo[2.2.1]hept-2-ene Double bond. Crystal Structures of Bicyclo[2.2.2]oct-2-ene,Bicyclo[2.2.1]hept-2-ene,and Bicyclo[2.1.1]hex-2-ene Systems

The crystal structures of (1R,4R,5S,8S)-9,10-dimethylidentricyclo[6.2.1.0^2,7]undec2(7)-ene-4,5-dicarboxylic anhydride ( 3 ), (1R,4R,5S,8S)11-isopropylidene-9,10-dimethylidenetricyclo[6.2.1.m^2,7]undec-2(7)-ene-4,5-dicarboxylic anhydride ( 6 ), (1R,4R,5S8S)-9,10-dimethylidenetricyclo[6.2.2.0^2,7]dodec-2(7)-ene-4,5-dicarboxylic anhydride ( 9 ), (1R4R5S8S)-TRICYCLO[6.2.2.0^2,7]dodeca-2(7), 9-diene-4,5-dicarboxylic anhydride ( 12 ) and (4R,5S)-tricyclo[6.1.1.0^2.7]dec-2(7)-ene-4,5-dicarboxylic acid ( 16 ) were established by X-ray diffraction. The alkyl substituents onto the endocyclic bicyclo[2.2.1]hept-2-ene double bond deviate from the C(1), C(2), C(3), C(4), plane by 13.5°4 in 3 and by 13.9° in 6 , leaning toward the endo-face. No such out-of-plane deformations were observed with the bicyclo[2.2.2]oct-2-ene derivatives 9 and 12 . The exocyclic s-cis-butadiene moieties in 3, 6 and 9 do not deviate significantly from planarity. The deviation from planarity of the double bond n bicyclo[2.2.1]hept-2-ene derivatives and planarity in bicyclo[2.2.2]oct-2-ene analogues is shown to be general by analysis of all known structures in the Cambridge Crystallographic Data File. The non-planarity of the bicyclo[2.2.1]hept-2-ene double bond cannot be attributed only to bond-angle deformations which would favour rehybridizatoin of the olefinic C-atoms since the double bond in the more strained bicyclo[2.1.1]hex-2-ene drivative 16 deviates from planarity by less than 4°.     

Oxidation of 1-vinyl-2-thiabicyclo[3.2.0]-hept-3-ene

Conclusions Oxidation of 1-vinyl-2-thiabicyclo[3.2. 0]hept-3-ene by hydrogen peroxide leads to 1-vinyl-2-thiabicyclo-[3.2.0]hept-3-ene 2-oxide (cis- and trans-isomers) and 1-vinyl-2-thiabicyclo[3.2. 0]hept-3-ene 2,2-dioxide.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1883–1885, August, 1984.