73679-39-7Relevant academic research and scientific papers
EXPERIMENTAL EVIDENCE ESTABLISHING AN UPPER LIMIT TO THE ACTIVATION BARRIER FOR THE BUTTERFLY BENDING OF THE DOUBLE BOND IN ANTI-SESQUINORBORNENE
Williams, Richard Vaughan,Sung, Chiu-Lien Ann,Kurtz, Henry A.,Harris, Thomas M.
, p. 19 - 20 (1988)
Low temperature 13C NMR and theoretical results are presented which imply that in the groundstate of anti-sesquinorbornene the double bond is either pyramidal with a very low barrier to inversion or planar.
A Synthon for C2 Polycyclic 1,4,5,8-Tetrahydronaphthalenes via Double Diels-Alder Cycloaddition
Lucchi, Ottorino De,Cossu, Sergio
, p. 1089 - 1090 (1992)
2-Chloro-1,4-benzodithiin-S,S'-tetroxide 1 is a synthon for C2 because its Diels-Alder adducts, after dehydrochlorination, react further with another molecule of diene and the resulting product can be desulfonylated into the same hydrocarbons that would have formed from C2.
SYNTHESIS OF anti-SESQUINORBORNENE AND RELATED POLYCYCLIC ALKENES via REDUCTIVE ELIMINATION OF VICINAL DICYANO DERIVATIVES
Lucchi, Ottorino De,Piccolrovazzi, Nicoletta,Licini, Giulia,Modena, Giorgio,Valle, Giovanni
, p. 401 - 408 (2007/10/02)
A methodology for the preparation of both endocyclic unsaturated molecules via reductive elimination of vicinal dicyano derivatives is reported.The method is useful for the preparation of anti-sesquinorbornene and related hitherto unknown molecules starting from the respective vicinal dicyano derivatives which are readily available via Diels-Alder reactions.From a practical point of view, the best decyanation procedure for these substrates is to use finely dispersed sodium in tetrahydrofuran under sonication.The X-ray analysis of anti-1,4,4a,5,8,8a-hexahydro-1,4;5,8-dimethanonaphthalene-4a,8a-dicarbonitrile, 3, is reported.Crystal data: orthorhombic, space group P212121; Z=4; a=16.059(5), b=8.920(3), c=7.592(3) Angstroem; V=1087.5 Angstroem3, Dc=1.27 g*cm-3.
SYNTHESIS OF POLYCYCLIC ALKENES VIA REDUCTIVE ELIMINATION OF β-DICYANO DERIVATIVES: A FACILE PREPARATION OF ANTI-SESQUINORBORNENE AND RELATED MOLECULES
Lucchi, Ottorino De,Piccolrovazzi, Nicoletta,Modena, Giorgio
, p. 4347 - 4350 (2007/10/02)
Anti-Sesquinorbornene 1b, the hitherto unknown related unsaturated molecules 1a,c and the dienes 13 and 14 are among the endocyclic alkenes which can be prepared via reductive elimination of the respective, readily available β-dicyano derivatives.
Addition Reactions to syn- and anti-Sesquinorbornenes Involving Ionic Mechanisms. The Role of Tetracyanoethylene
Bartlett, Paul D.,Roof, Antonius A. M.,Subramanyam, Ravi,Winter, William J.
, p. 1875 - 1880 (2007/10/02)
Addition of bromine or of acids to anti-sesquinorbornene is more rapid and less readily reversible than that to the syn isomer, whereas other addition reactions proceeding by concerted or free-radical mechanisms show a small rate advantage for syn-sesquinorbornene and no reversibility.Tetracyanoethylene (TCNE) does not undergo cycloaddition with syn- or anti-sesquinorbornene, nor can any dipolar ion from TCNE and sesquinorbornene be trapped by methanol, as in the case of TCNE and vinyl ethers.However, under the conditions of such experiments TCNE catalyzes the addition of methanol to yield sesquinorbornyl methyl ether, or of water to yield sesquinorbornanol, the TCNE undergoing no apparent chemical change.From a comparative study of TCNE and p-toluenesulfonic acid it is concluded that the TCNE reaction is an example of acid catalysis, probably by the complex between TCNE and the alcohol or water. syn-Sesquinorbornene adds methanol in CD3CN with the lower equilibrium constant of about 0.54 +/- 0.05 L/mol at ca. 30 deg C. anti-Sesquinorbornene in similar additions shows an equilibrium more favorable to addition by about 3 orders of magnitude.These reactions are discussed in light of the general character and behavior of the sesquinorbornenes.A new route to anti-sesquinorbornene is described that gives better yields than the former electrolytic preparation.
Improved synthesis of anti-sesquinorbornene
Kopecky, Karl R.,Miller, Alan J.
, p. 1840 - 1844 (2007/10/02)
Treatment of methyl hydrogen decahydro-1,4:5,8-exo,endo-dimethanonaphthalene-4a,8a-dicarboxylate with lead tetraacetate in benzene-acetic acid replaces the carboxyl group by an acetoxy group.Hydrolysis of this product with 25percent sulfuric acid at 130 deg C forms 8a-hydroxydecahydro-1,4:5,8-exo,endo-dimethanonaphthalene-4a-carboxylic acid 10.The reaction between 10 and benzenesulfonyl chloride in pyridine containing triethylamine at 95 deg C produces anti-sesquinorbornene 1 in 34percent yield.In the absence of triethylamine 1 is converted to the hydrochloride.The iodohydroperoxide of 1 is converted by silver acetate at 0 deg C to the diketone in a luminescent reaction.The 1,2-dioxetane could not be isolated.Decahydro-1,4:5,8-exo,exo-dimethanonaphthalene-4a,8a-dicarboxylic anhydride is converted slowly by methoxide ion in methanol at 150 deg C to the monomethyl ester which then undergoes demethylation.The isomeric exo,endo anhydride undergoes reaction readily with methoxide ion at 80 deg C.
