ChemInform Abstract: SYNTHESIS, CONFIGURATION, AND NMR SPECTRA OF NORBORNANE EPOXIDES

Kas'yan, L. I.; Samitov, Yu. Yu.; Malinovskii, M. S.; Khmelevskaya, N. D.; Vnukova, V. V.; Kompanichenko, L. P.

doi:10.1002/chin.197707171

Cited by 2 publications

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“…Esteri®cation of 2 with diazomethane furnished the epoxy ester 5 which could be reduced to the primary alcohol 6 using LiAlH 4 . The steric shielding effect of the methylene bridge on the epoxide ring leads to a remarkable stability against this strong reducing reagent [16]. By oxidation of 6 with pyridinium chlorochromate, 5,6-epoxy-isocamphenilanal (7) was obtained which could be transformed into its tosylhydrazone 8 without dif®culties.…”

Section: Resultsmentioning

confidence: 98%

Syntheses in the Isocamphane Series XLI [1]. Derivatives of Epoxyisocamphenilanic Acid, Epoxycamphene, and a New Access to 7-syn-Hydroxycamphene

Buchbauer

Spreitzer

Worm

et al. 1998

Monatshefte fuer Chemie

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The syntheses of the title compounds are described. Epoxidation of the endocyclic norbornene double bond leads to a series of epoxy derivatives of this class of terpenic compounds, which on account of their biological decomposability might turn out to be valuable microbiocides. Cleavage of the epoxide bridge of 5,6-epoxy-camphene opens a new access to the fragrance compound 7-syn-hydroxy-camphene via a rearrangement.

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Section: Resultsmentioning

confidence: 98%

Syntheses in the Isocamphane Series XLI [1]. Derivatives of Epoxyisocamphenilanic Acid, Epoxycamphene, and a New Access to 7-syn-Hydroxycamphene

Buchbauer

Spreitzer

Worm

et al. 1998

Monatshefte fuer Chemie

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“…Compounds having exo-oriented substituents (such as carboxy, methoxycarbonyl, carbamoyl, acylamino, sulfonylamino, and other groups) react with peroxy acids to afford only the corresponding epoxy derivatives, while their endo isomers could give rise to heterocyclization, depending on the substituent nature. The formation of bis-epoxides as major products in the oxidation of amides Vb and Vd indicates strong steric hindrances to location of one cage-like fragment at the rear (endo) area of the other; such arrangement is necessary for intramolecular attack by the nucleophilic carbonyl oxygen atom at the electrophilic carbon atom of the activated epoxy ring [25]. Heterocyclization to azabrendane structures like IXd occurred only after subsequent reduction of epoxy derivatives IXc with lithium tetrahydridoaluminate [9].…”

Section: VIIImentioning

confidence: 99%

Amides containing two norbornene fragments. Synthesis and chemical transformations

et al. 2004

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Reactions of stereochemically pure bicyclo[2.2.1]hept-5-en-exo-and endo-2-ylmethylamines with bicyclo[2.2.1]hept-2-ene-5-carbonyl chlorides gave the corresponding carboxamides having two norbornene fragments. Their conformations and steric strains were studied by the MM2 molecular mechanics method, and electron density distribution in their molecules was determined by PM3 quantum-chemical calculations. The results of calculation of the energy of activation for epoxidation of the dienes in the gas phase and in solution (COSMO) showed that chemoselective oxidation of only one double bond therein is impossible. The corresponding diepoxy derivatives were synthesized by oxidation of the dienes with peroxyacetic acid; the oxidation of amides with endo orientation of the carbonyl group was accompanied by heterocyclization with formation of exo- 2-hydroxy-4-oxatricyclo[4.2.1.0 3,7 ]nonan-5-one. Reduction of the amides and their epoxy derivatives with lithium tetrahydridoaluminate afforded the corresponding secondary amines possessing two cage-like fragments; the reduction products were functionalized at the nitrogen atom by treatment with p-nitrobenzenesulfonyl chloride and p-toluenesulfonyl isocyanate. The structure of the prepared compounds was confirmed by the IR and 1 H and 13 C NMR spectra. IIaAmine 2.73, 2.59 5.96, 6.03 3 J 2, 3 = 6.0, 3 J 2, 1 = 2.8, 3 J 3, 4 = 2.8 1.35 1.14 2 J exo-6, endo-6 = 11.3, 3 J exo-6, 1 = 8.0 1.04 3 J endo-6, 5 = 3.6 1.14, 1.22 2.65 1.13 IIb Amine 2.81, 2.72 5.86, 6.07 3 J 2, 3 = 5.8, 3 J 2, 1 = 2.8, 3 J 3, 4 = 3.0 2.03 1.75 2 J exo-6, endo-6 = 11.4, 3 J exo-6, 5 = 9.2, 3 J exo-6, 1 = 3.9 0.42 3 J endo-6, 5 = 4.1, 4 J endo-6, syn-7 = 2.6 1.37, 1.18 2 J syn-7, anti-7 = 7.9 2.37, 2.29 2 J 8A, 8B = 12.2, 3 J 8A, 5 = 7.3, 3 J 8B, 5 = 8.2 Vc Amine 2.81 6.16, 5.96 3 J 2, 3 = 3.0, 3 J 2, 1 = 2.4, 3 J 3, 4 = 2.7 2.20 1.84 2 J exo-6, endo-6 = 12.6, 3 J exo-6, 5 = 9.0, 3 J exo-6, 1 = 3.9 0.54 3 J endo-6, 5 = 3.0, 4 J endo-6, syn-7 = 2.2 1.42, 1.27 2 J syn-7, anti-7 = 8.1 2.95, 3.03 2 J 8A,8B = 13.5, 3 J 8A, 5 = 7.2, 3 J 8B, 5 = 5.7 VIa Acid 2.88, 2.85 6.06, 6.01 3 J 2, 3 = 5.5, 3 J 2, 1 = 3.0, 3 J 3, 4 = 3.0 1.95 1.27 2 J exo-6, endo-6 = 11.1, 3 J exo-6, 5 = 8.5, 3 J exo-6, 1 = 2.5 1.88 3 J endo-6, 5 = 3.7, 4 J endo-6, syn-7 = 3.7 1.32, 1.68 2 J syn-7, anti-7 = 8.4 a 4.39, 4.34 a 5.79 VIb Acid 2.92, 3.16 6.23, 5.98 2.91 1.93 2 J exo-6, endo-6 = 12.8, 3 J exo-6, 5 = 9.4, 3 J exo-6, 1 = 3.8 1.41 3 J endo-6, 5 = 4.0, 4 J endo-6, syn-7 = 2.7 1.46, 1.29 2 J syn-7, anti-7 = 7.9 a 4.43, 4.35 a 6.02 a Benzyl CH 2 group. VIIa Amine 2.57, 2.25 3.00-3.10 1.60 1.36 2 J exo-6, endo-6 = 11.5, 3 J exo-6, 5 = 8.4, 3 J exo-6, 1 = 2.4 1.05 1.25, 0.81 2 J syn-7, anti-7 = 10.2 3.00-3.10 5.72 Acid 2.47, 2.41 3.00-3.10 2.08 1.64 2 J exo-6, endo-6 = 12.4 1.20 1.39, 1.18 2 J syn-7, anti-7 = 8.3 --VIIc Amine 2.51, 2.48 3.28, 3.09 3 J 2, 3 = 3.0 1.50 1.73 2 J exo-6, endo-6 = 12.7, 3 J exo-6, 5 = 10.7, 3 J exo-6, 1 = 4.3 0.81 3 J endo-6, 5 = 4.9, 4 J endo-6, syn-7 = 2.3 1.37, 0.76 2 J syn-7, anti-7 = 10.0 3.20-3.32 2 J 8A,...

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ChemInform Abstract: SYNTHESIS, CONFIGURATION, AND NMR SPECTRA OF NORBORNANE EPOXIDES

Cited by 2 publications

References 0 publications

Syntheses in the Isocamphane Series XLI [1]. Derivatives of Epoxyisocamphenilanic Acid, Epoxycamphene, and a New Access to 7-syn-Hydroxycamphene

Syntheses in the Isocamphane Series XLI [1]. Derivatives of Epoxyisocamphenilanic Acid, Epoxycamphene, and a New Access to 7-syn-Hydroxycamphene

Amides containing two norbornene fragments. Synthesis and chemical transformations

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