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85022254449
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Studies by 27,A1 NMR have shown that the association of A1CI3 with acetyl chloride in CH2Cl2 solution gives only the donor-acceptor complex and not an ion pair including acylium ion; see
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Studies by 27,A1 NMR have shown that the association of A1CI3 with acetyl chloride in CH2Cl2 solution gives only the donor-acceptor complex and not an ion pair including acylium ion; see: Wilinski, J.; Kurland, R. J. J. Am. Chem. Soc. 1978, 100, 2233.
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0001196105
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Acetylation of excess cyclohexane in the presence of AIC13 results in the formation of l-acetyl-2-methylcyclopentane as the main product; see
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Acetylation of excess cyclohexane in the presence of AIC13 results in the formation of l-acetyl-2-methylcyclopentane as the main product; see: Vol’pin, M.; Akhrem, I.; Orlinkov, A. New J. Chem. 1989, 13, 771.
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1-Methyl-1-cyclopentyl cation was generated in superacid medium from cyclohexyl- or cyclopentyl-type precursors, see
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1-Methyl-1-cyclopentyl cation was generated in superacid medium from cyclohexyl- or cyclopentyl-type precursors, see: (a) Olah, G. A. Top. Curr. Chem. 1979, 80, 19.
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This tertiary cation shows high stability in strong acid solutions, although both carbon and hydrogen scrambling occurs; see ref 2c, p 84.
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Vancik, H.; Sunko, D. E. J. Am. Chem. Soc. 1989, 111, 3742. This tertiary cation shows high stability in strong acid solutions, although both carbon and hydrogen scrambling occurs; see ref 2c, p 84.
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Three mechanisms have been invoked to account for the acylation of olefins. Electrophilic attack
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Cyclic transfer of the γ-hydrogen to oxygen: Groves, J. K. Chem. Soc. Rev. 1972, 1, 73.
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Diacetylation of 1-methyl-1-cyclohexene by Ac20-ZnCl2 occurs via acylation of the dienolate of 2-methyl-1 -acetyl- 1-cyclohexene
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Diacetylation of 1-methyl-1-cyclohexene by Ac20-ZnCl2 occurs via acylation of the dienolate of 2-methyl-1 -acetyl- 1-cyclohexene; see: Dubois, M.; Cazaux, M. Bull. Soc. Chim. Fr. 1975, 274.
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The alkylation of benzene also occurs selectively with cis-decalin; see
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Pentalenone 8a has been used in syntheses of propellane sesquiterpenes; see
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Pentalenone 8a has been used in syntheses of propellane sesquiterpenes; see: (a) Schostarez, H.; Paquette, L. A. J. Am. Chem. Soc. 1981, 103, 722.
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Mixtures of AlCl3 and cupric sulfate are known to be active for the isomerization of paraffins at room temperature; see ref 2c, p 56 and
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For a review on the Nazarov cyclization, see: Santelli-Rouvier, C.; Santelli, M. Synthesis 1983, 429.
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84987344402
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For an example of methyl migration during a protic catalyzed Nazarov cyclization, see
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For an example of methyl migration during a protic catalyzed Nazarov cyclization, see: Ohloff, G.; Schutte-Elte, K. H.; Demole, E. Helo. Chim. Acta 1971, 54, 2913.
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Tertiary cycloalkyl cations frequently undergo ring expansion or contraction; see
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Tertiary cycloalkyl cations frequently undergo ring expansion or contraction; see: Kirchen, R. P.; Sorensen, T. S.; Wagstaff, K. E. J. Am. Chem. Soc. 1978, 100, 5134.
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0000393810
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Nevertheless, the methylcyclohexyl cation is stable; see
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Nevertheless, the methylcyclohexyl cation is stable; see: Kirchen, R. P.; Ranganayakulu, K.; Sorensen, T. S. J. Am. Chem. Soc. 1987, 109, 7811.
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It is well-known that the effect of the replacement of hydrogen by deuterium on the proton noise-decoupled 13C NMR spectrum is to reduce the intensity of the signal due to the carbon bearing the deuterium; for examples, see
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It is well-known that the effect of the replacement of hydrogen by deuterium on the proton noise-decoupled 13C NMR spectrum is to reduce the intensity of the signal due to the carbon bearing the deuterium; for examples, see: Brownstein, S.; Burton, G. W.; Hughes, L.; Ingold, K. U. J. Org. Chem. 1989, 54, 560.
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The 2-methyl-2-butyl cation shows degenerate properties with interchange of the two types of methyl group protons, not affecting the methylene group. For a review, see
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The 2-methyl-2-butyl cation shows degenerate properties with interchange of the two types of methyl group protons, not affecting the methylene group. For a review, see: Ahlberg, P.; Jonsall, G.; Engdahl, C. Adv. Phys. Org. Chem. 1988, 19, 223.
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In the same way, the chain elongation observed by treatment in acidic medium of 2,3-dimethyl-4-penten-2-ol could result from a methyl 1,4-migration; see
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In the same way, the chain elongation observed by treatment in acidic medium of 2,3-dimethyl-4-penten-2-ol could result from a methyl 1,4-migration; see: Deno, N. C.; Lastomirsky, R. R. J. Org. Chem. 1975, 40, 514.
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Methyl 1,4-migrations have been invoked in Fischer indole cylizations; see
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Methyl 1,4-migrations have been invoked in Fischer indole cylizations; see: (a) Miller, B.; Matjeka, E. R. J. Am. Chem. Soc. 1980, 102, 4772.
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In rearrangement of 10,10-dibenzyl-9-anthranols, see
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In rearrangement of 4,4-disubstituted-2-cyclohexenols, see
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In rearrangements of bicyclo[3.1.0]hexenyl carbonium ions, see, Marchand, A. P., Lehr, R. E., Eds.; Academic Press: New York.
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In rearrangements of bicyclo[3.1.0]hexenyl carbonium ions, see: Sorensen, T. S.; Rauk, A. In Pericyclic Reactions; Marchand, A. P., Lehr, R. E., Eds.; Academic Press: New York, 1977; Vol. 11, p 59.
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For examples of the slow delivery of bromine from NBS, see, J. Wiley & Sons: New York. For examples of the in situ preparation of Grignard reagents (Barbier reaction), see
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For examples of the in situ formation of methyl vinyl ketone in the Robinson annulation reaction, see
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|