• Archives of Pharmacal Research
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• v.5 no.2
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• pp.97-101
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• 1982

Depending upon the results obtained by the bromolactonization of olefinic acids (9-11) by means of N-bromosaccharin (4), the influence of the stabilities of the imidic anions resulted from heterolytic cleavage of N-haloimides, such as N-bromosuccinimide (1), N-bromophthalimde (2), and N-bromosaccharin (3) in dry N, N-dimethylformamide on the reactivity is elucidated.

• Archives of Pharmacal Research
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• v.8 no.1
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• pp.39-41
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• 1985

Bromocycloetherification of a series of 3-and 4-olefinic alcohols using NBS-acetonitrile gave corresponding bromo-tetrahydrofuran with high regio and steroselectivity.

• Journal of Photoscience
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• v.10 no.1
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• pp.89-96
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• 2003

Two important types of $\alpha$-heterolytic fragmentation reactions of aminium radicals are discussed. In these fragmentation processes, transfer of electrofugal groups from the aminium radicals to either Lowry-Bronsted or Lewis bases produces $\alpha$-amino radicals. The results of recent studies that provided key information about the dynamics of the important aminium radical fragmentation reactions, deprotonation, desilylation, are summarized. Finally, selected examples, which demonstrate how knowledge of the relative rates of aminium radical cleavage can be used to design synthetically relevant SET-promoted photocyclization reactions, are presented.

• Bulletin of the Korean Chemical Society
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• v.3 no.1
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• pp.30-33
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• 1982

Photochemical and thermal solvolysis of 2,3,4-picolyl chlorides (2,3,4-PC) were studied in amine solvents and the results were correlated with the electronic structures calculated by PPP-SCF-MO CI method. Activation parameters show that the thermal solvolysis of PC is $S_N2$ type rcaction. The rates of thermal reaction in pyridine or t-butylamine solvent decrease in the order of 2-PC > 3-PC > 4-PC. These results are consistent with the predictions based on the electron densities of picolyl chlorides. In photosolvolysis, the same products as those of thermal reactions were obtained. The results indicate that photochemical solvolysis undergoes through heterolytic cleavage. Relative quantum yields of photosolvolysis of 2,3,4-picolyl chlorides in t-butylamine solvent were determined to be 0.73, 1, and 0.50 respectively. These results are in good agreement with the electron densities of the excited triplet state of picolyl chlorides.

• Bulletin of the Korean Chemical Society
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• v.19 no.4
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• pp.462-466
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• 1998

The homobimetallic anion, $({\eta}^5-MeCp)Mn(CO)_2Mn(CO)_5-M^+\; (M^+=Na^+, PPN^+$) was disrupted by $PR_3\;(R=C_6H_5,\;C_2H_5,\;OCH_3)$ in THF at various temperatures (r.t. ∼65℃) under the pseudo first order reaction conditions where excess of $PR_3$ was employed under a nitrogen atmosphere. For the reaction involving $PPN^+$ analog, Mn-Mn heterolytic cleavage occurred, leading to $PPN^+Mn(CO)_5^-\; and \;({\eta}^5-MeCp)Mn(CO)_2PR_3$ as products; however, in case of $Na^+\; analog,\; Na^+$ seems to play a novel counter ion effect on the disruption reaction by transferring one terminal CO from the $Mn(CO)_5$ moiety on to the $({\eta}^5-MeCp)Mn(CO)_2$ of the corresponding homobimetallic complex, eventually resulting in $Na^+Mn(CO)_4PR_3^-\;and\;({\eta}^5-MeCp)Mn(CO)_3$. This reaction is of overall first order with respect to [homobimetallic complex] with the activation parameters (ΔH≠=23.0±0.7 kcal/mol, ΔS≠= - 8.7±0.8 e.u. for $Na^+$ analog; ΔH≠=28.8±0.4 kcal/mol, ΔS≠=15.7±0.6 e.u. for $PPN^+$ analog reaction).