The Photochemical Reduction of Bromotrichloromethane by Derivatives of 1,4-Dihydropyridine

Kurz, Joseph L.; Hutton, Robert F.; Westheimer, F. H.

doi:10.1021/ja01464a021

Cited by 70 publications

(29 citation statements)

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“…N-Methylated Hantzsch 1,4-dihydropyridines were prepared according to the literature. [39] 10-Methyl-9,10-dihydroacridine (AcrH 2 ) was prepared according to the literature. [40] 1-(4-Substituted phenyl)-1,4-dihydronicotinamides were prepared according to the following general methods: the appropriate aniline (1 mmol) dissolved in dry methanol (15 mL) was added to a solution of 1-(2,4-dinitrophenyl)nicotinamide chloride (1 mmol) in methanol (100 mL).…”

Section: Methodsmentioning

confidence: 99%

Determination of the C4H Bond Dissociation Energies of NADH Models and Their Radical Cations in Acetonitrile

Zhu

et al. 2003

Chemistry A European J

150

134

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Heterolytic and homolytic bond dissociation energies of the C4-H bonds in ten NADH models (seven 1,4-dihydronicotinamide derivatives, two Hantzsch 1,4-dihydropyridine derivatives, and 9,10-dihydroacridine) and their radical cations in acetonitrile were evaluated by titration calorimetry and electrochemistry, according to the four thermodynamic cycles constructed from the reactions of the NADH models with N,N,N',N'-tetramethyl-p-phenylenediamine radical cation perchlorate in acetonitrile (note: C9-H bond rather than C4-H bond for 9,10-dihydroacridine; however, unless specified, the C9-H bond will be described as a C4-H bond for convenience). The results show that the energetic scales of the heterolytic and homolytic bond dissociation energies of the C4-H bonds cover ranges of 64.2-81.1 and 67.9-73.7 kcal mol(-1) for the neutral NADH models, respectively, and the energetic scales of the heterolytic and homolytic bond dissociation energies of the (C4-H)(.+) bonds cover ranges of 4.1-9.7 and 31.4-43.5 kcal mol(-1) for the radical cations of the NADH models, respectively. Detailed comparison of the two sets of C4-H bond dissociation energies in 1-benzyl-1,4-dihydronicotinamide (BNAH), Hantzsch 1,4-dihydropyridine (HEH), and 9,10-dihydroacridine (AcrH(2)) (as the three most typical NADH models) shows that for BNAH and AcrH(2), the heterolytic C4-H bond dissociation energies are smaller (by 3.62 kcal mol(-1)) and larger (by 7.4 kcal mol(-1)), respectively, than the corresponding homolytic C4-H bond dissociation energy. However, for HEH, the heterolytic C4-H bond dissociation energy (69.3 kcal mol(-1)) is very close to the corresponding homolytic C4-H bond dissociation energy (69.4 kcal mol(-1)). These results suggests that the hydride is released more easily than the corresponding hydrogen atom from BNAH and vice versa for AcrH(2), and that there are two almost equal possibilities for the hydride and the hydrogen atom transfers from HEH. Examination of the two sets of the (C4-H)(.+) bond dissociation energies shows that the homolytic (C4-H)(.+) bond dissociation energies are much larger than the corresponding heterolytic (C4-H)(.+) bond dissociation energies for the ten NADH models by 23.3-34.4 kcal mol(-1); this suggests that if the hydride transfer from the NADH models is initiated by a one-electron transfer, the proton transfer should be more likely to take place than the corresponding hydrogen atom transfer in the second step. In addition, some elusive structural information about the reaction intermediates of the NADH models was obtained by using Hammett-type linear free-energy analysis.

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Section: Methodsmentioning

confidence: 99%

Determination of the C4H Bond Dissociation Energies of NADH Models and Their Radical Cations in Acetonitrile

Zhu

et al. 2003

Chemistry A European J

150

134

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“…Direct reaction between BNAH and CHCl3 in the absence of the radical was negligible, which was confirmed by the lower yield of the product, although a thermal reaction was reported. 26 The ratio of the rate of thermal reaction to that of polymerization in CHC13 may be estimated from the results in Tables I1 and I11 obtained in the absence of polymerization initiator to be about 0.075. Kosower and S~h w a g e r~~ demonstrated that the reaction between a pyridinyl radical and halocarbons gave pyridinium halides by the abstraction of a halide by the radical.…”

Section: Polymerization Of Vcph In Chcl3 and Reaction Of Its Model Comentioning

confidence: 99%

Synthesis and polymerization of N‐(p‐vinylbenzyl)‐3‐carbamoyl‐1,4‐dihydropyridine and redox behavior of the oligomer

Tsuchida

Hasegawa

Ohno

1977

J. Polym. Sci. Polym. Chem. Ed.

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In order to prepare a soluble dihydropyridine‐type redox polymer, N‐(p‐vinylbenzyl)‐3‐carbamoyl‐1,4‐dihydropyridine was synthesized and characterized by elemental analysis, infrared spectroscopy, and nuclear magnetic resonance spectroscopy. The polymerization of the vinyl monomer in N,N‐dimethylformamide or chloroform was also studied. Only oligomers were obtained by radical polymerization. The reduction of various compounds by the oligomer thus prepared was examined in heterogeneous or homogeneous solution.

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“…A variety of reagents have been utilized for this oxidative conversion: nitric acid [7], nitric oxide [8], urea nitrate [9], peroxodisulfate‐Co(II) [9], clay‐supported ferric and cupric nitrate[10], BrCCl 3 /hν [11], N ‐methyl‐ N ‐nitroso‐ p ‐toluenesulfonamide [12], DDQ [13], Zr(NO 3 ) 4 [14], Mn(OAc) 3 [15], Pd/C [16], I 2 /MeOH [17], manganese dioxide–bentonite clay [18], chromium trioxide [19], potassium permanganate [20], pyridinium chlorochromate [21], ceric ammonium nitrate (CAN) [22], clayfen [23], bismuth trinitrate [24], ruthenium trichloride [25], Fe(ClO 4 ) 3 /HOAc [26], tert‐butylhydroperoxide [27], silica gel supported ferric nitrate (silfen) [28], MnO 2 [29], and vanadium salts [30].…”

Section: Introductionmentioning

confidence: 99%

A novel, facile, simple and convenient oxidative aromatization of Hantzsch 1,4‐dihydropyridines to pyridines using polymeric iodosobenzene with KBr

Kumar¹

2010

Journal of Heterocyclic Chem

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The Photochemical Reduction of Bromotrichloromethane by Derivatives of 1,4-Dihydropyridine

Cited by 70 publications

References 0 publications

Determination of the C4H Bond Dissociation Energies of NADH Models and Their Radical Cations in Acetonitrile

Determination of the C4H Bond Dissociation Energies of NADH Models and Their Radical Cations in Acetonitrile

Synthesis and polymerization of N‐(p‐vinylbenzyl)‐3‐carbamoyl‐1,4‐dihydropyridine and redox behavior of the oligomer

A novel, facile, simple and convenient oxidative aromatization of Hantzsch 1,4‐dihydropyridines to pyridines using polymeric iodosobenzene with KBr

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