5058-19-5Relevant articles and documents
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Lightner et al.
, p. 571,572 (1970)
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Intramolecular Photochemical Hydrogen Abstraction in 2-Alkylpyrazines and 2-Alkylpyridines
Mukherjee, Ashis,Duggan, Sandhya A. M.,Agosta, William C.
, p. 178 - 181 (1994)
Photochemical hydrogen abstraction in 2-alkylpyrazines 5-8 and 2-alkylpyridines 9-11 proceeds analogously to the process of eq 1.Hydroxylic solvent causes quantum yields for pyrazine fragmentation products (Φp) to increase about 1 order of magnitude.Pyridine fragmentation takes place from both singlet and triplet states.Pyrazine fragmentations follow Stern-Volmer kinetics with modest bond strength selectivity (1 deg : 3 deg ca. 1:17 for 5a and 5c).Methyl substitution lowers the rate of abstraction in pyrazines and trifluoromethyl substitution increases Φp in pyridines.It is suggested that these effects reflect changes in the n?* and ??* character of the reactive excited states.
Odd-Even Effect on the Spin-Crossover Temperature in Iron(II) Complex Series Involving an Alkylated or Acyloxylated Tripodal Ligand
Ishida, Takayuki,Kashiro, Atsushi,Kohno, Wakana
supporting information, (2020/08/05)
In the context of magneto-structural study, a relatively short alkyl group was introduced to anionic spin-crossover (SCO) building blocks based on [Fe(py3CR)(NCS)3]-, where py3CR stands for tris(2-pyridyl)methyl derivatives. The linear alkyl and acyloxyl derivatives of Me4N[Fe(py3CR)(NCS)3] with R = CnH2n+1 (n = 1-7) and CnH2n+1CO2 (n = 1-6) were synthesized, and the magnetic study revealed that all the compounds investigated here exhibited SCO. The SCO temperature (T1/2) varied in 289-338 K for the alkylated compounds, and those of the acyloxylated ones were lower with a narrower variation width (T1/2 = 216-226 K). The crystal structures of the former with n = 3, 4, and 5 and the latter with n = 1, 4, 5, and 6 were determined, and various molecular arrangements were characterized. There is no structural evidence for a molecular fastener effect. The plots on T1/2 against n displayed a pronounced odd-even effect; the SCO temperatures of the homologues with even n are relatively higher than those of the homologues with odd n. The odd-even effect on T1/2 may be related with the entropy difference across the SCO, rather than crystal field modification or intermolecular interaction. The present work will help molecular design to fine-tune T1/2 by means of simple chemical modification like alkylation and acyloxylation.
The one-pot synthesis of pyridine derivatives from the corresponding 1,5-dicarbonyl compounds
Mihara, Hiromichi,Miyakoshi, Takeru,Kikuchi, Yui,Konno, Hiroyuki
, p. 1375 - 1383 (2019/12/23)
The optimization of the one-pot, acid-promoted synthesis of pyridine and alkylpyridine derivatives from simple alkyl-1,5-dicarbonyl derivatives and via the corresponding oxime intermediate is described. Of all the combinations of and solvents tested, the use of HCl in refluxing dioxane was found to result in the highest chemical yields. Twelve pyridines were prepared using this method.