The Preparation of Heterocyclic Fluorine Compounds by the Schiemann Reaction. I. The Monofluoropyridines

Roe, Arthur; Hawkins, G. F.

doi:10.1021/ja01202a057

Cited by 68 publications

(34 citation statements)

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“…The etheral solution was dried over potassium hydroxide, filtered, distilled twice over potassium hydroxide to yield pure 3-fluoropyridine (2.1 g, 2 0 7 3 (b.p. = 107 "C) (literature 107 C) [8][9][10][11].…”

Section: Muterialsmentioning

confidence: 99%

Preparation and Properties of 3-Halopyridine-adenine Dinucleotides, NAD + Analogues and of Model Compounds

et al. 1976

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The preparation of model compounds 1-(2',6'-dichlorobenzyl)-3-halogenopyridiniurn and the study of their properties were achieved. Their chemical reduction to the corresponding 1,4-dihydropyridines is proved by spectroscopic analysis. 3-Iodopyridine-adenine dinucleotide was prepared by enzymic transglycosidation while the 3-chloro, 3-bromo and 3-iodo pyridine-adenine dinucleotides were synthesized from 3-amino-pyridine-adenine dinucleotide. The 3-halogenopyridine -adenine dinucleotides were proved to be active as hydrogen acceptors with alcohol as a substrate. The absorption band at 290 nm of cinnamaldehyde appeared to be a very sensitive tool for studying the enzymic reaction. With the alcohol dehydrogenase from yeast, only slight activity was detected. 3-Halogenopyridine -adenine dinucleotides are competitive inhibitors with respect to nicotinamide--adenine dinucleotide with alcohol dehydrogenase from yeast, lactate dehydrogenase and malate dehydrogenase. The use of 3-iodopyridine -adenine dinucleotide as a heavy-atom derivative for X-ray structure det6rmination is proposed.Although the analogues of NAD+ with structural modification at the pyridinium ring are numerous, their differences with NAD' are only slight considering the similarity of the group at C-3. We thought that halo3PdAD+, where the amide group is replaced by a halogen, may be interesting analogues for the study of the NAD+ binding site of dehydrogenases.The carbon-halogen distances vary from 2.05 A for iodine [l] to 1.35 A for fluorine [2]. Moreover the possibility of using io3PdAD+ as a heavy-atom derivative for the X-ray structure determination of some dehydrogenases and as a photochemical label [3] seemed interesting.

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Section: Muterialsmentioning

confidence: 99%

Preparation and Properties of 3-Halopyridine-adenine Dinucleotides, NAD + Analogues and of Model Compounds

et al. 1976

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“…These data have been mentioned briefly before [1], but experimental details and a discussion of the results are now presented for the first time. The Balz-Schiemann technique was used to convert 2-amino-3-methylpyridine into 2-fluoro-3-methylpyridine (1) (Scheme 2), permanganate oxidation of this to acid 2 followed by its conversion to acyl chloride 3 was conducted according to literature instructions [14][15][16][17]. Rosenmund reduction was used to transform the acyl chloride into carboxaldehyde 4.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of some fluorine-containing pyridinealdoximes of potential use for the treatment of organophosphorus nerve-agent poisoning

Timperley

Banks

Young

et al. 2011

Journal of Fluorine Chemistry

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“…Experimental Section 3-Fluoropyridine (b. p. 105 °C at 752 Torr [27] and 2,6-Difluoropyridine (b.p. 123 °C at 743 Torr [28] both colourless liquids, were purchased from Pfaltz and Bauer and PCR Research Chemicals Inc. re spectively.…”

Section: Introductionmentioning

confidence: 99%

Nonlocal Susceptibilities and Molecular Electric Quadrupole Moments of 3-Fluoropyridine and 2,6-Difluoropyridine, a Rotational Zeeman Effect Study

Hübner

Stolze

Sutter

1981

Zeitschrift Für Naturforschung A

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The rotational Zeeman effect spectra of 3-Fluoropyridine and 2,6-Difluoropyridine have been measured. The molecular <7-values are gaa = -0.0917(5), gbb = -0.0476(5), gC c = +0.0194(5) for 3-Fluoropyridine and gaa = -0.0573(6), gbb = -0.0311(6), gcc= + 0.0102(6) for 2,6-Difluoropyridine. The values for the magnetic susceptibility anisotropics in units of 10~6 erg/(G2 mol) are 2Xaa-\-Xbb + Xcc = 53.3(8), 2Xbb -Xcc -Xaa -60.5(7) for 3-Fluoropyridine and 2Xaa~X bb -_X "C C = 48.4(11), 2Xbb -XC c -X-aa = 51.7(11) for 2,6-Difluoropyridine. Subtraction of the local atom contributions to the magnetic susceptibilities indicates that Fluorine quenching of the nonlocal out of plane contribution depends on the position of the substituent. Further, the data suggest a linear correlation between Xj°nl0Cil and the "CNDO/2-7r-density alternation", which is used to predict susceptibility anisotropics of Fluorobenzenes and Fluoropyridines not yet mea sured.The molecular quadrupole moments are calculated from the Zeeman data and compared with the experimental values obtained for various fluorosubstituted Pyridines and Benzenes. If the quadrupole moments perpendicular to the molecular plane are referred to the centers of the six membered rings and are plotted against the number of Fluoroine substituents, n-p, the plots closely follow a straight line with identical slopes for the Pyridine-and Benzenefamilies, but with different intercepts at np = 0. From the "np = 0 intercept" for the Fluorobenzenes we conclude that the Benzene quadrupole moment proposed earlier by Shoemaker and Flygare should probably be revised.

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The Preparation of Heterocyclic Fluorine Compounds by the Schiemann Reaction. I. The Monofluoropyridines

Cited by 68 publications

References 0 publications

Preparation and Properties of 3-Halopyridine-adenine Dinucleotides, NAD + Analogues and of Model Compounds

Preparation and Properties of 3-Halopyridine-adenine Dinucleotides, NAD + Analogues and of Model Compounds

Synthesis of some fluorine-containing pyridinealdoximes of potential use for the treatment of organophosphorus nerve-agent poisoning

Nonlocal Susceptibilities and Molecular Electric Quadrupole Moments of 3-Fluoropyridine and 2,6-Difluoropyridine, a Rotational Zeeman Effect Study

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