CCXLV.—Bromination of compounds containing the carbonyl group. (a) Pyruvic acid. (b) Acetophenone

1923 ◽  
Vol 123 (0) ◽  
pp. 2207-2213 ◽  
Author(s):  
Charles Frederick Ward
Keyword(s):  
1989 ◽  
Vol 67 (6) ◽  
pp. 998-1009 ◽  
Author(s):  
Gunnar Grue-Sørensen ◽  
Ian D. Spenser

It is shown by 13C nuclear magnetic resonance spectroscopy that the labelled C2 fragment of [2,3-13C2]pyruvic acid is transferred intact into the C-methyl group and the adjacent carbon atom of the Ephedra alkaloids, norephedrine, ephedrine, norpseudoephedrine, and pseudoephedrine, in growing plants of Ephedragerardiana. This finding serves to identify pyruvate as the elusive precursor of the aliphatic C2 terminus of the skeleton of the alkaloids. In earlier experiments with C-labelled substrates, label from [3-14C]pyruvic acid was incorporated mainly, but not exclusively, into the C-methyl group of ephedrine, and label from [2-14C]pyruvate was incorporated similarly into the carbon atom adjacent to the C-methyl group. A C6–C1 unit related to benzaldehyde or benzoic acid has long been known to generate the benzylic fragment of the carbon skeleton of the Ephedra alkaloids. It is likely that the carbon skeleton of ephedrine is generated from pyruvate and either benzaldehyde or benzoic acid, by a reaction analogous to the formation of acetoin or diacetyl from pyruvate and acetaldehyde or acetic acid, respectively. Keywords: biosynthesis of ephedrine, Ephedra alkaloids, 13C NMR spectra, ephedrine, biosynthesis of pyruvic acid, incorporation into ephedrine13C NMR spectra.


1995 ◽  
Vol 117 (15) ◽  
pp. 4240-4260 ◽  
Author(s):  
Saul Wolfe ◽  
Chan-Kyung Kim ◽  
Kiyull Yang ◽  
Noham Weinberg ◽  
Zheng Shi

1961 ◽  
Vol 39 (6) ◽  
pp. 1184-1189 ◽  
Author(s):  
Denys Cook

The infrared spectra of 2,6-dimethyl-4-pyrone in solution, and in complexes with HgCl2, ZnCl2, BF3, SbCl5, and HBr have been recorded. A band at 1639 cm−1 in the free pyrone moves to progressively lower frequencies in the complexes as the Lewis acid strength increases, identifying this band as the carbonyl stretching frequency and the donor site as the carbonyl group. A higher-frequency band, at 1678 cm−1 in the free pyrone, moves to lower frequency on complex formation, but to a much smaller extent, and is to be identified with a stretching mode of the ring. The site of protonation in 2,6-dimethyl-4-pyrone salts has been unequivocally shown to be the carbonyl oxygen atom.


1933 ◽  
Vol 9 (6) ◽  
pp. 574-582 ◽  
Author(s):  
C. F. H. Allen ◽  
H. R. Sallans

In the presence of alkali, cyclohexanone and its homologues add to chalcones to form either semicyclic diketones or dicyclic keto-alcohols; the latter contain a carbonyl bridge, and the former can be converted into closed ring structures and dehydrated to form substances having a carbonyl bridge. In these dicyclic ketones the bridge is not removed by heating, in contrast to the behavior of certain other compounds having a similar ring system.A second mode of ring closure gives rise to pyryllium salts; the isolation of a methyl ether has made it possible to devise a plausible mechanism for this hitherto obscure reaction. Four varieties of salts are described, the perchlorates being obtained by a different procedure than that previously employed.


1987 ◽  
Vol 28 (46) ◽  
pp. 5713-5716 ◽  
Author(s):  
Masayo Fujii ◽  
Shunichi Yamakage ◽  
Hiroshi Takaku ◽  
Tsujiaki Hata

Author(s):  
Stanko Uršić ◽  
Viktor Pilepić ◽  
Valerije Vrček ◽  
Mario Gabričević ◽  
Branka Zorc

1970 ◽  
Vol 48 (9) ◽  
pp. 1436-1445 ◽  
Author(s):  
N. R. Hunter ◽  
G. A. MacAlpine ◽  
H. J. Liu ◽  
Z. Valenta

Photo-cycloaddition of vinyl acetates to 2-cyclohexenones followed by hydrolysis of the acetate group and by oxidative fragmentation leads to 2-alkyl-2-cyclohexenones in which the newly introduced alkyl group bears a 2′-carbonyl group. A similar, less generally applicable method, involving photo-cycloaddition, bromination, and heterolytic fragmentation is also described. Possible applications of this sequence in organic synthesis are discussed.


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