LYCOPODIUM ALKALOIDS: VIII. LYCOPODINE

1959 ◽  
Vol 37 (10) ◽  
pp. 1757-1763 ◽  
Author(s):  
D. B. MacLean ◽  
W. A. Harrison
Keyword(s):  
Nitrogen Atom ◽  
Carbonyl Group ◽  
Lycopodium Alkaloids

Information pertaining to the position of the carbonyl group relative to the nitrogen atom and to the size of one of the nitrogen rings in lycopodine has been obtained through a study of the reactions of α- and β-cyanobromolycopodine.

LYCOPODIUM ALKALOIDS: IV. REACTIONS OF α-CYANOBROMOLYCOPODINE AND ITS DERIVATIVES

1956 ◽  
Vol 34 (11) ◽  
pp. 1519-1527 ◽  
Author(s):  
L. R. C. Barclay ◽  
David B. MacLean
Keyword(s):  
Nitrogen Atom ◽  
Carbonyl Group ◽  
Lycopodium Alkaloids ◽  
Hydrolysis Of ◽  
Methylene Group

The hydrogenolysis and hydrolysis of α-cyanobromolycopodine to the secondary tricyclic base, α-des-dihydrolycopodine, is reported. The latter compound was converted to the methiodide in poor yield so that further degradations of the molecule through this derivative were not feasible. Hydride reductions of α-cyanobromolycopodine and some of its derivatives are recorded. The presence of a methylene group adjacent to the carbonyl group in lycopodine has been proved. Evidence is presented which suggests that the carbonyl group and the nitrogen atom are relatively close to one another in the molecule.

Sur l'aptitude à l'extension du noyau pipéridique en fonction de la substitution de l'atome d'azote: réaction du diazométhane avec quelques pipéridones-4 et désamination nitreuse des aminométhyl-alcools correspondants

1971 ◽  
Vol 49 (19) ◽  
pp. 3075-3085 ◽  
Author(s):  
H. Favre ◽  
Z. Hamlet ◽  
R. Lanthier ◽  
M. Ménard
Keyword(s):  
Nitrogen Atom ◽  
Carbonyl Group ◽  
Nitrous Acid ◽  
Ring Expansion ◽  
Nucleophilic Attack ◽  
Electronic Effects ◽  
Field Effects ◽  
Benzoyl Group ◽  
La Substitution

Aptitude to ring expansion in the piperidine series, measured by the ratio of ring expanded ketone to epoxide, varies considerably according to the nitrogen atom substituent. This ratio is essentially the same in the case of the reaction of diazomethane on 4-piperidones and the nitrous acid deamination of the corresponding aminoalcohols. The values of the ratio are 0.01–0.1 for a phenylsulfonyl group, of the order 0.3–0.6 for a benzoyl group and slightly greater than 1 for a benzyl group. Electronic effects (inductive and field effects) are the cause of these differences. Parallels between the two reactions indicate that nucleophilic attack of diazomethane on the carbonyl group can lead to the ring expanded ketone and the epoxide.

Umsetzungen von 2-chlor- und 2-organoaminosubstituierten 5.6-Benzo-1,3-dimethyl-1,3,2-diazaphosphorinan-4-onen mit Aziden / Reactions of 2-Chloro- and 2-Organoamino-Substituted 5.6-Benzo-1,3-dimethyl-1,3,2-diazaphosphorinane-4-ones with Azides

1994 ◽  
Vol 49 (2) ◽  
pp. 171-175 ◽  
Author(s):  
Ion Neda ◽  
Thomas Kaukorat ◽  
Reinhard Schmutzler
Keyword(s):  
Nmr Spectroscopy ◽  
Nitrogen Atom ◽  
Ir Spectroscopy ◽  
Carbonyl Group ◽  
Related Compound ◽  
Phosphorus Pentachloride ◽  
Trimethylsilyl Azide

The reaction of 5,6-benzo-2-chloro-1,3-dimethyl-1,3,2-diazaphosphorinane-4-one (1) with trimethylsilyl azide led to the substituted cyclotriphosphazene (3). A monomeric reaction product was not observed by NMR spectroscopy. The diazaphosphorinane 2, with the 2-chloroethyl substituent bonded to the nitrogen atom in a-position to the carbonyl group, did not react with trimethylsilyl azide. An attempt to prepare 3 from N,N'-dimethylanthranilamide 5 and hexachlorocyclotriphosphazene 4 failed, as did the attempt to react 5 with phosphorus pentachloride. The reaction of 5,6-benzo-2-{bis(2-chloroethyl)amino}-1,3-dimethyl- 1.3.2-diazaphosphorinane-4-one (7) and of the related compound 9, bearing only one 2-chloroethyl substituent, with 4-nitrobenzoyl azide furnished, in a normal Staudinger fashion, the monomeric products 8 and 10. In the case of 10, intramolecular P=O···H interaction was demonstrated by IR spectroscopy.

LYCOPODIUM ALKALOIDS: II SOME REACTIONS OF THE PERMANGANATE OXIDATION PRODUCT OF ANOTININE

1953 ◽  
Vol 31 (6) ◽  
pp. 543-549 ◽  
Author(s):  
David B. MacLean ◽  
H. C. Prime
Keyword(s):  
Nitrogen Atom ◽  
Oxidation Product ◽  
Permanganate Oxidation ◽  
Clemmensen Reduction ◽  
Lycopodium Alkaloids

The permanganate oxidation product of annotinine is shown to be an amide that contains the ether ring of annotinine still intact. The Clemmensen reduction of this compound to the saturated base, C16H23O2N, was re-examined. A number of intermediates were isolated from the system and these were also prepared from the oxidation product by other methods. Analogous reactions of annotinine chlorohydrin were also studied. From these results suggestions are presented regarding the size of the ether ring and its position relative to the nitrogen atom.

scholarly journals Synthesis of New Bis(spiro-β-lactams) via Interaction of Methyl 1-Bromocycloalcanecarboxylates with Zinc and N,N′-Bis(arylmethylidene)benzidines

2019 ◽  
Vol 2019 ◽  
pp. 1-7 ◽  
Author(s):  
N. F. Kirillov ◽  
E. A. Nikiforova ◽  
D. V. Baibarodskikh ◽  
T. A. Zakharova ◽  
L. S. Govorushkin
Keyword(s):  
Nitrogen Atom ◽  
Carbonyl Group ◽  
Nucleophilic Addition ◽  
Ring Closure ◽  
Amide Nitrogen ◽  
Ester Carbonyl ◽  
Ester Carbonyl Group ◽  
Amide Nitrogen Atom

Interaction of the Reformatsky reagents, prepared from methyl 1-bromocyclopentane-1-carboxylate or methyl 1-bromocyclohexane-1-carboxylate, with N,N′-bis(arylmethylidene)benzidines has given rise to a set of intermediates as a result of nucleophilic addition to the C=N group of a substrate. Further intramolecular attack of the amide nitrogen atom onto the ester carbonyl group is responsible for the ring closure, which affords two series of spirocompounds: 2,2′-([1,1′-biphenyl]-4,4′-diyl)bis(3-aryl-2-azaspiro[3.4]octan-1-one) or 2,2′-([1,1′-biphenyl]-4,4′-diyl)bis(3-aryl-2-azaspiro[3.5]nonan-1-ones).

INFRARED SPECTRA OF COMPLEXES OF 4-PYRIDONES

1963 ◽  
Vol 41 (2) ◽  
pp. 515-521 ◽  
Author(s):  
Denys Cook
Keyword(s):  
Nitrogen Atom ◽  
Carbonyl Group ◽  
Lewis Acid ◽  
Infrared Spectra ◽  
Lewis Acids ◽  
Donor Site ◽  
Acid Strength ◽  
Ring Mode ◽  
Lower Frequencies

The infrared spectra of many complexes of Lewis acids with some 4-pyridones have been recorded. Large shifts to lower frequencies of about 100 cm−1 have been observed in a band near 1560 cm−1 as the Lewis acid strength increased. Much smaller shifts of about 5 to 10 cm−1 in a band near 1640 cm−1 were noted. The former band has therefore been designated as the carbonyl frequency, and the latter as a ring mode involving CC stretching.The donor site of 4-pyridones is therefore the carbonyl group, and not the nitrogen atom. Protonated 4-pyridones have similar spectra, and are consistent with O-, not N-protonation.

Infrared Absorption of the Carbonyl Group of Semicarbazides, Semicarbazones, and Pyrazolecarboxamides

1968 ◽  
Vol 22 (3) ◽  
pp. 167-169 ◽  
Author(s):  
Tze Seng Wang
Keyword(s):  
Nitrogen Atom ◽  
Carbonyl Group ◽  
Infrared Absorption ◽  
Phenyl Group ◽  
Frequency Region ◽  
The Third ◽  
Alkyl Groups ◽  
Carbonyl Absorption

The carbonyl frequency in semicarbazides, semicarbazones, and pyrazolecarboxamides is higher than that in ureas. A phenyl group attached to the third nitrogen atom of semicarbazides lowers the carbonyl frequency. A phenyl group substituted on the first nitrogen atom shifts the carbonyl absorption in semicarbazides to a higher frequency region than do alkyl groups.

LYCOPODIUM ALKALOIDS: IX. CYCLIZED PRODUCTS FROM α- AND β-CYANOBROMOLYCOPODINE

1960 ◽  
Vol 38 (4) ◽  
pp. 528-538 ◽  
Author(s):  
D. B. MacLean ◽  
Won-Ryul Song ◽  
W. A. Harrison
Keyword(s):  
Carbonyl Group ◽  
Potassium Hydroxide ◽  
Indirect Method ◽  
Potassium Acetate ◽  
Cyclic Ether ◽  
Cyclization Reaction ◽  
Enol Ether ◽  
Lycopodium Alkaloids

A study has been made of the products formed on treatment of α- and β-cyanobromolycopodine with potassium hydroxide in methanol and potassium acetate in ethanol, respectively. The product derived from the α-isomer is apparently formed in a cyclization reaction taking place alpha to the carbonyl group while that formed from the β-isomer may be an enol ether. The olefin expected from a normal dehydrobromination of α-cyanobromolycopodine has been prepared by an indirect method. Attempts to prepare the analogous olefin in the β-series led to the formation of a saturated cyclic ether. The hydrogenolysis product of β-cyanobromolycopodine has been prepared.

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