LYCOPODIUM ALKALOIDS: XVI. ANNOTINE

1964 ◽  
Vol 42 (11) ◽  
pp. 2584-2594 ◽  
Author(s):  
W. A. Szarek ◽  
K. A. H. Adams ◽  
M. Curcumelli-Rodostamo ◽  
D. B. MacLean
Keyword(s):  
Double Bond ◽  
Nitrogen Atom ◽  
Hydroxyl Group ◽  
Tertiary Nitrogen Atom ◽  
Chemical Studies ◽  
Group A ◽  
Instrumental Methods ◽  
Tertiary Hydroxyl ◽  
Plausible Structure ◽  
Tertiary Nitrogen

Annotine, C16H21O3N, is shown to be pentacyclic and to contain a tertiary hydroxyl group, a lactone function, a tertiary nitrogen atom, and a dialkylated double bond. The position of the double bond and the tertiary hydroxyl group relative to the nitrogen atom has been established by Emde degradation of annotine methiodide. The presence of a lactone function is inferred from the reduction of annotine to dihydroannotinol, a hemiacetal, which reacts with 1 mole of ethyl mercaptan. The reduction of the lactone to a diol in an annotine derivative has been carried out. The chemical studies and the examination of annotine and its derivatives by modern instrumental methods allow the assignment of a plausible structure to the alkaloid.

The constituents of Cryptocarya pleurosperma White & Francis. I. Pleurospermine: A new alkaloid of the leaves

1959 ◽  
Vol 12 (1) ◽  
pp. 90 ◽  
Author(s):  
E Gellert
Keyword(s):  
Nitrogen Atom ◽  
Oxygen Atom ◽  
Hydroxyl Group ◽  
Veratric Acid ◽  
The Third ◽  
Tertiary Nitrogen Atom ◽  
Group A ◽  
Francis I ◽  
Alcoholic Hydroxyl ◽  
Tertiary Nitrogen

A new alkaloid pleurospermine, C14Hl9O3N, has been isolated from the leaves of Cryptocarya pleurosperma. Pleurospermine contains a methoxyl group, a phenolic hydroxyl group, and a tertiary nitrogen atom. The third oxygen atom is possibly present as an alcoholic hydroxyl group. On heating with palladium-charcoal the alkaloid yields 4-hydroxy-3-methoxyacetophenone (I), while methylation followed by oxidation gives veratric acid.

scholarly journals C-Lactam Derivatives of Oleanolic Acid. The Synthesis of C-lactam by Beckmann Rearrangement of C-oxime

2011 ◽  
Vol 6 (12) ◽  
pp. 1934578X1100601
Author(s):  
Barbara Bednarczyk – Cwynar
Keyword(s):  
Double Bond ◽  
Nitrogen Atom ◽  
Oleanolic Acid ◽  
Structure Elucidation ◽  
Beckmann Rearrangement ◽  
Hydroxyl Group ◽  
Chemical Transformations ◽  
Group A ◽  
Derivatives Of ◽  
Carbonyl Function

Oleanolic acid, one of the most known triterpenes, was subjected to different chemical transformations within C-3 β-hydroxyl group, a double bond between C-12 and C-13, and a carboxyl function at C-17 in order to obtain new derivatives. The key compound consists of four six-membered rings (A, B, D, E) and one enlarged ring (C ring) containing a nitrogen atom and a carbonyl function – lactam. This type of derivative can be obtained by Beckmann rearrangement of the appropriate oxime. The lactam can be transformed into thiolactam with the use of Lavesson's reagent. The method is also presented for new derivatives synthesis, as well as their structure elucidation by spectroscopic means.

Zur Chemie des Phorbols, VIII

1968 ◽  
Vol 23 (12) ◽  
pp. 1584-1597 ◽  
Author(s):  
Michael Gschwendt ◽  
Erich Hecker
Keyword(s):  
Allyl Alcohol ◽  
Lead Tetraacetate ◽  
Hydroxyl Group ◽  
Structural Elements ◽  
Complete Structure ◽  
Relative Configuration ◽  
Alcohol Group ◽  
Partial Structures ◽  
Group A ◽  
Tertiary Hydroxyl

Oxidation of phorbol with one mole of lead tetraacetate yields bisdehydrophorbol, tiglophorbol and small amounts of phorbolacton-semiacetal. By chemical and spectroscopic investigations of bisdehydrophorbol and its derivatives its complete structure 16 is derived based upon the partial structures and structural elements of phorbol (1 - 3) which have been deduced in preceding communications. By consideration of the mechanism of the oxidative scission of the cyclopropanol unit in phorbol the structure 15 of this new tetracyclic diterpene is obtained. 15 has a pentamethyl-tetradecahydro-1H-cyclopropabenzazulene skeleton (tiglian) carrying as functional groups a tertiary hydroxyl group, an α,β-unsaturated tertiary 1.2-ketol group, a primary allyl alcohol group and a α- [hydroxycyclopropyl] -carbinol group. Phorbol is 4.9.12β.13.20-pentahydroxy-tigliadien- (1.6) -on- (3) (15) , bisdehydrophorbol 4.9.12β.20-tetrahydroxy-13.15-seco-tigliatrien- (1.6.15) -dion- (3.13) (16) the conformations of which have been determined. The structure of phorbolacton-semiacetal is determined in the following communication of this series. Based upon the structure of phorbol and additional chemical and spectroscopic evidence the structure of tiglophorbol (17) is also derived. With the data provided the relative configuration and the conformation of six out of the eight asymmetric centers of phorbol is determined.

Carnaubadiol, a triterpene from carnauba wax

1965 ◽  
Vol 18 (9) ◽  
pp. 1411 ◽  
Author(s):  
CS Barnes ◽  
MN Galbraith ◽  
E Ritchie ◽  
WC Taylor
Keyword(s):  
Hydroxyl Group ◽  
Side Chain ◽  
Spectroscopic Methods ◽  
Carnauba Wax ◽  
Group A ◽  
Tertiary Hydroxyl

By chemical and spectroscopic methods, carnaubadiol, C31H54O2, a constituent of carnauba wax, was shown to contain one secondary and one tertiary hydroxyl group, and one isopropenyl group. A series of degradative reactions yielded a heptanorketone, identical with the known 3β-acetoxyhexanordammaran-20-one, previously obtained from dammarenediol. The structure and configuration of the side-chain were established by oxidation of dihydrocarnaubadiol to the known (-)-(S)-5,6-dimethylheptan-2-one. Carnaubadiol was thus shown to be 24β-methyl- dammar-25-ene-3β,20ξ-diol.

The Alkaloids of Kopsia longiflora Merrill. I. Isolation of the Alkaloids

1955 ◽  
Vol 8 (1) ◽  
pp. 129 ◽  
Author(s):  
WD Crow ◽  
M Michael
Keyword(s):  
Nitrogen Atom ◽  
Rain Forest ◽  
Forest Tree ◽  
Triterpene Alcohol ◽  
Carbonyl Groups ◽  
Alcohol Acetate ◽  
Ultraviolet Spectra ◽  
Tertiary Nitrogen Atom ◽  
Neutral Media ◽  
Tertiary Nitrogen

The bark and leaves of the rain-forest tree Kopsia longiflora Merrill (Apocynaceae) contain four new alkaloids ; kopsinine, C21H26O2N2, (0.2 per cent.), kopsilongine, C24H30O6N2 (0.06 per cent.), and kopsamine, C25H30O7N2 (0.02 per cent.) occurring in the bark ; and kopsilongine (0.07 per cent.), kopsamine (0.3 per cent.), and kopsiflorine, C23H28O5N2, (0.04 per cent.) in the leaves. The bark also contains β-amyrin (0.35 per cent.) while the leaves afford a mixture of paraffin hydrocarbons, mainly n-hentri- acontane, β-sitosterol, a sterol, C29H50O2, and a triterpene alcohol acetate, C32H52O2. Kopsamine, kopsilongine, and kopsiflorine each contain two methoxyl groups, while kopsinine contains only one ; kopsamine and kopsilongine also contain methylene-dioxy-groups. No reactive carbonyl groups were detected. The alkaloids all titrated as monoacid bases and formed monomethiodides: while the ultraviolet spectra recorded in acid and neutral media show that the basic (tertiary) nitrogen atom does not contribute to the chromophoric system.

The environment of tertiary alcohols from nuclear magnetic resonance spectral shifts on formation of trichloroacetylcarbamates

1976 ◽  
Vol 54 (1) ◽  
pp. 189-191 ◽  
Author(s):  
David R. Taylor
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Double Bond ◽  
Magnetic Resonance ◽  
Allylic Alcohol ◽  
Hydroxyl Group ◽  
Methyl Groups ◽  
Tertiary Alcohols ◽  
Spectral Shifts ◽  
Nmr Signals ◽  
Tertiary Hydroxyl

Reaction of tertiary alcohols with trichloroacetylisocyanate causes a marked downfield shift of the nmr signals of protons β to the hydroxyl group. This can be used to reveal the presence of methyl groups adjacent to a tertiary hydroxyl group and of other β protons which are sufficiently deshielded to be observed. This method has also been used to assign the geometry of the double bond of an allylic alcohol.

The use of 7-(2-bromoethoxy)coumarin for the quantitative fluorometric analysis of drug preparations containing a tertiary nitrogen atom

1985 ◽  
Vol 19 (6) ◽  
pp. 430-434
Author(s):  
A. Z. Abyshev ◽  
V. G. Klimov ◽  
S. S. Krylov ◽  
E. V. Semenov ◽  
I. P. Sidorova
Keyword(s):  
Nitrogen Atom ◽  
Tertiary Nitrogen Atom ◽  
Fluorometric Analysis ◽  
Tertiary Nitrogen
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