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.

Construction of Cyclic Ether-Fused Tricyclic Naphthoquinone Derivatives by Intramolecular Cyclization Reaction

Heterocycles ◽  
2018 ◽  
Vol 97 (1) ◽  
pp. 107 ◽  
Author(s):  
Tokutaro Ogata ◽  
Tetsutaro Kimachi
Keyword(s):  
Intramolecular Cyclization ◽  
Cyclic Ether ◽  
Cyclization Reaction

Flavan derivatives. XVII. Epimerization of the benzylic 4-hydroxyl group in flavan-3,4-diols and the formation of 4-alkyl ethers by solvolysis

1967 ◽  
Vol 20 (10) ◽  
pp. 2151
Author(s):  
JW Clark-Lewis ◽  
LR Williams
Keyword(s):  
Aqueous Media ◽  
Cyclic Ether ◽  
Hydroxyl Group ◽  
Mechanism Of Formation ◽  
Enol Ether ◽  
Mild Conditions ◽  
Ethoxyl Group ◽  
Alkyl Ethers ◽  
By Products ◽  
Thermodynamic Factors

Epimerization and solvolysis of the benzylic 4-hydroxyl group is shown to be a general property of flavan-3,4-diols, and the diols give 4- ethoxyflavan-3-ols with ethanolic hydrochloric acid (1%). The diols are first converted into epimeric mixtures of 3,4-cis- and 3,4-trans-diols and in aqueous media cis-cis-flavan-3,4-diols yield mainly 2,3-cis-3,4- trans-diols. These 2,3-cis-3,4-diols undergo solvolysis to yield 2,3- cis-3,4-trans-4-ethoxyflavan-3-ols in which the 3,4-trans- stereochemistry is controlled by participation of the neighbouring 3ax- hydroxyl group. 2,3-trans-Flavan-3,4-diols give mixtures of trans- trans-diols and 2,3-trans-3,4-cis-diols and solvolysis first yields 2.3-trans-3,4-cis-4-ethoxyflavan-3-ols and then mixtures of the 3,4- cis- and 3,4-trans-ethers; the final proportion of these two ethers is controlled by thermodynamic factors. Solvolysis under mild conditions gives minor products considered to be 3-oxoflavans (or their enols) because of their immediate conversion into antho-cyanidins by cold acids in the presence of air, and from the formation of an enol-ether on prolonged solvolysis under more vigorous conditions. The relevance of these observations to the mechanism of formation of anthocyanidins from flavan-3,4-diols is discussed. Other by-products of solvolysis reactions include a dimeric cyclic ether (dioxan derivative) of 2,3- trans-3,4-cis-7,8,4?-trimethoxyflavan-3,4-diol. The structure and stereochemistry of solvolysis products were established by N.M.R. data; the 4-ethoxyl group in the ethers generally gave rise to an ABX3 multiplet.

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.

THE ALKALOIDS OF LYCOPODIUM SPECIES: XI. NATURE OF THE OXYGEN ATOM IN LYCOPODINE; SOME REACTIONS OF THE BASE

1950 ◽  
Vol 28b (8) ◽  
pp. 460-467 ◽  
Author(s):  
R. H. F. Manske ◽  
Léo Marion ◽  
David B. MacLean
Keyword(s):  
Oxygen Atom ◽  
Methyl Bromide ◽  
Potassium Hydroxide ◽  
Cyanogen Bromide ◽  
Quaternary Salt ◽  
Secondary Alcohol ◽  
Potassium Acetate ◽  
Ethanolic Solution ◽  
Neutral Compound ◽  
Neutral Product

Lycopodine gives rise to a hydrazone, is reduced to a secondary alcohol, and reacts with phenyl-lithium to form a tertiary carbinol; hence, the oxygen atom of the base is present in a keto group. The base reacts with cyanogen bromide to form two cyanobromolycopodines, α and β. α-Cyanobromolycopodine is converted by potassium acetate in alcohol to α-cyanoacetoxylycopodine, hydrolyzable to α-cyanohydroxylycopodine, which can be oxidized to an acid. The action of methanolic potassium hydroxide on α-cyanobromolycopodine gives rise to a nonoxidizable, nonreducible neutral compound, while a similar isomeric and equally inert substance is produced by the action of a boiling ethanolic solution of potassium acetate on β-cyanobromolycopodine. Both α- and β-cyanobromolycopodines are hydrogenated catalytically to two isomeric products C17H26ON2. α-Cyanobromolycopodine with trimethylamine forms of quaternary salt which, when subjected to the conditions of the Hofmann degradation, gives rise to a base differing from the quaternary salt by the elements of methyl bromide, and to the same neutral product obtainable from α-cyanobromolycopodine by the action of methanolic potassium hydroxide.

The voluntary intake of silage by sheep:II. The effects of acetate on silage intake

1971 ◽  
Vol 77 (3) ◽  
pp. 539-543 ◽  
Author(s):  
K. J. Hutchinson ◽  
R. J. Wilkins
Keyword(s):  
Acetic Acid ◽  
Perennial Ryegrass ◽  
Potassium Hydroxide ◽  
Potassium Acetate ◽  
Ad Libitum ◽  
Per Se ◽  
Voluntary Intake

SUMMARYA perennial ryegrass silage was treated to give a range of acetic acid contents (2·0–8·8); pH and moistvire levels were held constant by adding solutions of the acid and of potassium hydroxide. When fed to sheep, ad libitum, the pattern of eating during the day was affected by acetate content in the silage but the intake over 24 h was unaffected. In a second experiment the infusion of acetic acid into the rumen depressed silage intake but this effect was not observed when part of the infusate was replaced by potassium acetate. It is considered unlikely that high acetate level per se will result in a low intake of silage.

Bridged-ring steroids. V. The total synthesis of 1,4-methano steroids by a modified Torgov sequence

1988 ◽  
Vol 66 (9) ◽  
pp. 2268-2278 ◽  
Author(s):  
Peter Yates ◽  
Stephen P. Douglas ◽  
Sushil K. Datta ◽  
Jeffrey F. Sawyer
Keyword(s):  
Total Synthesis ◽  
Sodium Borohydride ◽  
Potassium Hydroxide ◽  
Hydrolysis Product ◽  
Diels Alder ◽  
Allylic Alcohol ◽  
Hydroxy Derivative ◽  
Enol Ether ◽  
Zinc Amalgam ◽  
Alder Adduct

The Diels–Alder adduct, 17, of cyclopentadiene and 2-methoxy-5-methyl-1,4-benzoquinone was reduced with sodium borohydride to the ketol 18, whose acetate 19 was further reduced with zinc amalgam to the monoketone 20. Reaction of 20 with vinyllithium gave the allylic alcohol 21, which underwent very ready dehydration with rearrangement to give the tricyclic enol ether 27, which was hydrolyzed to ketone 28a. Hydrogenation of 19 gave the dihydro product 30, which was reduced with zinc amalgam to the ketone 31. Treatment of the latter with vinyllithium gave the allylic alcohol 32. This was more stable than its analogue 21, but underwent hydrolysis and dehydration to the dienone 33. Treatment of 32 with 2-methyl-1,3-cyclo-pentanedione (5) in the presence of Triton B gave the tricyclic intermediate 35, its hydrolysis product 36, and the hydroxy derivative of the latter, 37. In the absence of base, 32 and 5 gave largely product 36. Hydrogenation of 36 gave the dihydro product 38, which on treatment with methanolic potassium hydroxide gave (±)-(1β,4β,5β,8α,9β,10β,13β,14β)-14-hydroxy-1,4-methanoandrostane-7,17-dione (39). Dehydration of 39 with p-toluenesulfonic acid gave first (±)-(1β,4β,5β,9β,10β,13β)-1,4-methanoandrost-8(14)-ene-7,17-dione (40), which was converted in turn to (±)-(1β,4β,5β,8α,9β,10β,13β,14β)-1,4-methanoandrost-15-ene-7,17-dione (41). Similar dehydration of 36 gave (±)-(1β,4β,5β,10β,13β,14β)-1,4-methanoandrosta-8,15-diene-7,17-dione (45).

LYCOPODIUM ALKALOIDS: III. FUNCTIONAL GROUPS OF SOME MINOR ALKALOIDS OF L. ANNOTINUM

1956 ◽  
Vol 34 (9) ◽  
pp. 1189-1199 ◽  
Author(s):  
G. S. Perry ◽  
David B. MacLean
Keyword(s):  
Infrared Spectroscopy ◽  
Double Bond ◽  
Carbonyl Group ◽  
Functional Groups ◽  
Ring System ◽  
Molecular Compound ◽  
Ether Linkage ◽  
Chemical Methods ◽  
Lycopodium Alkaloids ◽  
Hydroxyl Absorption

Four minor alkaloids of L. annotinum have been examined by chemical methods and infrared spectroscopy for their functional groups. Acrifoline (L.27) C16H23O2N has a double bond, a carbonyl group, and an hydroxyl function. Annotine (L.11) C16H21O3N has a double bond, a carbonyl group, an hydroxyl function, and an inert oxygen probably present in an ether linkage. Alkaloid L.12 (C18H25O3N) is O-acetylacrifoline. Alkaloid L.8 (C16H25O2N) has only been studied by infrared spectroscopy where it shows carbonyl and hydroxyl absorption. All four alkaloids therefore contain a basic tetracyclic ring system as do the majority of other lycopodium alkaloids. Annotoxine, a molecular compound of acrifoline and annotine, has been isolated from extracts of Canadian plant material.

Purification and Characterization of Tissue-Type Plasminogen Activator in Maxillary Mucosa with Chronic Inflammation

1985 ◽  
Vol 54 (02) ◽  
pp. 485-489 ◽  
Author(s):  
Yukiyoshi Hamaguchi ◽  
Masuichi Ohi ◽  
Yasuo Sakakura ◽  
Yasuro Miyoshi
Keyword(s):  
Plasminogen Activator ◽  
Chronic Inflammation ◽  
Gel Filtration ◽  
Potassium Acetate ◽  
Tissue Type ◽  
Purification And Characterization ◽  
Tissue Type Plasminogen Activator ◽  
Urokinase Inhibitor ◽  
Type Plasminogen Activator

SummaryTissue-type plasminogen activator (TPA) was purified from maxillary mucosa with chronic inflammation and compared with urokinase. Purification procedure consisted of the extraction from delipidated mucosa with 0.3M potassium acetate buffer (pH 4.2), 66% saturation of ammonium sulfate, zinc chelate-Sepharose, concanavalin A-Sepharose and Sephadex G-100 gel filtration chromatographies.The molecular weight of the TPA was approximately 58,000 ± 3,000. Its activity was enhanced in the presence of fibrin and was quenched by placental urokinase inhibitor, but not quenched by anti-urokinase antibody. The TPA made no precipitin line against anti-urokinase antibody, while urokinase did.All these findings indicate that the TPA in maxillary mucosa with chronic inflammation is immunologically dissimilar to urokinase and in its affinity for fibrin.

Sign in / Sign up

Export Citation Format

Share Document