Pigments of marine animals. XIV. Polyketide sulfates from the crinoid Comatula pectinata

1981 ◽  
Vol 34 (11) ◽  
pp. 2385 ◽  
Author(s):  
JA Rideout ◽  
MD Sutherland
Keyword(s):  
Sodium Bicarbonate ◽  
Sodium Salt ◽  
Aqueous Ethanol ◽  
Aqueous Acetone ◽  
Chromatographic Mobility ◽  
Sulfate Ester ◽  
Marine Animals ◽  
Free Phenol ◽  
Tertiary Alcohols ◽  
Trimethyl Ether

The polyhydroxyanthraquinones known from the crinoid Comatula pectinata are shown to be present largely as (fish repellent) sulfate monoesters. The sodium salt of the 3-O-sulfate of 4-butyryl-1,3-dihydroxy-6,8-dimethoxy-9,10-anthraquinone was isolated by its chromatographic mobility on alumina in aqueous acetone or on sodium bicarbonate in aqueous ethanol. The sulfate hydrolyses readily to the free phenol and is methylated (Me2SO4/K2CO3 in refluxing acetone) to 4-butyryl-1,3,6,8-tetramethoxyanthraquinone. Methylated in the presence of tertiary alcohols however, the sulfate ester resists cleavage, yielding the 1,6,8-trimethyl ether, hydrolysable to 4-butyryl-3-hydroxy-1,6,8-trimethoxyanthraquinone.

2,4-D and Salt Combinations Affect Glyphosate Phytotoxicity

1992 ◽  
Vol 6 (2) ◽  
pp. 322-327 ◽  
Author(s):  
John D. Nalewaja ◽  
Robert Matysiak
Keyword(s):  
Sodium Bicarbonate ◽  
Calcium Chloride ◽  
Sodium Salt ◽  
Nonionic Surfactants ◽  
Ferric Sulfate ◽  
Inorganic Salts ◽  
Diammonium Sulfate

Experiments conducted in the greenhouse indicated that 2,4-D antagonism of glyphosate toxicity to wheat was sodium salt = butoxyethyl ester ≥ diethanolamine. Isopropylamine salt of 2,4-D generally was not antagonistic to glyphosate phytotoxicity. Isopropylamine salt of 2,4-D did not influence the antagonism of glyphosate by inorganic salts in the spray carrier. Antagonism of glyphosate toxicity to wheat by 2,4-D increased when sodium bicarbonate, calcium chloride, and ferric sulfate were in the spray carrier water. Isopropylamine alone as an adjuvant enhanced glyphosate toxicity to wheat, and overcame ferric sulfate and sodium bicarbonate antagonism of glyphosate. Diammonium sulfate adjuvant overcame antagonism to glyphosate phytotoxicity from 2,4-D, sodium bicarbonate, and calcium chloride each alone or the salts in combination with 2,4-D. Nonionic surfactants differed in enhancement of glyphosate but none overcame antagonism from salts or 2,4-D.

ELECTROPHILIC CATALYSIS IN SOLVOLYTIC REACTIONS: VII. SOLVENT EFFECT

1965 ◽  
Vol 43 (6) ◽  
pp. 1770-1777 ◽  
Author(s):  
R. Anantaraman ◽  
K. Saramma
Keyword(s):  
Solvent Effect ◽  
Mercuric Chloride ◽  
Aqueous Ethanol ◽  
Chloride Ions ◽  
Aqueous Acetone ◽  
Normal Reaction ◽  
Suggested Explanation

The rates of mercuric chloride catalyzed solvolysis of some alkyl chlorides in aqueous acetone and ethanol solvents have been compared. It is found that the increase in rate on changing from the acetone to the ethanol solvent is less in the catalyzed than in the normal reaction. On the basis that the electrophilic activity of the catalyst is less in aqueous ethanol than in aqueous acetone an explanation for the anomaly has been suggested. The effect, on the rates of solvolysis, of added chloride ions is in accord with the suggested explanation.

Pigments of marine animals. X. Substituted naphthopyrones from the crinoid Comantheria perplexa

1970 ◽  
Vol 23 (11) ◽  
pp. 2325 ◽  
Author(s):  
RA Kent ◽  
IR Smith ◽  
MD Sutherland
Keyword(s):  
Acid Hydrolysis ◽  
Dimethyl Ether ◽  
Sodium Salt ◽  
Crude Extract ◽  
Synthetic Activity ◽  
Marine Animals ◽  
Dehydration Product ◽  
Aromatic Polyketides ◽  
Stalked Crinoids ◽  
Hydrolysis Of

Acetone extraction of the flesh of the comatulid crinoid Comantheria perplexa (H. L. Clark) yields a mixture of substances from which the sodium salt of the sulphuric ester (12) of 8-hydroxy-5,6-dimethoxy-2-methyl-4H-naphtho[2,3-b]pyran-4-one (8) has been isolated. Acid hydrolysis of (12) yields the phenol (8) which on methylation is converted into rubrofusarin dimethyl ether and on partial demethylation yields a product identical with a dehydration product (10) of fonsecin. Hydrolysis of the crude extract from C. perplexa yields (8), (10), and 8-hydroxy-5,6-dimethoxy-2-n-propyl-4H-naphtho[2,3-b]pyran-4-one (13). The structures of the isolated substances suggest a polyketide-type synthetic activity by this species. The stalked crinoids Endoxocrinus parrae (Gervais) and Neocrinus decorus (Wyville Thomson) yield negligible quantities of aromatic polyketides.

ATTEMPTED DELIGNIFICATIONS WITH SODIUM BICARBONATE - CARBON DIOXIDE, AND WITH ANHYDROUS LIQUID AMMONIA, UNDER PRESSURE

1956 ◽  
Vol 34 (11) ◽  
pp. 1582-1590 ◽  
Author(s):  
M. M. Yan ◽  
C. B. Purves
Keyword(s):  
Carbon Dioxide ◽  
Sodium Bicarbonate ◽  
Ammonium Chloride ◽  
Sodium Salt ◽  
Liquid Ammonia ◽  
Sodium Cyanide ◽  
Excess Carbon ◽  
Aqueous Sodium ◽  
Spruce Wood ◽  
Rye Straw

Finely divided spruce wood was heated with aqueous sodium bicarbonate and excess carbon dioxide up to 160° and about 400 p.s.i. in attempts to carboxylate the lignin according to the Kolbe–Schmitt method and to extract the product as a soluble sodium salt. Only small amounts of lignin were removed, together with larger amounts of the holocellulose. Heating the wood with anhydrous liquid ammonia up to 100° and about 900 p.s.i. extracted only small amounts of material from the softwood spruce, but 25 to 30% of the lignin was removed from the hard woods beech, birch, and maple and 52% from rye straw. The solution of ammonium chloride or sodium cyanide in the liquid ammonia increased these percentages substantially, and also the concomitant extraction of holocellulose.

Transformations of 3-(methylene)dihydro-2(3H)-furanone derivatives

1984 ◽  
Vol 49 (11) ◽  
pp. 2509-2519 ◽  
Author(s):  
Ctibor Mazal ◽  
Zdeněk Jurka ◽  
Jaroslav Jonas
Keyword(s):  
Vinyl Ether ◽  
Sodium Salt ◽  
Alkaline Hydrolysis ◽  
Sodium Azide ◽  
Potassium Cyanide ◽  
Aqueous Acetone ◽  
H Nmr ◽  
Nmr Spectrometry ◽  
High Yields ◽  
Hydrolysis Of

(E) and (Z)-3-(4-toluenesulfonyloxymethylene)dihydro-2(3H)-furanones ((E)-I) and ((Z-I) react with piperidine, pyrrolidine, morpholine, butanethiol, 4-toluenethiol, and 2-naphthalenethiol to give (E)-isomers of the corresponding enamines II-IV and thiomethylene derivatives V-VII in high yields. As has been shown, the reactions proceed with retention of configuration; the initially formed (Z)-II, (Z)-III, (Z)-IV, and (Z)-V isomerize rapidly to the thermodynamicaly more stable (E)-isomers. Ether IX was obtained by reaction of (E)-I with the (E)-isomer of sodium salt of 3-(hydroxymethylene)dihydro-2(3H)-furanone ((E)-VIII) and a mixture of ethers IX and X resulted from reaction of (Z)-I with sodium salt of (E)-VIII. Compounds (E)-I and (Z)-I afforded the corresponding azides(E)-XI and (Z)-XI upon treatment with sodium azide, and hydroxybutanoic acids (E)-XII and (Z)-XII with sodium hydroxide in aqueous acetone. Chloride (E)-XIII, prepared by reacting (E)-I with methanolic hydrogen chloride, furnished with piperdine, pyrrolidine, morpholine, or 2-naphthalenethiol the corresponding (E)-II, (E)-III, (E)-IV, and (E)-VII. Potassium cyanide reacted with (E)-I in dimethylsulfoxide to yield nitrile (E)-XIV. Cycloaddition of the azide (E)-XI to isobutyl vinyl ether or cyclohexyl vinyl ether proceeds quantitatively to give the respective triazolines (E)-XV and (E)-XVI. Alkaline hydrolysis of IX afforded the acid XVII. reduction of (E)-I, (Z)-I, and (E)-VII with chloralane gave the respective butanediols (E)-XVIII, (Z)-XVIII, and (E)-XIX, respectively. Configurations of these substances were elucidated by 1H NMR spectrometry.

Optimum Acetone and Ethanol Extraction of Polyphenols from Pinus caribaea Bark: Maximizing Tannin Content Using Response Surface Methodology

2011 ◽  
Vol 6 (1) ◽  
Author(s):  
Nana S. A. Derkyi ◽  
Benjamin Adu-Amankwa ◽  
Daniel Sekyere ◽  
Nicholas A. Darkwa
Keyword(s):  
Response Surface Methodology ◽  
Response Surface ◽  
Aqueous Ethanol ◽  
Aqueous Acetone ◽  
Extraction Temperature ◽  
Pinus Caribaea ◽  
Ethanol Extraction ◽  
Solid Ratio ◽  
Acetone Extraction ◽  
The Individual

The bark extracts of various commercially important trees contain polyphenolics, which in the form of tannins can form condensation products with formaldehyde to produce wood adhesives. In the present work, aqueous acetone and aqueous ethanol were used as solvents to extract tannin from Pinus caribaea bark. The Stiasny number was determined as well as the amount of sugar co-extracted. Batch experiments were performed at different extraction times (30-180 min), extraction temperature (35-60°C for aqueous acetone; 35-80°C for aqueous ethanol), solvent concentration (10-100 percent), stage extraction (1-6) and liquid-solid ratio (10-50). A mathematical model was proposed to identify the effects of the individual interactions of these variables on the extraction of tannin using the two different solvents. The results have been modeled using response surface methodology. The response surface method was developed using five levels (-2, -1, 0, +1, +2) with the above mentioned factors except the stage extraction factor. The second order quadratic regression model fitted the experimental data with Prob > F to be < 0.0001 for the aqueous ethanol extraction and Prob > F to be < 0.006 for the aqueous acetone extraction. The experimental values were found to be in good agreement with the predicted values, with a satisfactory correlation coefficient of R2 = 0.82 in the case of aqueous ethanol extraction and R2 = 0.45 in the case of aqueous acetone extraction. The maximum predicted tannin yield of 20.68 percent was obtained under the optimum extraction conditions of 71.46°C extraction temperature, 79.2 min extraction time, 21.9 percent ethanol concentration, and 26.4:1 liquid-solid ratio. The amount of total sugars and the Stiasny number predicted under these conditions were 4.94 percent and 80.47 percent, respectively.

ELECTROPHILIC CATALYSIS IN SOLVOLYTIC REACTIONS: IX. INDUCTOMERIC EFFECT

1966 ◽  
Vol 44 (20) ◽  
pp. 2415-2419 ◽  
Author(s):  
R. Anantaraman ◽  
M. R. Nair
Keyword(s):  
Mercuric Chloride ◽  
Aqueous Ethanol ◽  
Chloride Ions ◽  
Aqueous Acetone ◽  
Rate Of Hydrolysis ◽  
Presence And Absence ◽  
Catalyzed Reactions

The rates of solvolysis of 1-(p-alkylphenyl)ethyl chlorides (Alk = Me, Et, i-Pr, and t-Bu) in the presence and absence of mercuric chloride have been measured in aqueous acetone and ethanol solvents. In all cases, the Baker–Nathan order is followed. For all normal reactions and for the catalyzed reactions in 90% aqueous acetone and 90% aqueous ethanol there is an increase in the heats and entropies of activation as the series is ascended, while for the catalyzed reaction in 75% and 80% aqueous acetone, there is a decrease. It is suggested that in the more aqueous acetone solvents the catalyst calls into play an inductomeric effect. The effect of added chloride ions on the rate of hydrolysis has been studied and the results are discussed.

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