Microdetermination of Nodososide and Related Compounds Using Ceric Sulphate as Oxidizing Agent

1971 ◽  
Vol 26 (11) ◽  
pp. 1137-1139
Author(s):  
S. A. I. Rizvi ◽  
Tajwar Sultana
Keyword(s):  
Carbon Dioxide ◽  
Sulphuric Acid ◽  
Hydroxyl Groups ◽  
Oxidizing Agent ◽  
Cassia Occidentalis ◽  
Free Hydroxyl ◽  
Ceric Sulphate ◽  
Related Compounds ◽  
Acetic Acids

Nodososide and emodin from the flowers of Cassia nodosa and physcion-1-glucoside and physcion from the seeds of Cassia occidentalis can be determined in micro amounts by oxidation with eerie sulphate in presence of sulphuric acid. The reactions required 48, 26, 54 and 30 moles of oxidant respectively, resulting in the formation of formic and acetic acids in each case while carbon dioxide was also produced in the cases of nodososide and physcion-1-glucoside. The conditions of stoichiometric oxidation of the anthraquinones have been studied. Methylation of the hydroxyl groups has been found to retard the rate of oxidation of the anthraquinones whereas free hydroxyl groups are easily attacked by ceric ions. The ranges of errors observed are 0.2 -1.7%, 0.3 - 2.9%, 0.2 -3.5% and 0.2 - 3.5% respectively.

STUDIES ON LIGNIN AND RELATED COMPOUNDS: IX. ETHERS OF GLYCOL-LIGNIN

1931 ◽  
Vol 5 (3) ◽  
pp. 302-305
Author(s):  
Harold Hibbert ◽  
Léo Marion
Keyword(s):  
Sodium Hydroxide ◽  
Sodium Salt ◽  
Aqueous Sodium Hydroxide ◽  
Hydroxyl Groups ◽  
Acidic Properties ◽  
Aqueous Sodium ◽  
Spruce Wood ◽  
Free Hydroxyl ◽  
Chloro Derivatives ◽  
Related Compounds

Glycol-lignin prepared from spruce wood has been found to form a sodium salt which reacts with chloro-derivatives, giving rise to the corresponding glycol-lignin ethers. These compounds are insoluble in aqueous sodium hydroxide but still contain free hydroxyl groups which can be methylated without the ethereal linkage being broken. Hence glycol-lignin contains several free hydroxyl groups, one or more of which possess acidic properties. Both the methoxymethyl ether and the 2:4-dinitrophenyl ether of glycol-lignin have been prepared. The evidence would seem to indicate the presence of both phenolic and aliphatic hydroxyl groups.

The hydroxyl stretching frequencies and conformations of Flavan-4-ols and Thiaflavan-4-ols

1969 ◽  
Vol 22 (11) ◽  
pp. 2337 ◽  
Author(s):  
GF Katekar ◽  
AG Moritz
Keyword(s):  
Carbon Tetrachloride ◽  
Benzene Ring ◽  
Hydroxyl Group ◽  
Hydroxyl Groups ◽  
Frequency Shifts ◽  
Characteristic Frequencies ◽  
Carbon Tetrachloride Solution ◽  
Free Hydroxyl ◽  
Related Compounds

The hydroxyl stretching frequencies of some 2,4-cis and 2,4-trans flavan-4-ols, thiaflavan-4-ols, and related compounds have been measured in dilute carbon tetrachloride solution. Characteristic frequencies are observed at 3626�2 cm-1 (free hydroxyl), 3616�1, and 3597�2 cm-1. The 3616 and 3597 cm-1 bands are assigned to pseudo-axial and pseudo-equatorial hydroxyl groups respectively. Evidence is presented to show that the frequency shifts arise from differences in the interaction of the hydroxyl group with the π-electrons of the fused benzene ring, and that these flavans and thiaflavans exist in half- chair, rather than sofa conformations.

STUDIES ON LIGNIN AND RELATED COMPOUNDS: XXVII. METHYLATION AND STRUCTURE OF METHANOL LIGNIN (SPRUCE)

1937 ◽  
Vol 15b (1) ◽  
pp. 38-45 ◽  
Author(s):  
Jack Compton ◽  
Harold Hibbert
Keyword(s):  
Solvent Extraction ◽  
Sodium Hydroxide ◽  
Sulphuric Acid ◽  
Dimethyl Sulphate ◽  
Soluble Fraction ◽  
Anhydrous Methanol ◽  
Hydroxyl Groups ◽  
Slight Excess ◽  
Pure Methanol ◽  
Related Compounds

The composition of spruce methanol lignin prepared by the action of anhydrous methanol-hydrogen chloride on spruce meal was found to vary with the temperature and time of extraction. The reaction mixture contains two products, having methoxyl contents of 21.6 and 24%, respectively. Higher temperatures and longer time of heating favor formation of the latter. Long continued extraction of the crude methanol lignin with ether removed the second product (OCH3, 24%). This showed that this was a true "ether-soluble" fraction, but it was not found possible to isolate the pure methanol lignin (OCH3, 21.6%) by this process. The two substances can be separated either by solvent extraction or, as now shown, by use of 8–10% sodium hydroxide. Methylation of methanol lignin with dimethyl sulphate and alkali gives rise to the formation of new hydroxyl groups, the extent of the changes increasing markedly with rise in temperature of methylation and with increase in concentration of alkali used.A methanol lignin (OCH3, 22.3%) on repeated methylation yields a methylated lignin containing 37.2% methoxyl. Degradation during methylation is restricted by the use of acetone as solvent and only a slight excess of alkali (5–10%) at 20 °C. The results indicate the necessity for caution in the interpretation of data based on methylation experiments involving the use of alkali, and point to the presence of heterocyclic oxygen rings, non-furane in type, as part of the lignin structure. When refluxed for 48 hr. with 65 % aqueous methyl alcohol containing 9% sulphuric acid, ether-insoluble methanol lignin (OCH3, 22.3%) yielded a product with methoxyl content 21.3% which decreased to 20.9% when the product was treated for a further 52 hr.

Gas-phase pyrolysis of thiopheneacetic acids, thienylethanols, and related compounds — protophilicity of ring π-electrons and relative acidities of hydrogen-bond donors of hydroxyl groups

2002 ◽  
Vol 80 (5) ◽  
pp. 499-503 ◽  
Author(s):  
Ibtehal A Al-Juwaiser ◽  
Nouria A Al-Awadi ◽  
Osman ME El-Dusouqui
Keyword(s):  
Carbon Dioxide ◽  
Hydrogen Bond ◽  
Gas Phase ◽  
Kinetic Data ◽  
Reaction Pathway ◽  
Hydroxyl Groups ◽  
Pyrolysis Kinetics ◽  
Elimination Reactions ◽  
Related Compounds ◽  
Phase Elimination

Based on kinetic data of thermal gas-phase elimination reactions, the following Arrhenius log A (s–1) and Ea (kJ mol–1) values, respectively, are obtained: 10.76 and 153.5 for 3-thiopheneacetic acid (1), 10.08 and 149.4 for 2-thiopheneacetic acid (2), 12.04 and 207.1 for 2-(3-thienyl)ethanol (3), 11.55 and 203.3 for 2-(2-thienyl)ethanol (4), 10.91 and 123.4 for 2-thiopheneglyoxylic acid (5), 11.05 and 223.8 for 1-(2-thienyl)propan-1-one (6), and 10.33 and 149.8 for 3-thiophenemalonic acid (7). The products of these pyrolytic reactions were either carbon dioxide or formaldehyde in addition to methylthiophene or thiophenecarboxaldehyde. Both positional and molecular reactivities of the substrates and related compounds are compared, and the results are rationalized on the basis of a reaction pathway involving a concerted six-membered transition state.Key words: thiophenes, gas-phase, pyrolysis, kinetics, mechanism.

The synthesis and structure of silica-supported bis(h5-cyclopentadienyl)dichlorotitanium(IV) complexes

1986 ◽  
Vol 51 (7) ◽  
pp. 1430-1438 ◽  
Author(s):  
Alena Reissová ◽  
Zdeněk Bastl ◽  
Martin Čapka
Keyword(s):  
Free Surface ◽  
Hydroxyl Groups ◽  
Titanium Complex ◽  
Surface Hydroxyl ◽  
Surface Hydroxyl Groups ◽  
Free Hydroxyl ◽  
Cyclopentadienyl Anion

The title complexes have been obtained by functionalization of silica with cyclopentadienylsilanes of the type Rx(CH3)3 - xSi(CH2)nC5H5 (x = 1-3, n = 0, 1, 3), trimethylsilylation of free surface hydroxyl groups, transformation of the bonded cyclopentadienyl group to the cyclopentadienyl anion, followed by coordination of (h5-cyclopentadienyl)trichlorotitanium. The effects of single steps of the above immobilization on texture of the support, the number of free hydroxyl groups, the coverage of the surface by cyclopentadienyl groups and the degree of their utilization in anchoring the titanium complex have been investigated. ESCA study has shown that the above anchoring leads to formation of the silica-supported bis(h5-cyclopentadienyl)dichlorotitanium(IV) complex.

Substitutional and solvation effects on conformational equilibria. Effects on the interaction between opposing axial oxygen atoms

1969 ◽  
Vol 47 (23) ◽  
pp. 4441-4446 ◽  
Author(s):  
R. U. Lemieux ◽  
A. A. Pavia
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Hydrogen Bonding ◽  
Magnetic Resonance ◽  
Hydroxyl Groups ◽  
Evidence Based ◽  
Electrostatic Repulsion ◽  
Hydrogen Bridge ◽  
Conformational Equilibria ◽  
Free Hydroxyl ◽  
Oxygen Atoms

Evidence based both on nuclear magnetic resonance and rotation data primarily obtained from methyl 3-deoxy-β-L-erythro-pentopyranoside and a number of its derivatives is interpreted to show that the electrostatic repulsion between the oxygen atoms at the 2 and 4 positions is substantially less when these oxygens are linked to acyl groups than when in the form of either methyl ethers or as hydroxyl groups hydrogen bonded to solvent. Also, experimental evidence is presented which requires the hydrogen bridge between two axially disposed hydroxyl groups to be substantially strengthened by hydrogen bonding of the free hydroxyl by solvent.

Light-Mediated Cross-Coupling of Anomeric Trifluoroborates

2021 ◽  
Author(s):  
Eric Miller ◽  
Maciej Walczak
Keyword(s):  
Cross Coupling ◽  
Hydroxyl Groups ◽  
Anomeric Effect ◽  
Computational Studies ◽  
Carbohydrate Chemistry ◽  
New Class ◽  
Free Hydroxyl ◽  
Anomeric Carbon ◽  
Stereoselective Reactions

Stereoselective reactions at the anomeric carbon constitute the cornerstone of preparative carbohydrate chemistry. Here, we report the synthesis of axial C1 trifluoroborates and stereoselective C-arylation and etherification reactions under photoredox conditions. These reactions are characterized by high anomeric selectivities for 2-deoxysugars and broad substrate scope (24 examples), including disaccharides and trifluoroborates with free hydroxyl groups. Computational studies show that high axial selectivities for these reactions originate from a combination of kinetic anomeric effect of the intermediate C1 radical and stereoelectronic stabilization of Ni(III) through the metallo-anomeric effect. Taken together, this new class of carbohydrate reagents adds the palette of anomeric nucleophile reagents suitable for efficient installation C-C and Cheteroatom bonds.

STUDIES ON THE BACTERIAL OXIDATION OF 2,3-BUTANEDIOL AND RELATED COMPOUNDS

1944 ◽  
Vol 22b (5) ◽  
pp. 140-153 ◽  
Author(s):  
R. Y. Stanier ◽  
Sybil B. Fratkin
Keyword(s):  
Carbon Dioxide ◽  
Aeromonas Hydrophila ◽  
The Other ◽  
Bacterial Oxidation ◽  
Aerobacter Aerogenes ◽  
Aerobic Conditions ◽  
Related Compounds

Aerobacter aerogenes, Aerobacillus polymyxa, and Aeromonas hydrophila, representatives of the three genera characterized by a butanediol fermentation, can all oxidize 2,3-butanediol under aerobic conditions. The configuration of the 2,3-butanediol has considerable bearing on its decomposability: Aerobacter aerogenes is inactive on the l-isomer, but attacks both meso- and d-isomers; Aeromonas hydrophila attacks the meso-isomer but not the l- and probably not the d-isomer; Aerobacillus polymyxa can oxidize both l- and meso-2,3-butanediol, but the rate with the former is many times greater than with the latter. Aerobacter aerogenes oxidizes both 2,3-butanediol and acetoin to carbon dioxide and water, a large part of the substrate being simultaneously assimilated. The other two organisms oxidize 2,3-butanediol to acetoin, but can further oxidize the acetoin thus formed only very slowly, if at all. Both Aerobacter aerogenes and Aerobacillus polymyxa are unable to attack 1,3-butanediol, 2-methyl-1,2-propanediol and 1,2-ethancdiol. However they can oxidize 1,2-propanediol to acetol.

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