Syothesis of 3-Deoxy-3-nitro-D-xylose

1971 ◽  
Vol 49 (19) ◽  
pp. 3238-3239 ◽  
Author(s):  
Jan Kovář ◽  
Hans H. Baer
Keyword(s):  
Acid Hydrolysis ◽  
Title Compound ◽  
Periodate Oxidation ◽  
Borohydride Reduction ◽  
Hydrolysis Of

Crystalline 3-deoxy-3-nitro-α-D-xylose (5) was obtained in 40% over-all yield by periodate oxidation of 3-deoxy-1,2-O-isopropylidene-3-nitro-α-D-glucofuranose (2) followed by borohydride reduction and acid hydrolysis. In addition to the intermediate 3-deoxy-1,2-O-isopropylidene-3-nitro-α-D-xylofuranose (4), a small amount of an isomer probably having the D-ribo configuration was isolated. The title compound (5) was also obtained by hydrolysis of its methyl β-pyranoside (1).

THE STRUCTURAL ANALYSIS OF SOME ACIDIC XYLANS BY PERIODATE OXIDATION

1962 ◽  
Vol 40 (2) ◽  
pp. 348-352 ◽  
Author(s):  
G. G. S. Dutton ◽  
A. M. Unrau
Keyword(s):  
Acid Hydrolysis ◽  
Glucuronic Acid ◽  
Periodate Oxidation ◽  
Small Degree ◽  
Degree Of Polymerization ◽  
Borohydride Reduction ◽  
Mild Acid Hydrolysis ◽  
Degree Of Branching ◽  
Hydrolysis Of ◽  
Mild Acid

By determining the amount of formaldehyde produced on periodate oxidation of borohydride-reduced apple- and cherry-wood xylans the degree of polymerization was shown to be 155 and 100 respectively. Acid hydrolysis of the polyols obtained by periodate oxidation and borohydride reduction gave ethylene glycol in amounts indicating that these xylans have a small degree of branching. Mild acid hydrolysis of the polyols demonstrated that in these xylans D-glucuronic acid as well as 4-O-methyl-D-glucuronic acid was present and that some of the former occupied non-terminal positions.

STRUCTURE OF THE EXTRACELLULAR POLYSACCHARIDE PRODUCED BY XANTHOMONAS ORYZAE

1962 ◽  
Vol 40 (12) ◽  
pp. 2204-2213 ◽  
Author(s):  
A. Misaki ◽  
S. Kirkwood ◽  
J. V. Scaletti ◽  
F. Smith
Keyword(s):  
Acid Hydrolysis ◽  
Glucuronic Acid ◽  
Periodate Oxidation ◽  
Extracellular Polysaccharide ◽  
Xanthomonas Oryzae ◽  
Sodium Borohydride Reduction ◽  
Glycoside Hydrolysis ◽  
Hydrolysis Of ◽  
Structural Significance ◽  
Molecular Proportion

The extracellular polysaccharide isolated from cultures of Xanthomonas oryzae is composed of D-glucose (5 molecular proportions), D-glucuronic acid (2 molecular proportions), and D-mannose (5 molecular proportions). Acid hydrolysis of this polysaccharide, which contains 0.3% combined pyruvic acid, yields 2-O-β-D-glucopyranosyluronic acid D-mannose, which has been characterized as its crystalline fully methylated β-glycoside. Hydrolysis of the methylated polysaccharide gives 2,3,4,6-tetra-O-methyl-D-mannose (3 molecular proportions), 2,3,4-tri-O-methyl-D-glucuronic acid (1 molecular proportion), 2,3,6-tri-O-methyl-D-glucose (4 molecular proportions), 3,4,6-tri-O-methyl-D-mannose (2 molecular proportions), 2,6-di-O-methyl-D-glucose (3 molecular proportions), 2,3-di-O-methyl-D-glucose (1 molecular proportion). The polyalcohol derived from the polysaccharide by periodate oxidation followed by sodium borohydride reduction gives upon acid hydrolysis glycerol (2 molecular proportions), erythritol (1 molecular proportion), and D-glucose (1 molecular proportion). The general structural significance of these findings is discussed.

A New Approach to 3′-Amino-3′-deoxynucleosides. Synthesis of 9-(3-Amino-3-deoxy-α-L-ribofuranosyl)adenine

1971 ◽  
Vol 49 (4) ◽  
pp. 568-573 ◽  
Author(s):  
Hans H. Baer ◽  
Monika Bayer
Keyword(s):  
Catalytic Hydrogenation ◽  
Title Compound ◽  
Condensation Product ◽  
Periodate Oxidation ◽  
Borohydride Reduction ◽  
New Approach

Methyl 2,3,4-tri-O-acetyl-6-deoxy-6-nitro-α-D-glucopyranoside (1) was acetolyzed to give 1,2,3,4-tetra-O-acetyl-6-deoxy-6-nitro-α-D-glucopyranose (2). Compound 2 (or alternatively, 6-deoxy-1,2-O-isopropylidene-6-nitro-α-D-glucofuranose 4) was converted into 2,3,4-tri-O-acetyl-6-deoxy-6-nitro-α- D-glucopyranosyl bromide (3) which was condensed with chloromercuri 6-benzamidopurine. De-O-acetylation of the condensation product 5 afforded 6-benzamido-9-(6-deoxy-6-nitro-β-D-glucopyranosyl)purine (6) which could be hydrogenated to the corresponding 6′-amino nucleoside 7. Periodate oxidation of 6 followed by internal Henry cyclization and borohydride reduction gave 6-benzamido-9-(3-deoxy-3-nitro-α-L-ribofuranosyl)purine (10) which upon catalytic hydrogenation and subsequent de-N-benzoylation produced the title compound, 12. The sensitivity of certain nitro intermediates towards alkali is commented upon.

A Stereospecific Synthesis of L-Desosamine

1974 ◽  
Vol 52 (1) ◽  
pp. 122-124 ◽  
Author(s):  
Hans H. Baer ◽  
Chung-Wai Chiu
Keyword(s):  
Acid Hydrolysis ◽  
Nitro Group ◽  
Catalytic Hydrogenation ◽  
Glycosidic Bond ◽  
Stereospecific Synthesis ◽  
Borohydride Reduction ◽  
Amino Glycoside ◽  
Hydrolysis Of

L-Desosamine (3,4,6-trideoxy-3-dimethylamino-L-xylo-hexose), the enantiomer of a widely distributed antibiotics component, was synthesized by borohydride reduction of methyl 3,4,6-trideoxy-3-nitro-α-L-erythro-hex-3-enopyranoside followed by catalytic hydrogenation of the nitro group, N,N-dimethylation of the resulting saturated amino glycoside, and acid hydrolysis of the glycosidic bond.

scholarly journals IMMUNOCHEMICAL STUDIES ON BLOOD GROUPS

1971 ◽  
Vol 133 (1) ◽  
pp. 39-52 ◽  
Author(s):  
Ten Feizi ◽  
Elvin A. Kabat ◽  
Giuseppe Vicari ◽  
Byron Anderson ◽  
W. Laurence Marsh
Keyword(s):  
Acid Hydrolysis ◽  
Blood Group ◽  
Ovarian Cyst ◽  
Periodate Oxidation ◽  
Human Saliva ◽  
Mild Acid Hydrolysis ◽  
Group B ◽  
Hydrolysis Of ◽  
Substantial Heterogeneity ◽  
Mild Acid

A partially purified blood group-like substance obtained from milk showed I activity with 2 of 21 anti-I sera. With these antisera, certain human ovarian cyst substances considered to be precursors of the A, B, H, Lea, and Leb substances also showed I activity comparable to the milk material. Strong I activity could be produced by one-stage periodate oxidation and Smith degradation of human ovarian cyst A and B substances, or of hog mucin A + H substance, or by mild acid hydrolysis of human saliva or ovarian cyst blood group B substance. The two sera indicate that I specificity appears at intermediate stages in the biosynthesis of the A, B, H, Lea, and Lea substances. Anti-I sera differ strikingly in their specificities, indicating substantial heterogeneity of the I determinants.

CONSTITUTION OF A DEGRADED POLYSACCHARIDE FROM WHEAT BRAN

1957 ◽  
Vol 35 (2) ◽  
pp. 108-114 ◽  
Author(s):  
J. Schmorak ◽  
C. T. Bishop ◽  
G. A. Adams
Keyword(s):  
Acid Hydrolysis ◽  
Wheat Bran ◽  
Glucuronic Acid ◽  
Periodate Oxidation ◽  
Glycosidic Bond ◽  
Cellulolytic Enzyme ◽  
Acidic Polysaccharide ◽  
Hydrolysis Of ◽  
End Group ◽  
Acid Unit

Graded acid hydrolysis of a soluble wheat bran hemicellulose containing L-arabinose (50%), D-xylose (38.5%), and D-glucuronic acid (9.0%) preferentially removed the L-arabinose giving an insoluble acidic polysaccharide in approximately 25% yield by weight. Methylation studies, periodate oxidation data, and hypoiodite end group estimations showed that the degraded polysaccharide was composed of repeating units of 7-8 D-xylopyranose residues joined by β,1 → 4 linkages. To this repeating unit, one D-glucuronic acid unit was attached by a 1 → 2 glycosidic bond. The cellulolytic enzyme of Myrotheciumverrucaria, which is specific for β,1 → 4 glycosidic linkages, hydrolyzed the degraded polysaccharide although it had no effect on the parent hemicellulose

THE WATER-SOLUBLE POLYSACCHARIDES OF DERMATOPHYTES: III. A GALACTOMANNAN FROM TRICHOPHYTON INTERDIGITALE

1964 ◽  
Vol 42 (12) ◽  
pp. 2862-2871 ◽  
Author(s):  
F. Blank ◽  
M. B. Perry
Keyword(s):  
Formic Acid ◽  
Acid Hydrolysis ◽  
Copper Complex ◽  
Periodate Oxidation ◽  
Water Soluble ◽  
Mild Acid Hydrolysis ◽  
Trichophyton Interdigitale ◽  
Soluble Polysaccharide ◽  
Hydrolysis Of ◽  
Mild Acid

The water-soluble polysaccharide preparation from Trichophytoninterdigitale was fractionated to give two distinct galactomannans and a glucan. A galactomannan isolated via its insoluble copper complex had [α]D +75° (water) and was composed of D-galactose (12%) and D-mannose (88%). On periodate oxidation, the galactomannan consumed 1.73 mole periodate and released 0.67 mole formic acid and 0.12 mole formaldehyde per anhydrohexose unit. Hydrolysis of the methylated galactomannan gave 2,3,5,6-tetra-O-methyl-D-galactose (1 part), 2,3,4,6-tetra-O-methyl-D-mannose (1 part), 2,3,4-tri-O-methyl-D-mannose (4 parts), and3,4-di-O-methyl-D-mannose (2 parts). Mild acid hydrolysis of the galactomannan removed all the galactose residues, leaving a mannan having [α]D +84° (water) whose structure was analyzed by periodate oxidation and methylation techniques.

Complexes of Nickel(II) and Copper(II) With 5,5,7-Trimethyl-1,4-Diazepane. Preparation and Kinetics of Acid-Hydrolysis

1986 ◽  
Vol 39 (2) ◽  
pp. 239 ◽  
Author(s):  
NF Curtis
Keyword(s):  
Acid Hydrolysis ◽  
Acid Concentration ◽  
Reaction Rates ◽  
Borohydride Reduction ◽  
Kinetics Of Hydrolysis ◽  
Rapid Reaction ◽  
Kinetics Of ◽  
Hydrolysis Of

The cyclic diamine 5,5,7-trimethyl-1,4-diazepane, tmdz, is formed by borohydride reduction of 5,7,7-trimethyl-2,3,6,7-tetrahydro-1H-1,4- diazepine , which is formed by a rapid reaction between ethanediamine and 4-methylpent-3-en-2-one. Salts of the cations [Ni( tmdz )2]2+ and [Cu( tmdz )2]2+ were prepared, and their properties are reported. The kinetics of hydrolysis of [Ni( tmdz )2]2+ and [Cu( tmdz )2]2+ and bis (1,4- diazepane )nickel(II), [Ni( dach )2]2+, in aqueous HCl/NaCl media have been studied. Reaction rates are independent of acid concentration over the ranges used . Ni2+,0.1-1 mol l-1 H+ in 1 mol l-1 Cl -, kobs(25°C) = 9.1(1)×10-7 s-1, kobs(50°C) = 2.0(1)×10-5 s-1,ΔH‡96(2)kJ mol-1,0.08-4 mol l-1, H+ in 4 mol l-1 Cl -, kobs (25°pC) = 2.0(3)°10-7 s-1. Cu2+, 0.04-1 mol l-1 H+, 1 mol l-1 Cl -, kobs (25°C) = 0.028(2) s-1, for the displacement of the second ligand . [Ni( dach )2]2+, 0.1-1 mol l-1 H+, 1 mol l-1 Cl -, kobs (25°C) = 0.051(2) s-1. [Ni( tmdz )2]2+ reacts more rapidly with NaOH/edta : 1 mol l-1 NaOH , 0.1 mol l-1, Na2(edtaH2), kobs (25°C) = 7.3(3)×10-3 s-1, 0.5 mol l-1 NaOH , 0.1 mol l-1 Na2(edtaH2), kobs (25°C) = 4.5(3)×10-3 s-1.

A MANNAN PRODUCED BY BACILLUS POLYMYXA

1959 ◽  
Vol 37 (6) ◽  
pp. 1012-1017 ◽  
Author(s):  
D. H. Ball ◽  
G. A. Adams
Keyword(s):  
Molecular Weight ◽  
Acid Hydrolysis ◽  
Periodate Oxidation ◽  
Methylation Data ◽  
Bacillus Polymyxa ◽  
Hydrolysis Of

During the fermentation of glucose, sucrose, or lactose by Bacilluspolymyxa, a mixture of polysaccharides is formed, one of which has been isolated by mild procedures and shown to contain mannose as the only sugar together with approximately 13% protein. Acid hydrolysis of the methylated mannan gave 2,3,4,6-tetra-O-methyl-D-mannose, 2,4,6-tri-O-methyl-D-mannose, 3,4,6-tri-O-methyl-D-mannose, and 3,4-di-O-methyl-D-mannose in the approximate ratio 2:1:1:2. Periodate oxidation results are in agreement with the methylation data and indicate a molecular weight of approximately 3000.

THE STRUCTURE OF A SYNTHETIC ARABINAN

1965 ◽  
Vol 43 (4) ◽  
pp. 924-927 ◽  
Author(s):  
G. G. S. Dutton ◽  
A. M. Unrau
Keyword(s):  
Vapor Phase ◽  
Paper Chromatography ◽  
Methyl Ether ◽  
Periodate Oxidation ◽  
Borohydride Reduction ◽  
Terminal Units ◽  
Branched Structure ◽  
Hydrolysis Of

Hydrolysis of the fully methylated synthetic arabinan showed it to have a highly branched structure in which about 16% of the terminal units were furanose and 2,3-di-O-methyl-L-arabinose was the principal di-O-methyl ether. A method has been developed whereby mixtures of isomeric di- or mono-O-methyl arabinoses may be qualitatively analyzed by successive borohydride reduction, periodate oxidation, and borohydride reduction. The resulting fragments may be separated directly by vapor phase chromatography or by paper chromatography after demethylation.

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