135. Sugar nitrates. Part I. Syntheses of 2 : 4-dimethyl β-methylglucoside and 2 : 4 : 6-trimethyl β-methylglucoside

Dewar, John; Fort, G.

doi:10.1039/jr9440000492

Cited by 10 publications

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“…After standing for two months in a desiccator over phosphorus pentoxide, a sample of Sirup 1 (Table I) deposited in 5y0 yield the crystalline 3,6-dinitrate, which was identified by its rotation and melting point. This identity was confirmed by a quantitative methylation t o the uncrystallized methyl 2,4-dimethyl-P-glucoside-3,G-dinitrate (13), and by hydrogenolysis of the latter in !%yo yield to crystalline methyl 2,4-climethyl- Can series of experiments, analogo~~s to those already described, recovered the 4-methyl, and the acetylated, unidentified mononlethyl, derivatives of methyl glucoside from this trinitrate, but no other substances were iclentified. Sirup 1, after the partial removal of the 3,6-dinitrate by crystallization, was also acetylated, but fractional crystallization of the mixed acetate nitrates did not yield chemical individuals.…”

Section: Calc From Yields and Sz~bstitutions Of The Three Conzponentmentioning

confidence: 67%

“…I t was assumed that Sirup 5 contained an acetyl group resistant to saponification by sodium or barium methylate, or of the type encountered by Helferich and Lang (21) and Dewar and Fort (13). T h e remainder of Sirup 5 was again submitted to de-acetylation, this time with aqueous sodium hydroxide (21), and 55y0 was recovered as crystalline methyl 2,4-dimethyl-P-glucoside with the correct melting point and rotation (13). T h e structure of this substance was confirmed by its failure to react with aqueous sodium periodate, by its hydrolysis to 2,4-dimethyl glucose, and by the capacity of the latter to yield the crystalline 4-methyl glucose phenylosazone (1,13) with elimination of a methyl group.…”

Section: Calc From Yields and Sz~bstitutions Of The Three Conzponentmentioning

confidence: 99%

“…Although de-acetylation appeared to b6 complete, a portion of the product could not be methylated with silver oxide and methyl iodide beyond OCH3, 50.1, 49.6y0, and no methyl tetramethyl P-glucoside (OCH3, G2y0) was recovered by fractional distillation of the methylated sample. I t was assumed that Sirup 5 contained an acetyl group resistant to saponification by sodium or barium methylate, or of the type encountered by Helferich and Lang (21) and Dewar and Fort (13). T h e remainder of Sirup 5 was again submitted to de-acetylation, this time with aqueous sodium hydroxide (21), and 55y0 was recovered as crystalline methyl 2,4-dimethyl-P-glucoside with the correct melting point and rotation (13).…”

Section: Calc From Yields and Sz~bstitutions Of The Three Conzponentmentioning

confidence: 99%

“…The substance had the expected behavior toward aqueous sodium periodate, reducing 0.99 mole without the liberation of formic acid or formaldehyde. Acid hydrolysis yielded 4-methyl glucose (32) and its crystalline phenylosazone (13).…”

Section: Calc From Yields and Sz~bstitutions Of The Three Conzponentmentioning

confidence: 99%

“…I t therefore became desirable to apply the hydroxylamine-pyridine reaction to the fully nitrated derivative of a simpler carbohydrate related to cellulose, and to locate the nitrate group or groups removed by the reagent. T h e present research employed the tetranitrates of methyl a-and P-glucopyranoside for this purpose, because data were available concerning their well-characterized, partly denitrated derivatives (13,14,15,16,35) which could also be converted, by methylation and subsequent denitration, to one or other of the known methyl ethers of methyl a-or p-glucoside (7,13,14,15). Gladding and Purves (16) and Ansell, Honeyman, and Williams (4, 5) described the action of aqueous and alcoholic alkali on monosaccharide nitrates, but reports concerning organic bases seemed to be restricted to one by Wigner (40), who found in 1903 t h a t pyridine alone removed one nitrate group selectively from mannitol hexanitrate.…”

Section: Introductionmentioning

confidence: 99%

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THE ACTION OF HYDROXYLAMINE ON METHYL ALPHA- AND BETA-D-GLUCOPYRANOSIDE TETRANITRATE IN PYRIDINE

Hayward¹,

Purves²

1954

Can. J. Chem.

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The ~nethyl glucoside tetranitrates reacted vigorously a t room temperature with a n escess of hydroxylamine base dissolved in anhydrous pyridine. Gas consisting of 91% nitrogen and anlounti~lg to 1.25 to 1.3 moles per mole was evolved within 20 min. and only n little more during the next 12 hr. Approximately 1.35 moles of nitrate groups in the original tetranitrate had been replaced by hydrosyl groups, for the most part a t least without Walden inversions or other change, because hydrogenation of the sirupy product reduced it in more than 80% yield to crystallille nlethyl glucoside. The product from methyl-B-glucoside tetranitrate consisted of the 2,3,G-trinitrate (2S%), the 3,G-dinitrate (17%), and a n unidentified trinitrate (8%) which might have been a mixture.The structures of the first two compounds were confirmed by preparing the fully methylated derivatives, denitrating the latter, and identifying the resulting known, partly methylated methyl-p-glucosides. New syntheses of methyl-pglucoside-3,6-dinitrate, methyl 2,4-din~ethyl-B-glucoside, and methyl-4-methyl-B-glucoside were found.

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Section: Calc From Yields and Sz~bstitutions Of The Three Conzponentmentioning

confidence: 67%

Section: Calc From Yields and Sz~bstitutions Of The Three Conzponentmentioning

confidence: 99%

Section: Calc From Yields and Sz~bstitutions Of The Three Conzponentmentioning

confidence: 99%

Section: Calc From Yields and Sz~bstitutions Of The Three Conzponentmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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THE ACTION OF HYDROXYLAMINE ON METHYL ALPHA- AND BETA-D-GLUCOPYRANOSIDE TETRANITRATE IN PYRIDINE

Hayward¹,

Purves²

1954

Can. J. Chem.

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Additive Tendency of Substituent Effects onto Rate Constant of Acidic Hydrolysis of Methyl 4‐O‐Methyl‐β‐d‐Glucopyranoside

2016

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All eight types of differently methyl-substituted methyl 4-Omethyl-b-d-glucopyranosides were chemically synthesized, analytically characterized including 13 C NMR analysis, and subjected to acid-catalyzed hydrolytic cleavage of the glucosides. The 13 C NMR resonances of the ring-carbons shift apprx. 10 ppm down-field by methyl substitution. Acid hydrolysis (3 mol·L À1 DCl/D 2 O) was followed by 1 H NMR to determine the rate constants (k) which all were of first order. Methyl substitution at any position (2-O, 3-O and 6-O) was found to have a simple additive effect on the reaction rate. This was also shown as a linear free energy relationship (LFER). The substituent effects upon mono-substitution depend on the substitution position: 2-O-methyl or 6-O-methyl substitution decreased the reaction rate, while 3-O-methyl substitution accelerated the hydrolysis. In cases of di-or tri-substitutions these effects were additive.[a] Dr. Scheme 1. Two proposed acid hydrolysis mechanisms of glycosides.

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Contribution of the O-benzoyl groups of tetra-O-benzoyl-α,β-l-arabinopyranoses to the formation of 1,1-bis(benzamido)-1-deoxy-l-arabinitol

Leicach¹,

Cadenas²,

Sproviero³

1993

Carbohydrate Research

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135. Sugar nitrates. Part I. Syntheses of 2 : 4-dimethyl β-methylglucoside and 2 : 4 : 6-trimethyl β-methylglucoside

Cited by 10 publications

References 0 publications

THE ACTION OF HYDROXYLAMINE ON METHYL ALPHA- AND BETA-D-GLUCOPYRANOSIDE TETRANITRATE IN PYRIDINE

THE ACTION OF HYDROXYLAMINE ON METHYL ALPHA- AND BETA-D-GLUCOPYRANOSIDE TETRANITRATE IN PYRIDINE

Additive Tendency of Substituent Effects onto Rate Constant of Acidic Hydrolysis of Methyl 4‐O‐Methyl‐β‐d‐Glucopyranoside

Contribution of the O-benzoyl groups of tetra-O-benzoyl-α,β-l-arabinopyranoses to the formation of 1,1-bis(benzamido)-1-deoxy-l-arabinitol

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