THE ACTION OF SODIUM IODIDE ON <i>O</i>-<i>p</i>-TOLUENE-SULPHONYL-1,4;3,6-DIANHYDRIDES OF <scp>D</scp>-MANNITOL, <scp>D</scp>-GLUCITOL, AND <scp>L</scp>-IDITOL

Jackson, M.B.; Hayward, L. D.

doi:10.1139/v59-151

Cited by 13 publications

(8 citation statements)

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“…After 2.5 hours the solutions were cooled to roo111 temperature and the sodium tosylate was recovered by filtration and weighed as described by Jacltson and Ha)-\yard (2). Coinpound V yielded 0.060 g (7.4% theory) and I yielded 1.78 g (92% theory) of sodium p-toluenesulphonate.…”

Section: Reaction Of Sodium Iodide Wit16 I and Vmentioning

confidence: 99%

“…However, Cope and Shen ( I ) reported uilequivocal evidence that a transtosylation reaction can take place under these coilditioils and, conseque~ltly, the moilotosylate may have had the tosyl group a t the endo-5-position as shown in structure I. Recently, Jacksoil and Hayward (2) have showil the compouild to undergo replacement of the tosyloxy group when heated with sodium iodide dissolved in acetic anhydride. This observatioil was taken as proof that the tosyloxy group was a t the endo-5-position.…”

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confidence: 99%

“…This observatioil was taken as proof that the tosyloxy group was a t the endo-5-position. I t is conceivable, however, that the endo-acetoxy group of 2-0-tosyl 5-0-acetyl isosorbide (V) can participate in the solvolysis of the tosyloxy group to lead to a 2,sbridged acetosonium ion, which could then react with iodide ion to give the iodoacetate isolated by Jacltson and Hay~vard (2). Thus, the reaction of the compound with sodium iodide could not be talteil as unequivocal evidence that it possesses the structure I.…”

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THE PREFERENTIAL TOSYLATION OF THE ENDO-5-HYDROXYL GROUP OF 1,4;3,6-DIANHYDRO-D-GLUCITOL

Lemieux¹,

McInnes²

1960

Can. J. Chem.

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Reaction of 1,4;3,6-dianhydro-D-glucitol (isosorbide) with an equimolar amount of tosyl chloride in pyridine gave a fourfold greater yield of the endo-5-tosylate (IV) than of the exo-2-tosylate (III). Compound III reacted about 1.4 times more rapidly with tosyl chloride than did IV. The structures of III and IV were established by infrared spectroscopy and by their reaction with sodium methoxide. The exo-tosyloxy group of the monoacetate of III resists replacement by iodide ion.

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Section: Reaction Of Sodium Iodide Wit16 I and Vmentioning

confidence: 99%

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THE PREFERENTIAL TOSYLATION OF THE ENDO-5-HYDROXYL GROUP OF 1,4;3,6-DIANHYDRO-D-GLUCITOL

Lemieux¹,

McInnes²

1960

Can. J. Chem.

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“…The three known isomeric 1,4;3,6-dianhydrohexitols (the cis-isohexides) and their derivatives have been shown to behave characteristically in certain types of reactions clue to differences in their restricted conformations (4,5 ) . In an attempt to determine the mechanism of the pyridine -nitrate ester reaction the dinitrates of the isohexides (1-111, Fig.…”

Section: Introductionmentioning

confidence: 99%

The Action of Pyridine on the Dinitrate Esters of 1,4;3,6-Dianhydrohexitols

Jackson¹,

Hayward²

1960

Can. J. Chem.

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In contrast to the rapid and selective replacement of a secondary 0-nitro group by hydrogen in the hexitol hexanitrates a t 25-50' C, the dinitrate esters of the 1,4;3,6-dianhydrides of D-n~annitol, D-glLIcitoI, and L-iditol (cis-isohexides) reacted slowly in anhydrous pyridine a t 87-115" C. The chief products were a polymer, nitrogen oxides, and pyridinium nitrate; the yield of mononitrates did not exceed lOyo and none of the parent diols were formed.The relative rates of the first-order decon~position of the nitroxy groups in the isomeric dinitrates were in reverse order to that for S N~ reaction a t carbon in these compounds.Activation energies and frequency factors were determined and water was shown to have a retarding effect.Thermal decomposition of the dinitrates in solution in nitrobenzene, nl-xylene, or syintetrachloroethane was much slower than the pyridine reaction a t the same temperature and was independent of the polarity of the solvent and the conformation of the ester. INTRODUCTIONDulcitol and D-inannitol hexanitrates have been shown to react selectively with pyridine to yield the corresponding 1,2,4,5,6-pentanitrates (1, 2). The rate of reaction was different for the two hexitol derivatives and the resulting pentanitrates were essentially stable to pyridine under the same conditions. Sorbitol hexanitrate reacted similarly with pyridine but the pentanitrate was not fully characterized (3). The reaction was inconveniently fast for kinetic studies even a t 25" C and the n~ultiplicity of nitroxy groups and inolecular conformations further complicated the problem of sorting out the reaction mechanism.The three known isomeric 1,4;3,6-dianhydrohexitols (the cis-isohexides) and their derivatives have been shown to behave characteristically in certain types of reactions clue to differences in their restricted conformations (4, 5 ) . In an attempt to determine the mechanism of the pyridine -nitrate ester reaction the dinitrates of the isohexides (1-111, Fig. 1) were selected for study since observation of similar steric effects in their reactions with pyridine would aid in diagnosis of the type of mechanism involved. The presence of only two, non-vicinal, secondary, nitroxy groups in these isomers was also expected t o simplify analysis of the results. RESULTS A N D DISCUSSIONThe three isohexide dinitrates (Fig. 1) were prepared in crystalline form and characterized through their nitrogen contents, infrared spectra, and nearly quantitative conversion to the parent diols. The physical constants and nitrogen contents of the isomers are show11 in Table I. The dinitrates dissolved readily in pyridine and the colorless solutions were stable over several weeks a t roorn temperature. No vigorous reaction occurred on heating under reflux; however, slow decomposition, accoinpailied by a red coloration of the solution and evolution of oxides of nitrogen, began a t temperatures above 50" C.At 115" C 0.424 M solutions of the isohexide dinitrates in anhydrous pyridine decoinposed according to an apparent firs...

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“…7) Candidiasis overgrowth is usually due to inhibition of normal host defenses by local corticosteroid administration. 8) Candidiasis can be seen in the oral mucosa where inhaled corticosteroids are likely to have contacted, which has been suggested to be a consequence of immunosuppression on the oral mucosal surface. 9) In three cases of esophageal candidiasis rated as Grade 3, the symptoms disappeared in two and decreased to Grade 1 in one by simply changing the FP-DPI inhalation administration periods to before breakfast and before dinner.…”

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Kinetic Analysis of Effects of Mouth Washing on Removal of Drug Residues Following Inhalation of Fluticasone Propionate Dry Powder

Yokoyama

Yamamura

Ozeki

et al. 2007

Biological & Pharmaceutical Bulletin

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Inhaled corticosteroids are widely used for treatment of asthma, though local adverse effects, such as candidiasis and hoarseness, are often seen in patients treated with those drugs. Therefore, the Packaging Inserts enclosed with such medications recommend mouth washing after inhalation for prevention of local adverse effects. In spite of that recommendation, candidiasis has been reported by patients who washed their mouth after inhalation.1) Therefore, we carried out a series of studies to investigate the influence of different methods of mouth washing on the removal rates of inhaled corticosteroids. More than 90% of the drug was recovered by washing mouth twice, when the mouth washing procedure was gargling and rinsing for 5 s each.2) However, since no significant differences were observed among 3 methods tested in a previous study, we could not conclude which was most effective. On the other hand, a relationship was observed between the amount of drug residue removed by mouth washing and the number of times of mouth washing was employed in 2 phases. 3,4)Based on those results, we speculated that drug residue remained in different amounts in easy and difficult to remove areas following mouth washing. In the present study, we investigated the differences in removal efficiency of drug residues from both easy and difficult to remove areas using 3 different methods of mouth washing; gargling and rinsing in combination, rinsing alone, and gargling alone, using a compartment model. MATERIALS AND METHODS Compartment Model for Analysis of Removal Efficiency of Drug Residues by Mouth WashingFlutide ® (FP-DPI) 50, 100, and 200 Rotadisk ® dosages were used in the present study. In addition, we employed our previously reported experimental data in the analysis, in which 3 healthy volunteers (2 males, 1 female; mean age 38.3Ϯ9.3 years old, range 28-45 years) participated.3) In the present experiment, mouth washing was started immediately following sprinkling directly in the mouth or inhalation of 1 blister, and consisted of gargling and rinsing with water for 5 s each, then the procedures were repeated 5 times. The total volume of water used for each mouth washing was 100 ml, which was divided into 5 aliquots of 20 ml each. We also developed a compartment model, in which inhaled FP-DPI residue was distributed into 2 different areas, one from which the drug was easily removed and the other from which it was difficult to remove by mouth washing. The equations used for the model were as follows:In those, X 1 and X 2 represent the amount of drugs in areas from which drugs are easily removed and difficult to remove, respectively. X 0 , F, T, and n represent the medication dose, ratio of amount of dose removed by mouth washing to medication dose, ratio of amount of dose removed from the difficult to remove area by mouth washing to total amount of dose removed by mouth washing, and the number of times of mouth washing, respectively. Further, k 1 and k 2 represent the constants of removal efficiency of X 1 and X 2 , respectively....

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THE ACTION OF SODIUM IODIDE ON O-p-TOLUENE-SULPHONYL-1,4;3,6-DIANHYDRIDES OF D-MANNITOL, D-GLUCITOL, AND L-IDITOL

Cited by 13 publications

References 2 publications

THE PREFERENTIAL TOSYLATION OF THE ENDO-5-HYDROXYL GROUP OF 1,4;3,6-DIANHYDRO-D-GLUCITOL

THE PREFERENTIAL TOSYLATION OF THE ENDO-5-HYDROXYL GROUP OF 1,4;3,6-DIANHYDRO-D-GLUCITOL

The Action of Pyridine on the Dinitrate Esters of 1,4;3,6-Dianhydrohexitols

Kinetic Analysis of Effects of Mouth Washing on Removal of Drug Residues Following Inhalation of Fluticasone Propionate Dry Powder

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