THE SYNTHESIS OF SOME DERIVATIVES OF 3,4-METHYLENEDIOXYBENZENE

1964 ◽  
Vol 42 (8) ◽  
pp. 1901-1905 ◽  
Author(s):  
Pritam Singh ◽  
Louis Berlinguet
Keyword(s):  
Aqueous Solution ◽  
Hydrochloric Acid ◽  
Acetic Anhydride ◽  
Hydrazine Hydrate ◽  
Propionic Acid ◽  
Sodium Acetate ◽  
Potassium Chlorate ◽  
Ammonium Formate ◽  
Dilute Aqueous Solution ◽  
Derivatives Of

A few derivatives of 3,4-methylenedioxy-α-nitromethylbenzyl alcohol (I) have been prepared. Chlorination with hydrochloric acid and potassium chlorate gave 6-chloro-3,4-methylenedioxy-α-nitromethylbenzyl alcohol (II) which on refluxing with acetic anhydride and sodium acetate gave 6-chloro-3,4-methylenedioxy-ω-nitrostyrene (III). Attempted reduction of (I) with ammonium formate resulted in dehydration to give 3,4-methylenedioxy-ω-nitrostyrene (IV). Reduction of (I) with hydrazine hydrate gave an isobenzaldoxime (VI).β-(3,4-Methylenedioxyphenyl) serine (VII) was prepared by the condensation of piperonal with glycine. α,β-Dibromo-β-(3,4-methylenedioxyphenyl) propionic acid could not be aminated by a dilute aqueous solution of ethylamine. Decarboxylation and elimination of HBr took place to give ω-bromo-3,4-methylenedioxystyrene (VIII).

THE PREPARATION OF 9-HYDROXYPYRAZOLO[3,4-b]QUINOLINES

1966 ◽  
Vol 44 (17) ◽  
pp. 2009-2014 ◽  
Author(s):  
R. T. Coutts ◽  
J. B. Edwards
Keyword(s):  
Acetic Acid ◽  
Acetic Anhydride ◽  
Hydrazine Hydrate ◽  
Sodium Borohydride ◽  
Sodium Acetate ◽  
The Other ◽  
Reduction Product ◽  
Type I

4-(2-Nitrobenzylidene)-2-pyrazolin-5-ones (I) were best prepared by heating o-nitrobenzaldehyde and 2-pyrazolin-5-ones in acetic anhydride containing fused sodium acetate (cf. Erlenmeyer azlactone synthesis). Pyrazolones of type I were reductively cyclized with cyclohexene and palladium–charcoal, and gave 3a,4,9,9a-tetrahydro-9-hydroxy-1H-pyrazolo-[3,4-b]quinolines (II) which, as expected, were amphoteric compounds. Of the three other methods of reduction used in this study, two (zinc and acetic acid; sodium borohydride and palladium–charcoal) were capable of producing pyrazoloquinolines, but were less reliable. The other method employed (hydrazine hydrate and palladium–charcoal) caused degradation of the pyrazolone molecule in the two cases examined, and in both, bis(2-aminobenzylidene) hydrazine (V) was the reduction product isolated.

Stability of the Nerve Gas Antidote BIS (4-Hydroxyiminomethyl-1-Pyridinomethyl) Ether Dichloride (Toxogonin®)

1968 ◽  
Vol 2 (9) ◽  
pp. 234-243 ◽  
Author(s):  
Inga Christenson
Keyword(s):  
Aqueous Solution ◽  
Hydrochloric Acid ◽  
Sodium Hydroxide ◽  
Rate Constants ◽  
Kinetics Of Hydrolysis ◽  
Dilute Aqueous Solution ◽  
Nerve Gas ◽  
Ph Range ◽  
Kinetics Of ◽  
Hydrolysis Of

The products and kinetics of hydrolysis of the nerve gas antidote bis(4-hydroxyiminomethyl - 1 - pyridinemethyl) ether dichloride (Toxogonin ®) have been investigated. A survey of these studies is given: The hydrolytic reactions were studied in the pH range 1 M hydrochloric acid to 1 M sodium hydroxide at 25, 45, 75 and 85° C. Rate constants were determined in dilute aqueous solution, generally with an initial Toxogonin concentration of 0.01 mg per ml. In addition, a report is given concerning two-year storage of 25 percent (w/v) Toxogonin solutions at pH 2.5, 3.0 and 3.5. The solutions were stored in glass or polypropylene ampuls at 5, 15, 25 and 45°C. At 5 and 15C° decomposition was negligible, at 25 and 45 °C average decomposition was 1.5 percent and 3.3 percent, respectively.

scholarly journals The effect of solvent on reaction velocity. V.-The interaction of N-chloroacetanilide and hydrobromic acid in dilute aqueous solution

1934 ◽  
Vol 144 (853) ◽  
pp. 643-655
Keyword(s):  
Aqueous Solution ◽  
Hydrochloric Acid ◽  
Hydrobromic Acid ◽  
Ion Concentration ◽  
True Rate ◽  
Simultaneous Formation ◽  
Ion Concentrations ◽  
Hückel Theory ◽  
Dilute Aqueous Solution ◽  
Acid Reaction

The interaction of N-chloroacetanilide and hydrobromic acid to form p - bromoacetanilide and hydrochloric acid has, unlike the corresponding reaction with hydrochloric acid. received comparatively little attention from a kinetic standpoint. It possesses, however, the advantage over the hydrochloric acid reaction, that its speed is much greater. It thus allows of the examination of mixtures containing only 0·001 M hydrobromic acid and of salt effects in the region of dilute concentration where the Debye-Hückel theory applies. The mechanism of the interaction is analogous to that of the chloroamine- hydrochloric acid reaction, where the first stage C 6 H 5 NClAC + HCL I → Cl 2 + C 6 H 5 NHAc II → ClC 6 H 4 NHAc +HCl determines the rate of transformation of the chloroamine in aqueous solution. Two corrections are necessary in this reaction if the true rate of interaction of chloroamine and acid is to be determined. The first correction is for the hydrolysis of the chloroamine under the influence of the acid, a rate mainly dependent on the H • ion concentration. Since the rate of the transformation depends on the product of the H • and Cl' ion concentrations, the correction for hydrolysis cannot l>e regarded as forming a constant fraction of the observed speed, particularly when the ratio of these ion concentrations is widely varied. The second correction is for the simultaneous formation of the chloroamim of the chloroanilides present. These chloroamines, which are formed pro-gressively, appear in the chloroamine titre and cause the measured reaction rate to be slower by 4-10% than the actual rat* of production of chlorine. This complication can be avoided by the presence of easily chlorinated sub-stances. such as anisole, p -cresol, or acetanilide, which remove the chlorine as formed.

Amphiphilic Derivatives of Propylene Glycol Alginate:  A Revisit of Their Physicochemical Behavior in Dilute Aqueous Solution

Langmuir ◽  
1996 ◽  
Vol 12 (16) ◽  
pp. 3779-3782 ◽  
Author(s):  
A. Sinquin ◽  
M. C. Houzelle ◽  
P. Hubert ◽  
L. Choplin ◽  
M. L. Viriot ◽  
...  
Keyword(s):  
Aqueous Solution ◽  
Propylene Glycol ◽  
Propylene Glycol Alginate ◽  
Dilute Aqueous Solution ◽  
Derivatives Of

scholarly journals II. Contributions to the history of the orcins.—No. IV. On the iodo-derivatives of the orcins

1874 ◽  
Vol 22 (148-155) ◽  
pp. 53-55
Keyword(s):  
Aqueous Solution ◽  
Potassium Iodide ◽  
Detailed Account ◽  
Mercuric Oxide ◽  
Iodine Monochloride ◽  
Mercuric Iodide ◽  
Molecular Weights ◽  
Dilute Aqueous Solution ◽  
History Of ◽  
Derivatives Of

A preliminary notice on these compounds has already appeared in the ‘Chemical News,’ vol. xxvi. p. 279; and the present paper contains a more detailed account of my experiments. In 1864 I published an account of a crystalline teriodorcin obtained by precipitating an aqueous solution of orcin with a solution of iodine monochloride, but I found I was unable to prepare any other iodine derivative of orcin by this process. It seems probable, however, that the method devised some years ago by Prof. Hlasiwetz, and communicated by him at the meeting of the “Naturforscher und Aerzte in Innsbruck,” would yield the lower substitution compounds. This was found to be the case; for on agitating an ethereal solution containing equal molecular weights of orcin and iodine with dry precipitated mercuric oxide, the colour rapidly disappears, and monoiodorcin is formed; this may be obtained by distilling off the ether and crystallizing the residue from benzol, in order to separate an uncrystallizable oily compound which accompanies it. It is, however, still contaminated with a small quantity of mercuric iodide, which obstinately adheres to the substance, and can only be removed by recrystallization from a dilute aqueous solution of potassium iodide; this difficulty arises from the circumstance that mercuric iodide is more or less soluble in most of the liquids usually employed as solvents. For this reason I found it advisable to substitute plumbic oxide for the corresponding mercury compound originally proposed by Hlasiwetz.

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