Reexamination of the Kirkwood–Westheimer theory of electrostatic effects. V. Effect of charged substituents on the rates of alkaline hydrolysis of substituted strychnines

1997 ◽  
Vol 75 (4) ◽  
pp. 441-448
Author(s):  
Khamis A. Abbas ◽  
Phillip Hurst ◽  
John T. Edward
Keyword(s):  
Sodium Hydroxide ◽  
Alkaline Hydrolysis ◽  
Kinetic Data ◽  
Aqueous Sodium Hydroxide ◽  
Second Order ◽  
Electrostatic Effects ◽  
Third Order ◽  
Aqueous Sodium ◽  
Hydrolysis Of ◽  
Positively Charged

The rates of hydrolysis in aqueous sodium hydroxide of the alkaloid strychnine and seven of its derivatives have been determined at 50 and 75 °C. The kinetic data indicate that all the compounds, except strychninesulfoni acid-I, hydrolyze by competing second- and third-order mechanisms, involving one and two hydroxide ions, respectively; strychninesulfonic acid-I hydrolyzes by the second-order mechanism only. The quantitative effect of positively charged groups in enhancing, and negatively charged groups in depressing, the rates of hydrolysis is in rough agreement with calculations using Kirkwood–Westheimer theory. Keywords: Kirkwood–Westheimer theory; strychnine derivatives, hydrolysis of; lactams, hydrolysis of; electrostatic effects on rates of alkaline hydrolysis; alkaloids, reactions of.

KINETICS OF THE ALKALINE HYDROLYSIS OF PROPIONITRILE

1942 ◽  
Vol 20b (9) ◽  
pp. 185-188 ◽  
Author(s):  
B. S. Rabinovitch ◽  
C. A. Winkler
Keyword(s):  
Activation Energy ◽  
Sodium Hydroxide ◽  
Alkaline Hydrolysis ◽  
Aqueous Sodium Hydroxide ◽  
Alkali Concentration ◽  
Aqueous Sodium ◽  
Velocity Constant ◽  
Total Ammonia ◽  
Kinetics Of ◽  
Hydrolysis Of

Some contradictory points recorded for the alkaline hydrolysis of nitriles have been clarified by a study of propionitrile hydrolysis in aqueous sodium hydroxide solutions of concentration 0.3 to 4 N. It has been shown that the rate of alkaline hydrolysis of propionitrile is given by the rate of formation of total ammonia and intermediate amide and not by that of ammonia alone. The relative rates of propionitrile and propionamide hydrolysis were found to be approximately 1:10 over the whole alkali concentration range. The bimolecular velocity constant is essentially independent of alkali concentration. An activation energy of 20,300 cal. was determined for the reaction in 0.65 N alkali.

Benzenesulfonyl chloride with primary and secondary amines in aqueous media — Unexpected high conversions to sulfonamides at high pH

2005 ◽  
Vol 83 (9) ◽  
pp. 1525-1535 ◽  
Author(s):  
James F King ◽  
Manjinder S Gill ◽  
Petru Ciubotaru
Keyword(s):  
Sodium Hydroxide ◽  
Sulfonyl Chloride ◽  
Second Order ◽  
Secondary Amines ◽  
Third Order ◽  
Benzenesulfonyl Chloride ◽  
Aqueous Sodium ◽  
First Order ◽  
The Third ◽  
Primary And Secondary Amines

We have determined pH–yield profiles under pseudo-first-order conditions of the reactions of benzenesulfonyl chloride with a set of primary and secondary water-soluble alkylamines, and have found with certain amines, such as dibutylamine, a profile taking the form of a sigmoid pH&#150yield curve with relatively high yields of the sulfonamide persisting with increasing basicity up to and including 1.0 mol/L sodium hydroxide. This behaviour is quantitatively accounted for by invoking, in addition to the usual second-order reaction of the sulfonyl chloride with the amine, two third-order terms (i) one first-order in sulfonyl chloride, amine and hydroxide anion, and (ii) another first-order in sulfonyl chloride and second-order in the amine. The importance of the third-order terms correlates approximately with the total number of alkyl carbon atoms in the amine, and this in turn is regarded as related to the hydrophobic character of the amine. Experiments to test this picture included: (i) observation of a bell-shaped curve with bis(2-methoxyethyl)amine, (ii) in the reaction of dibutylamine in THF&#150H2O (1:1), and also (iii) in the reaction of dibutylamine in 1.0 mol/L tetrabutylammonium bromide, and (iv) increase in the contributions of the third-order terms in 1.0 mol/L aqueous sodium chloride. Preparative reactions with dibutylamine, 1-octylamine, and hexamethylenimine in 1.0 mol/L aqueous sodium hydroxide with a 5% excess of benzenesulfonyl chloride gave, respectively, 94%, 98%, and 97% yields of the corresponding sulfonamides. Key words: sulfonyl chlorides, primary and secondary amines, pH–yield profiles, organic synthesis in water, hydrophobic effects.

Solubility and rate of hydrolysis of chlorine in aqueous sodium hydroxide at 273 K

AIChE Journal ◽  
1981 ◽  
Vol 27 (5) ◽  
pp. 856-859 ◽  
Author(s):  
O. C. Sandall ◽  
I. B. Goldberg ◽  
S. C. Hurlock ◽  
H. O. Laeger ◽  
R. I. Wagner
Keyword(s):  
Sodium Hydroxide ◽  
Aqueous Sodium Hydroxide ◽  
Aqueous Sodium ◽  
Rate Of Hydrolysis ◽  
Hydrolysis Of

Novel Rearrangement of 5-Arylazo-2-thiohydantoin Derivatives with Alkali and Aromatic Amines

1978 ◽  
Vol 33 (8) ◽  
pp. 937-941 ◽  
Author(s):  
A. F. A. Shalaby ◽  
H. A. Daboun ◽  
M. A. Abdel Aziz
Keyword(s):  
High Temperature ◽  
Sodium Hydroxide ◽  
Hydrazine Hydrate ◽  
Carboxylic Acids ◽  
Cinnamic Acid ◽  
Aromatic Amines ◽  
Acid Hydrazide ◽  
Aqueous Sodium Hydroxide ◽  
Aqueous Sodium ◽  
Hydrolysis Of

Abstract 5-Arylazo-2-thiohydantoin derivatives (2a,c) were cleaved and rearranged by aqueous sodium hydroxide to give the corresponding 1-aryl-⊿2-1,2,4-trazole-5-imino-3-carboxylic acids (3a-c). 3 a was decarboxylated to 1-phenyl-⊿2 -1,2,4-triazoline-5-imine (5). Hydrolysis of 5-arylazo-1-phenyl-2-thiohydantoins (6a-c) behaved in different manner affording 1-aryl-4-phenyl-⊿2 -1,2,4-triazoline-5-thione-3-carboxylic acids (7a-c). Fusing (2a-c) with aromatic amines at high temperature gave the corresponding anilides (8a-h). Treatment of 5-arylidene-2-thiohydantoin derivatives (9a-c) with hydrazine hydrate gave colourless products of thioureido cinnamic acid hydrazide derivatives (10a-c), while refluxing 5-arylidene-2-methylmercaptohydantoin (11a-d) with hydrazine hydrate and/or benzo-phenone hydrazone gave the corresponding glycocyamidine derivatives (12a-g).

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