An analysis of complex alkyl‐substituent effects in the water‐catalyzed hydrolysis of 1‐acyl‐1,2,4‐triazoles

Mooij, Herman J.; Engberts, Jan B. F. N.; Charton, Marvin

doi:10.1002/recl.19881070316

Cited by 11 publications

(2 citation statements)

References 24 publications

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“…Sodium dodecylsulfate (SDS) (99%, Fluka), sodium methylsulfate (NMS) (98%, TCI), p -anisoyl chloride (99%, Acros Organics), p -toluoyl chloride (99%, Acros Organics), benzoyl chloride (99%, Acros Organics), p -chlorobenzoyl chloride (99%, Aldrich), p -(trifluoromethyl)benzoyl chloride (98%, Acros Organics), p -nitrobenzoyl chloride (99%, Fluka), 1,2,4-triazole (purum, ≥98%, Fluka), p -toluic acid (98%, Aldrich), p -(trifluoromethyl)benzoic acid (99%, Acros Organics), and Reichardt’s E T (30) dye (90%, Aldrich) were used as received. The substituted 1-benzoyl-1,2,4-triazoles 1a – f were synthesized according to literature procedures …”

Section: Methodsmentioning

confidence: 99%

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The Nature of the Sodium Dodecylsulfate Micellar Pseudophase as Studied by Reaction Kinetics

Onel

Buurma

2011

J. Phys. Chem. B

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The nature of the rate-retarding effects of anionic micelles of sodium dodecyl sulfate (SDS) on the water-catalyzed hydrolysis of a series of substituted 1-benzoyl-1,2,4-triazoles (1a-f) has been studied. We show that medium effects in the micellar Stern region of SDS can be reproduced by simple aqueous model solutions containing small-molecule mimics for the surfactant headgroups and tails, namely sodium methyl sulfate (NMS) and 1-propanol, in line with our previous kinetic studies for cationic surfactants ( Buurma et al. J. Org. Chem. 2004 , 69 , 3899 - 3906 ). We have improved our mathematical description leading to the model solution, which has made the identification of appropriate model solutions more efficient. For the Stern region of SDS, the model solution consists of a mixture of 35.3 mol dm(-3) H(2)O, corresponding to an effective water concentration of 37.0 mol dm(-3), 3.5 mol dm(-3) sodium methylsulfate (NMS) mimicking the SDS headgroups, and 1.8 mol dm(-3) 1-propanol mimicking the backfolding hydrophobic tails. This model solution quantitatively reproduces the rate-retarding effects of SDS micelles found for the hydrolytic probes 1a-f. In addition, the model solution accurately predicts the micropolarity of the micellar Stern region as reported by the E(T)(30) solvatochromic probe. The model solution also allows the separation of the individual contributions of local water concentration (water activity), polarity and hydrophobic interactions, ionic strength and ionic interactions, and local charge to the observed local medium effects. For all of our hydrolytic probes, the dominant rate-retarding effect is caused by interactions with the surfactant headgroups, whereas the local polarity as reported by the solvatochromic E(T)(30) probe and the Hammett ρ value for hydrolysis of 1a-f in the Stern region of SDS micelles is mainly the result of interactions with the hydrophobic surfactant tails. Our results indicate that both a mimic for the surfactant tails (NMS) and a mimic for the surfactant headgroups (1-propanol) are required in a model solution for the micellar pseudophase to reproduce all medium effects experienced by a variety of different probes.

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Section: Methodsmentioning

confidence: 99%

“…The substituted 1-benzoyl-1,2,4-triazoles 1aÀf were synthesized according to literature procedures. 50 Spectrophotometric Measurements. Aqueous solutions were prepared in water purified using an ELGA option-R 7BP water purifier.…”

mentioning

confidence: 99%

The Nature of the Sodium Dodecylsulfate Micellar Pseudophase as Studied by Reaction Kinetics

Onel

Buurma

2011

J. Phys. Chem. B

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ChemInform Abstract: An Analysis of Complex Alkyl‐Substituent Effects in the Water‐Catalyzed Hydrolysis of 1‐Acyl‐1,2,4‐triazoles

1988

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Reaction of 4‐benzylidene‐2‐methyl‐5‐oxazolone with amines, Part 2: Influence of substituents in para‐position in the phenyl ring and a substituent on amine nitrogen atom on the reaction kinetics

Betłakowska¹,

Banecki²,

Czaplewski³

et al. 2002

Int J of Chemical Kinetics

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An influence of a structure of the amine (benzylamine, N-methyl-benzylamine, N-isopropyl-benzylamine, N-methyl-butylamine, N-ethyl-butylamine, sec-butylamine, and tertbutylamine) on a rate constant of the ring-opening reaction of 4-benzylidene-2-methyl-5-oxazolone (Ox) was studied. The good correlation between logarithm of the rate constants and Charton's steric substituent constant ν as well as good correlation with a form of the simple branching equation indicate that there is a steric effect because of substitution at C1 carbon atom of nucleophile which decreases the reaction rate. Additionally, an influence of a structure of the benzylidene moiety of Ox on a rate of the oxazolone ring-opening reaction was studied. REACTION OF 4-BENZYLIDENE-2-METHYL-5-OXAZOLONE WITH AMINES 149The substituents ( OH, OCH 3 , N(CH 3 ) 2 , Cl, NO 2 ) in para-position of the phenyl ring of Ox substantially modified the rate of the reaction with benzylamine in acetonitrile. The rate of the Ox ring-opening reaction decreased with increase of the electron-donating properties of the substituent. A good correlation between the rate constants of the reaction of 4-(4 -substitutedbenzylidene)-2-methyl-5-oxazolones with benzylamine and the electron density at the reaction center (carbon C5 of the oxazolone ring), calculated using ab initio method, and the Hammett substituent constants, and CR equation were established.

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An analysis of complex alkyl‐substituent effects in the water‐catalyzed hydrolysis of 1‐acyl‐1,2,4‐triazoles

Cited by 11 publications

References 24 publications

The Nature of the Sodium Dodecylsulfate Micellar Pseudophase as Studied by Reaction Kinetics

The Nature of the Sodium Dodecylsulfate Micellar Pseudophase as Studied by Reaction Kinetics

ChemInform Abstract: An Analysis of Complex Alkyl‐Substituent Effects in the Water‐Catalyzed Hydrolysis of 1‐Acyl‐1,2,4‐triazoles

Reaction of 4‐benzylidene‐2‐methyl‐5‐oxazolone with amines, Part 2: Influence of substituents in para‐position in the phenyl ring and a substituent on amine nitrogen atom on the reaction kinetics

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