Micellar catalysis of anilide hydrolysis

1978 ◽  
Vol 31 (7) ◽  
pp. 1525 ◽  
Author(s):  
TJ Broxton ◽  
LW Deady ◽  
NW Duddy

The rate of hydrolysis of several anilides is catalysed by cationic micelles (cetyltrimethylammonium bromide), and inhibited by anionic micelles (sodium lauryl sulfate). The magnitude of catalysis is greatest for those anilides which contain the most hydrophobic R groups (R = C7H15 and Ph) and is less for those containing less hydrophobic R groups (R = Me). The magnitude of catalysis is greater for compounds activated by nitro groups than for those activated by a ring nitrogen atom. The catalysis is inhibited by added sodium bromide. There is no evidence that anilide hydrolysis in a micellar environment involves dianionic intermediates. Micellar catalysis of anilide hydrolysis is much greater than for ester hydrolysis.

1980 ◽  
Vol 33 (8) ◽  
pp. 1771 ◽  
Author(s):  
TJ Broxton ◽  
NW Duddy

The basic hydrolysis of a number of α-substituted N-methyl-N-p- nitrophenylacetamides has been studied both in the presence and absence of micelles of cetyltrimethylammonium bromide (ctab). Unlike the related p-nitrophenyl esters of a-substituted acetic acids, no evidence for the operation of the E1cb mechanism in the basic hydrolysis has been detected. Reasons for the differences between the amides and esters are discussed. Substituent effects on the hydrolysis of the amides have been studied both by single-parameter and dual-parameter analysis.


Author(s):  
Abanish Kumar

Hydrolysis of bis-p-methoxyphenyl phosphate ester (bis-p-MPPE) was studied in micellar solutions of cityltrimethylammoniumbromide n-C16H33N+(CH3)3Br- (CTABr) at pH-9.0. The hydrolysis followed first order kinetics with respect to bis-p-MPPE concentration. At the concentration of critical micelle concentration (CMC) the rate of hydrolysis increased with increasing CTABr concentration. Surfactant with cationic or polar head group form micelles in water with hydrocarbon like interior or polar groups at the surface and bind cationic solute. The binding constant of micelle for bis-p-MPPE and the rate constant in micellar pseudo phase were determined from kinetic data using the pseudophase model. 


1988 ◽  
Vol 66 (7) ◽  
pp. 1566-1570 ◽  
Author(s):  
Trevor J. Broxton ◽  
Xenia Sango ◽  
Sallyanne Wright

The basic hydrolysis of diazepam and several N-alkyl nitrazepam derivatives has been studied in the presence of reactive counterion micelles of cetyltrimethylammonium hydroxide (CTAOH) and vesicles of didodecyldimethylammonium hydroxide (DDAOH). In both surfactants, the rate of hydrolysis of all compounds was found to be dependent on the hydroxide concentration at constant surfactant concentration and this was interpreted as evidence for initial amide hydrolysis. The hydrolysis in CTAOH was inhibited by added salts in the order Br− < NO3− < SO42−. At concentrations above 3 mM surfactant, the rate of hydrolysis of each compound was similar in CTAOH and in DDAOH. At lower concentrations of CTAOH, however, the rate of hydrolysis was significantly lower than that in DDAOH. On the basis of this evidence, it was concluded that the cmc of CTAOH was between 2–3 mM, which is in good agreement with the value of 1.8 mM obtained by Zana from conductivity measurements. For diazepam, a mechanistic change is indicated on transfer from water to either micelles or vesicles and since vesicles are considered good models of biological membranes, this suggests that conclusions concerning the bioavailability of diazepam should not be based on studies in water but rather on studies in either micelles or vesicles.


1981 ◽  
Vol 34 (8) ◽  
pp. 1615 ◽  
Author(s):  
TJ Broxton

The hydrolysis of N-methyl-N-(4'-nitrophenyl)-2-phenoxyacetamide has been studied in the presence and absence of micelles of cetyltrimethylammonium bromide. The micellar catalysis depends on the reaction system being used. Hydrolysis in the presence of sodium hydroxide, and in the presence of borate, carbonate/bicarbonate and triethylamine/triethylammonium chloride buffers has been examined. The magnitude of catalysis is shown to depend on the buffer system used, the concentration of detergent, the concentration of the buffer, the pH and the presence of any added salts. The results confirm that it is unrealistic to compare independent sets of results on different compounds unless the conditions for obtaining those results are identical. ��� Hydrolysis in the presence of carbonate/bicarbonate buffers is shown to be subject to buffer catalysis and, by analogy with results for p-nitrophenyl acetate, nucleophilic catalysis by carbonate ions is suggested.


1981 ◽  
Vol 34 (11) ◽  
pp. 2313 ◽  
Author(s):  
TJ Broxton

The rates of basic hydrolysis of N-methyl-N-(4'-nitrophenyl)octanamide and N,4-dimethyl-N- (3'-nitrophenyl)benzamide in the presence of cetyltrimethylammonium fluoride and acetate and the SNAr reactions of sodium nitrite with 2,4-dinitrofluorobenzene and 1-chloro-2,4-dinitrobenzene in the presence of cetyltrimethylammonium fluoride have been measured and compared to the rate in the presence of cetyltrimethylammonium bromide. The identity of the micellar counter ion (i.e. fluoride, acetate or bromide) has only a small effect on the rate of reaction despite quite substantial differences in exchange constants for the appropriate nucleophile/counter ion pairs; this is explained by a considerable amount of reaction between substrate molecules in the micellar pseudophase and the nucleophile in the aqueous intermicellar phase.


Author(s):  
G. O. Zhdanova ◽  
◽  
K. D. Zyuzina ◽  
S. E. Sergienko ◽  
M. N. Saksonov ◽  
...  

Pollution of natural objects with surfactants is relevant, including for the lake Baikal. Here, until the near future, there was a constant increase in the tourist flow and, as a result, the ingress of these pollutants into the reservoir. First of all, the inhabitants of the littoral zone come into contact with the incoming pollutants. In this regard, the work evaluated the effect of surfactants on the survival rate of the Baikal endemic oligochaetes Mesenchytraeus bungei Michaelsen, 1901. These enchitreids are a common species. They are widespread throughout the lake from the water's edge to the deepest depths. Therefore, M. bungei is recommended as an indicator object for ecological monitoring of the lake Baikal. The tested compounds are representatives of different types of surfactants: anionic – sodium lauryl sulfate, cationic –cetyltrimethylammonium bromide and nonionic – tween-80. Baikal oligochaetes M. bungei Michaelsen, 1901 were collected in July – August 2020 in the splash zone of Lake Baikal in settlement Bolshiye Koty (South Baikal). Enchitreid about 1.8-2.0 cm long was used in the experiments. After adaptation to laboratory conditions (2 days with water aeration using a microcompressor), further incubation was carried out in glass or plastic cages with nonsterile Baikal water at a temperature of 8–10 °C and an illumination of 250-300 lux. River sand was placed at the bottom, the layer thickness of which was 0.8-1.5 cm. Baikal oligochaetes M. bungei Michaelsen, 1901 turned out to be sensitive to the anionic surfactant sodium lauryl sulfate and cationic cetyltrimethylammonium bromide at a content of 0.005-0.006 mM. So, with the addition of 0.006 mM sodium lauryl sulfate for 3 days of the experiment, the proportion of dead individuals of the test object was 40%, at 0.0125 mM – 60%, at 0.025 mM – 90%, and at 0.05 mM complete death of all enchitreid individuals was observed. Adding CTAB at a concentration of 0.005 mM increased the proportion of dead oligochaetes to 40%. TAB twice – up to 0.01 mM – led to the death of all worms. The nonionic surfactant tween-80 did not have a negative effect on the Baikal oligochaetes in the concentration range from 1 to 60 mM. The tested surfactants to reduce the degree of their effect on the survival of oligochaetes can be arranged in the following row: cetyltrimethylammonium bromide (LC100 = 0.01 mM)> sodium lauryl sulfate (LC100 = 0.05 mM)> tween-80 (harmless up to 60 mM inclusive).


1988 ◽  
Vol 41 (3) ◽  
pp. 325
Author(s):  
TJ Broxton ◽  
JR Christie ◽  
SM Mannas

The basic hydrolyses of phenyl acetate, N,4-dimethyl-N-(3′- nitrophenyl ) benzamide , methyl N-methyl-N-(4′-nitrophenyl) carbamate and methyl N-(3′,5′-dinitrophenyl)-N-methylcarbamate have been studied in cationic micelles of cetyltrimethylammonium bromide (ctab) and sulfate (ctas). Hydrolysis of phenyl acetate and the 4′-nitro carbamate, which involve rate-determining hydroxide attack, exhibit weak catalysis by both micelles, and the observed rates in each micelle are similar. The hydrolysis of the benzamide and the 3′,5′-dinitro carbamate, which involve rate determining C-N bond breaking, show larger catalysis, and, furthermore, micelles of ctab are more effective than micelles of ctas. The observed rates can be explained by the pseudo-phase kinetic model. For reactions involving rate-determining hydroxide attack, the calculated second-order rate constants in micelles of ctab and ctas are similar and much less than those for reaction in water. For reactions involving rate-determining C-N bond breaking the calculated second-order rate constants in micelles of ctab are greater than in micelles of ctas, and similar to those for reaction in water.


1973 ◽  
Vol 51 (12) ◽  
pp. 1959-1964 ◽  
Author(s):  
Leo Ka-Ming Lam ◽  
Donald E. Schmidt Jr.

p-n-Butylaniline ([nBA] = 1 × 10−3 M) incorporated in cationic micelles of cetyltrimethylammonium bromide ([CTABr] = 6 × 10−3M) was found to enhance the rate of decarboxylation of oxalacetic acid (OAA) 45-fold while nBA alone only increases the rate six-fold as compared to the rate of spontaneous decarboxylation at the same pH. Anionic micelles of sodium dodecyl sulfate ([SDS] = 6 × 10−3 M) completely inhibited the catalytic effect of nBA. Together with the effects of added salts and the change of pH on the rate of the reaction the role of micelles in the decarboxylation of OAA is discussed.


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