Micellar catalysis of organic reactions. 32. SNAr reactions of 1,5-difluoro-2,4-dinitrobenzene and related compounds in the presence of cationic micelles

1991 ◽  
Vol 56 (20) ◽  
pp. 5958-5960 ◽  
Author(s):  
Trevor J. Broxton
Keyword(s):  
Micellar Catalysis ◽  
Organic Reactions ◽  
Cationic Micelles ◽  
Related Compounds

Micellar catalysis of organic reactions. 22. A comparison of the basic hydrolysis of benzodiazepinones in the presence of reactive counterion micelles and vesicles

1988 ◽  
Vol 66 (7) ◽  
pp. 1566-1570 ◽  
Author(s):  
Trevor J. Broxton ◽  
Xenia Sango ◽  
Sallyanne Wright
Keyword(s):  
Surfactant Concentration ◽  
Biological Membranes ◽  
Micellar Catalysis ◽  
Organic Reactions ◽  
Conductivity Measurements ◽  
Amide Hydrolysis ◽  
Rate Of Hydrolysis ◽  
Basic Hydrolysis ◽  
Hydrolysis Of ◽  
Good Agreement

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.

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