Organic quaternary ammonium ions, effect

Organic quaternary ammonium ions are effective in forming silicate anions with cage-like structures. 

Effect of the Structure of Organic Quaternary Ammonium Ions. The tetramethylammonium ion (N C J ), first introduced in zeolite synthesis by Barrer and Denny (30), and Kerr and Kokotailo (21) is effective in forming the cubic octameric silicate anion (Sig02Q°, cubic octamer) (2-16). In the tetramethylammonium silicate aqueous solutions at higher S3.O2 concentrations or cation-to-silica molar ratios (abbreviated to the N/Si ratios), the cubic octamer is singularly formed. 

Effect of Addition of Sodium Ions to Tetramethylammonium Silicate Aqueous Solution. In zeolite synthesis, alkali metal cations are combined with organic quaternary ammonium ions to produce zeolites with different structures from the one produced with only the organic quaternary ammonium ion (2) It is then expected that other types of silicate species are formed in the silicate solutions when organic quaternary ammonium ions and alkali metal cations coexist. In such silicate aqueous solutions, however, alkali metal cations only act to suppress the ability of the organic quaternary ammonium ions to form selectively silicate species with cage-like structures (13,14,28,29). 

We have determined the ion-pair formation-partition equilibrium constant with picrate anion for a number of primary, secondary, tertiary and quaternary ammonium ions 23>. In aqueous media of pH 5-6, the ammonium ions and picrate are considered to exist almost completely as unpaired counter ions. When the aqueous solution is mixed with an immiscible organic solvent, the ions are partitioned into the organic phase as the ion pair. We expected that the steric effect of N-substituents in the ion-pair formation-partition equilibrium could be analyzed by a procedure similar to Eq. 24, and derived Eq. 27 for the set of quaternary ions 23). 

In the two phase Williamson ether synthesis, the base used is concentrated aqueous sodium hydroxide. Ordinarily, 50% aqueous sodium hydroxide is used, but even more concentrated solutions seem to be more effective. The alcohol in solution is deprotonated by hydroxide either in the aqueous phase or at the interface and then solubilized in the organic phase by ion pairing with the quaternary ammonium ion. 

Generally, where the anion is poorly solvated in the aqueous phase, there is a greater propensity for the ion-pair to reside in the organic phase and, consequently, the overall effect of the quaternary ammonium catalyst is influenced by the initial choice of counter anion of the catalyst or by the anion that is generated in the... 

In many reactions, transfer of the anion across the interface and subsequent diffusion into the bulk of the organic phase will not be the rate-determining step when lipophilic catalysts are used, but the effect of less lipophilic catalysts may be influenced more by the anion and the mechanism of the transfer process. Thus, for example, the reactive anion is frequently produced in base-initiated reactions by proton extraction from the substrate at the two-phase interface and diffusion of the ion-pair contributes to the overall kinetics of the reaction. Additionally, the reactivity of the anion depends on its degree of hydration and on its association with the quaternary ammonium cation. In most situations, the activity of the transferred anion is enhanced, compared with its reactivity in aqueous media, as its degree of hydration is reduced, whereas a relatively weak electrostatic interaction between the two ions resulting from the bulkiness of the cation enhances the reactivity of the anion by making it more available for reaction and will be a major factor in the ratedetermining step. 

The catalytic effect of quaternary ammonium salts in the basic liquid liquid two-phase alkylation of amines [1-3] is somewhat unexpected in view of the low acidity of most amines (pKfl>30). Aqueous sodium hydroxide is not a sufficiently strong base to deprotonate non-activated amines in aqueous solution and the hydroxide ion is not readily transferred into the organic phase to facilitate the homogeneous alkylation (see Chapter 1). Additionally, it is known that ion-pairs of quaternary ammonium cations with deprotonated amines are decomposed extremely rapidly by traces of water [4]. However, under solidrliquid two-phase conditions, the addition of a quaternary ammonium salt has been found to increase the rate of alkylation of non-activated amines by a factor of ca. 3-4 [5]. Similarly, the alkylation of aromatic amines is accelerated by the addition of the quaternary ammonium salt the reaction is accelerated even in the absence of an inorganic base, although under such conditions the amine is deactivated by the formation of the hydrohalide salt, and the rate of the reaction gradually decreases. Hence, the addition of even a weak base, such as... 

Although the effect of quaternary ammonium salts on the stereochemistry of the two-phase condensation reaction of a-chloroacetonitrile with acrylonitriles to form cyclopropanes [4, 7] is not as pronounced as with the Darzens reaction, it can be rationalized in an analogous manner (Scheme 12.2). In the absence of the catalyst, the more highly stabilized anion (4a) is favoured leading to the preferential production of the cis isomer (5). As with the Darzens reaction, addition of the catalyst causes diffusion of the anions (4a) and (4b), as ion-pairs, into the bulk of the organic phase where their relative stabilities are similar and a more equal ratio of the two isomeric cyclopropanes (5) and (6) results (Table 12.2). 

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