Onium salt catalyst

Other Onium Salt Catalysts. We have examined several quaternary ammonium and phosphonium salts in this process. And while they vary in their effectiveness, most seem to have at least some activity. In the case of symmetrical onium salts, substituents having four or more carbon atoms are preferred (Table III). This likely originates from a more favorable partitioning into the organic phase as the size of the substitutents increase. Herriott has reported that there is a... 

The use of PTC conditions has proved beneficial in several cases and the method of choice in large scale operations. m-Dinitrobenzene was converted to m-nitroanisole in 81 % yield on the mole scale by treatment for 2 h with MeONa in chlorobenzene at 80 C in the presence of a catalytic amount of trioc-tylmethylammonium chloride (Aliquat 336).155 No reaction occurred in the absence of the onium salt catalyst.155 Analogous results were obtained by performing the reaction in HMPA.83... 

Gamma irradiation curing of epoxy resins for structural adhesives — Radiation cure polymerization of commercial diglycidyl ether of bisphenol F epoxy resin has been achieved using Co-60 irradiation source, compounding the monomer with and onium salt catalyst [9],... 

Scheme 5.48 Novel quaternary onium salt catalyst complemented by useful organic anion...

A NEW CROSSLINKING REACTION OF POLYACRYLIC ELASTOMER BY ONIUM SALT CATALYST... 

In this paper, we describe the effect of various onium salt catalysts on the crosslinking reaction of polyacrylic elastomers which contain both... 

In crosslinking reaction of polyacrylic elastomer which contains carboxyl and epoxy groups as cure-sites by onium salt catalyst, the effective center is an active carboxylate onium salt. The catalytic activity showed good agreement with the nucleophilicity of the counter anion of onium salt and followed I > Br > Clo... 

The rate of crosslinking of a polyacrylic elastomer containing epoxy groups as cure-sites with an onium salt catalyst is enhanced by the addition of a dicarboxylic acid as an external curing agent. However, the enhancement in the cure rate decreases as the number of methylene carbons in the alkylene chain of the dicarboxylic acid increases. This behavior can be explained by the dissociation constants, and of the dicarboxylic acid. 

In this system, the polymerization proceeded even without use of catalyst leading to polysulfide XXIEL with inherent viscosity of 0.2 dL/g. Among the quaternary onium salt catalysts employed, BTEAC and CTMAC were found to be effective for producing high molecular weight polymer XXm. Crown ethers such as 18-C-6 and DC 18-C-6 were quite ineffective for this type of polycondensation. 

Scheme 1. Nylon 4 Synthesis with Onium Salts Catalyst Preparation...

For practical appHcation in mixtures of water—organic solvent, only ammonium and phosphonium salts containing 15 or more C atoms are sufficiently lipophilic. In empirical catalyst comparisons crown ethers (hexaoxacyclooctodecanes) (1)—(3) were often as effective as the best onium salts. 

Benzyltriethylammonium chloride [56-37-1] is the most widely used catalyst under strongly basic conditions. Methyltrioctylammonium chloride [5137-55-3] (Ahquat 336, Adogen 464) is probably the least expensive catalyst. Others of high activity and moderate price are tetra- -butylammonium chloride [1112-67-0] bromide [1643-19-2] hydrogen sulfate [32503-27-8], tetra- -butylphosphonium chloride [2304-30-5], and other phosphonium salts of a similar number of C atoms. Many other onium salts can also be utilized. 

In the chlorination of 2,4-dichlorophenol it has been found that traces of amine (23), onium salts (24), or triphenylphosphine oxide (25) are excellent catalysts to further chlorination by chlorine ia the ortho position with respect to the hydroxyl function. During chlorination (80°C, without solvent) these catalysts cause traces of 2,4,5-trichlorophenol ( 500 1000 ppm) to be transformed iato tetrachlorophenol. Thus these techniques leave no 2,4,5-trichlorophenol ia the final product, yielding a 2,4,6-trichlorophenol of outstanding quaUty. The possibiUty of chlorination usiag SO2CI2 ia the presence of Lewis catalysts has been discussed (26), but no mention is made of 2,4,5-trichlorophenol formation or content. 

For enantioselectivity to be possible multipoint interaction between the catalyst and the reactant in the transition state is necessary. The most effective chiral onium salts are derivatives of cinchona alkaloids (see Fig. 3.59). 

A multiphase system consisting of a hydrocarbon solvent, a strong alkaline solution, and a quaternary onium salt, in the presence of a Pd/C catalyst with hydrogen that was bubbled at atmospheric pressure through the organic phase, allows the rapid displacement of chlorine from polyhalogenated benzenes. The onium salt, insoluble in both phases, is localized in the interfaces, coats the Pd/C catalyst, and constitutes the phase in which the reaction takes... 

Abstract Phase transfer catalysts including onium salts or crown ethers transfer between heterogeneous different phases and catalytically mediate desired reactions. Chiral non-racemic phase transfer catalysts are useful for reactions producing new stereogenic centers, giving chiral non-racemic products. Recent developments in this rapid expanding area will be presented. 

Oxidation of —CHtOH — —CHO (cf., 12,479-480). This oxidation can be effected in high yield with sodium hypochlorite (slight excess) in buffered H20/ CH2C12 with this nitroxyl radical and KBr as the catalysts.1 The oxidation is exothermic, and the temperature should be maintained at 0-15° with a salt-ice bath. Saturated primary alcohols are converted to aldehydes in 88-93% yield yields are lower in the case of unsaturated substrates. Addition of quaternary onium salts permits further oxidation to carboxylic acids. 

Onium salts, crown ethers, alkali metal salts or similar chelated salts, quaternary ammonium and phosphonium are some of the salts which have been widely used as phase transfer catalysts (PTC). The choice of phase transfer catalysts depends on a number of process factors, such as reaction system, solvent, temperature, removal and recovery of catalyst, base strength etc. 

With a view to producing catalysts that can easily be removed from reaction products, typical phase-transfer catalysts such as onium salts, crown ethers, and cryptands have been immobilized on polymer supports. The use of such catalysts in liquid-liquid and liquid-solid two-phase systems has been described as triphase catalysis (Regen, 1975, 1977). Cinquini et al. (1976) have compared the activities of catalysts consisting of ligands bound to chloromethylated polystyrene cross-linked with 2 or 4% divinylbenzene and having different densities of catalytic sites ([126], [127], [ 132]—[ 135]) in the... 

The choice of the catalyst is an important factor in PTC. Very hydrophilic onium salts such as tetramethylammonium chloride are not particularly active phase transfer agents for nonpolar solvents, as they do not effectively partition themselves into the organic phase. Table 5.2 shows relative reaction rates for anion displacement reactions for a number of common phase transfer agents. From the table it is clear that the activities of phase transfer catalysts are reaction dependent. It is important to pick the best catalyst for the job in hand. The use of onium salts containing both long and very short alkyl chains, such as hexade-cyltrimethylammonium bromide, will promote stable emulsions in some reaction systems, and thus these are poor catalysts. 

The nature of this ionic/hydrophilic liquid phase can be quite diverse it can be made by an onium salt (e.g., ammonium or phosphonium), by an ionic liquid (e.g., imidazolium salts), by polyethyleneglycols, and even water. What is required is that the catalyst-philic phase is not miscible with the other phases... 

Onium salts, such as tetraethylammonium bromide (TEAB) and tetra-n-butylammonium bromide (TBAB), were also tested as PTCs immobilized on clay. In particular, Montmorillonite KIO modified with TBAB efficiently catalyzed the substitution reaction of a-tosyloxyketones with azide to a-azidoketones, in a biphasic CHCI3/water system (Figure 6.13). ° The transformation is a PTC reaction, where the reagents get transferred from the hquid to the solid phase. The authors dubbed the PTC-modified catalyst system surfactant pillared clay that formed a thin membrane-hke film at the interface of the chloroform in water emulsion, that is, a third liquid phase with a high affinity for the clay. The advantages over traditional nucleophilic substitution conditions were that the product obtained was very pure under these conditions and could be easily recovered without the need for dangerous distillation steps. 

The first catalysts utilized in phase transfer processes were quaternary onium salts. In particular, benzyltriethylammonium chloride was favored by Makosza (7 ) whereas Starks utilized the more thermally stable phosphonium salts (6,8). In either case, the catalytic process worked in the same way the ammonium or phosphonium cation exchanged for the cation associated with the nucleophilic reagent salt. The new reagent, Q+Nu , dissolved in the organic phase and effected substitution. 

Quaternary onium salts were the first phase-transfer catalysts used subsequently, a number of compounds (linear polyethers, polypodands, crown-ethers, cryptands, cage-compounds, etc.) were found effective for the anion activation in two-phase systems. These structurally different systems must satisfy at least two fundamental conditions in order to behave as phase-transfer catalysts i) solubility in the organic phase ii) steric hindrance around the cationic center leading to a good cation-anion separation within the ion-pair. 

---