Tricaprylylmethylammonium chloride

Fig. 12a and b. Transport of amino acids through a toluene barrier a from basic to acid aqueous phases using a positively charged carrier (N +, tricaprylylmethylammonium chloride, Aliquat 336) b from acid to basic aqueous phases using a negatively charged carrier (DNNS ", dinonylnaphthalene-sulfonate). (Cited from Ref.70))... 

Absorption rates of carbon dioxide were measured in organic solutions of glycidyl methacrylate at 101.3 kPa to obtain the reaction kinetics between carbon dioxide and glycidyl methacrylate using tricaprylylmethylammonium chloride(Aliquat 336) as catalysts. The reaction rate constants were estimated by the mass transfer mechanism accompanied by the pseudo-first-order fast reaction. An empirical correlation between the reaction rate constants and the solubility parameters of solvents, such as toluene, A-methyl-2-pirrolidinone, and dimethyl sulfoxide was presented. 

It is worth mentioning at this point that according to Normant et al. (1975) simple polyamines such as tetramethylethylenediamine (TMEDA) are even more active than [2.2.2]-cryptand in the benzylation of acetates in acetonitrile under liquid-solid conditions. These authors suggested that the activity was due to salt solubilization by cation complexation and not to formation of a quaternary ammonium ion since the latter showed no activity. This statement, however, is not in line with the results of Cote and Bauer (1977), who were unable to detect any interaction between K+ and TMEDA in acetonitrile. Furthermore, Vander Zwan and Hartner (1978) found Aliquat 336 (tricaprylylmethylammonium chloride) to be almost as effective as TMEDA in this reaction (Table 30). It might well be, however, that in amine-catalysed benzylation reactions the quaternary salt formed in situ acts both as a reactant and as a phase-transfer catalyst, since Dou et al. (1977) have shown that the benzyltriethylammonium ion is a powerful benzylation agent. 

When the reaction was carried out using 0.033 mole equivalent of tricaprylylmethylammonium chloride (aliquat 336), obtained from General Mills Company, Chemical Division, Kankakee, Illinois, as catalyst, the reaction required about 10 hours for its completion. 

The reaction of 81 with KCN in the presence of tricaprylylmethylammonium chloride (aliquat 336) in 1 1 benzene-water gives the nitrile 82 (Scheme 15) <1996FES425>. 

Ruthenium compounds have been extensively studied as catalysts for the aerobic oxidation of alcohols [142]. They operate under mild conditions and offer possibilities for both homogeneous and heterogeneous catalysts. The activity of common ruthenium precursors such as RuCl2PPh3, can be increased by the use of ionic liquids as solvents (Fig. 4.58). Tetramethylammoniumhydroxide and aliquat 336 (tricaprylylmethylammonium chloride) were used as solvent and rapid conversion of benzyl alcohol was observed [145]. Moreover the tetra-methylammonium hydroxide/RuCl2(PPh3)3 could be reused after extraction of the product. 

Aliquat 336 (tricaprylylmethylammonium chloride) was purchased from Aldrich Chemical Company, Inc. 

One complication that can arise when using Fremy s salt is that the substrate may be insoluble in the aqueous reaction medium, despite the use of organic cosolvents. Olson et al introduced an organic-soluble version of Fremy s salt in their synthesis of a-tocopherol. Hexahydrofamesolacetone (13) was transformed to the phenol (14), which was oxidized in nearly quantitative yield to the tocopheryl quinone (15) using a mixture of Fremy s salt and tricaprylylmethylammonium chloride in a two-phase water/ben-zene solvent system. The oxidizing agent was presumed to be the bis(tricaprylylmethyl)ammonium ni-trodisulfonate. The quinone (15) is a known precursor of a-tocopherol (16 Scheme 4). 

SYNS ALIQUAT336 AIJQUAT336N ALIQUAT 336-PTC N-METHYL-N,N-DIOCTYL-l-OCTAN-AiMINIUM CHLORIDE METHYLTRICAPRYLYL-AMMONIUM CHLORIDE 1-OCTANAMINIUM, N-METHYDN.N-DIOCTYL-, CHLORIDE (9CI) TRICAPRYLMETHYLAMMONIUM CHLORIDE TRICAPRYLYLMETHYLAMMONIUM CHLORIDE TRIOCTYLMETHYLAMMONIUM CHLORIDE... 

Indian chem ists report that other cationic agents are even more eflicient for generation of dichlorocarbene, for example, cetyltrimethylammonium chloride and an Indian detergent sold under the trademark Cetrimide. Starks" has used in the same way a tricaprylylmethylammonium chloride, " in which the alkyl groups are a mixture of Cs"C,2 straight chains. 

Tricaprylylmethylammonium chloride Ammonium, methyl-trioctanoyl-, chloride (8) 1-Octanaminium, /V-methyl-1 -oxo-N,N-bis(l-oxooctyl)-, chloride (9) (13275-89-3)... 

Tertiary amine, [tri-(C8-C10) amine] Tricaprylylmethylammonium chloride Bis(2,4,4-trimethylpentyl) phosphinic acid A,A-di-n-hexyl octanamide Di(2-ethylhexyl) phosphoric acid 1 1 (v/v) mixture of LIX 84-1 and LIX 860N-I... 

Starks found that tricaprylylmethylammonium chloride catalyzed the hydrolysis of A2-dodecanesulfonyl chloride by aqueous hydroxide. Quantitative yields of the sulfonic acid were obtained in the presence of the quaternary ammonium catalyst whereas little reaction was observed in its absence [6, 7]. The hydrolysis of trichloro-methylbenzene to benzoic acid (see Eq. 9.16) was likewise catalyzed by a quaternary ammonium salt [37]. 

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