Esters from Reactions of Alkyl Halides and Salts of Carboxylic Acids. Reactions of Primary Alkyl Chlorides and Sodium Salts of Carboxylic Acids

Hennis, Henry E.; Easterly, J. P.; Collins, Lee R.; Thompson, Leonard R.

doi:10.1021/i360023a012

Cited by 29 publications

(7 citation statements)

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“…Reuben and Sjoberg (1981) stated that poison occurred in the phase-transfer catalytic reaction if the catalyst or reactants contained iodide ion. In contrast to this viewpoint, Hennis et al (1967Hennis et al ( ,1968 stated that the iodide ion played the cocatalytic role. In our earlier studies, the so-called "iodide ion effect" was investigated in detail in the synthesis of benzyl benzoate (Chang et al, 1983(Chang et al, ,1984, benzyl phenyl ether (Yeh et al, 1985) and benzyl n-butyl phthalate (Yeh et al, 1988).…”

mentioning

confidence: 94%

Kinetics of the phase-transfer synthesis of benzyl esters using tertiary amines

Hwu¹,

Hwang²,

Yeh³

et al. 1990

Ind. Eng. Chem. Res.

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mentioning

confidence: 94%

Kinetics of the phase-transfer synthesis of benzyl esters using tertiary amines

Hwu¹,

Hwang²,

Yeh³

et al. 1990

Ind. Eng. Chem. Res.

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“…Carboxylate intermediate G is expected to react directly with the alkyl iodide partner to form an ester byproduct at slightly elevated temperatures. 29 Thus, the high anhydride selectivity is enabled by the light-mediated conditions that access reactivity at ambient temperature. We expect that replacement of K2CO3 with other weak nucleophiles will provide access to other acyl pseudohalide products, and such explorations are currently underway.…”

mentioning

confidence: 99%

Light-mediated synthesis of aliphatic anhydrides by Cu-catalyzed carbonylation of alkyl halides

Tung

Mankad

2022

Preprint

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Acid anhydrides are valuable in the chemical industry for their role in synthesizing polymers, pharmaceuticals, and other commodities, but their syntheses often involve multiple steps with precious metal catalysts. The simplest anhydride, acetic anhydride, is currently produced by two Rh-catalyzed carbonylation reactions on bulk scale for its use in synthesizing products ranging from aspirin to cellulose acetate. Here, we report a light-mediated, Cu-catalyzed process for producing aliphatic, symmetric acid anhydrides directly by carbonylation of alkyl (pseudo-)halides in a single step without any precious metal additives. The transformation requires only simple Cu salts and abundant bases to proceed, maintains high efficiency and selectivity upon scale up, and operates by radical mechanism with several beneficial features. This discovery will enable engineering of bulk processes for producing commodity anhydrides efficiently and sustainably.

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“…However, more than fifty years lapsed before the catalytic role of an ammonium salt generated in situ was determined [Hennis, 1967]. One alkyl group of the ammonium ion must be quite long, and benzylammonium salts are not useful.…”

Section: Meomentioning

confidence: 99%

Phase Transfer Reactions

Ho¹

1998

Distinctive Techniques for Organic Synthesis

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Chemical reactions involving two or more molecules usually proceed at higher rates in one phase. However, it is not always feasible or expedient to render some reactions under homogeneous conditions. In such cases the phase transfer technique should be considered. Improvement of reactions by phase transfer catalysis (PTC) represents a breakthrough in chemical technology. Although sporadic reports appeared before the 1960s, consolidation of the concept through a series of publications on the theme of extractive alkylation [Markosza, 1965], a patent describing catalysis of heterogeneous reactions [Starks, 1968], and the observations concerning reactions of quaternary ammonium salts in nonpolar media [Brandstrom, 1969[Brandstrom, , 1972 initiated an avalanche of research in the methodology.While the most common phase transfer technique deals with reactants in two immiscible liquids, its scope encompasses gas-liquid, gas-solid, liquid-solid, and presumably solid-solid systems. In comparison with conventional methods, PTC holds considerable advantages in terms of cost (which avoids expensive anhydrous dipolar aprotic solvents), time, mildness, and simplicity. It is often observed that reactivities and selectivities are enhanced under such conditions.From an electrochemical study [Tan, 1994] of the Williamson ether synthesis under phase transfer catalysis, it is concluded that the role of the catalyst is to establish a Galvani distribution potential difference between the two phases which acts as the driving force for transferring the reactive ions from the aqueous medium to the organic layer.The general features of a typical PTC substitution reaction carried out in a system of organic and aqueous phases specifies reaction taking place in the organic layer. The phase transfer agent is present in catalytic amount and capable of moving one reactant in its resident solvent into that of the other reactant or the interfacial region. Only then the two species can react with reasonable speed. Needless to say that strong agitation is a most crucial to maximize reaction rates.Actually there are two mechanistic models for the PTC reaction. In the Starks extraction mechanism the catalyst is biphilic, thus well qualified by a quaternary ammonium or phosphonium salt, either of which having finite solubility in both phases on account of its charge and organophilicity, capable of ferrying the counter anion from the aqueous phase to the organic layer by the partition phenomenon. The 1 Distinctive Techniques for Organic Synthesis Downloaded from www.worldscientific.com by PURDUE UNIVERSITY on 04/13/15. For personal use only.2 Distinctive Techniques for Organic Synthesis anion generated from reaction will pair with the quaternary onium species and enter the aqueous phase and a second catalytic cycle starts at this point. The interfacial mechanism (proposed by Makosza and modified by Brandstrom and Montanari) describes cases in which the catalyst is highly organophilic and it functions by anion exchange in the interfacial region. In ot...

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Esters from Reactions of Alkyl Halides and Salts of Carboxylic Acids. Reactions of Primary Alkyl Chlorides and Sodium Salts of Carboxylic Acids

Cited by 29 publications

References 4 publications

Kinetics of the phase-transfer synthesis of benzyl esters using tertiary amines

Kinetics of the phase-transfer synthesis of benzyl esters using tertiary amines

Light-mediated synthesis of aliphatic anhydrides by Cu-catalyzed carbonylation of alkyl halides

Phase Transfer Reactions

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