An efficient one-pot synthesis of nitriles from acid chlorides

Hulkenberg, A.; Troost, J. J.

doi:10.1016/s0040-4039(00)87144-0

Cited by 29 publications

(8 citation statements)

References 2 publications

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“…The dehydration of aldoximes is of significant value compared to the existing methods. 20,21 These catalysts provide a new and improved alternative to the existing methods in modern synthetic chemistry. Hence, during the course of these studies, we initially investigated the transformation of benzaldoxime to benzonitrile in the presence of tetrabutylammonium hydrogen sulfate, 25% NaOH and methoxymethyl bromide in very low yield (21%) and after a longer time period (6 h).…”

Section: Resultsmentioning

confidence: 99%

A new reagent for efficient synthesis of nitriles from aldoximes using methoxymethyl bromide

Uludag¹,

GIDEN²

2019

Rev.Roum.Chim.

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This study outlines an efficient, high-yielding, and rapid method by which to access diverse nitriles from aldoximes with methoxymethyl bromide (MOM-Br) in THF. It represents the first application of MOM-Br as a deoximation reagent to synthesize nitriles. The reaction was performed at reflux to ensure excellent yield (79-96%) of the nitriles within 20-45 minutes. Furthermore, this method has been successfully applied to the synthesis of the synthesis precursor of aromatic, heteroaromatic, cyclic, and acyclic aliphatic.

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Section: Resultsmentioning

confidence: 99%

A new reagent for efficient synthesis of nitriles from aldoximes using methoxymethyl bromide

Uludag¹,

GIDEN²

2019

Rev.Roum.Chim.

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“…Rather unsuitable method for production of cykloalkancarbonitriles especially in terms of availability of starting materials and waste disposal is based on dehydratation reaction of cycloalkane carboxylic acids functional derivatives [16] [17]. Additional procedures for preparation of (5) are presented in literature [18]- [23]. Relatively a large number of these methods are not acceptable for (5) manufacturing but several industrial patents have been made though [24]- [27].…”

Section: Introductionmentioning

confidence: 99%

New One-Pot Methods for Preparation of Cyclohexanecarbonitrile—Green Chemistry Metrics Evaluation for One-Pot and Similar Multi-Step Syntheses

Šimbera¹,

Ševčík²,

Pazdera³

2014

GSC

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Three new multi-step one-pot processes for high-yielding cyclohexanecarbonitrile synthesis starting from cyclohexanone were developed for industrial application. In contrast to the current synthetic process, all of the processes described were designed to proceed completely in methanol as a uniform solvent and the key oxidation step can be realized either as stoichiometric or catalytic. Atom efficiency of processes is relatively advanced with high regioselectivity, reaction by-products are either from environmental pool-carbon dioxide and nitrogen-or they can be reusedsodium chloride. Solvent-methanol-and other auxiliaries-cyclohexane, copper catalyst-can be reused after recycling as well. EcoScale for all three designed processes was evaluated and compared with current synthesis described in the past. Green chemistry metrics, including newly introduced evaluative tool-Sustainability Index of the Synthesis (SIS), were applied to evaluate design of described one-pot syntheses.

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confidence: 99%

Novel stereoselective synthesis of (E)-cinnamonitriles via Heck arylation of acrylonitrile catalysed by a silica-supported bidentate arsine palladium(0) complex

Cai

Tong

Chen

et al. 2004

Journal of Chemical Research

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Cinnamonitriles are important synthetic intermediates and many methods can be used for the synthesis of cinnamonitriles, such as the reaction of cinnamaldehydes with dimethylsulfur diimides, 1 Wittig-Horner reaction of (EtO) 2 POCH 2 CN with aldehydes 2 and the treatment of acid chlorides with sulfonamides. 3 In recent years, more attention has been given to the stereoselective synthesis of (E) and (Z)-cinnamonitriles. Huang et al. 4 reported that (Z)-cinnamonitriles were prepared in 78-98% yields by the desulfonylation of α-phenylsulfonylcinnamonitriles in the presence of NaHTe. Guo and Zhang 5 found that (E)-cinnamonitriles could be obtained in 68-85% yields by a procedure of reduction of α-phenylsulfonylcinnamonitriles with SmI 2 in THF-MeOH solution. Although these methods have provided useful routes for stereoselective synthesis of (E) and (Z)-cinnamonitriles, sometimes the α-phenylsulfonylcinnamonitriles are not readily available. A convenient alternative technical synthesis of (E)-cinnamonitriles is the Heck arylation of aryl iodides with acrylonitrile, the homogeneous palladium complexes such as [Pd(OAc) 2 ] or [PdCl 2 (PPh 3 ) 2 ] are usually used as the catalysts in the arylation reaction. 6,7 The amount of catalyst used is about 1 mol% of reactant; however, use of homogeneous palladium catalysts is still uneconomic for large-scale preparation in the laboratory and for industrial production. As Heck 8 has noted, practical application of the reaction under such conditions is not feasible due to its expense. Polymer-bound organotransition metal complexes having high activity and selectivity offer several significant advantages in synthetic and industrial chemistry; among these, the ease of separation of the catalyst from the desired reaction products and the ease of recovery and reuse of the catalyst are most important. Recently, we have found that the silica-supported bidentate arsine palladium(0) complex ['Si'-2As-Pd(0)] is a highly active catalyst for Heck arylation of styrene and acrylic acid with aryl iodides. 9 Herein we wish to report that (E)-cinnamonitriles can be synthesised stereoselectively via Heck arylation of acrylonitrile with aryl iodides catalysed by a silica-supported bidentate arsine palladium(0) complex (Scheme 1).Treatment of iodobenzene (2 mmol) with acrylonitrile (4 mmol) in p-xylene (0.3 ml) at 90°C for 6 h in the presence of 'Si'-2As-Pd(0) (0.01 mmol), and Bu 3 N (2.2 mmol) afforded (E)-cinnamonitrile in 89% yield. When [Pd(OAc) 2 ] (0.01 mmol) was used as the catalyst, (E)-cinnamonitrile was obtained in 78% yield under same conditions. We applied the reaction to various substituted iodobenzenes, typical results are summarised in Table 1. As seen from the Table 1, the arylation reactions of acrylonitrile with substituted iodobenzenes also proceeded smoothly and a variety of substituted (E)-cinnamonitriles were obtained in high yields. The arylation reaction can tolerate a variety of functional

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An efficient one-pot synthesis of nitriles from acid chlorides

Cited by 29 publications

References 2 publications

A new reagent for efficient synthesis of nitriles from aldoximes using methoxymethyl bromide

A new reagent for efficient synthesis of nitriles from aldoximes using methoxymethyl bromide

New One-Pot Methods for Preparation of Cyclohexanecarbonitrile—Green Chemistry Metrics Evaluation for One-Pot and Similar Multi-Step Syntheses

Novel stereoselective synthesis of (E)-cinnamonitriles via Heck arylation of acrylonitrile catalysed by a silica-supported bidentate arsine palladium(0) complex

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