Alkylation Of Phenylacetonitrile Research Articles

Experimental Investigation and Modeling Approach of the Phenylacetonitrile Alkylation Process in a Microreactor

AbstractThe application of microreaction technology has the potential to intensify chemical processes. It is therefore of great interest to investigate the operating efficiency of a multiphase process such as the alkylation of phenylacetonitrile in a microreactor and to compare the performance to a batch reactor. The undeniable advantages of continuous microreactor systems for this process were demonstrated. Furthermore, the influence of the organic to aqueous phase ratio in the microreactor was investigated. A model of the reaction course was formulated based on experimental data. This model was used in the analysis and modeling of the alkylation process in a microreactor and found to be adequate. The optimal microreactor performance conditions were determined using the numerical optimization technique (Harrington's desirability function) and confirmed by experiments.

Synthesis and characterization of novel soluble multi-site phase transfer catalyst; its efficiency compared with single-site phase transfer catalyst in the alkylation of phenylacetonitrile as a model reaction

The kinetics of C-alkylation of phenylacetonitrile with 1-bromobutane has been studied using a novel α, α′, α″- N-hexakis(triethylammoniummethylene chloride)-melamine as a multi-site phase transfer catalyst (MPTC) using a low concentration of aqueous sodium hydroxide as a base. The reaction was carried out at 50 °C under pseudo-first-order conditions by keeping aqueous base and 1-bromobutane in excess. The formation of the product was monitored by GLC. The effects of various experimental parameters such as [substrate], [NaOH], [catalyst] and temperature on the rate of the reaction have been studied. The results obtained and also the thermodynamic parameters are discussed. The catalytic efficiency of the multi-site catalyst was compared with efficiencies of the commercially available single-site catalysts.

Phase-Transfer-Catalyzed Alkylation of Phenylacetonitrile in Supercritical Ethane

The first example of a phase-transfer-catalyzed alkylation reaction under supercritical fluid conditions is reported. The reaction is that of phenylacetonitrile and ethyl bromide in the presence of tetrabutylammonium bromide and potassium carbonate in supercritical ethane at 45, 60, and 75 °C and 138 bar. Results show that the reaction will go to completion in less than 24 h in the presence of the catalyst but that only a few percent conversion is achieved without it during the same period of time. The effects of catalyst concentration, temperature, and cosolvents are investigated. Catalyst solubility estimates and kinetic analyses suggest that the reaction takes place on the surface of the potassium carbonate particles. When the same reaction is attempted in supercritical carbon dioxide, both carboxylation and alkylation are observed. Cycloalkylation reactions between phenylacetonitrile and dibromoalkanes are also discussed.

Trimethyl Orthoformate as a Highly Selective Mono-C-Methylating Agent for Arylacetonitriles

The mono-C-methylation of arylacetonitriles (ArCH2CN, 1) to produce 2-arylproprionitriles [ArCH(CH3)CN, 2] represents a valuable reaction especially from a pharmaceutical standpoint. In fact, a number of compounds 2 are key intermediates for the synthesis of nonsteroidal analgesics of the hydratropic acid (2-arylpropanoic acid) class.1 Common well-known examples are Ibuprofen, Ketoprofen, and Naproxen (Chart 1). However, synthetic procedures for the direct monomethylation of 1 fail with classical alkylating agents (methyl halides and dimethyl sulfate) because mixtures of monoand dimethylated products are always obtained (Scheme 1).2 For instance, the alkylation of phenylacetonitrile with CH3I is reported with a monoto dimethyl selectivity of 84%, at a conversion of 86%.3 Although a number of multistep alkylation methods have been developed for the preparation of 2-arylpropanoic acids,1 the achievement of an effective one-pot procedure still represents a challenging task and may deserve attention from both the economical standpoint and the synthetic feasibility. Concerning this, a very efficient procedure is the ruthenium-catalyzed reductive methylation of active methylene compounds carried out at 135-230 °C with paraformaldehyde.4 However, we extensively reported that direct highly selective mono-C-methylations of CH2acidic compounds (YCH2X) can also be performed by the use of dimethyl carbonate (DMC) as a methylating agent, without any metal catalyst.5-11 Thus, at 180-210 °C in the presence of weak bases (K2CO3), aryland aroxyacetonitriles, methyl aryland aroxyacetates (Y ) Ar, ArO; X ) CN, CO2CH3), and R-methylene sulfones (Y ) Ar, X ) SO2Ar, SO2R) yield the corresponding mono-Cmethyl derivatives with selectivities >99% at a complete substrate conversion. In addition, the procedure is a true environmentally benign one: DMC is a nontoxic reagent, the base can be used catalytically, and neither organic nor inorganic byproducts are formed and need to be disposed of.12,13

Influence of ultrasound power on the alkylation of phenylacetonitrile under solid-liquid phase transfer catalysis conditions

The influence of ultrasound power on the C-alkylation of phenylacetonitrile by ethyl bromide was studied under solid-liquid phase transfer catalysis in the presence of potassium hydroxide and tetrabutylammonium hydrogenosulfate. Experimental results are reported on the influence of the ultrasonic power on the yields. The optimum efficiency of ultrasound is determined and the way in which ultrasound power may affect the yields is discussed.

Crosslinked Poly(ethylene oxide) as a Phase Transfer Catalyst in Reactions of C- and O-Alkylation

Gels of radiation crosslinked poly(ethylene oxide) (PEO) and modified with poly(ethyleneimine) PEO were used as highly active phase transfer catalysts in the alkylation of phenylacetonitrile with 1-bromobutane in the presence of aqueous potassium hydroxide. The reaction of alkylation was found to be second order reaction up to 40% conversion of phenylacetonitrile and the rate is proportional to the amount of added catalysts. The activity of the PEO gels has been studied as a function of the composition, degree of crosslinking and addition order of reagents. Modified with poly(ethyleneimine) PEO (up to 10 mol%) exhibited the highest catalytic activity. Ultrasound promotes extremely effective intermixing of the aqueous and organic phases resulting in greatly increased alkylation rate. The recovered catalysts could be re-used without decrease in activity.

ChemInform Abstract: Alkylation in Solid‐Liquid Two‐Phase Systems. Part 4. Alkylation of Phenylacetonitrile Using Potassium Carbonate as a Base.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Tetrakis-sulphoxides: a new type of phase-transfer catalyst for nucleophilic displacements and alkylations

Tetrakis(alkylsulphinylmethyl)methanes have been shown to serve as good phase-transfer catalysts which accelerate SN2 type displacements of octyl bromide with various nucleophiles (thiocyanate, cyanide, phenoxide, and thiolate) in solid–liquid two-phase systems. Alkylation of phenylacetonitrile with alkyl halides has also been carried out in liquid–liquid two-phase systems in the presence of the above sulphoxides to afford the corresponding mono-alkylated products in high yields.

Chiral functional polymers as catalysts in phase transfer reactions

The preparation of linear and crosslinked functional polymers designed for catalytic applications in phase transfer reactions is reported. Polymers containing either quaternary ammonium groups or oligoether moieties (glymes and crown ethers) in the side chain, experiencing a prevailing chirality, are described. Procedures based on direct polymerization of a chiral monomer with a functional comonomer, chemical transformation of preformed chiral copolymers and the use of optically active porogens have been adopted for the formulation of catalytically active polymers. Reduction of prochiral alkyl ketones, alkylation of phenylacetonitrile and oxidation of racemic alcohols have been taken as test reactions for catalyst activity, in terms of chemical kinetics and stereochemical control. In spite of the improved chemical stability and maintenance of the chiral integrity, the polymeric catalysts investigated do not seem able to exert enantio-selective discrimination on any of the prochiral or chiral substrates examined.

Mechanisms of polymer-supported catalysis. 4. Alkylation of phenylacetonitrile with 1-bromobutane catalyzed by aqueous sodium hydroxide and polystyrene-bound benzyltrimethylammonium ions

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTMechanisms of polymer-supported catalysis. 4. Alkylation of phenylacetonitrile with 1-bromobutane catalyzed by aqueous sodium hydroxide and polystyrene-bound benzyltrimethylammonium ionsT. Balakrishnan and Warren T. FordCite this: J. Org. Chem. 1983, 48, 7, 1029–1035Publication Date (Print):April 1, 1983Publication History Published online1 May 2002Published inissue 1 April 1983https://doi.org/10.1021/jo00155a020RIGHTS & PERMISSIONSArticle Views174Altmetric-Citations31LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (952 KB) Get e-Alerts Get e-Alerts

Alkylation of phenylacetonitrile under organic-aqueous alkali hydroxide two phase system in the presence of poly (ethylene glycol)s or their ethers.

Alkylation of phenylacetonitrile under organic-aqueous alkali hydroxide two phase system in the presence of poly (ethylene glycol)s or their ethers.

The effect of polymer swelling on alkylation of phehylacetonitrile by polymer-supported phase transfer catalysis

Alkylation of phenylacetonitrile by 1-bromobutane with 50% sodium hydroxide and a polymer-supported phase transfer catalyst proceeds fastest when the phenylacetonitrile is added to the mixture before the 1-bromobutane.

Reactions of organic anionx. LXXIII. Alkylation of phenylacetonitrile at the interface with aqueous sodium hydroxide

Reactions of organic anionx. LXXIII. Alkylation of phenylacetonitrile at the interface with aqueous sodium hydroxide

Additions and Corrections: Stereochemical Course in the Alkylation of Phenylacetonitrile and Phenylacetic Acid with Opticaly Active a-Phenylethyl Chloride.

Additions and Corrections: Stereochemical Course in the Alkylation of Phenylacetonitrile and Phenylacetic Acid with Opticaly Active a-Phenylethyl Chloride.

Stereochemical Course in the Alkylation of Phenylacetonitrile and Phenylacetic Acid with Optically Active α-Phenylethyl Chloride1

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTStereochemical Course in the Alkylation of Phenylacetonitrile and Phenylacetic Acid with Optically Active α-Phenylethyl Chloride1William J. Chambers, Wallace R. Brasen, and Charles R. HauserCite this: J. Am. Chem. Soc. 1957, 79, 4, 879–881Publication Date (Print):February 1, 1957Publication History Published online1 May 2002Published inissue 1 February 1957https://doi.org/10.1021/ja01561a025RIGHTS & PERMISSIONSArticle Views37Altmetric-Citations15LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (362 KB) Get e-Alerts Get e-Alerts