13312-83-9

Basic information

• Product Name: 4-chloromandelonitrile
• Synonyms: 4-chloromandelonitrile
• CAS NO: 13312-83-9
• Molecular Weight: 167.595
• Mol File: 13312-83-9.mol

Chemical Properties

• CAS DataBase Reference: 4-chloromandelonitrile(CAS DataBase Reference)
• NIST Chemistry Reference: 4-chloromandelonitrile(13312-83-9)
• EPA Substance Registry System: 4-chloromandelonitrile(13312-83-9)

Safety Data

• Hazardous Substances Data: 13312-83-9(Hazardous Substances Data)

Upstream product

• 74-90-8 hydrogen cyanide 
• 104-88-1 4-chlorobenzaldehyde 
• 151-50-8 potassium cyanide 
• 613-90-1 benzoyl cyanide 
• 143-33-9 sodium cyanide 
• 66985-46-4 (+/-)-2-(4-chlorophenyl)-2-(trimethylsiloxy)-acetonitrile 
• 7677-24-9 trimethylsilyl cyanide 
• 412296-10-7 (R)-2-(4-chlorophenyl)-2-(trimethylsiloxy)acetonitrile 
• 873-76-7 para-Chlorobenzyl alcohol 
• 106-43-4 para-chlorotoluene 
• 99074-23-4 cyano(4-chlorophenyl)methyl acetate 
• 75-86-5 2-hydroxy-2-methylpropanenitrile 
• 773837-37-9 sodium cyanide 
• 108-05-4 vinyl acetate 

Downstream Products

• 58681-40-6 4-chloro-mandelimidic acid ethyl ester; hydrochloride 
• 71292-81-4 2-(4-chlorophenyl)-2-hydroxy-1-phenylethanone 
• 7138-34-3 p-chloromandelic acid 
• 102333-77-7 p-chlorophenyl-α-chloroacetic acid 
• 156-41-2 4-chlorophenylethylamine 
• 115353-28-1 (4-Chloro-phenyl)-(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-ylamino)-acetonitrile 
• 125237-13-0 p,p'-bis(α-cyano(4-chlorophenyl)methylhydrazinocarbonylmethoxy)diphenyl sulphones 
• 13014-48-7 4-chlorobenzoyl cyanide 
• 99074-23-4 cyano(4-chlorophenyl)methyl acetate 
• 139765-19-8 (R,S)-α-[(tert-butyldimethylsilyl)oxy]-α-(4-chlorophenyl)acetonitrile 
• 126641-86-9 (R)-acetoxy(4-chlorophenyl)acetonitrile 
• 136983-95-4 (S)-2-acetyloxy-2-(4-chlorophenyl)acetonitrile 
• 13312-83-9 (R)-(+)-4-chloromandelonitrile 
• 13312-83-9 (2S)-2-hydroxy-2-(4-chlorophenyl)acetonitrile 

Relevant articles and documents

Combining Photo-Organo Redox- and Enzyme Catalysis Facilitates Asymmetric C-H Bond Functionalization

In this study, we combined photo-organo redox catalysis and biocatalysis to achieve asymmetric C–H bond functionalization of simple alkane starting materials. The photo-organo catalyst anthraquinone sulfate (SAS) was employed to oxyfunctionalise alkanes to aldehydes and ketones. We coupled this light-driven reaction with asymmetric enzymatic functionalisations to yield chiral hydroxynitriles, amines, acyloins and α-chiral ketones with up to 99 % ee. In addition, we demonstrate functional group interconversion to alcohols, esters and carboxylic acids. The transformations can be performed as concurrent tandem reactions. We identified the degradation of substrates and inhibition of the biocatalysts as limiting factors affecting compatibility, due to reactive oxygen species generated in the photocatalytic step. These incompatibilities were addressed by reaction engineering, such as applying a two-phase system or temporal and spatial separation of the catalysts. Using a selection of eleven starting alkanes, one photo-organo catalyst and 8 diverse biocatalysts, we synthesized 26 products and report for the model compounds benzoin and mandelonitrile > 97 % ee at gram scale.

Synthesis of Acrylonitriles via Mild Base Promoted Tandem Nucleophilic Substitution-Isomerization of α-Cyanohydrin Methanesulfonates

Main observation and conclusion: We have developed an efficient synthesis of acrylonitriles via mild base promoted tandem nucleophilic substitution-isomerization of α-cyanohydrin methanesulfonates with alkenylboronic acids. This transition metal-free protocol works under simple and mild conditions and offers good chemical yields for a wide range of substrates and demonstrates good functional group tolerance. (Figure presented.).

CO2-Enabled Cyanohydrin Synthesis and Facile Iterative Homologation Reactions**

Thermodynamic and kinetic control of a chemical process is the key to access desired products and states. Changes are made when a desired product is not accessible; one may manipulate the reaction with additional reagents, catalysts and/or protecting groups. Here we report the use of carbon dioxide to accelerate cyanohydrin synthesis under neutral conditions with an insoluble cyanide source (KCN) without generating toxic HCN. Under inert atmosphere, the reaction is essentially not operative due to the unfavored equilibrium. The utility of CO2-mediated selective cyanohydrin synthesis was further showcased by broadening Kiliani–Fischer synthesis under neutral conditions. This protocol offers an easy access to a variety of polyols, cyanohydrins, linear alkylnitriles, by simply starting from alkyl- and arylaldehydes, KCN and an atmospheric pressure of CO2.

Postfunctionalized Metalloligand-Based Catenated Coordination Polymers: Syntheses, Structures, and Effect of Labile Sites on Catalysis

In this work, pyridyl-appended Co3+ complexes (1 and 2) have been postfunctionalized by using 4-(bromomethyl)benzoic acid, thus changing the functionalities from pyridyl-N donors to carboxylate-O donors. Using two such postfunctionalized metalloligands (3 and 4), several homo and heterometallic coordination polymers (HCPs) have been synthesized. Single crystal structural analyses revealed that all HCPs presented intriguing one-dimensional catenated architectures. Postsynthetic modification induced flexibility was found to be responsible for the nearly identical architectures for two sets of HCPs starting from two different postfunctionalized metalloligands, 3 and 4. Two sets of HCPs differed by the presence (3a-3d) or absence (4a-4b) of labile coordinated water molecules that demonstrated a profound effect on the heterogeneous catalysis of Knoevenagel condensation reactions and cyanation reactions.

Supported Ionic Liquid-Like Phases (SILLPs) as Immobilised Catalysts for the Multistep and Multicatalytic Continuous Flow Synthesis of Chiral Cyanohydrins

Supported Ionic Liquid-Like Phases have been found to be efficient organocatalysts for the synthesis of cyanohydrin esters under solvent-free conditions by an “electrophile-nucleophile dual activation” based on hydrogen bond formation. The combination of

Preparation of chitosan-supported urea materials and their application in some organocatalytic procedures

An efficient and mild procedure was developed for the preparation of three chitosan-supported ureas containing electron-withdrawing groups. These catalysts were characterized and employed as organocatalysts in different transformations, including the enan

Acceptorless and Base-free Dehydrogenation of Cyanohydrin with (η6-Arene)halide(Bidentate Phosphine)ruthenium(II) Complex

Ruthenium-catalyzed dehydrogenation of cyanohydrins under acceptorless and base-free conditions was demonstrated for the first time in the synthesis of acyl cyanide. As opposed to the thermodynamically preferred elimination of hydrogen cyanide, the dehydrogenation of cyanohydrins could be kinetically controlled with ruthenium (II) bidentate phosphine complexes. The effects of the arene, phosphine ligands and counter anions were investigated in regard to catalytic activity and selectivity. Selective dehydrogenation can occur via β-hydride elimination with the experimentally observed [(alkoxide)Ru] complex. (Figure presented.).

High-Throughput Preparation of Optically Active Cyanohydrins Mediated by Lipases

Cyanohydrins are versatile compounds with high applicability in organic synthesis; they are used as starting materials for the synthesis of other chemical targets with high industrial added value. Lipase-mediated kinetic resolution reactions are a promising route for the synthesis of optically active cyanohydrins. These reactions can be carried out through the acylation of cyanohydrins or the deacylation of cyanohydrin esters, with different biocatalysts and under different reaction conditions. Unfortunately, depending on the substrate structure, long reaction times can be required to achieve suitable enantiomeric excesses. In this context, we present a high-throughput protocol for the production of optically active cyanohydrins in continuous-flow mode. The products were obtained with moderate to good enantioselectivity (E values from 8 up to >200) and with productivity values from 2.4 to 8.7 times higher in continuous-flow mode than in batch mode. Moreover, the reaction times were reduced from hours in batch mode to minutes in continuous-flow mode.

P(NMe2)3-Mediated Umpolung Alkylation and Nonylidic Olefination of α-Keto Esters

A commercial phosphorus-based reagent (P(NMe2)3) mediates umpolung alkylation of methyl aroylformates with benzylic and allylic bromides, leading to either Barbier-type addition or ylide-free olefination products upon workup. The reaction sequence is initiated by a two-electron redox addition of the tricoordinate phosphorus reagent with an α-keto ester compound (Kukhtin-Ramirez addition). A mechanistic rationale is offered for the chemoselectivity upon which the success of this nonmetal mediated C-C bond forming strategy is based.

Fast microwave-assisted resolution of (±)-cyanohydrins promoted by lipase from Candida antarctica

Enzymatic kinetic resolution (EKR) of (±)-cyanohydrins was performed by using immobilized lipase from Candida antarctica (CALB) under conventional ordinary conditions (orbital shaking) and under microwave radiation (MW). The use of microwave radiation contributed very expressively on the reduction of the reaction time from 24 to 2 h. Most importantly, high selectivity (up to 92percent eep) as well as conversion was achieved under MW radiation (50-56percent).