529-19-1

Basic information

• Product Name: o-Tolunitrile
• Synonyms: O-CYANO TOLUENE;LABOTEST-BB LT01273178;2-CYANOTOLUENE;2-TOLUNITRILE;2-METHYLBENZENECARBONITRILE;2-METHYLBENZONITRILE;2-Methylbenzonitrile/o-Tolunitrile;o-toluenenitrile
• CAS NO: 529-19-1
• Molecular Formula: C₈H₇N
• Molecular Weight: 117.15
• EINECS: 208-451-7
• Product Categories: Aromatic Nitriles
• Mol File: 529-19-1.mol

Chemical Properties

• Melting Point: -13 °C
• Boiling Point: 205 °C(lit.)
• Flash Point: 184 °F
• Appearance: Clear colorless to slightly yellow/Liquid
• Density: 0.989 g/mL at 25 °C(lit.)
• Vapor Pressure: 0.243mmHg at 25°C
• Refractive Index: n20/D 1.5279(lit.)
• Storage Temp.: Store below +30°C.
• Solubility: Chloroform (Slightly), Methanol (Slightly)
• Explosive Limit: 1.1-6.7%(V)
• Water Solubility: <0.1 g/100 mL at 17℃
• Merck: 14,9537
• BRN: 1857417
• CAS DataBase Reference: o-Tolunitrile(CAS DataBase Reference)
• NIST Chemistry Reference: o-Tolunitrile(529-19-1)
• EPA Substance Registry System: o-Tolunitrile(529-19-1)

Safety Data

• Hazard Codes: Xi
• Statements: 38-52/53-36/37/38
• Safety Statements: 61-37-36-26-24/25
• RIDADR: 3276
• WGK Germany: 2
• RTECS: XV0600000
• TSCA: Yes
• Hazardous Substances Data: 529-19-1(Hazardous Substances Data)

Usage

Chemical Properties

clear colorless to slightly yellow liquid

Uses

o-Tolyl Cyanide, is a versatile intermediate, used in the synthesis of various pharmaceutical and biologically active compounds. It can be used in the preparation of highly efficient triarylene conjugated dyes for sensitized solar cells

Synthesis Reference(s)

The Journal of Organic Chemistry, 60, p. 2948, 1995 DOI: 10.1021/jo00114a060

General Description

Light blue clear liquid.

Air & Water Reactions

Insoluble in water.

Reactivity Profile

Nitriles, such as o-Tolunitrile, may polymerize in the presence of metals and some metal compounds. They are incompatible with acids; mixing nitriles with strong oxidizing acids can lead to extremely violent reactions. Nitriles are generally incompatible with other oxidizing agents such as peroxides and epoxides. The combination of bases and nitriles can produce hydrogen cyanide. Nitriles are hydrolyzed in both aqueous acid and base to give carboxylic acids (or salts of carboxylic acids). These reactions generate heat. Peroxides convert nitriles to amides. Nitriles can react vigorously with reducing agents. Acetonitrile and propionitrile are soluble in water, but nitriles higher than propionitrile have low aqueous solubility. They are also insoluble in aqueous acids.

Fire Hazard

o-Tolunitrile is combustible.

Purification Methods

Fractionally distil the nitrile, wash it with conc HCl or 50% H2SO4 at 60o until the smell of isonitrile has gone (this also removes any amines), then wash it with saturated NaHCO3 and dilute NaCl solutions, then dry it with K2CO3 and redistil it. [Beilstein 9 IV 1703.]

InChI:InChI=1/C8H7N/c1-7-4-2-3-5-8(7)6-9/h2-5H,1H3

Upstream product

• 74-90-8 hydrogen cyanide 
• 2028-34-4 o-toluene-diazonium chloride 
• 95-47-6 o-xylene 
• 78-30-8 tri-ortho-cresyl phosphate 
• 151-50-8 potassium cyanide 
• 89-71-4 2-Methyl-benzoic acid methyl ester 
• 94-69-9 2'-methylformanilide 
• 4943-59-3 N-o-tolyl-formimidic acid ethyl ester 
• 22695-18-7 N,N-di-o-tolylthiourea 
• 10468-64-1 o-tolyl isocyanide 
• 110-05-4 di-tert-butyl peroxide 
• 100-47-0 benzonitrile 
• 506-68-3 bromocyane 
• 108-88-3 toluene 

Downstream Products

• 10517-64-3 1-(2-Cyanophenyl)-1-phenyl-1-ethanone 
• 2040-14-4 2-methylpropiophenone 
• 875856-17-0 1-(o-tolyl)pentan-1-imine 
• 54494-15-4 5-(2-methylphenyl)-3-phenyl-1,2,4-oxadiazole 
• 5585-14-8 3,4-diphenyl-furazan 2-oxide 
• 577-16-2 2-Methylacetophenone 
• 109866-09-3 4-isopropylidene-2,2-dimethyl-5-o-tolyl-3,4-dihydro-2H-pyrrole 
• 87-24-1 ethyl 2-methylbenzoate 
• 91854-81-8 1-(2-methylphenyl)ethan-1-imine 
• 861303-20-0 1-(2-methylphenyl)--1-imine 
• 16620-71-6 isopropyl o-tolyl ketimine 
• 875856-04-5 1-o-tolyl-butan-1-one-imine 
• 7055-03-0 2-methyl-N-phenylbenzamide 
• 412025-76-4 [9]phenanthryl-o-tolyl ketone 

Relevant articles and documents

Using Data Science To Guide Aryl Bromide Substrate Scope Analysis in a Ni/Photoredox-Catalyzed Cross-Coupling with Acetals as Alcohol-Derived Radical Sources

Ni/photoredox catalysis has emerged as a powerful platform for C(sp2)–C(sp3) bond formation. While many of these methods typically employ aryl bromides as the C(sp2) coupling partner, a variety of aliphatic radical sources have been investigated. In principle, these reactions enable access to the same product scaffolds, but it can be hard to discern which method to employ because nonstandardized sets of aryl bromides are used in scope evaluation. Herein, we report a Ni/photoredox-catalyzed (deutero)methylation and alkylation of aryl halides where benzaldehyde di(alkyl) acetals serve as alcohol-derived radical sources. Reaction development, mechanistic studies, and late-stage derivatization of a biologically relevant aryl chloride, fenofibrate, are presented. Then, we describe the integration of data science techniques, including DFT featurization, dimensionality reduction, and hierarchical clustering, to delineate a diverse and succinct collection of aryl bromides that is representative of the chemical space of the substrate class. By superimposing scope examples from published Ni/photoredox methods on this same chemical space, we identify areas of sparse coverage and high versus low average yields, enabling comparisons between prior art and this new method. Additionally, we demonstrate that the systematically selected scope of aryl bromides can be used to quantify population-wide reactivity trends and reveal sources of possible functional group incompatibility with supervised machine learning.

Cyanide-Free Cyanation of sp2 and sp-Carbon Atoms by an Oxazole-Based Masked CN Source Using Flow Microreactors

This work reports a cyanide-free continuous-flow process for cyanation of sp2 and sp carbons to synthesize aryl, vinyl and acetylenic nitriles from (5-methyl-2-phenyloxazol-4-yl) boronic acid [OxBA] reagent as a sole source of carbon-bound mask

Pd@CeO2-catalyzed cyanation of aryl iodides with K4Fe(CN)6·3H2O under visible light irradiation

Cyanation of aryl iodides is still challenging work for chemical researchers because of harsh reaction conditions and toxic cyanide sources. Herein, we have developed a new protocol based on the combination of the catalyst Pd@CeO2, nontoxic cyanide source K4[Fe (CN)6]·3H2O, and driving force visible light irradiation. The reaction is operated at relatively moderate temperature (55°C) and exhibits good catalytic efficiency of product aryl nitriles (yields of 89.4%). Moreover, the catalyst Pd@CeO2 possesses good reusability with a slight loss of photocatalytic activity after five consecutive runs. The reaction system based on the above combination shows a wide range of functional group tolerance under the same conditions. Reaction conditions such as temperature, time, the component of catalyst, and solutions are optimized by studying cyanation of 1-iodo-4-nitrobenzene as model reaction. According to these results, the possible mechanism of Pd@CeO2-catalyzed cyanation of aryl iodides under visible light irradiation is proposed based on the influence of visible light on the catalyst and reactant compounds. In all, we provided an environmental and economic method for preparation of aryl nitriles from cyanation of aryl iodides based on the goal of green chemistry for sustainable development.

Copper-promoted cyanation of aryl iodides with N,N-dimethyl aminomalononitrile

A copper-promoted cyanation of aryl iodides has been successfully developed by using N,N-dimethyl aminomalononitrile as the cyanide source with moderate toxicity and better stability. This reaction features broad substrate scope, excellent reaction yields, readily available catalyst, and simple reaction conditions.

Nickel-Catalyzed Reversible Functional Group Metathesis between Aryl Nitriles and Aryl Thioethers

We describe a new functional group metathesis between aryl nitriles and aryl thioethers. The catalytic system nickel/dcype is essential to achieve this fully reversible transformation in good to excellent yields. Furthermore, the cyanide- and thiol-free reaction shows high functional group tolerance and great efficiency for the late-stage derivatization of commercial molecules. Finally, synthetic applications demonstrate its versatility and utility in multistep synthesis.

Nickel-Catalyzed Cyanation of Aryl Thioethers

A nickel-catalyzed cyanation of aryl thioethers using Zn(CN)2 as a cyanide source has been developed to access functionalized aryl nitriles. The ligand dcype (1,2-bis(dicyclohexylphosphino)ethane) in combination with the base KOAc (potassium acetate) is essential for achieving this transformation efficiently. This reaction involves both a C-S bond activation and a C-C bond formation. The scalability, low catalyst and reagents loadings, and high functional group tolerance have enabled both late-stage derivatization and polymer recycling, demonstrating the reaction's utility across organic chemistry.

Iodine Promoted Conversion of Esters to Nitriles and Ketones under Metal-Free Conditions

We report a novel strategy to prepare valuable nitriles and ketones through the conversion of esters under metal-free conditions. By using the I2/PCl3 system, various substrates including aliphatic and aromatic esters could react with acetonitrile and arenes to afford the desired products in good to excellent yields. This method is compatible with a number of functional groups and provides a simple and practical approach for the synthesis of nitrile compounds and aryl ketones.

CuO-catalyzed conversion of arylacetic acids into aromatic nitriles with K4Fe(CN)6 as the nitrogen source

Readily available CuO was demonstrated to be effective as the catalyst for the conversion of arylacetic acids to aromatic nitriles with non-toxic and inexpensive K4Fe(CN)6 as the nitrogen source via the complete cleavage of the C[tbnd]N triple bond. The present method allowed a series of arylacetic acids including phenylacetic acids, naphthaleneacetic acids, 2-thiopheneacetic acid and 2-furanacetic acid to be converted into the targeted products in low to high yields.

A Combined Experimental–Theoretical Study on Diels-Alder Reaction with Bio-Based Furfural: Towards Renewable Aromatics

The synthesis of relevant renewable aromatics from bio-based furfural derivatives and cheap alkenes is carried out by using a Diels-Alder/aromatization sequence. The prediction and the control of the ortho/meta selectivity in the Diels-Alder step is an important issue to pave the way to a wide range of renewable aromatics, but it remains a challenging task. A combined experimental-theoretical approach reveals that, as a general trend, ortho and meta cycloadducts are the kinetic and thermodynamic products, respectively. The nature of substituents, both on the dienes and dienophiles, significantly impacts the feasibility of the reaction, through a modulation on the nucleo- and electrophilicity of the reagents, as well as the ortho/meta ratio. We show that the ortho/meta selectivity at the reaction equilibrium stems from a subtle interplay between charge interactions, favoring the ortho products, and steric interactions, favoring the meta isomers. This work also points towards a path to optimize the aromatization step.