140-29-4

Basic information

• Product Name: Benzeneacetonitrile
• Synonyms: phenyl acetyl nitrile;PHENYLACETONITRILE;TOLUNITRILE;(Cyanomethyl)benzene;2-Phenylacetonitrile;aceticacid,phenyl-nitrile;Acetonitrile, phenyl-;acetonitrile,phenyl-
• CAS NO: 140-29-4
• Molecular Formula: C₈H₇N
• Molecular Weight: 117.15
• EINECS: 205-410-5
• Product Categories: Pharmaceutical Intermediates;Organics;Agrochemical
• Mol File: 140-29-4.mol
• Article Data: 383

Chemical Properties

• Melting Point: −24 °C(lit.)
• Boiling Point: 233-234 °C(lit.)
• Flash Point: 215 °F
• Appearance: colourless liquid
• Density: 1.015 g/mL at 25 °C(lit.)
• Vapor Pressure: 0.1 mm Hg ( 20 °C)
• Refractive Index: n20/D 1.524
• Storage Temp.: Store below +30°C.
• Solubility: 0.1g/l
• Water Solubility: insoluble.
• Stability: Stable. Incompatible with strong oxidizing agents. May produce hydrogen cyanide in a fire.
• Merck: 14,1131
• BRN: 385941
• CAS DataBase Reference: Benzeneacetonitrile(CAS DataBase Reference)
• NIST Chemistry Reference: Benzeneacetonitrile(140-29-4)
• EPA Substance Registry System: Benzeneacetonitrile(140-29-4)

Safety Data

• Hazard Codes: T+,T
• Statements: 22-24-26-23/24/25
• Safety Statements: 28-36/37-45-23
• RIDADR: UN 2470 6.1/PG 3
• WGK Germany: 3
• RTECS: AM1400000
• F: 8-9
• TSCA: Yes
• HazardClass: 6.1(b)
• PackingGroup: III
• Hazardous Substances Data: 140-29-4(Hazardous Substances Data)

Usage

Chemical Properties

Different sources of media describe the Chemical Properties of 140-29-4 differently. You can refer to the following data:
1. colourless liquid
2. Benzyl cyanide is a colorless, oily liquid with an aromatic odor.

Uses

Different sources of media describe the Uses of 140-29-4 differently. You can refer to the following data:
1. Organic synthesis, especially penicillin precursors.
2. Phenylacetonitrile is used in organic synthesis for dyes, perfumes, pharmaceuticals, especially penicillin precursors. It is also used as a solvent.

Production Methods

Benzyl cyanide is synthesized by reaction of benzyl chloride with potassium cyanide or sodium cyanide . The nitrile is a natural constituent of plants and is a constituent of foods, particularly citrus fruits, papaya, cabbage, mushrooms, roasted onions, tomatoes, cocoa, tea, roasted peanuts and cauliflower .The benzyl cyanide, at least in part, is formed by breakdown of benzylglucosinolate in the plant material. Benzyl nitrile also is found in tap water, river water, sewage and in cigarette smoke ).

Definition

ChEBI: A nitrile that is acetonitrile where one of the methyl hydrogens is substituted by a phenyl group.

Synthesis Reference(s)

Canadian Journal of Chemistry, 39, p. 1340, 1961 DOI: 10.1139/v61-169Chemistry Letters, 13, p. 1511, 1984Organic Syntheses, Coll. Vol. 1, p. 107, 1941

General Description

A colorless oily liquid with an aromatic odor. Insoluble in water and slightly denser than water. Contact may irritate skin, eyes, and mucous membranes. May be toxic by ingestion. Used to make other chemicals.

Air & Water Reactions

Benzeneacetonitrile is moisture sensitive. Insoluble in water.

Reactivity Profile

PHENYLACETONITRILE can react with strong acids, strong bases, strong oxidizing agents and strong reducing agents. Benzeneacetonitrile may react vigorously with sodium hypochlorite. .

Hazard

Highly toxic, absorbed by skin.

Health Hazard

Different sources of media describe the Health Hazard of 140-29-4 differently. You can refer to the following data:
1. Benzyl cyanide is a highly toxic irritant that may be fatal if inhaled, swallowed or absorbed through the skin. The chemical causes eye, mucous membrane and skin irritation. Benzyl cyanide was applied as a 2% concentration in petroleum to the skin of 27 human volunteers and found to be nonsensitizing.
2. Poisonous. May be fatal if inhaled, swallowed, or absorbed through skin. Contact may cause burns to skin and eyes.

Fire Hazard

When heated to decomposition, Benzeneacetonitrile emits very toxic fumes of cyanide and nitrogen oxides. Container may explode in heat of fire. Runoff from fire control water may give off poisonous gases. Avoid sodium hypochlorite.

Industrial uses

Benzyl cyanide is employed as a chemical intermediate for the synthesis of amphetamine, phenobarbital and methyl phenidylacetate. It is also used for perfumes and flavors and is, therefore, added to soaps, detergents, creams and lotions.

Safety Profile

Poison by ingestion, inhalation, skin contact, subcutaneous, and intraperitoneal routes. A skin irritant. Explosive reaction with sodium hypochlorite. Used in production of drugs of abuse. When heated to decomposition it emits very toxic fumes of CNand NOx. See also NITRILES

Potential Exposure

(as CN): Benzyl cyanide is used in organic synthesis, especially of penicillin precursors. It is used as a chemical intermediate for amphetamines, phenobarbital; the stimulant, methyl phenidylacetate; esters as perfumes and flavors.

Metabolism

Giacosa isolated phenylaceturic acid from the urine of a dog dosed with benzyl cyanide, while Adeline et al showed that in the dog, benzyl cyanide formed both benzoic acid and a small amount of ethereal sulfate. In rabbits, a large proportion of the cyano group could be accounted for as thiocyanate ion in the urine. There was a sex difference in the conversion with female rabbits excreting 70% of the dose as thiocyanate and males only 50%. However, cyanide was liberated slowly from i.p. or orally administered benzyl cyanide in rats and excreted in the urine as cyanide and thiocyanate, the proportion of the former increasing with the dose . Benzyl cyanide is oxidized by mouse liver microsomes to benzaldehyde and cyanide ion presumably via the intermediate mandelonitrile. The microsomal metabolism of benzyl cyanide and other nitriles was significantly increased when mice were pre treated with ethanol , suggesting that the ethanol-inducible cytochrome P-450 may play an important role in the metabolism of such compounds.

Shipping

UN2470 Phenylacetonitrile, Hazard Class: 6.1; Labels: 6.1—Poisonous materials.

Purification Methods

Any benzyl isocyanide impurity can be removed by shaking vigorously with an equal volume of 50% H2SO4 at 60o, washing with saturated aqueous NaHCO3, then half-saturated NaCl solution, drying and fractionally distilling under reduced pressure. Distillation from CaH2 causes some decomposition of this compound: it is better to use P2O5. Other purification procedures include passage through a column of highly activated alumina, and distillation from Raney nickel. Precautions should be taken because of possible formation of free TOXIC cyanide, use an efficient fume cupboard.[Beilstein 9 IV 1663.]

Incompatibilities

Violent reaction with strong oxidizers; sodium hypochlorite, lithium aluminum hydride. Nitriles 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.

InChI:InChI=1/C6H6.C2H3N/c1-2-4-6-5-3-1;1-2-3/h1-6H;1H3

Upstream product

• 5873-91-6 phenyldithioacetic acid 
• 22259-83-2 2-chloro-2-phenylacetonitrile 
• 7028-48-0 Phenylacetaldehyde oxime 
• 108-24-7 acetic anhydride 
• 108-90-7 chlorobenzene 
• 75-05-8 acetonitrile 
• 1795-96-6 phenylalanine ethyl ester 
• 2577-90-4 methyl (2S)-2-amino-3-phenylpropanoate 
• 107-14-2 chloroacetonitrile 
• 71-43-2 benzene 
• 66003-78-9 triphenylsulfonium trifluoromethanesulfonate 
• 28557-00-8 phenylzinc chloride 
• 590-17-0 cyanomethyl bromide 
• 645-54-5 2-phenylthioacetamide 

Downstream Products

• 106736-67-8 3-hexyl-5-phenyl-3H-[1,2,3]triazol-4-ylamine 
• 102595-61-9 (4,5-diphenyl-oxazol-2-yl)-phenyl-acetonitrile 
• 877-95-2 methyl-N-(benzyl-methyl)-formamide 
• 93011-93-9 1-(6-hydroxy-2,3-dihydro-benzofuran-5-yl)-2-phenyl-ethanone 
• 24953-63-7 α-Phenyl-1-phthalazinacetonitril 
• 18592-05-7 cinnolin-4-yl-phenyl-acetonitrile 
• 36925-10-7 phenyl-quinazolin-4-yl-acetonitrile 
• 101733-94-2 1-(5-methoxy-2-methyl-indol-3-yl)-2-phenyl-ethanone 
• 38732-74-0 (3-oxo-3H-isobenzofuran-1-ylidene)-phenyl-acetonitrile 
• 35388-47-7 2-Phenyl-2-(1-piperidylethyl)-acetonitril 
• 130161-43-2 2-(benzo[d]thiazol-2-yl)-2-phenylacetonitrile 
• 860717-00-6 3-[2]quinolyl-3-imino-2-phenyl-propionitrile 
• 93326-48-8 phenyl-quinolin-4-yl-acetonitrile 
• 86213-36-7 (Z)-2-phenyl-3-(2-benzothienyl)acrylonitrile 

Relevant articles and documents

Microwave-assisted dehydration and chlorination using phosphonium salt

Microwave-assisted reaction using phosphonium salt for dehydration of primary amides and chlorination of hydroxyheteroaromatics was carried out. Copyright Taylor & Francis, Inc.

A convenient preparation of alkyl nitriles by the Mitsunobu procedure

A convenient preparation of alkyl nitriles from alcohols extending the use of the Mitsunobu reaction is described. Acetone cyanohydrin is the acidic component and the source of cyanide ion.

Construction of enantioenriched polysubstituted hexahydropyridazines via a sequential multicatalytic process merging palladium catalysis and aminocatalysis

An efficient multicatalytic strategy for the construction of nitrogen-containing heterocycles has been reported. The powerful combination of organic and metal catalysis in a single vessel allowed the formation of enantioenriched polysubstituted cyclic 6-membered hydrazines bearing a quaternary stereocenter in good yields and selectivities.

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Nucleophilic Substitution Reaction of Alkyl Halide by Anion on a Macroporous Polymer Resin

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Polycationic (Mixed) Core-Shell Dendrimers for Binding and Delivery of Inorganic/Organic Substrates

The convergent synthesis of a series of polycationic aryl ether dendrimers has been accomplished by a convenient procedure involving quantitative quaternarization of aryl(poly)amine core molecules. The series has been expanded to the preparation of the first polycationic, mixed core-shell dendrimer. All these dendrimers consist of an apolar core with a peripheral ionic layer which is surrounded by a less polar layer of dendritic wedges. These cationic, macromolecular species have been investigated for their ability to form assemblies with (anionic) guest molecules. The results obtained from UV/Vis and NMR spectroscopies, and MALDI-TOF-MS demonstrate that all the cationic sites throughout the dendrimer core are involved in ion pair formation with anionic guests giving predefined guest/host ratios up to 24. The large NMR spectroscopic shifts of resonances correlated with the groupings located in the core of the dendrimers, together with the relaxation time data indicate that the anionic guests are associated with the cationic core of these dendrimers. The X-ray molecular structure of the octacationic, tetra-arylsilane model derivative [Si(C6H3{CH2NMe3}2-3,5)4](8+) * 8I(-) shows that the iodide counterions are primarily located near the polycationic sphere. The new polycationic dendrimers have been investigated for their catalytic phase-transfer behavior and substrate delivery over a nanofiltration membrane.

Ionic liquids as catalytic green solvents for nucleophilic displacement reactions

We demonstrate the use of room-temperature ionic liquids as a catalytic, environmentally benign solvent for the cyanide displacement on benzyl chloride, replacing phase-transfer catalyzed biphasic systems and thus eliminating the need for a volatile organic solvent and hazardous catalyst disposal.

The hydrogenation of mandelonitrile over a Pd/C catalyst: Towards a mechanistic understanding

A carbon supported Pd catalyst is used in the liquid phase hydrogenation of the aromatic cyanohydrin mandelonitrile (C6H5CH(OH)CH2CN) to afford the primary amine phenethylamine (C6H5CH2CH2NH2). Employing a batch reactor, the desired primary amine is produced in 87% selectivity at reaction completion. Detection of the by-product 2-amino-1-phenylethanol (C6H5CH(OH)CH2NH2) accounts for the remaining 13% and closes the mass balance. The reaction mechanism is investigated, with a role for both hydrogenation and hydrogenolysis processes established.

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HPLC-based kinetics assay facilitates analysis of systems with multiple reaction products and thermal enzyme denaturation

Glucosinolates are plant secondary metabolites abundant in Brassica vegetables that are substrates for the enzyme myrosinase, a thioglucoside hydrolase. Enzyme-mediated hydrolysis of glucosinolates forms several organic products, including isothiocyanates (ITCs) that have been explored for their beneficial effects in humans. Myrosinase has been shown to be tolerant of non-natural glucosinolates, such as 2,2-diphenylethyl glucosinolate, and can facilitate their conversion to non-natural ITCs, some of which are leads for drug development. An HPLC-based method capable of analyzing this transformation for non-natural systems has been described. This current study describes (1) the Michaelis–Menten characterization of 2,2-diphenyethyl glucosinolate and (2) a parallel evaluation of this analogue and the natural analogue glucotropaeolin to evaluate effects of pH and temperature on rates of hydrolysis and product(s) formed. Methods described in this study provide the ability to simultaneously and independently analyze the kinetics of multiple reaction components. An unintended outcome of this work was the development of a modified Lambert W(x) which includes a parameter to account for the thermal denaturation of enzyme. The results of this study demonstrate that the action of Sinapis alba myrosinase on natural and non-natural glucosinolates is consistent under the explored range of experimental conditions and in relation to previous accounts.

Calixarene ionic liquids: Excellent phase transfer catalysts for nucleophilic substitution reaction in water

The first examples of calixarene ionic liquids 3 and 6 with 3D-shaped cavities were obtained in high yields by reacting calix[4]arene or thiacalix[4]arene with 1,6-dibromohexane and then refluxing in 1-methylimidazole. The experiments of phase transfer catalysis in water suggested that they possessed excellent catalytic properties of aromatic nucleophilic substitution reaction and benzyl nucleophilic substitution. The optimized yields of product in catalytic reaction were as high as approximate 97% under mild reaction conditions. The cavities of calixarene skeleton played the crucial roles in catalysis and the stable cone conformation was favorable for catalysis.

Polymer-Supported Reagents: The Use of Polymer-Supported Cyanide and Thiocyanate to Prepare Nitriles, Thiocyanates, and Isothiocyanates

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A poly(ethylene glycol)-supported quaternary ammonium salt: An efficient, recoverable, and recyclable phase-transfer catalyst

(matrix presented) A quaternary ammonium salt readily immobilized on a soluble poly(ethylene glycol) polymer support efficiently catalyzes different reactions carried out under phase-transfer catalysis conditions; the catalyst, easily recovered by precipitation and filtration, shows no appreciable loss of activity when recycled three times.

EFFECTS OF METAL IONS ON BENZYLGLUCOSINOLATE DEGRADATION IN LEPIDIUM SATIVUM SEED AUTOLYSATES

The effects of varying concentrations of Fe2+ (5E-5 - 5E-1 M) on benzylglucosinolate degradation in Lepidium sativum seed autolysates were investigated.Increased glucosinolate decomposition was observed over the whole range with a maximum effect at ca. 6E-3 M Fe2+, at which point glucosinolate degradation was more than three times that obtained in the absence of added Fe2+.Nitrile formation was especially enhanced in the presence of all concentrations of Fe2+ studied, and maximum amounts were obtained at ca. 6E-3 M Fe2+, when a more than four-fold increase over quantities produced in the absence of Fe2+ was observed.Thiocyanate formation was also promoted with a maximum at ca. 4E-3 M Fe2+, but isothiocyanate production was considerably reduced in all cases.It is suggested that Fe2+ inhibits isothiocyanate formation by interfering with the availability of ascorbic acid which is a proven co-factor for most thioglucosidase isoenzymes, but that an Fe2+-ascorbate complex might then be responsible for promoting enzymic production of nitrile.The effects of a limited range of concentrations of Fe3+ and Cu+ were also studied, and results related to those for Fe2+ The relevance of the findings to natural systems and to glucosinolate-containing foods is briefly discussed.Key Word Index-Lepidium sativum; Cruciferae; glucosinolate degradation.

Radical trifunctionalization of hexenenitrile via remote cyano migration

A novel radical-mediated trifunctionalization of hexenenitriles via the strategy of remote functional group migration is disclosed. A portfolio of functionalized hexenenitriles are employed as substrates. After difunctionalization of the unactivated alken

Facile dehydration of primary amides to nitriles catalyzed by lead salts: The anionic ligand matters

The synthesis of nitrile under mild conditions was achieved via dehydration of primary amide using lead salts as catalyst. The reaction processes were intensified by not only adding surfactant but also continuously removing the only by-product, water from the system. Both aliphatic and aromatic nitriles can be prepared in this manner with moderate to excellent yields. The reaction mechanisms were obtained with high-level quantum chemical calculations, and the crucial role the anionic ligand plays in the transformations were revealed.