1194-65-6

Basic information

• Product Name: 2,6-Dichlorobenzonitrile
• Synonyms: SILBENIL;NIAGARA 5006;2,6-DICHLOROBENZONITRILE;AKOS BBS-00004654;BARRIER;'LGC' (1113);H-133;CASORON
• CAS NO: 1194-65-6
• Molecular Formula: C₇H₃Cl₂N
• Molecular Weight: 172.01
• EINECS: 214-787-5
• Product Categories: Pharmaceutical Intermediates;FINE Chemical & INTERMEDIATES;Aromatic Nitriles;Nitriles;Building Blocks;C6 to C7;Chemical Synthesis;Cyanides/Nitriles;Nitrogen Compounds;Organic Building Blocks;intermediate
• Mol File: 1194-65-6.mol

Chemical Properties

• Melting Point: 143-146 °C(lit.)
• Boiling Point: 270-275 °C
• Flash Point: 270°C
• Appearance: white powder
• Density: 1.4980 (rough estimate)
• Vapor Pressure: 0.00406mmHg at 25°C
• Refractive Index: 1.6000 (estimate)
• Storage Temp.: 0-6°C
• Water Solubility: 25 mg/L (25 ºC)
• Merck: 14,3042
• BRN: 1909167
• CAS DataBase Reference: 2,6-Dichlorobenzonitrile(CAS DataBase Reference)
• NIST Chemistry Reference: 2,6-Dichlorobenzonitrile(1194-65-6)
• EPA Substance Registry System: 2,6-Dichlorobenzonitrile(1194-65-6)

Safety Data

• Hazard Codes: Xn,N,T,Xi
• Statements: 21-51/53
• Safety Statements: 36/37-61
• RIDADR: UN 3077 9/PG 3
• WGK Germany: 2
• RTECS: DI3500000
• HazardClass: 9
• PackingGroup: III
• Hazardous Substances Data: 1194-65-6(Hazardous Substances Data)

Usage

Uses

Used in Herbicide Applications:
2,6-Dichlorobenzonitrile is used as a herbicide for controlling many annual and perennial broad-leaved weeds. It is used as a pre-emergent and early post-emergent herbicide.
Used in Agricultural Industry:
2,6-Dichlorobenzonitrile is used as a herbicide in various agricultural fields such as cranberry bogs, dichondra, ornamentals, blackberry, raspberry, and blueberry fields, apple, pear, filbert and cherry orchards, vineyards, hybrid poplar-cottonwood plantations, and rights-of-way to control weeds. It acts on dandelion, prickly oxtongue (pre-emergence), and tree roots.
Used in Synthesis of Pharmaceuticals:
2,6-Dichlorobenzonitrile is used as a starting material for the synthesis of diclofenac sodium, oxacillin, and guanabenz acetate.
Note: 2,6-Dichlorobenzonitrile is not approved for use in EU countries and is actively registered in the U.S. It poses a threat to the environment and can easily penetrate the soil, contaminating groundwater and nearby streams. Immediate steps should be taken to limit its spread to the environment, as it can cause illness by inhalation, skin absorption, and/or ingestion.

Synthesis Reference(s)

Synthetic Communications, 20, p. 2785, 1990 DOI: 10.1080/00397919008051490Synthesis, p. 943, 1992 DOI: 10.1055/s-1992-26271

Air & Water Reactions

Not soluble in water.

Reactivity Profile

A halogenated nitrile. 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.

Health Hazard

SOLID: Harmful if swallowed.

Flammability and Explosibility

Nonflammable

Trade name

BARRIER?; BH Prefix D?; CARSORON?; CASORON? 133; CARSORON? G; CARSORON? G4; CARSORON? G20-SR; CODE H 133?; DECABANE?; DU-SPREX?; DYCLOMEC?; FYDULAN; FYDUMAS; FYDUSIT; H 133?; H 1313?; NIA 5996?; NIAGARA? 5006; NIAGARA 5,996; NOROSAC?; PREFIX D?

Environmental Fate

Biological. A cell suspension of Arthrobacter sp., isolated from a hydrosol, degraded dichlobenil to 2,6-dichlorobenzamide (71% yield) and several unidentified water soluble metabolites (Miyazaki et al., 1975). This microorganism was capable of rapidly degrading dichlobenil in aerobic sediment-water suspensions and in enrichment cultures (Miyazaki et al., 1975). Soil. The major soil metabolite is 2,6-dichlorobenzamide which undergoes further degradation to form 2,6-dichlorobenzoic acid. The estimated half-lives ranged from 1 to 12 months (Hartley and Kidd, 1987). Under field conditions, dichlobenil persists from 2 to 12 months (Ashton and Monaco, 1991). The disappearance of dichlobenil from a hydrosol and pond water was primarily due to volatilization and biodegradation. The time required for 50 and 90% dissipation of the herbicide from a hydrosol were approximately 20 and 50 days, respectively (Rice et al., 1974). Dichlobenil has a high vapor pressure and volatilization should be an important process. Williams and Eagle (1979) found that the half-life of dichlobenil was 4 weeks in soil 4–8 weeks after application. After 1 year following application, the half-life increased to 1 year. Plant. In plants, dichlobenil is transformed into glucose conjugates, insoluble residues and hydroxy products that are phytotoxic (Ashton and Monaco, 1991). These include three phytotoxic compounds, namely 2,6-dichlorobenzonitrile, 3-hydroxy-2,6-dichlorobenzonitrile and 4-hydroxy-2,6-dichlorobenzonitrile (Duke et al., 1991). Massini (1961) provided some evidence that dichlobenil is metabolized by plants. French dwarf beans, tomatoes, gherkin and oat plants were all exposed to a saturated atmosphere of dichlobenil at room temperature for 4 days. Most of the herbicide was absorbed and translocated by the plants in 3 days. After 6 days of exposure, bean seedlings were analyzed for residues using thinlayer plate chromatography. In addition to dichlobenil, another compound was found but it was not 2,6-dichlorobenzoic acid (Massini, 1963). Surface Water. The time required for 50 and 90% dissipation of the herbicide from New York pond water was approximately 21 and 60 days, respectively (Rice et al., 1974). Photolytic. When dichlobenil was irradiated in methanol with a 450-W mercury lamp and a Corex filter for 8 hours, o-chlorobenzonitrile and benzonitrile formed as the major and minor products, respectively (Plimmer, 1970). Chemical/Physical. Dichlobenil is hydrolyzed, especially in the presence of alkali, to 2,6-dichlorobenzamide (Briggs and Dawson, 1970; Worthing and Hance, 1991). Emits toxic fumes of nitrogen oxides and chlorine when heated to decomposition (Sax and Lewis, 1987).

Metabolic pathway

Twelve metabolites are isolated from either urine or bile from either rats (11 metabolites) or goats (seven metabolites) given single oral doses of 14C-labeled 2,6-dichlorobenzonitrile (DCBN). Five of these metabolites are also excreted in urine from rats dosed orally with 2,6-dichlorothiobenzamide (DCTBA) which is an acid amide analog. All metabolites from either DCBN or DCTBA are benzonitriles with the following ring substituents: Cl2, OH (three isomers); Cl2, (OH)2; Cl, (OH)2; Cl, OH, SH; Cl, OH, SCH3; SOCH3, OH; Cl2, S-(N-acetyl)cysteine; Cl, S-(N-acetyl)cysteine; Cl, OH, S-(N-acetyl)cysteine. The thiobenzamide moiety of DCTBA is converted to the nitrile in all extracted urinary metabolites. No hydrolysis of the nitrile in DCBN to either amide or an acid is detected. Urine is the major route for excretion; however, enterohepatic circulation occurs.

Purification Methods

Crystallise the nitrile from acetone. [Beilstein 9 IV 1006.]

InChI:InChI=1/C7H3Cl2N/c8-6-2-1-3-7(9)5(6)4-10/h1-3H

Upstream product

• 2008-58-4 2,6-dichlorobenzamide 
• 25185-95-9 2,6-dichlorobenzaldoxime 
• 83-38-5 2,6-dichlorobenzaldehyde 
• 55366-49-9 N-methyl-1,2,3,4,5,6-hexahydro-1-benzoazocine-2,6-dione 
• 78514-86-0 2,6-Dichlorobenzaldehyde 4-<2-Cyano-2-(ethoxycarbonyl)vinyl>3-methylisothiosemicarbazone 
• 151-50-8 potassium cyanide 
• 137041-62-4 indeno-isoxazolo-indole propellane 
• 4659-45-4 2,6-Dichlorobenzoyl chloride 
• 2828-47-9 (E)-2-(2,6-dchlorobenzylidene)-1,1-dimethylhydrazine 
• 6575-27-5 2,6-dichlorobenzylamine 
• 144-55-8 sodium hydrogencarbonate 
• 931-97-5 1-hydroxy-1-cyclohexanecarbonitrile 
• 50-30-6 2,6-dichlorobenzoic acid 
• 19393-92-1 1-bromo-2,6-dichlorobenzene 

Downstream Products

• 2040-05-3 2,6 dichloroacetophenone 
• 19574-27-7 1-Amino-2-cyano-1-(2,6-dichlorphenyl)-1-buten 
• 19389-50-5 1-Amino-2-cyano-1-(2,6-dichlorphenyl)-1-propen 
• 20925-99-9 3-chloro-2-cyano-N,N-dimethylaniline 
• 127667-12-3 2-Chloro-6-[cyano-(4-fluoro-phenyl)-methyl]-benzonitrile 
• 92161-49-4 3-chloro-2-cyano-2'-methoxydiphenyl ether 
• 121618-91-5 2-chloro-6-(2-methoxyphenoxy)benzoic acid 
• 83-38-5 2,6-dichlorobenzaldehyde 
• 65231-45-0 C-(2,6-Dichloro-phenyl)-C-p-tolyl-methyleneamine 
• 65231-41-6 2,6-Dichlorbenzophenonimin 
• 541-73-1 1,3-Dichlorobenzene 
• 3268-87-9 1,2,3,4,6,7,8,9-octachlorodibenzodioxin 
• 35822-46-9 HpCDD 1234678 
• 2008-58-4 2,6-dichlorobenzamide 

Relevant articles and documents

Investigation of BiVO4 structure variations on the dichlorotoluene ammoxidation performance

In this study, BiVO4 synthesized by hydrothermal and calcination methods were explored as catalysts in the ammoxidation of dichlorotoluenes to shed light on the structure-reactivity correlations. The BiVO4 samples were characterized by X-ray diffraction (XRD), temperature-programmed reduction (TPR), Brunauer–Emmett–Teller (BET), and UV–Vis spectrophotometry. The results showed that the catalytic activity of BiVO4 greatly relied on the structure variations. The hydrothermal prepared BiVO4 exhibited better catalytic activities as a consequence of its greater structure deformation, with maximum yields of 73.1, 72.2, and 70.8% for 3,4-, 2,4- and 2,6- dichlorobenzonitrles, respectively.

Straightforward conversion of arene carboxylic acids into aryl nitriles by palladium-catalyzed decarboxylative cyanation reaction

A one-pot procedure to convert aromatic carboxylic acids into aromatic nitriles is described. The methodology is based on a palladium(II)-catalyzed decarboxylative cyanation reaction using cyanohydrins as soluble cyanide sources. The described reaction worked on a panel of substrates and is additionally of particular interest for the straightforward preparation of 13C- or 14C-labeled compounds.

Hydrothermal Synthesis of Urchin-like W-V-O Nanostructures with Excellent Catalytic Performance

Urchinlike W-V-O microspheres have been successfully synthesized for the first time by a one-pot hydrothermal approach. The as-synthesized W-V-O material was characterized by several techniques such as XRD, SEM, TEM, FTIR, EDS, BET, and Raman spectroscopy. The characterization results have revealed that the W-V-O microspheres consist of numerous one-dimensional nanobelts radially grown from the center. The typical nanobelts display rectangular cross sections with lengths of several micrometers, widths of about 50 nm, and thicknesses of approximately 10-20 nm. Vanadium oxides are dispersed highly either on the external surface or inside the channel surface of the hexagonal WO3 structure. In addition, the as-obtained urchin-like W-V-O material was explored as a catalyst for the ammoxidation of 2,4- and 2,6-dichlorotoluene to the corresponding nitriles. The catalytic results have indicated that the W-V-O nanostructures show excellent performance with yields of 2,4- and 2,6-dichlorobenzonitrile respectively reaching up to 77.3 and 75.1%, which are the highest among the previously reported catalysts with two components. The formation process of the urchinlike W-V-O microspheres was simply investigated.

Hydrothermal synthesis of V-doped hexagonal WO3 microspheres comprising of nanoblocks for catalytic ammoxidation of dichlorotoluene

V-doped hexagonal WO3 microspheres comprising of nanoblocks were successfully prepared via a facile hydrothermal approach. Several techniques such as XRD, SEM, TEM, FTIR, EDS, TPR, BET and Raman have been performed and the characterization results reveal that V replaced W atoms into the hexagonal lattice-structure. The microspheres possess diameter of about 4.4 μm and the nanoblocks have thicknesses of 40–100 nm and widths of about 150 nm. In addition, the catalytic performance of the obtained V-doped WO3 nanomaterial was investigated in the ammoxidation of dichlorotoluene. The catalytic results indicate that the as-prepared nanostructures show significantly improved selective performance with the selectivities of 3,4-DCBN and 2,6-DCBN reaching up to 89.8% and 86.2%, respectively.

Effect of nitrogen-containing compounds on polychlorinated dibenzo-p-dioxin/dibenzofuran formation through de novo synthesis

An experimental study was conducted to clarify the suppression effect of nitrogen-containing compounds, that is, ammonia and urea, on the formation of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) through the de novo synthesis reaction. In the experiment, graphite and copper chloride contained in a mixture were used as sources of carbon and chlorine, respectively. The granulated sample mixture was charged as a packed-bed in the glass tube and heated at 300 °C in the flow of Ar-O 2 gas mixture. In some cases, urea was added as aqueous solution to the sample, while ammonia was added to the gas flowed through the sample bed. The amount of PCDD/Fs formed decreases significantly by the addition of both ammonia and urea. Particularly, the addition of urea reduces the amount of PCDD/Fs discharged in the outlet gas by approximately 90%. The oxidation rate of carbon in the early stage of the experiment, that is, the heating period, is promoted by the addition of nitrogen-containing compounds. However, soon after the temperature reaches 300 °C, the formation rate becomes lower than that of the case without the addition of nitrogen-containing compounds. On the other hand, organic compounds containing amino (-NH2) or cyanide (-CN) groups and those containing nitrogen within the carbon ring frame were detected in the outlet gas in the case of urea addition. Typically observed aromatic compounds are chlorobenzonitriles, chlorobenzeneamines, and chloropyridines. This suggests a possibility that hydrogen and/or chlorine combined with PCDD/Fs are also substituted by such nitrogen-containing groups, and this decreases the formation rate of their frame of carbon rings. This phenomenon was also consistent with the fact that a significant reduction was observed in the amount of PCDD/Fs released to the outlet gas when urea was added.

Electroorganic synthesis of nitriles via a halogen-free domino oxidation-reduction sequence

A direct electroorganic sequence yielding nitriles from oximes in undivided cells is reported. Despite the fact that intermediate nitrile oxides might be formed, the method is viable to prepare benzonitriles without substituents ortho to the aldoxime moiety. This constant current method is easy to perform for a broad scope of substrates and employs common electrodes, such as graphite and lead.

Ammoxidation of 2,6-dichloro toluene - From first trials to pilot plant studies

The scaling-up of the gas phase catalytic ammoxidation of 2,6-dichloro toluene (DCT) to 2,6-dichloro benzonitrile (DCBN) over a promoted vanadium phosphate (VPO) catalyst from first lab-scale experiments to pilot plant runs is reported. First experiments in a row of conversions of isomeric dichloro toluenes using simple, non-promoted VPO catalysts only show poor yield and selectivity. In particular, DCT ammoxidation is hindered due to bulky chlorine substituents probably preventing a sufficient interaction of the methyl group and lattice oxygen and/or N-containing surface species. Improved synthesis of VPO catalyst with the addition of promoters and γ-alumina or titania leads to significant increase in DCT conversion and DCBN yield. A Cr containing vanadyl pyrophosphate catalyst admixed with titania (anatase) showed conversion up to 97% with DCBN yields of ca. 80%. The same catalyst was also used for pilot plant runs, usually in the form of 5 mm × 3.5 mm shaped tablets that were prepared from a larger batch of solid synthesis. The scaling-up of the process using 100 ml of catalyst was investigated both by catalytic experiments and reactor simulations. The results showed that the temperature control will be crucial in scaling-up. Validation of simulation results with that of experimental results was also checked and a good agreement between measured and simulated results is observed.

Highly Modular Flow Cell for Electroorganic Synthesis

A highly modular electrochemical flow cell and its application in electroorganic synthesis is reported. This innovative setup facilitates many aspects: an easy adjustment of electrode distance, quick exchange of electrode material, and the possibility to easily switch between a divided or undivided cell. However, the major benefit of the cell is the exact thermal positioning of the electrode material into a Teflon piece. Thereby, the application of expensive and nonmachinable electrode materials like boron-doped diamond or glassy carbon can easily be realized in flow cells. By this geometry, the maximum surface of such valuable electrode materials is exploited. The cell size can compete with classical preparative approaches in terms of performance and productivity. The optimization of reaction parameters and an easy up-scaling to larger flow cells is possible. By using this cell, the starting material can be saved in the development of the electroorganic transformations. To demonstrate the utility of this particular cell, two transformations of important building blocks for the fine chemical and pharmaceutical industry were established including an efficient and simple workup protocol.

Method for catalyzing oxidation of amines to generate nitrile by using nonmetal mesoporous nitrogen-doped carbon material

The invention discloses a method for preparing nitrile by catalyzing amine oxidation with a non-metal mesoporous nitrogen-doped carbon material catalyst, which is applied to the field of synthesis, the material is prepared by using a nitrogen-containing organic ligand as a precursor and silica sol as a template agent, calcining in the atmosphere of inert gases such as N2 or Ar and then removing the template agent; oxygen or air is used as an oxygen source, the reaction is performed at 80-130 DEG C under the action of ammonia water in the presence of a solvent, the effect is good, and the product still keeps higher activity after being recycled for more than 8 times, and has a wide industrial application prospect. The invention provides a heterogeneous non-metal catalytic system for catalyzing amine oxidation to prepare nitrile for the first time, and compared with a reported metal catalyst, the heterogeneous non-metal catalytic system does not bring metal pollution to a product to influence the effect of cyano drugs.

Synthesis of nanoparticle-built FeVO4 microspheres with improved low temperature catalytic activity in ammoxidation

FeVO4 microspheres were successfully fabricated by a hydrothermal approach. Characterization results revealed that the FeVO4 microspheres are composed of numerous nanoparticles. In the ammoxidation of 2,6-dichlorotoluene (DCT) to 2,6-dichlorobenzonitrile (DCBN) catalyzed by FeVO4 microspheres, the conversion of DCT reaches up to 87% at a much lower temperature of 320 °C in comparison to previously reported catalysts (380–420 °C). The reason for this is that irons greatly improve the electron transport, leading to well reduction redox properties of vanadium species which are important to enhance the initial activation efficiency of C-H bond in methyl group.