111-69-3 Usage
Chemical Properties
Adiponitrile is a combustible, colorless transparent to yellow, oily liquid with a slight bitter taste. Soluble in methanol, ethanol, chloroform. Insoluble in water, cyclohexane, ether, carbon disulfide and carbon tetrachloride. It decomposes on heating to react violently with strong oxidants. Upon burning, the highly toxic hydrogen cyanide is produced.
Uses
Adiponitrile is mainly used in the production of hexamethylenediamine for manufacturing nylon 6,6. Lesser uses include that in organic synthesis and in the preparation of adipoguanamine, which is used as an extractant for aromatic hydrocarbons. This chemical is an important intermediate for the manufacture of synthetic fiber.
Production Methods
Adiponitrile may be prepared by reacting butadiene with hydrogen cyanide, by the
electrodimerization of acrylonitrile, by heating adipamide with acetic anhydride in
the presence of cobalt or by reacting 1,4-dichlorobutane with sodium cyanide
(HSDB 1988). Impurities such as propionitrile, bis (cyanoethyl) ether or acrylonitrile
may be present depending on the method of manufacture (Smiley 1981).
Application
Adiponitrile is used as a synthetic rubber accelerator, a rust inhibitor, an additive for detergents, a spinning solvent for acrylonitrile, methacrylonitrile and methyl methacrylate terpolymers, a solvent for wet spinning and dry spinning of polyvinyl chloride fibers , polyamide colorants, auxiliaries for fabric bleaches, acetate, propionate, butyrate and mixed ester plasticizers; and aromatic extracted extractants.
Preparation
The main method of industrial production of adiponitrile is the amination of adipic acid. Adipic acid and excess ammonia are reacted in the presence of catalyst phosphoric acid or its salts or esters at a temperature of 270-290°C to generate diammonium adipate, which is then heated and dehydrated to generate crude adiponitrile, The product is obtained by rectification.
Synthesis Reference(s)
Synthetic Communications, 10, p. 279, 1980 DOI: 10.1080/00397918008062751
General Description
Adiponitrile appears as a colorless to light yellow liquid which is fairly soluble and is less dense than water. Contact may irritate skin, eyes and mucous membranes. May be toxic by ingestion, inhalation and skin absorption.
Air & Water Reactions
Insoluble in water.
Reactivity Profile
1,4-Dicyanobutane is incompatible with strong oxidizers. 1,4-Dicyanobutane is also incompatible with strong acids, strong bases and strong reducing agents. .
Health Hazard
The acute toxicity of adiponitrile is somewhat lower than that of malononitrile. It is toxic by inhalation and oral routes. Inhalation of its vapors can cause nausea, vomiting, respiratory tract irritation, and dizziness. The symptoms are similar to those of other aliphatic mono- and dinitriles. Similar poisoning effects may be manifested from ingestion of this compound. However, its toxicity is very low from skin absorption. Short et al. (1990) reported mortality and reduced weight gain in rats within one week after exposed to adiponitrile at 493 mg/m3. However, at an exposure level of 99 mg/m3 for 13 weeks the animals showed the sign of slight anemia but no histopathological evidence of organ toxicity. LC50 value, inhalation (rats): 1710 mg/m3/ 4 hr LD50 value, oral (mice): 172 mg/kg There is no report of its teratogenicity or cancer-causing effects in animals or humans.
Fire Hazard
Combustion products may contain hydrocyanic acid (HCN). Vapor may explode if ignited in an enclosed area. When heated to decomposition, 1,4-Dicyanobutane emits highly toxic fumes. Avoid oxidizing material. Hazardous polymerization may not occur.
Industrial uses
Adiponitrile is used in nylon manufacturing, synthetic fiber synthesis, and in the
manufacture of rubber accelerators and corrosion inhibitors. It is also used as an
extractant for aromatic hydrocarbons (Smiley 1981).
Safety Profile
Poison by inhalation, ingestion, subcutaneous, and intraperitoneal routes. The nitrile group wdl behave as a cyanide when ingested or absorbed in the body. It produces disturbances of the respiration and circulation, irritation of the stomach and intestines, and loss of weight. Its low vapor pressure at room temperature makes exposure to harmful concentrations of its vapors unlikely if handled with Flammable when exposed to heat or flame. When heated to decomposition it emits toxic fumes of CN-. Can react with oxidizing materials. To fight fire, use foam, CO2, dry chemical. See also HYDROCYANIC ACID and NITRILESreasonable care in well-venulated areas.
Potential Exposure
Is used to manufacture corrosion inhibitors, rubber accelerators, and Nylon 66; and in organic synthesis.
Environmental Fate
The mechanism of adiponitrile’s toxicity relates to its ability to
release cyanide both in vitro and in vivo. Cyanide then forms
a stable complex with ferric iron in the cytochrome oxidase
enzyme. Since this enzyme occupies a central role in the utilization
of oxygen in practically all cells, inhibition produces an
inhibition of cellular respiration.
Metabolism
Animal studies indicated that the concentrations of thiocyanate in the blood and
urine of guinea pigs injected with adiponitrile were proportional to the doses
administered. Following administration of adiponitrile, 79% was eliminated as
thiocyanate in the urine of guinea pigs (H?rtung 1982). Of the cyanide antidotes,
thiosulfate was most effective in protecting against adiponitrile poisoning, and
nitrite was less effective. However, on the basis of the ratio between administered
adiponitrile dose and quantity of cyanide detected, Ghiringhelli, (1955) concluded
that a greater part of the dose was metabolized to cyanide.
Shipping
UN2205 Adiponitrile, Hazard Class: 6.1; Labels: 6.1-Poisonous materials
Purification Methods
Reflux adiponitrile over P2O5 and POCl3, and fractionally distil it, then fractionate it through an efficient column. The liquid is TOXIC and is an IRRITANT. [Braun & Rudolph Chem Ber 67 1770 1934, Reppe et al. Justus Liebigs Ann Chem 596 127 1955, Gagnon et al. Can J Chem 34 1662 1956, Copley et al. J Am Chem Soc 62 228 1940, Beilstein 2 IV 1947.]
Toxicity evaluation
Adiponitrile will exist solely as a vapor in the ambient atmosphere.
The chemical can be degraded in air by photochemically
produced hydroxyl radicals with a half-life of 23 days.
Adiponitrile is expected to have very high mobility in soil, with
volatilization from soil or water surfaces not expected to be an
important fate process. The chemical is expected to biodegrade
in aquatic and soil systems. The potential for bioconcentration
in aquatic organisms is low.
Incompatibilities
May form explosive mixture with air. Incompatible with oxidizers (chlorates, nitrates, peroxides, permanganates, perchlorates, chlorine, bromine, fluorine, etc.); contact may cause violent reactions: fires or explosions. Keep away from alkaline materials, strong bases, strong acids, oxoacids, epoxides. Also incompatible with strong reducing agents such as hydrideds and active metals. Permissible Exposure Limits in Air
Waste Disposal
Add excess alcoholic KOH. Than evaporate alcohol and add calcium hypochlorite. After 24 hours, flush to sewer with water. Can also be incinerated with afterburner and scrubber to remove nitrogen oxides.
Check Digit Verification of cas no
The CAS Registry Mumber 111-69-3 includes 6 digits separated into 3 groups by hyphens. The first part of the number,starting from the left, has 3 digits, 1,1 and 1 respectively; the second part has 2 digits, 6 and 9 respectively.
Calculate Digit Verification of CAS Registry Number 111-69:
(5*1)+(4*1)+(3*1)+(2*6)+(1*9)=33
33 % 10 = 3
So 111-69-3 is a valid CAS Registry Number.
111-69-3Relevant articles and documents
Misono et al.
, p. 931,934 (1967)
Baizer
, p. 973,974 (1963)
One-step Synthesis of Adiponitrile by Catalytic Ammoxidation over Antimony-Vanadium Phosphorus Oxide/γ-Alumina Catalyst
Reddy, B. Mahipal,Manohar, B.
, p. 330 - 331 (1993)
The selective synthesis of adiponitrile from cyclohexanol, cyclohexanone,cyclohexane and n-hexane in a single step by vapour-phase ammoxidation over an antimony-promoted vanadium phosphorus oxide catalyst supported on alumina is reported.
Electrochemical synthesis of adiponitrile from the renewable raw material glutamic acid
Dai, Jian-Jun,Huang, Yao-Bing,Fang, Chi,Guo, Qing-Xiang,Fu, Yao
, p. 617 - 620 (2012)
Current affairs: Adiponitrile, used to produce nylon 6.6, is prepared from the renewable compound glutamic acid by an electrochemical route, involving electro-oxidative decarboxylation and Kolbe coupling reactions. The new route is an example of the use of glutamic acid as a versatile substrate in the transformation of biomass into chemicals. Also, it highlights the use of electrochemical methods in biomass conversion.
A new simple method for the synthesis of cyclobutyl cyanide
Cohen, Shlomo,Rothenberg, Gadi,Sasson, Yoel
, p. 3093 - 3094 (1998)
A clean and efficient intramolecular cyclization of δ- halovaleronitrile to cyclobutyl cyanide was achieved using NaOH and phase- transfer catalysts in a solid-liquid system at 70°C.
Linear relationship between activity of a new Ru-catalyst and acidity of substituted benzoic acids in the dimerization of acrylonitrile
Kashiwagi, Kohichi,Sugise, Ryoji,Shimakawa, Toshihiro,Matuura, Tunao,Shirai, Masashi
, p. 186 - 187 (2006)
A new type of catalyst system using ruthenium and carboxylic acid is useful for the tail-to-tail dimerization of acrylonitrile, proceeding without the formation of undesired by-product propionitrile. Carboxylic acids having pK a 3.5-5 are suitable as co-catalysts for the dimerization of acrylonitrile. The relationship between the logarithm of the relative rate in the dimer formation and the pKa of m- and p-substituted benzoic acids (Bronsted plot) was linear (R2 = 0.946) with a slope of -0.199. The role of the carboxylic acids can be considered to be effective protonation in the protonolysis of the carbon-ruthenium bond of an intermediate Ru complex. Copyright
Ahlgren et al.
, p. 303,305,307,310,311,312 (1971)
Improvement of catalyst activity in the Ru-catalyzed dimerization of acrylonitrile by using diphenyl ether as a solvent
Kashiwagi, Kohichi,Sugise, Ryoji,Shimakawa, Toshihiro,Matuura, Tunao
, p. 1384 - 1385 (2007)
For the catalyst system of ruthenium and carboxylic acid, which is useful for the efficient tail-to-tail dimerization of acrylonitrile, the TON increases as the ruthenium catalyst concentration is decreased. Furthermore, the addition of aromatic solvents of equal volume to that of acrylonitrile improves the catalyst activity. Especially, the use of diphenyl ether leads to a 1.7 time improvement of the TON. Copyright
Ligand descriptor analysis in nickel-catalysed hydrocyanation: A combined experimental and theoretical study
Burello, Enrico,Marion, Philippe,Galland, Jean-Christophe,Chamard, Alex,Rothenberg, Gadi
, p. 803 - 810 (2005)
The problem of choosing the 'right chelating ligand' for a homogeneously catalysed reaction is outlined. A model is introduced that combines mechanistic information and ligand descriptors. This model is used together with automated synthesis tools to study the structure-activity relationship in a diverse set of forty-two ligands, and extract information on active regions in the catalyst space. The concept is demonstrated on nickel-catalysed hydrocyanation, using bidentate phosphine and phosphite ligands. The charge at the ligating atoms, the rigidity of the molecules, the steric crowding around the Ni atom, and the bite angle are found to be the most important descriptors. A comparison is made with literature hydrocyanation data and approaches for designing new homogeneous catalysts are discussed.
Facile dehydration of primary amides to nitriles catalyzed by lead salts: The anionic ligand matters
Ruan, Shixiang,Ruan, Jiancheng,Chen, Xinzhi,Zhou, Shaodong
, (2020/12/09)
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.
Production of adiponitrile
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Paragraph 0057-0058, (2021/08/19)
The invention relates to production of adiponitrile. The present invention provides a process for producing a nitrile product, the method comprising: reacting a nitrile product in a reaction zone in the presence of a Bronsted acid catalyst, a carboxylic acid or amide, in particular adipic acid, cyanovaleric acid, adipamide or cyanovaleramide is contacted with a feedstock nitrile selected from a group consisting of acetonitrile and branched C5-C 12 nitriles under conditions effective to maintain the carboxylic acids and/or amides in the liquid phase and to convert at least a portion of the carboxylic acids and amides into a nitrile product different from the feedstock nitrile, in particular adiponitrile; a reaction effluent containing the nitrile product is then recovered from a reaction zone.
METHOD FOR PRODUCING epsilon-CAPROLACTAM
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Paragraph 0142; 0155; 0161, (2020/03/09)
The present invention is a method of producing ε-caprolactam through adipamide as an intermediate, and characteristically includes a lactamization step of reacting adipamide, formed from a material compound, with hydrogen and ammonia in the presence of a catalyst containing: a metal oxide mainly containing an oxide(s) of one or more metallic elements selected from the group consisting of metallic elements of group 5 and groups 7 to 14 in the 4th to 6th periods of the periodic table; and a metal and/or a metal compound having a hydrogenation ability. The method can increase the selectivity of ε-caprolactam.
