108-94-1 Usage
Chemical Description
Cyclohexanone is a cyclic ketone used in organic synthesis.
Chemical Description
Cyclohexanone is a cyclic ketone used as a solvent and in the production of nylon.
Chemical Description
Cyclohexanone is a cyclic ketone, benzylamine is an amine with a benzyl group, methyl malonyl chloride is an ester of malonic acid, N,N-diethylaniline is a tertiary amine, sodium hydride is a strong base, N-chlorosuccinimide is a chlorinating agent, and the organic solvents mentioned include benzene, tetrahydrofuran, and petroleum ether.
Uses
Used in Chemical Industry:
Cyclohexanone is used as a chemical intermediate for the production of nylon 6,6 and nylon 6, as well as cyclohexanone oxime, which gives caprolactam on rearrangement.
Used in Paint and Coating Industry:
Cyclohexanone is used as an industrial solvent for cellulose acetate resins, vinyl resins, rubber, and waxes. It also serves as a solvent sealer for polyvinyl chloride and a coating solvent in audio and videotape production.
Used in Pharmaceutical Industry:
Cyclohexanone is used in the manufacture of pharmaceuticals, including cyclohexene ethylamine, which is an intermediate for some drugs.
Used in Agricultural Industry:
Cyclohexanone is used as a solvent for pesticides, such as organophosphate insecticides.
Used in Textile Industry:
Cyclohexanone is used as a leveling agent for dyeing and fading silk, and as a degreasing agent for polishing metal.
Used in Lubricant Industry:
Cyclohexanone is used as a viscous solvent for piston aviation lubricants.
Used in Adhesive and Sealant Industry:
Cyclohexanone is used as a chemical reaction medium, adhesives, and sealants.
Used in Solvent Industry:
Cyclohexanone is used as a solvent for nitrocellulose, cellulose acetate, resins, fats, waxes, shellac, and DDT.
Used in Manufacturing of Caprolactam:
Cyclohexanone is used in the production of adipic acid for making nylon and in the preparation of cyclohexanone resins.
Used in Paints and Varnishes:
Cyclohexanone-derived resins are used in paints and varnishes, causing contact dermatitis in some individuals.
Used in Production of Nylon Intermediates:
Cyclohexanone is mostly captively consumed in the production of nylon intermediates (adipic acid and caprolactam), with around 4% being used in other markets such as solvents for paints, dyes, and pesticides.
Used in Films, Soaps, and Coatings:
Cyclohexanone is also used in the manufacture of films, soaps, and coatings.
Production method
In the 1940s, the industrial production of cyclohexanone mainly applied hydrogenation of phenol to generate cyclohexanol, followed by dehydrogenation to give cyclohexanone. In the 1960s, with the development of petrochemical industry, the cyclohexane oxidation production method gradually dominated. In 1967, the one step method of phenol hydrogenation, developed by the Netherlands National Mining Company (DSM) was industrialized. This method has short production process, good product quality and high yield, but the raw materials of phenol and catalyst are expensive, so the majority of the industry still adopts the cyclohexane oxidation method.
1. Phenol method takes nickel as a catalyst; first apply hydrogenation of phenol to give cyclohexanol, followed by dehydrogenation to give cyclohexanone using zinc as the catalyst for zinc.
2. Cyclohexane oxidation method uses cyclohexane as the raw material; first apply non-catalyst condition; use oxygen-rich air for oxidation to give cyclohexyl hydroperoxide, followed by decomposition into the mixture of cyclohexanol, cyclohexanone, alcohol and ketone in the presence of tert-butyl chromate catalyst; further apply a series of distillation refinement to get qualified products. Raw material consumption quota: cyclohexane (99.6%) 1040kg / t.
3. Benzene hydrogenation oxidation method; benzene subjects to hydrogenation (with hydrogen) at 120-180 ℃ in the presence of nickel catalyst to generate cyclohexane; cyclohexane has oxidation reaction with air at 150-160 ℃, 0.908MPa to obtain the mixture of cyclohexanol and cyclohexanone; separate them to obtain the cyclohexanone product. Cyclohexanol is dehydrogenated at 350-400 ° C in the presence of a zinc-calcium catalyst to produce cyclohexanone. Raw material consumption quotas: benzene (99.5%) 1144kg / t, hydrogen (97.0%) 1108kg / t, caustic soda (42.0%) 230kg / t.
Synthesis Reference(s)
Canadian Journal of Chemistry, 62, p. 1031, 1984 DOI: 10.1139/v84-171Tetrahedron Letters, 25, p. 3309, 1984 DOI: 10.1016/S0040-4039(01)81371-X
Air & Water Reactions
Flammable. Soluble in water.
Reactivity Profile
Cyclohexanone forms an explosive peroxide with H2O2, and reacts vigorously with oxidizing materials (nitric acid).
Health Hazard
Inhalation of vapors from hot material can cause narcosis. The liquid may cause dermatitis.
Health Hazard
The toxicity of cyclohexanone in test specieswas found to be low to moderate. Exposureto its vapors can produce irritation in the eyesand throat. Splashing into the eyes can damagethe cornea. Throat irritation in humansmay occur from 3–5 minute exposure to a50-ppm concentration in air. The symptomsof chronic toxicity in animals from its inhalationwere liver and kidney damage, as wellas weight loss. However, its acute toxicitywas low below 3000 ppm. The symptomsin guinea pigs were lacrimation, salivation,lowering of heart rate, and narcosis. Exposureto 4000 ppm for 4–6 hours was lethalto rats and guinea pigs. The oral toxicity of this compound waslow. Ingestion may cause narcosis and depressionof the central nervous system. It canbe absorbed through the skin.LD50 value, dermal (rabbits): 1000 mg/kgLD50 value, intraperitoneal (rats): 1130 mg/kg.
Fire Hazard
HIGHLY FLAMMABLE: Will be easily ignited by heat, sparks or flames. Vapors may form explosive mixtures with air. Vapors may travel to source of ignition and flash back. Most vapors are heavier than air. They will spread along ground and collect in low or confined areas (sewers, basements, tanks). Vapor explosion hazard indoors, outdoors or in sewers. Runoff to sewer may create fire or explosion hazard. Containers may explode when heated. Many liquids are lighter than water.
Flammability and Explosibility
Flammable
Chemical Reactivity
Reactivity with Water No reaction; Reactivity with Common Materials: No reaction; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent.
Contact allergens
Used as a polyvinyl chloride solvent, cyclohexanone caused contact dermatitis in a woman manufacturing PVC fluidotherapy bags. Cyclohexanone probably does not cross-react with cyclohexanone resin. A cyclohexanone-derived resin used in paints and varnishes caused contact dermatitis in painters
Safety Profile
Suspected carcinogen.
Moderately toxic by ingestion, inhalation,
subcutaneous, intravenous, and
intraperitoneal routes. A skin and severe eye
irritant. Human systemic effects by
inhalation: changes in the sense of smell,
conjunctiva irritation, and unspecified
respiratory system changes. Human irritant
by inhalation. Mdd narcotic properties have
also been ascribed to it. Human mutation
data reported. Experimental reproductive
effects. Flammable liquid when exposed to
heat or flame; can react vigorously with
oxidizing materials. Slight explosion hazard
in its vapor form, when exposed to flame.Reaction with hydrogen peroxide + nitric
acid forms an explosive peroxide. To fight
fire, use alcohol foam, dry chemical, or COa.
When heated to decomposition it emits
acrid smoke and irritating fumes. See also
KETONES and CYCLOHEXANE.
Synthesis
It may be synthesized on a laboratory scale by the oxidation of cyclohexanol.
Potential Exposure
May form explosive mixture with air.
Contact with oxidizing agents or nitric acid may cause a
violent reaction. Do not use brass, copper, bronze, or lead
fittings. Attacks many coatings and plastic materials.
Carcinogenicity
IARC considers the animal data for cyclohexanone as
inadequate evidence of carcinogenicity and listed cyclohexanone
as not classifiable for carcinogenicity (IARC
Category 3).
Environmental fate
Biological. In activated sludge inoculum, 96.0% COD removal was achieved. The average rate
of biodegradation was 30.0 mg COD/g?h (Pitter, 1976).
Photolytic. Atkinson (1985) reported an estimated photooxidation rate constant of 1.56 x 10-11
cm3/molecule?sec for the reaction of cyclohexanone and OH radicals in the atmosphere at 298 K.
Chemical/Physical. Cyclohexanone will not hydrolyze because it has no hydrolyzable
functional group.
At an influent concentration of 1,000 mg/L, treatment with GAC resulted in effluent
concentration of 332 mg/L. The adsorbability of the carbon used was 134 mg/g carbon (Guisti et
al., 1974). Similarly, at influent concentrations of 10, 1.0, 0.1, and 0.01 mg/L, the GAC adsorption
capacities were 36, 6.2, 1.1, and 0.19 mg/g, respectively (Dobbs and Cohen, 1980).
Shipping
UN1915 Cyclohexanone, Hazard Class: 3;
Labels: 3-Flammable liquid.
Purification Methods
Dry cyclohexanone with MgSO4,CaSO4, Na2SO4 or Linde type 13X molecular sieves, then distil it. Cyclohexanol and other oxidisable impurities can be removed by treatment with chromic acid or dilute KMnO4. More thorough purification is possible by conversion to the bisulfite addition compound, or the semicarbazone, followed by decomposition with Na2CO3 and steam distillation. [For example, equal weights of the bisulfite adduct (crystallised from water) and Na2CO3 are dissolved in hot water and, after steam distillation, the distillate is saturated with NaCl and extracted with Et2O which is then dried (anhydrous MgSO4 or Na2SO4), filtered and the solvent evaporated prior to further distillation.] FLAMMABLE [Beilstein 7 III 14, 7 IV 15.]
Incompatibilities
May form explosive mixture with air.
Contact with oxidizing agents or nitric acid may cause a
violent reaction. Do not use brass, copper, bronze, or lead
fittings. Attacks many coatings and plastic materials.
Waste Disposal
Dissolve or mix the material
with a combustible solvent and burn in a chemical incinera-
tor equipped with an afterburner and scrubber. All federal,
state, and local environmental regulations must be
observed.
Check Digit Verification of cas no
The CAS Registry Mumber 108-94-1 includes 6 digits separated into 3 groups by hyphens. The first part of the number,starting from the left, has 3 digits, 1,0 and 8 respectively; the second part has 2 digits, 9 and 4 respectively.
Calculate Digit Verification of CAS Registry Number 108-94:
(5*1)+(4*0)+(3*8)+(2*9)+(1*4)=51
51 % 10 = 1
So 108-94-1 is a valid CAS Registry Number.
InChI:1S/C6H10O/c7-6-4-2-1-3-5-6/h1-5H2
108-94-1Relevant articles and documents
Chemiluminescence-promoted oxidation of alkyl enol ethers by NHPI under mild conditions and in the dark
Anderson,Andia, Alexander A.,Woerpel
, (2021)
The hydroperoxidation of alkyl enol ethers using N-hydroxyphthalimide and molecular oxygen occurred in the absence of catalyst, initiator, or light. The reaction proceeds through a radical mechanism that is initiated by N-hydroxyphthalimide-promoted autoxidation of the enol ether substrate. The resulting dioxetane products decompose in a chemiluminescent reaction that allows for photochemical activation of N-hydroxyphthalimide in the absence of other light sources.
One-step hydroxylation of benzene to phenol via a Pd capillary membrane microreactor
Wang, Xiaobin,Tan, Xiaoyao,Meng, Bo,Zhang, Xiongfu,Liang, Qi,Pan, Hui,Liu, Shaomin
, p. 2380 - 2391 (2013)
A novel Pd capillary membrane microreactor for one-step hydroxylation of benzene to phenol was synthesized and investigated to showcase the effectiveness of 'Niwa concept'. Reaction parameters including H2/O2 ratio and temperature were systematically studied for their effects on benzene conversion and phenol yield. A detailed examination of different membrane reactors, feed mode and long-term reaction stability was also conducted. Pd capillary membrane displayed good stability for low temperature separation and reaction due to the excellent anchorage of Pd layer into the porous α-alumina support. An optimum H2/O2 ratio was identified at 473 K with the benzene conversion of 19.6% and phenol yield of 18.1%. An increase in reaction temperature caused not only an increase in benzene conversion but also a decrease in phenol selectivity. A comparison between our work and the literature results was also made to discuss the feasibility of the membrane reactor concept. Experimental results proved that narrow flow channels and larger Pd membrane surface area-to-volume ratios provided more effective area of Pd interface and promoted the radial diffusion of reactants, enabling the reactive species more opportunities to react directly with benzene resulting in high benzene conversion. The Royal Society of Chemistry 2013.
Improved Rhodium Hydrogenation Catalysts Immobilized on Oxidic Supports
Merckle,Bluemel
, p. 584 - 588 (2003)
Wilkinson-type rhodium hydrogenation catalysts immobilized on oxidic supports via mono-and bidentate phosphine linkers have been studied by 31P solid-state NMR, and their recycling stability and lifetime with respect to hydrogenation of 1-dodecene, 2-cyclohexen-1-one, and 4-bromostyrene have been improved substantially.
Synthesis of 1,1′-bishydroperoxydi(cycloalkyl) peroxides by homocoupling of 11-15-membered gem-bis(hydroperoxy)cycloalkanes in the presence of boron trifluoride
Terent'ev,Kutkin,Platonov,Starikova,Ogibin,Nikishin
, p. 1214 - 1218 (2005)
A procedure was developed for the synthesis of 1,1′- bishydroperoxydi(C11-C15-cycloalkyl) peroxides based on homocoupling of geminal 11-15-membered bis(hydroperoxy)cycloalkanes in the presence of BF3·OEt2.
Polypyrrole films containing rhodium(I) and iridium(I) complexes: Improvement in their synthesis and electrocatalytic activity in aqueous media
Hamar-Thibault, Sylvaine,Moutet, Jean-Claude,Tingry, Sophie
, p. 31 - 37 (1997)
Functionalized polypyrrole films containing M1(L)(diene)]+ complexes (M = rhodium or iridium, L = substituted 2,2′-bipyridine or 1,10-phenanthroline) have been synthesized by complexation of [M1(diene)CL]2 precu
Role of keto intermediates in the hydrodeoxygenation of phenol over Pd on oxophilic supports
De Souza, Priscilla M.,Rabelo-Neto, Raimundo C.,Borges, Luiz E. P.,Jacobs, Gary,Davis, Burtron H.,Sooknoi, Tawan,Resasco, Daniel E.,Noronha, Fabio B.
, p. 1318 - 1329 (2015)
The performance of Pd catalysts supported on SiO2, Al2O3 and ZrO2 for the hydrodeoxygenation (HDO) of phenol has been compared in the gas phase, at 300 °C and 1 atm using a fixed bed reactor. While Pd supported on SiO2 and Al2O3 exhibits high selectivity to cyclohexanone, when supported on an oxophilic support such as ZrO2, it favors the selectivity toward benzene, reducing the formation of ring-hydrogenated products, cyclohexanone and cyclohexanol. Diffuse reflectance infrared Fourier transform spectroscopy experiments support the participation of a keto-tautomer intermediate (2,4-cyclohexadienone) in the reaction. This intermediate can be hydrogenated in two different pathways. If the ring is hydrogenated, cyclohexanone and cyclohexanol are dominant products, as in the case of Pd/SiO2 and Pd/Al2O3 catalysts. By contrast, if the carbonyl group of the keto-intermediate tautomer is hydrogenated, benzene is directly formed via rapid dehydration of the unstable cyclohexadienol intermediate. This is observed in the case of Pd/ZrO2 catalyst. These results demonstrate that the selectivity for HDO of phenol can be controlled by using supports of varying oxophilicity. (Chemical Equation Presented).
Cobalt immobilized on hydroxyapatite as a low-cost and highly effective heterogeneous catalyst for alkenes epoxidation under mild conditions
Mekrattanachai, Pagasukon,Cao, Changyan,Li, Zhaohua,Li, Huining,Song, Weiguo
, p. 37303 - 37306 (2018)
Transition metal Co immobilized on hydroxyapatite with a loading of 0.05 wt% (denoted 0.05 wt% Co/HAP) could catalyze partial oxidation of cyclic alkenes, aromatic alkenes and aliphatic alkenes to yield epoxide products with excellent selectivity at 30 °C with O2 and iso-butyraldehyde as co-oxidant. The TOF value was as high as 6261 h?1 for epoxidation of cyclohexene. In addition, the prepared 0.05 wt% Co/HAP catalyst can be re-used at least 6 times without significant loss of catalytic activity and selectivity.
Catalytic Activity of a Polymerizable tris(β-ketoesterate)Iron(III) Complex towards the Oxidation of Organic Substrates
Mastrorilli, Piero,Nobile, Cosimo Francesco
, p. 4193 - 4196 (1994)
The facile oxidation of alkenes, aldehydes, cyclic ketones, alkanes, sulfides and alcohols is achieved by a polymerizable b-ketoesterato complex under Mukaiyama's conditions (atmospheric pressure of molecular oxygen in the presence of a sacrificial aldehyde at room temperature).
"Solvent-free" synthesis of thermally stable and hierarchically porous aluminophosphates (SF-APOs) and heteroatom-substituted aluminophosphates (SF-MAPOs)
Zhang, Pengling,Wang, Liang,Ren, Limin,Zhu, Longfeng,Sun, Qi,Zhang, Jian,Meng, Xiangju,Xiao, Feng-Shou
, p. 12026 - 12033 (2011)
Hierarchically porous aluminophosphates (SF-APOs) and metal substituted aluminophosphates (SF-MAPOs, M = Co, Fe, Cr) have been synthesized via simple grinding and heating in the absence of solvent. Characterization results show that these mesoporous aluminophosphates have a hierarchically microporous/mesoporous structure. In addition, metal atoms can be efficiently incorporated into the walls of mesoporous aluminophosphates, and the SF-CoAPO sample shows high catalytic activity in cyclohexene oxidation compared with microporous samples. Special features of the "solvent-free" synthesis route, such as increasing product yield, saving energy, elimination of pollution, and convenience for incorporation of heterogeneous atoms, ensure its great potential in the synthesis of porous materials. The Royal Society of Chemistry 2011.
ORGANOBORANES FOR SYNTHESIS. 4. OXIDATION OF ORGANOBORANES WITH PYRIDINIUM CHLOROCHROMATE. A DIRECT SYNTHESIS OF ALDEHYDES FROM TERMINAL ALKENES VIA HYDROBORATION
Brown, Herbert C.,Kulkarni, Surendra U.,Rao, C. Gundu,Patil, Vemanna D.
, p. 5515 - 5522 (1986)
The oxidation of trialkylboranes containing primary alkyl groups with pyridinium chlorochromate (PCC) in methylene chloride provides the corresponding aldehydes in good yields.The stoichiometry for the oxidation of alcohols, borate esters and trialkylboranes with PCC has been examined.In view of the poor regioselectivity (only 94percent primary alkyl groups) and functional group tolerance observed in the hydroboration with borane (BH3*THF or BH3*SMe2), a more selective hydroborating agent, bis(3-methyl-2-butyl)borane (disiamylborane), was utilized for the preparation of aldehydes from terminal alkenes.However, the formation of 3-methyl-2-butanone as a by-product, and the requirement of six moles of PCC per mole of aldehyde are major disadvantages in this method.This difficulty was circumvented by employing monochloroborane-dimethyl sulfide for hydroboration.This reagent exhibits high regioselectivity (> 99percent primary alkyl groups) in the hydroboration of terminal alkenes.Oxidation of the resulting dialkylchloroborane following hydrolysis affords the desired aldehydes in satisfactory yields.Consequently, the hydroboration of terminal alkenes, followed by PCC oxidation, represents a direct convenient method for the transformation of alkenes into the corresponding aldehydes.
