Cyclohexylamine Chemical Properties
- Melting point:
- -17 °C
- Boiling point:
- 134 °C(lit.)
- 0.867 g/mL at 25 °C(lit.)
- vapor density
- 3.42 (vs air)
- vapor pressure
- 10 mm Hg ( 22 °C)
- refractive index
- Flash point:
- 90 °F
- storage temp.
- Flammables area
- organic solvents: miscible
- 10.66(at 24℃)
- 11.5 (100g/l, H2O, 20℃)
- explosive limit
- Water Solubility
- Air Sensitive
- Exposure limits
- TLV-TWA 10 ppm (～40 mg/m3) (ACGIH).
- CAS DataBase Reference
- 108-91-8(CAS DataBase Reference)
- NIST Chemistry Reference
- EPA Substance Registry System
- Cyclohexylamine (108-91-8)
- Hazard Codes
- Risk Statements
- Safety Statements
- UN 2357 8/PG 2
- WGK Germany
- Autoignition Temperature
- 559 °F
- HS Code
- 2921 30 10
- Hazardous Substances Data
- 108-91-8(Hazardous Substances Data)
- LD50 orally in rats: 0.71 ml/kg (Smyth)
Cyclohexylamine Usage And Synthesis
Physical and Chemical Properties
Cyclohexylamine is a kind of transparent and colorless liquid with a strong fishy taste and ammonia-like smelling. It is flammable with a relative molecular mass being 99.18, the relative density being 0.8191, the melting point being-17.7 ℃, boiling point being 134.5 ℃, 118.9 ℃ (6.67 × 104Pa), 102.5 ℃ (4.00 × 104Pa), 72.0 ℃ (1.33 × 104Pa), 56.0 ℃ (6.67 × 103Pa), 45.1 ℃ (4.00 × 103Pa), 41.3 ℃ (3.33 × 103Pa ), 36.4 ℃ (2.67 × 103Pa), 30.5 ℃ (1.99 × 103Pa), 25.0 ℃ (1.17 × 103Pa), the refractive index being 1.4372, the flash point being 32 ℃ and the ignition point being 265 ℃. It is soluble in water and can be miscible with common organic solvents such as ethanol, ethyl ether, acetone, ethyl acetate, chloroform, heptane, benzene and the like. Cyclohexylamine can be evaporated together with the steam and can absorb the carbon dioxide in the air to form a white crystalline carbonate. It can form azeotrope with water with the co-boiling point being 96.4 ℃ and water content being 55.8%. Its aqueous solution is alkaline. The pH of 0.01% aqueous solution of 0.01% is 10.5. Its steam can form explosive mixture with air. This product is toxic and irritating to the skin and mucous membranes, causing gangrene; inhaling its vapors has a narcotic effect but without causing blood poisoning. Rat oral administration: LD50: 710 mg/kg. The maximal allowable concentration in workplace is 10 × 10-6.
Heating cyclohexylamine together with hydrogen iodide in a sealed tube at 200 ℃ can generate methyl cyclopentane. Heating cyclohexylamine together with dimethyl sulfate in ether generate methyl cyclohexane and a small amount of dimethyl cyclohexylamine as well. Its hydrochloride can have reaction with sodium nitrite salt to generate cyclohexanol. Its reaction with excess amount of ammonia and zinc chloride can generate 2-methyl-pyridine.
Preparation: they finished product of cyclohexylamine can produced through catalyzing the reduction action of aniline at a high temperature and high pressure (with nickel or cobalt as the catalyst); it can also be produced by taking the cyclohexanol and cyclohexanone as the raw material produced from catalytic reduction of phenol, and further go through amination action with ammonia to prepare it. In industry, cyclohexylamine is mainly used as the thiazole vulcanization accelerator of rubber as well as being used as the tank cleaning agent, dyeing auxiliaries and surfactants.
The above information is edited by the Chemicalbook of Dai Xiongfeng.
The main purpose
Cyclohexylamine can be used as the raw materials of surfactants for production of alkylbenzene sulfonate for being used as emulsifier and foaming agent;
It can be used as the raw materials of making perfume for production of cyclohexyl allyl propionate;
It can be used as the raw materials of production of dye such as being used for production of Acidic Blue 62, disperse fluorescent yellow, fluorescent yellow dispersion H5GL, weak acid blue BRN, Disperse Blue 6 and dye additives;
It can be used as the raw material of food additives sweeteners; cyclohexylamine can also be used to produce cyclohexylamine sulfonate salts and Sodium Cyclamate; the later one is a sweeter which is 30 times as sweet as sucrose. The Ministry of health of China has approved it for being applied to pickles, sauces, wine preparation, cakes, biscuits, bread, frozen drinks, beverage with the maximum allowable amount being 0.65g /kg.
It can be used as the raw materials of pesticide such as insecticide "propargite" for fruit tree production, herbicides “WilBur” and bactericidal agent;
It can be used in the preparation of the additives used in petroleum products, the treatment agent of boiler feed water and corrosion remover;
It can be used as the raw material for production of thiazole vulcanization accelerator of rubber CZ; this kind of vulcanization accelerator has an excellent efficacy which is especially suitable for SBR and FDA rubber.
It can be used as a rust inhibitor for producing anti-rust paper;
It can be used as a tank cleaning agent;
It can be use as antifreeze agent;
It can be used as Antistatic agents (Textile auxiliaries), latex agglutination agents and additives for petroleum products;
Owing to the alkalinity of the cyclohexylamine aqueous solution, it can be used as the absorber for removing carbon dioxide and sulfur dioxide.
It is colorless liquid with an unpleasant odor. It is miscible with various kinds of organic solvents.
It can be used as the vulcanization accelerator of rubber; and also used as the raw material of synthetic fibers, dyes, and gaseous-phase corrosion inhibitor.
It can be used for the manufacture of dyes, softener VS and drugs such as Antiradon, thio-TEPA and solaziquone; it can also be used in medicine, pesticides.
Cyclohexylamine is the intermediate of herbicides “Hexazinone” as well as the intermediate of rubber accelerators, oil additives, and corrosion inhibitors.
This product can be used for the preparation of cyclohexanol, cyclohexanone, caprolactam, cellulose acetate and nylon 6 and the like. Cyclohexylamine itself is a solvent and can be used in resins, paints, fat, and paraffin oils. It can also be used for making desulfurization agent, rubber antioxidant, vulcanization accelerator, chemical auxiliaries of plastics and textile, the treatment agent of boiler feed water, metal corrosion inhibitors, emulsifiers, preservatives, anti-static agents, latex coagulants, oil additives , fungicides, pesticides and dye intermediates. The sulfonate salt of cyclohexylamine can be used as artificial sweeteners for being applied to foods, beverages and pharmaceuticals.
It can be used in organic synthesis, plastic synthesis, also used as a preservative and acid gas absorbent.
It can be used for the production of water treatment chemicals, artificial sweeteners, and the intermediate of rubber processing chemicals and agrochemicals.
It can be used as acidic gas absorbent for organic synthesis.
It is derived from the catalyzed hydrogenation of aniline. The process can be divided into normal pressure method and reduced pressure method. In addition, other routes such as the catalytic aminolysis of either cyclohexane or cyclohexanol, the reduction of nitro cyclohexane, and the catalyzed aminolysis of cyclohexanone can also be applied for produce cyclohexylamine.
The preparation method is using aniline as raw materials and going through catalytic hydrogenation. Mix the aniline vapor and hydrogen gas and pour into the catalytic reactor; carry out the hydrogenation reaction at 130 to 170 ℃ in the presence of a cobalt catalyst with the finished product obtained after cooling and further distillation.
Oral-rat LD50: 156 mg/kg; Oral-Mouse LD50: 224 mg/kg
Skin-rabbit 2 mg/24 hours Mild; Eyes-Rabbit 0.05 mg/24 hours, severe.
Hazardous characteristics of explosive
Being mixed with air can be explosive.
Flammability and hazard characteristics
it is flammable in case of fire, heat, and oxidants with combustion producing toxic fumes of nitrogen oxides.
Treasury: ventilation, low-temperature and drying; store it separately with oxidants and acids.
Dry powder, dry sand, carbon dioxide, foam, 1211 fire extinguishing agent.
TWA 40 mg/m3
Cyclohexylamine is a colorless to yellow liq- uid (amines, primary aromatic). It has an unpleasant fishy odor.
Cyclohexylamine is a derivative of ammonia in which one of the hydrogen atoms
has been replaced with a six-carbon, saturated ring. It is a very strong base and
forms salts with all acids, including carbon dioxide which it rapidly absorbs from
the air. It undergoes the usual reaction of aliphatic amines with carbon disulfide to
form dithiocarbamates. Cyclohexylamine reacts with long-chain fatty acids to form
soaps (Carswell and Morrill 1937). With nitrous acid, it forms cyclohexanol with
the release of nitrogen (Schweizer 1978). Cyclohexylamine reacts with organic
compounds containing an active halogen atom, acid anhydrides, and alkylene
oxides to replace one or both hydrogens on the nitrogen atom.
Cyclohexylamine attacks all copper alloys and lead. When hot, it attacks aluminum very slowly (Carswell et al 1937).
In organic synthesis, manufacture of insecticides, plasticizers, corrosion inhibitors, rubber chemicals, dyestuffs, emulsifying agents, dry-cleaning soaps, acid gas absorbents.
Cyclohexylamine is used in the manufactureof a number of products, including plasticizers, drycleaning soaps, insecticides, andemulsifying agents. It is also used as a cor rosion inhibitor and in organic synthesis.
ChEBI: A primary aliphatic amine consisting of cyclohexane carrying an amino substituent.
Cyclohexylamine is produced by the reaction of ammonia and cyclohexanol at elevated temperature and pressure in the presence of a silica-alumina catalyst (SRI 1985). It is also prepared by a similar process of catalytic hydrogenation of aniline at elevated temperature and pressure. Fractionation of the product of this reaction yields CHA, aniline, and a high-boiling residue containing n-phenylcyclohexylamine and dicyclohexylamine (Carswell and Morrill 1937). In 1982, U.S. production was 4.54 metric tons and 739.3 metric tons were imported into the U.S. (SRI 1985).
A clear colorless to yellow liquid with an odor of ammonia. Flash point 90°F. Irritates the eyes and respiratory system. Skin contact may cause burns. Less dense than water. Vapors heavier than air. Toxic oxides of nitrogen produced during combustion.
Air & Water Reactions
Highly flammable. Sensitive to air and light. Soluble in water.
Cyclohexylamine neutralizes acids in exothermic reactions to form salts plus water. May be incompatible with isocyanates, halogenated organics, peroxides, phenols (acidic), epoxides, anhydrides, and acid halides. Flammable gaseous hydrogen may be generated in combination with strong reducing agents, such as hydrides.
This is classified as very toxic -- probable oral lethal dose is 50-500 mg/kg or between 1 teaspoon and 1 ounce for a 70 kg (150 lb.) person. It is considered a nerve poison. This is a weak methemoglobin-forming substance.
When humans were exposed to a 25% solution of aqueous cyclohexylamine in
skin patch tests, irritation was reported as severe and sensitization as slight
(Malette and von Haam 1952). Exposure to high concentrations may cause nausea
and narcotic effects (Windholz et al 1983). Three cases of transitory systemic toxic
effects due to acute accidental industrial exposure have been reported (Watrous
and Schultz 1950). Victims reported lightheadedness, drowsiness, anxiety, apprehension
and nausea. One person suffered from slurred speech, vomiting and
pupillary dilation. Workers exposed to 4 to 10 p.p.m. however, had no negative
Oral administration of cyclohexylamine (5 and 10 mg/kg) to adult male humans caused headache, blurring of vision and shivering in the exposed subjects (Eichelbaum et al 1974).
When cyclohexylamine was administered orally to humans (2.5, 5.0 and 10 mg/kg), a dose-dependent rise in arterial blood pressure was observed (Eichelbaum et al 1974). The investigators calculated that plasma levels of cyclohexylamine of 0.7 to 0.8 μg/ml were required to cause a significant increase. Only the highest dose (11 mg/ml) produced a significant increase in plasma free fatty acids and cumulative excretion of catecholamines. These data suggest that cyclohexylamine is an indirect acting sympathomimetic substance, although of relatively low potency and are in good correlation with results obtained from animal studies (Classen and Marquardt 1969; Rosenblum and Rosenblum 1968a, 1968b; Wechsler et al 1969; Yamamura et al 1968).
Cyclohexylamine is a severe irritant to theeyes, skin, and respiratory passage. Skincontact can produce burns and sensitization;contact of the pure liquid or its concentratedsolutions with the eyes may cause loss ofvision.
The acute oral and dermal toxicity ofcyclohexylamine was moderate in test sub jects. The toxic effects include nausea, vom iting, and degenerative changes in the brain,liver, and kidney. Inhalation of its vaporsat high concentrations may cause a narcoticeffect.
LD50 value, oral (rats): 156 mg/kg
LD50 value, skin (rabbits): 277 mg/klg
Cyclohexylamine may be mutagenic, thetest for which has so far given inconclusiveresults. Administration of this compoundin animals produced a reproductive effect,including embryotoxicity and a reductionin male fertility. Intraperitoneal injectionof the amine in rats caused a dose dependent increase in chromosomal breaks.Roberts and coworkers (1989) studied themetabolism and testicular toxicity of cyclohexylamine (a metabolite of cyclamate)in rats and mice. Chronic dietary administration of 400 mg/kg/day for 13 weeksshowed decrease in organ weigh, histological changes, and testicular atrophy in boththe Wistar and dark agouti DA rats, but to awidely varying extent, while mice exhibitedno evidence of testicular damage.
There is no evidence of carcinogenicityin animals or humans caused by cyclohexy lamine.
When heated to decomposition, Cyclohexylamine emits highly toxic fumes. Vapor may travel a considerable distance to source of ignition and flash back. Toxic oxides of nitrogen are produced during combustion. Nitric acid; reacts vigorously with oxiding materials. Stable, avoid physical damage, storage with oxidizing material.
The primary use of cyclohexylamine is as a corrosion inhibitor in boiler water treatment and in oil field applications (HSDB 1989). It is also a chemical intermediate for rubber processing chemicals, dyes (acid blue 62, former use), cyclamate artificial sweeteners and herbicides and a processing agent for nylon fiber production (SRI 1985). Windholz et al (1983) reports its use in the manufacture of insecticides, plasticizers, emulsifying agents, dry-cleaning soaps, and acid gas absorbents.
A poison by ingestion, skin contact, and intraperitoneal routes. Experimental teratogenic and reproductive effects. A severe human skin irritant. Can cause dermatitis and convulsions. Human mutation data reported. Questionable carcinogen. Flammable liquid. Dangerous fire hazard when exposed to heat, flame, or oxidizers. To fight fire, use alcohol foam, CO2, dry chemical. When heated to decomposition it emits toxic fumes of NOx.
CHA is used in making dyes, chemi- cals, dry cleaning chemicals; insecticides, plasticizers, rub- ber chemicals; and as a chemical intermediate in the production of cyclamate sweeteners. Used in water treat- ment and as a boiler feedwater additive. It is also used in rubber production to retard degradation.
According to the International Agency for Research of
Cancer (IARC) working group, there is no evidence that
cyclohexylamine is teratogenic or carcinogenic.
Price et al. reported the development of bladder tumors in Charles River rats fed cyclohexylamine sulfate for 2 years at doses of 0, 0.15, 1.5, and 15 mg/kg/day, 25 male and 25 female per dosage group. During the first year, there was only a slight depression of weight gain in the males of the high-dose group; no other signs of toxicity were observed. At the end of 2 years (104 weeks) 13–16 animals were still alive in the 0.15- and 1.5- mg/kg groups, and eight males and nine females in the 15- mg/kg group. An invasive transitional-cell carcinoma of the bladder was observed in one of eight male survivors of the high-dose group. The author noted that spontaneous bladder tumors were very rare in the strain of rats used. No other relevant findings were noted. Gaunt used the same dosages for a 2 year diet feeding study in Wistar rats. They observed no evidence of carcinogenicity, slight anemia, failure to produce normally concentrated urine, and an increase in the number of animals with foamy macrophages in the pulmonary alveoli at the highest dosage level. Decreased food intake caused the lessened body weight gain and organ weights as compared to the controls. Animals that received 2000 or 6000 ppm showed testicular atrophy or tubules with few spermatids. The no-untoward-effect level in both of these studies was 600 ppm, equivalent to an intake of about 30 mg/kg/day.
Cyclamate is metabolized
to cyclohexylamine by the gut flora in the rat (Renwick and Williams 1969;
Bickel et al 1974; Tesoriero and Roxon 1975) and is excreted in the urine after
cyclamate ingestion by rats, rabbits, dogs, monkeys, and humans (Asahina et al
1971; Coulston et al 1977; Kojima and Ichibagase 1968; Leahy et al 1967; Oser et
al 1968). There is individual variation in the ability to biotransform cyclamate to
cyclohexylamine, probably due to the presence or absence of the necessary
bacteria. Bacteria exposed to cyclamate seem to acquire the ability to convert
cyclamate. Those individuals that do produce cyclohexylamine have been categorized
by researchers as convertors. Rhesus monkeys fed cyclamate for eight years
converted 0.5% of the dose to cyclohexylamine which in turn was metabolized to
cyclohexanone and cyclohexanol to the extent of 1-2% (Coulston et al 1977).
Generally, cyclohexylamine is readily absorbed and rapidly excreted from the body. After administration to rats, cyclohexylamine appears in body tissues with the highest concentrations in the lungs, spleen, liver, adrenals, heart, gastrointes- tinal tract and kidneys (Estep and Wiegand 1967 as reported by Bopp et al 1986).
After oral administration (0.2 g/kg) to rabbits, cyclohexylamine gave rise to unchanged cyclohexylamine and 7V-hydroxycyclohexylamine in the urine (Elliott et al 1968). When [14C]-labelled cyclohexylamine was administered, 68% of the radioactivity was recovered in the urine after 60 h. A small amount (0.5%) was eliminated in the breath and 45% of the administered dose was shown to be excreted in the urine as unconjugated cyclohexylamine, 0.2% as JV-hydroxycyclohexylamine in conjugated form, and 2.5% as cyclohexanone oxime. The authors postulated the latter metabolite to be an artifact formed from the glucuronide of TV-hydroxy cyclohexylamine during the hydrolysis procedure.
In contrast to rabbits, man, as well as rats and guinea pigs, excrete 90% or more of a dose of [14C]-labelled cyclohexylamine unchanged in the urine (Renwick and Williams 1972). Small amounts of radioactivity were found in the feces, 1% or less in man, rat and rabbit, and 4-7% in the guinea pig. Only 4-5% of the dose was metabolized in 24 h in the rat and guinea pig and 1-2% in man. The metabolites identified indicated that in rats, the metabolism of cyclohexylamine was mainly through hydroxylation of the cyclohexane ring, in man by deamination and in guinea pigs and rabbits by ring hydroxylation and deamination. The metabolites to cyclohexylamine were excreted in both free and conjugated forms.
When cyclohexylamine was administered orally to healthy adult humans at doses of 2.5, 5, and 10 mg/kg body weight, 86-95% of the dose was excreted in the urine in 48 h as unchanged cyclohexylamine (Eichelbaum et al 1974). Dose dependency was shown by the plasma half-lives which ranged from 3.5 to 4.8 h. A study by Roberts and Renwick (1985) showed other species and strain differences in metabolism of cyclohexylamine. After administration of [14C]- cyclohexylamine (35-500 mg/kg) to male mice and rats, 80% of the dose was excreted in the urine 24 h after dosing. In Wistar rats, 14-19% of the 14C was present as 3- and 4-aminocyclohexanols, while in the DA strain rat, aminocyclohexanols accounted for only 1-2% of the activity, and in mouse, <1%. Dose or route of administration did not significantly affect metabolism.
When [14C]-cyclohexylamine hydrochloride was administered to pregnant rhesus monkeys by infusion into the antecubital vein, maternal and fetal levels of radioactivity were virtually identical over a period of 6 h (Pitkin et al 1969) indicating that cyclohexylamine freely crosses the hemochorial placenta.
Rabbit liver microsomes have been shown to deaminate cyclohexylamine to cyclohexanone in the presence of NADPH and molecular oxygen (Kurebayashi et al 1979). The hexanone was then reduced to the alcohol (approximately 75% of the deaminated product). Carbon monoxide, SKF 525A, metyrapone, potassium cyanide and mercuric chloride inhibited the deamination. These results suggest that the deamination is catalyzed by a microsomal cytochrome P-450 monooxygenase system.
UN2357 Cyclohexylamine, Hazard class: 8; Labels: 8-Corrosive material, 3-Flammable liquid.
Dry the amine with CaCl2 or LiAlH4, then distil it from BaO, KOH or Na, under N2. Also purify it by conversion to the hydrochloride (which is crystallised several times from water), then liberation of the amine with alkali and fractional distillation under N2. The hydrochloride has m 205-207o (dioxane/EtOH). [Lycan et al. Org Synth Coll Vol II 319 1943, Beilstein 12 III 10, 12 IV 8.]
May form explosive mixture with air. Cyclohexylamine is a strong base: it reacts violently with acid. Contact with strong oxidizers may cause fire and explosion hazard. Incompatible with organic anhydrides; isocyanates, vinyl acetate; acrylates, substituted allyls; alkylene oxides; epichlorohydrin, ketones, aldehydes, alco- hols, glycols, phenols, cresols, caprolactum solution; lead. Corrosive to copper alloys, zinc, or galvanized steel.
Incineration; incinerator equipped with a scrubber or thermal unit to reduce nitrogen oxides emissions.
Cyclohexylamine Preparation Products And Raw materials
- O,O-diisopropyl hydrogen dithiophosphate, compound with cyclohexylamine (1:1)
- N-[[5-(dimethylamino)-1-naphthyl]sulphonyl]-L-methionine, compound with cyclohexylamine (1:1)
- TRANS-2-AMINOCYCLOHEXANOL HYDROCHLORIDE
- 1-Amino-1-cyclohexanecarboxylic acid
- Sodium N-cyclohexylsulfamate
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