109-73-9 Usage
Chemical Description
Butylamine and cyclohexylamine are organic compounds used as solvents and reagents in chemical reactions.
Description
n-Butylamine is one of the four isomeric amines of butane, the others being sec-butylamine,
tert-butylamine, and isobutylamine. It is a colourless to yellow liquid and is highly
flammable. It is stable and incompatible with oxidising agents, aluminium, copper, copper
alloys, and acids. n-Butylamine finds its uses in the manufacture of pesticides (such as
thiocarbazides), pharmaceuticals, and emulsifiers. It is also a precursor for the manufacture
of N,N′-dibutylthiourea, a rubber vulcanisation accelerator, and n-butylbenzenesulphonamide,
a plasticiser of nylon.
Chemical Properties
n-Butylamine is a derivative of ammonia in which one of the hydrogen atoms is
replaced with an alkyl group of four carbons. As such, it reacts with water and
acids to form bases and salts, respectively. Acting as a very weak acid, it can react
with acyl halides, anhydrides, and esters. With carbon disulfide and carbon
dioxide, it forms the butyl ammonium salt of dithiocarbamic and carbamic acids,
respectively. With isocyanic acid and alkyl or aryl isocyanates, it forms substituted
ureas. When reacted with nitrous acid, rc-butylamine forms butyl alcohol with the
release of nitrogen (Schweizer et al 1978).
In the presence of water, rc-butylamine may corrode some metals (General
Electric Co 1986) and attack glass (Schweizer et al 1978). Liquid n-butylamine
also will attack some forms of plastics, rubber, and coatings (NIOSH 1981).
Physical properties
Butylamine has an ammoniacal odor (fishy, pungent). Clear, colorless liquid with a strong or pungent, ammonia-like odor. Slowly becomes pale yellow on prolonged storage. Experimentally determined detection and recognition odor threshold concentrations were 240 μg/m3 (80 ppbv) and 720 μmg/m3 (240 ppbv), respectively (Hellman and Small, 1974).
Occurrence
Reported found in mulberry leaves, kale, tomato, tilsit cheese, cheddar and other cheeses, caviar, fish, cooked
chicken, cooked beef, beer, sherry and red wine.
Uses
Different sources of media describe the Uses of 109-73-9 differently. You can refer to the following data:
1. n-Butylamine is used as an intermediatefor various products, including dyestuffs,pharmaceuticals, rubber chemical, synthetictanning agents, and emulsifying agents. It isused for making isocyanates for coatings.
2. Intermediate for pharmaceuticals, dyestuffs, rubber chemicals, emulsifying agents, insecticides, synthetic tanning agents.
Definition
ChEBI: A primary aliphatic amine that is butane substituted by an amino group at position 1.
Production Methods
n-Butylamine is usually manufactured by the catalytic alkylation of ammonia with
butyl alcohol, or similarly from butyraldehyde and ammonia in the presence of
Raney nickel. U.S. production in 1982 was approximately 1109 metric tons (SRI
1985). Some n-butylamine is also produced as a result of fertilizer manufacture,
fish processing, rendering plant operations, and sewage treatment and has been
reported to be a component of animal waste (Graedel 1978).
Preparation
Catalytic alkylation of ammonia with butyl alcohol.
Aroma threshold values
Detection: 50 ppm
General Description
A clear colorless liquid with an ammonia-like odor. Flash point 10°F. Less dense (6.2 lb / gal) than water. Vapors heavier than air. Produces toxic oxides of nitrogen during combustion.
Air & Water Reactions
Highly flammable. Dissolves in water with evolution of heat. The resulting solutions are basic.
Reactivity Profile
N-BUTYL AMINE reacts violently with strong oxidizing agents and acids. Attacks copper and copper compounds [Handling Chemicals Safely 1980 p. 123]. Reacts with hypochlorites to give N-chloroamines which may be explosive when isolated [Bretherick 1979 p. 108].
Hazard
Skin irritant. Flammable, dangerous fire
risk. Eye and upper respiratory tract irritant.
Health Hazard
n-Butylamine is a severe irritant to the eyes,skin, and respiratory tract. Contact of theliquid with the skin and eyes can producesevere burns. Irritation effect on rabbits’ eyeswas as severe as that produced by ethylamine(ACGIH 1986). Exposure can cause irritationof the nose and throat, and at high concen trations, pulmonary edema. Scherberger andassociates (1960) have reported erythema ofthe face and neck occurring within 3 hoursafter exposure to n-butylamine, along with aburning and itching sensation.n-Butylamine is more toxic than is eithern-propylamine or ethylamine. A 4-hourexposure to 3000-ppm concentration in airwas lethal to rats. Toxic symptoms in animalsfrom ingestion include increased pulse rate,labored breathing, and convulsions. Cyanosisand coma can occur at near-lethal dose.LD50 value, oral (rats): 366 mg/kgLD50 value, skin (guinea pigs): 366 mg/kg.
Flammability and Explosibility
Flammable
Chemical Reactivity
Reactivity with Water No reaction; Reactivity with Common Materials: May corrode some metals in presence of water; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Flush with water; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent.
Industrial uses
n-Butylamine is an important intermediate in the production of pharmaceuticals,
dyestuffs, synthetic tanning agents, insecticides, emulsifying agents, rubber accelerators,
vulcanizing agents, and antioxidants (HSDB 1988). A flavor ingredient
in seafood and chocolate, n-butylamine is also reported to be used in alcoholic
beverages, ice cream, candy, baked goods, gelatins, and puddings all at a concentration
of 0.1 p.p.m. (Fenaroli 1975). It is estimated that 50% of the n-butylamine
produced is used for rubber processing chemicals and 50% as an intermediate in
pesticide production (SRI 1982).
Potential Exposure
Alert: (n-isomer): Possible risk of
forming tumors, suspected of causing genetic defects, suspected reprotoxic hazard, Primary irritant (w/o allergic
reaction), (sec-isomer): Drug. n-Butylamine is used in
pharmaceuticals; dyestuffs, rubber, chemicals, emulsifying
agents; photography, desizing agents for textiles; pesticides, and synthetic agents. sec-Butylamine is used as a
fungistate. tert-Butylamine is used as a chemical intermediate in the production of tert-Butylaminoethyl methacrylate
(a lube oil additive); as an intermediate in the production
of rubber and in rust preventatives and emulsion deterrents
in petroleum products. It is used in the manufacture of
several drugs
Carcinogenicity
The concentrated liquid produced severe
eye damage and skin burns in animals.
Environmental fate
Photolytic. Low et al. (1991) reported that the photooxidation of aqueous primary amine
solutions by UV light in the presence of titanium dioxide resulted in the formation of ammonium
and nitrate ions.
Chemical/Physical. Reacts with mineral acids forming water-soluble salts.
At an influent concentration of 1.0 g/L, treatment with GAC resulted in effluent concentration
of 480 mg/L. The adsorbability of the carbon used was 103 mg/g carbon (Guisti et al., 1974).
Metabolism
Considering the industrial importance of this amine, it is surprising that no
thorough studies of its metabolism have been completed. Aliphatic amines, in
general, are well-absorbed from the gut and respiratory tract and readily metabolised
(Beard and Noe 1981; Magos and Manson 1983). After oral administration of
n-butylamine hydrochloride to humans, little n-butylamine was recovered in the
urine (Rechenberger 1940) suggesting that extensive metabolism occurs. Deamination
of n-butylamine has been shown to occur in slices of rat liver and brain cortex
(Pugh and Quastel 1937). It is assumed that monoamine oxidase plays a role in the
detoxication process by catalyzing the deamination of n-butylamine to ammonia,
hydrogen peroxide, and butyraldehyde. The ammonia produced is then converted
to urea and the hydrogen peroxide is reduced by catalase. The aldehyde is
probably converted to the corresponding carboxylic acid by aldehyde oxidase
(Beard and Noe, 1981).
Solubility in water
Butylamine can dissolve in water by forming hydrogen bonds with water. Oxygen atoms in water hydrogen-bond to hydrogen atoms on the amine group.
storage
n-Butylamine should be protected against physical damage. Store in a cool, dry, wellventilated location, away from any area where the fi re hazard may be acute. Outside or
detached storage is preferred. Separate from incompatibles. Containers should be bonded
and grounded for transfer to avoid static sparks.
Shipping
UN1125 n-Butylamine, Hazard Class: 3; Labels:
3—Flammable liquid, 8—Corrosive material. UN2014
Isobutylamine, Hazard Class: 3; Labels: 3—Flammable
liquid, 8—Corrosive material
Purification Methods
Dry it with solid KOH, K2CO3, LiAlH4, CaH2 or MgSO4, then reflux it with, and fractionally distil it from P2O5, CaH2, CaO or BaO. Further purification is by precipitation as the hydrochloride, m 213-213.5o, from ethereal solution by bubbling HCl gas into it. This is re-precipitated three times from EtOH by adding ether, followed by liberation of the free amine using excess strong base. The amine is extracted into ether, which is separated, dried with solid KOH, the ether removed by evaporation and then the amine is distilled. It is stored in a desiccator over solid NaOH [Bunnett & Davis J Am Chem Soc 82 665 1960, Lycan et al. Org Synth Coll Vol II 319 1943]. [Beilstein 4 IV 540.] SKIN IRRITANT.
Incompatibilities
May form explosive mixture with air.
May accumulate static electrical charges, and may causeignition of its vapors. n-Butylamine is a weak base; reacts
with strong oxidizers and acids, causing fire and explosion
hazard. Incompatible with organic anhydrides; isocyanates,
vinyl acetate; acrylates, substituted allyls; alkylene oxides;
epichlorohydrin, ketones, aldehydes, alcohols, glycols, phenols, cresols, caprolactum solution. Attacks some metals in
presence of moisture. The tert-isomer will attack some
forms of plastics
Waste Disposal
Use a licensed professional
waste disposal service to dispose of this material. Dissolve
or mix the material with a combustible solvent and burn in
a chemical incinerator equipped with an afterburner andscrubber. All federal, state, and local environmental regulations must be observed.
Check Digit Verification of cas no
The CAS Registry Mumber 109-73-9 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 9 respectively; the second part has 2 digits, 7 and 3 respectively.
Calculate Digit Verification of CAS Registry Number 109-73:
(5*1)+(4*0)+(3*9)+(2*7)+(1*3)=49
49 % 10 = 9
So 109-73-9 is a valid CAS Registry Number.
InChI:InChI=1/C4H11N/c1-2-3-4-5/h2-5H2,1H3/p+1
109-73-9Relevant articles and documents
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Vaughan et al.
, p. 819,821 (1955)
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Kinetics of Amine Addition to Benzylidenemalonodialdehyde in 50percent Me2SO-50percent water
Bernasconi, Claude F.,Stronach, Michael W.
, p. 1993 - 2001 (1991)
The kinetics of the reaction of benzylidenemalonodialdehyde with piperidine, morpholine, n-butylamine, 2-methoxyethylamine, glycinamide, glycine ethyl ester, cyanomethylamine, and semicarbazide have been determined in 50percent aqueous Me2SO at 20 deg C.The reaction leads to a zwitterionic adduct, PhCH(RR'NH(1+))C(CHO)2(1-) (TA(+/-)), that is in fast acid-base equilibrium with the anionic adduct, PhCH(RR'N)C(CHO)2(1-) (TA(1-)).With strongly basic amines at high pH there is also attack of the amine on one of the carbonyl groups, which acts as a rapid preequilibrium.Rate constants for the formation of TA(+/-) (k1) and its reverse (k-1), as well as equilibrium constants (K1 = k1/k-1) and the pKa of TA(+/-) were determined for all the amines.Intrinsic rate constants (k0 = k1 = k-1 when K1 = 1) were calculated.The intrinsic rate constants are lower than those for amine addition to benzylidene Meldrum's acid.This is consistent with the greater role played by resonance in stabilizing TA(+/-) derived from benzylidenemalonodialdehyde.However, k0 for piperidine/morpholine addition to benzylidenemalonodialdehyde is much higher than for the reaction of benzylideneacetylacetone with the same amines, indicating that the rate-depressing effect of intramolecular hydrogen bonding in TA(+/-) derived from benzylidenemalonodialdehyde is much smaller than that in TA(+/-) derived from benzylideneacetylacetone.Even though semicarbazide is an α-effect nucleophile, no enhancement of k1 was observed, but K1, estimated on the basis of a structure-reactivity relationship, is larger than expected based on the pKa of the amine.This result is attributed to a low νnucn value.
-
Davis,Yelland
, p. 1998 (1937)
-
Kinetic and equilibrium studies of σ-adduct formation and nucleophilic substitution in the reactions of trinitro-activated benzenes with aliphatic amines in acetonitrile
Crampton, Michael R.,Lord, Simon D.
, p. 369 - 376 (1997)
Rate and equilibrium constants are reported for reactions in acetonitrile of butylamine, pyrrolidine and piperidine with 1,3,5-trinitrobenzene, 1, and with ethyl 2,4,6-trinitrophenyl ether, 4a, and phenyl 2,4,6-trinitrophenyl ether, 4b. Rapid nucleophilic attack at unsubstituted ring-positions may yield anionic σ-adducts via zwitterionic intermediates, while slower attack at the 1-position of 4a and 4b may lead to substitution to give 2,4,6-trinitroaniline derivatives. Base catalysis in the substitution reaction reflects rate-limiting proton transfer which may be from the zwitterionic intermediates to amine in the case of 4b, or from a substituted ammonium ion to the ethoxy leaving group in the case of 4a. Comparisons with values in DMSO indicate that values of overall equilibrium constants for adduct formation are ca. 104 lower in acetonitrile, while rate constants for proton transfer are ca. 104 higher. These differences may reflect strong hydrogen-bonding between DMSO and -NH+ protons in ammonium ions and in zwitterions. In acetonitrile homoconjugation of substituted ammonium ions with free amine is an important factor.
Charged states of proteins. Reactions of doubly protonated alkyldiamines with NH3: Solvation or deprotonation. Extension of two proton cases to multiply protonated globular proteins observed in the gas phase
Peschke, Michael,Blades, Arthur,Kebarle, Paul
, p. 11519 - 11530 (2002)
The apparent gas-phase basicities (GBapp'S) of basic sites in multiply protonated molecules, such as proteins, can be approximately predicted. An approach used by Williams and co-workers was to develop an equation for a diprotonated system, NH
Electron Spin Resonance Monitoring of Ligand Ejection Reactions Following Solid-State Reduction of Cobalt Globin and Cobalt Protoporphyrin Complexes
Dickinson, L. Charles,Symons, M. C. R.
, p. 917 - 921 (1982)
Cobaltihemoglobin, isolated α and β chains, and cobaltimyoglobin in aqueous solution at neutral pH were irradiated at 77 K with 3 Mrd of 60Co γ-rays.These diamagnetic Co(III) species are converted to paramagnetic Co(II) species in high yield.The EPR spectra are identical with those of authentic six-coordinate cobalt(II) porphyrins.Upon partial annealing of the species, the EPR spectrum transforms irreversibly to that of a five-coordinate species, indicating that at 77 K these cobaltiglobins are cobaltichromes in analogy to the hemichromes of the native iron species.Differences are seen among all of the six-coordinate, reduced protein ligated species.This ejection of the sixth ligand with thermal annealing after addition of one electron to the dz2 orbital of the cobalt porphyrin also occurs in aqueous glasses of cobalt protoporphyrin IX in pyridine, n-butylamine, or quinuclidine.The five-coordinate species in aqueous media are stable with annealing to room temperature.
Selective Transformations of Triglycerides into Fatty Amines, Amides, and Nitriles by using Heterogeneous Catalysis
Jamil, Md. A. R.,Siddiki, S. M. A. Hakim,Touchy, Abeda Sultana,Rashed, Md. Nurnobi,Poly, Sharmin Sultana,Jing, Yuan,Ting, Kah Wei,Toyao, Takashi,Maeno, Zen,Shimizu, Ken-ichi
, p. 3115 - 3125 (2019)
The use of triglycerides as an important class of biomass is an effective strategy to realize a more sustainable society. Herein, three heterogeneous catalytic methods are reported for the selective one-pot transformation of triglycerides into value-added chemicals: i) the reductive amination of triglycerides into fatty amines with aqueous NH3 under H2 promoted by ZrO2-supported Pt clusters; ii) the amidation of triglycerides under gaseous NH3 catalyzed by high-silica H-beta (Hβ) zeolite at 180 °C; iii) the Hβ-promoted synthesis of nitriles from triglycerides and gaseous NH3 at 220 °C. These methods are widely applicable to the transformation of various triglycerides (C4–C18 skeletons) into the corresponding amines, amides, and nitriles.
Amination of ω-Functionalized Aliphatic Primary Alcohols by a Biocatalytic Oxidation-Transamination Cascade
Pickl, Mathias,Fuchs, Michael,Glueck, Silvia M.,Faber, Kurt
, p. 3121 - 3124 (2015)
Amination of non-activated aliphatic fatty alcohols to the corresponding primary amines was achieved through a five-enzyme cascade reaction by coupling a long-chain alcohol oxidase from Aspergillus fumigatus (LCAO-Af) with a ω-transaminase from Chromobacterium violaceum (ω-TA-Cv). The alcohol was oxidized at the expense of molecular oxygen to yield the corresponding aldehyde, which was subsequently aminated by the PLP-dependent ω-TA to yield the final primary amine product. The overall cascade was optimized with respect to pH, O2 pressure, substrate concentration, decomposition of H2O2 (derived from alcohol oxidation), NADH regeneration, and biocatalyst ratio. The substrate scope of this concept was investigated under optimized conditions by using terminally functionalized C4-C11 fatty primary alcohols bearing halogen, alkyne, amino, hydroxy, thiol, and nitrile groups.
Reilly, J.,Hickinbottom, W. J.
, p. 974 - 985 (1918)
N,N-Chelate nickel(II) complexes bearing Schiff base ligands as efficient hydrogenation catalysts for amine synthesis
Xu, Mengyin,Wang, Yang,Zhou, Yifeng,Yao, Zi-Jian
, (2021/12/09)
Five N, N-chelate nickel (II) complexes bearing N-(2-pyridinylmethylene)-benzylamine ligands with different substituent groups were synthesized in good yields. The nickel complexes exhibited prominent catalytic efficiency toward amine synthesis from nitro compounds by using NaBH4 or H2 as hydrogen source through two catalytic systems. Various amines with different substituents were obtained in moderate to excellent yields. All substrates with electron-donating and electron-withdrawing properties were tolerated in the two reduction systems. Given the efficient catalytic activity, broad substance scope, and mild reduction conditions, the nickel catalysts have potential applications in industrial production.
Method for preparing amine through catalytic reduction of nitro compound by cyclic (alkyl) (amino) carbene chromium complex
-
Paragraph 0015, (2021/04/17)
The cyclic (alkyl) (amino) carbene chromium complex is prepared from corresponding ligand salt, alkali and CrCl3 and used for catalyzing pinacol borane to reduce nitro compounds in an ether solvent under mild conditions to generate corresponding amine. The method for preparing amine has the advantages of cheap and accessible raw materials, mild reaction conditions, wide substrate application range, high selectivity and the like, and is simple to operate.
