関: aminomethane、monomethylamine

WordNet

a methyl with the hydrogen atom replaced by an amino radical

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出典(authority):フリー百科事典『ウィキペディア（Wikipedia）』「2014/02/24 15:53:05」(JST)

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Methylamine is the organic compound with a formula of CH₃NH₂. This colorless gas is a derivative of ammonia, but with one H atom replaced by a methyl group. It is the simplest primary amine. It is sold as a solution in methanol, ethanol, THF, and water, or as the anhydrous gas in pressurized metal containers. Industrially, methylamine is transported in its anhydrous form in pressurized railcars and tank trailers. It has a strong odor similar to fish. Methylamine is used as a building block for the synthesis of many other commercially available compounds. Over 1 million tonnes are produced annually.^[1]

Industrial production[edit]

Methylamine is prepared commercially by the reaction of ammonia with methanol in the presence of a silicoaluminate catalyst. Dimethylamine and trimethylamine are coproduced; the reaction kinetics and reactant ratios determine the ratio of the three products. The product most favoured by the reaction kinetics is trimethylamine.^[2]

CH₃OH + NH₃ → CH₃NH₂ + H₂O

In this way, more than 400 tons are produced annually.^{[citation needed]}

Laboratory methods[edit]

Methylamine was first prepared in 1849 by Wurtz by the hydrolysis of methyl isocyanate and related compounds.^[3]^[4] An example of this process includes the use of Hofmann rearrangement to yield methylamine from acetamide and bromine gas.^[5]^[6]

In the laboratory methylamine hydrochloride is readily prepared by various other methods. One method entails treating formaldehyde with ammonium chloride.^[7]

NH₄Cl + H₂CO → [CH₂=NH₂]Cl + H₂O

[CH₂=NH₂]Cl + H₂CO + H₂O → [CH₃NH₃]Cl + HCOOH

The colorless hydrochloride salt can be converted to the amine by the addition of strong base, like NaOH:

[CH₃NH₃]Cl + NaOH → CH₃NH₂ + NaCl + H₂O

Another method entails reducing nitromethane with zinc and hydrochloric acid.^[8]

Reactivity and applications[edit]

Methylamine is a good nucleophile as it is highly basic and unhindered, although, as an amine it is considered a weak base. Its use in organic chemistry is pervasive. Some reactions involving simple reagents include: with phosgene to methyl isocyanate, with carbon disulfide and sodium hydroxide to the sodium methyldithiocarbamate, with chloroform and base to methyl isocyanide and with ethylene oxide to methylethanolamines. Liquid methylamine has solvent properties analogous to those for liquid ammonia.^[9]

Representative commercially significant chemicals produced from methylamine include the pharmaceuticals ephedrine and theophylline, the pesticides carbofuran, carbaryl, and metham sodium, and the solvents N-methylformamide and N-methylpyrrolidone. The preparation of some surfactants and photographic developers require methylamine as a building block.^[3]

Biological chemistry[edit]

Methylamine arises as a result of putrefaction and is a substrate for methanogenesis.^[10]

Safety[edit]

The LD₅₀ (mouse, s.c.) is 2.5 g/kg.^[11]

The Occupational Safety and Health Administration (OSHA) and National Institute for Occupational Safety and Health (NIOSH) have set occupational exposure limits at 10 ppm or 12 mg/m³ over an eight hour time-weighted average.^[12]

Methylamine is also controlled as a List 1 precursor chemical by the United States Drug Enforcement Administration due to its use in the production of methamphetamine.

References[edit]

^ S.N. Bizzari (November 2008). "CEH Marketing Research Report: ALKYLAMINES (C1-C6)". Chemical Economics Handbook. SRI consulting. Retrieved July 2011.
^ Corbin D.R.; Schwarz S.; Sonnichsen G.C. (1997). "Methylamines synthesis: A review". Catalysis Today 37 (2): 71–102. doi:10.1016/S0920-5861(97)00003-5.
^ ^a ^b Karsten Eller, Erhard Henkes, Roland Rossbacher, Hartmut Höke "Amines, Aliphatic" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2005. doi:10.1002/14356007.a02_001
^ Charles-Adolphe Wurtz (1849) "Sur une série d'alcalis organiques homologues avec l'ammoniaque" (On a series of homologous organic alkalis containing ammonia), Comptes rendus … , 28 : 223-226. Note: Wurtz's empirical formula for methylamine is incorrect because chemists in that era used an incorrect atomic mass for carbon (6 instead of 12).
^ Mann, F. G.; Saunders, B. C. (1960). Practical Organic Chemistry, 4th Ed.. London: Longman. p. 128. ISBN 9780582444072.
^ Cohen, Julius (1900). Practical Organic Chemistry 2nd Ed.. London: Macmillan and Co., Limited. p. 72.
^ Marvel, C. S.; Jenkins, R. L. (1941), "Methylamine Hydrochloride", Org. Synth. ; Coll. Vol. 1: 347
^ Gatterman, Ludwig; and Wieland, Heinrich (1937). Laboratory Methods of Organic Chemistry. Edinburgh, UK: R & R Clark, Limited. p. 157-158.
^ M. G. DeBacker, El B. Mkadmi, F. X. Sauvage, J.-P. Lelieur, M. J. Wagner, R. Concepcion. J. Kim, L. E. H. McMills, J. L. Dye "The Lithium−Sodium−Methylamine System: Does a Low-Melting Sodide Become a Liquid Metal?" J. Am. Chem. Soc., 1996, vol. 118, pp 1997–2003. doi:10.1021/ja952634p
^ Thauer, R. K., "Biochemistry of Methanogenesis: a Tribute to Marjory Stephenson", Microbiology, 1998, 144, 2377-2406.
^ The Merck Index, 10th Ed. (1983), p.864, Rahway: Merck & Co.
^ CDC - NIOSH Pocket Guide to Chemical Hazards

English Journal

A novel liquid chromatography-mass spectrometric method for the simultaneous determination of trimethylamine, dimethylamine and methylamine in fishery products.

Baliño-Zuazo L1, Barranco A2.
Food chemistry.Food Chem.2016 Apr 1;196:1207-14. doi: 10.1016/j.foodchem.2015.09.086. Epub 2015 Sep 28.
A novel multianalyte method has been developed to determine the concentration of trimethylamine (TMA), dimethylamine (DMA) and methylamine (MA) in fish. The optimal points of the key parameters (pH 8, 60 °C and 60 min of reaction time) were determined for the reaction with tert-butyl bromoacetate.
PMID 26593608

Reactions of Methanesulfonic Acid with Amines and Ammonia as a Source of New Particles in Air.

Chen H1, Varner ME1, Gerber RB1, Finlayson-Pitts BJ1.
The journal of physical chemistry. B.J Phys Chem B.2016 Mar 3;120(8):1526-36. doi: 10.1021/acs.jpcb.5b07433. Epub 2015 Oct 5.
New particle formation (NPF) from gaseous precursors as a significant source of aerosol needs to be better understood to accurately predict the impacts on visibility, climate change, and human health. While ternary nucleation of sulfuric acid, amines/NH3, and water is recognized as a significant dri
PMID 26379061

Reaction Mechanism for Direct Proton Transfer from Carbonic Acid to a Strong Base in Aqueous Solution I: Acid and Base Coordinate and Charge Dynamics.

Daschakraborty S1, Kiefer PM1, Miller Y2, Motro Y2, Pines D2, Pines E2, Hynes JT1,3.
The journal of physical chemistry. B.J Phys Chem B.2016 Mar 2. [Epub ahead of print]
Protonation by carbonic acid H2CO3 of the strong base methylamine CH3NH2 in a neutral contact pair in aqueous solution is followed via Car-Parrinello molecular dynamics simulations. Proton transfer (PT) occurs to form an aqueous solvent-stabilized contact ion pair within 100 fs, a fast time scale as
PMID 26879554

Japanese Journal

Hydrothermal Conversion of Poly(ethylene naphthalate) to Naphthalene Dicarboxylic Acid and Ethylene Glycol in the Presence of Trimethylamine

, ,
JOURNAL OF CHEMICAL ENGINEERING OF JAPAN 47(12), 908-913, 2014
… Three amines (methylamine, dimethylamine, and trimethylamine) were evaluated as reactants for depolymerization of PEN and compared with ammonia. … The total yield of both monomers (NDC+EG) on the basis of the carbon mass of the initial PEN pellets, at 493 K and 5.0 MPa, for a reaction time of 50 min, using an amine concentration of 0.6 mol/kg was highest with trimethylamine (97.2%) followed by methylamine (86.6%) and dimethylamine (89.8%) in succession. …
NAID 130004722519

Conformational Analysis of Hexakis-Methylamine Nickel(II) Complex on the Basis of Computational Group Theory and Density Functional Theory

,
Journal of Computer Chemistry, Japan 13(4), 223-228, 2014
… Computational group theory (CGT) method investigations have been conducted for a hexakis-methylamine nickel(II) complex cation [Ni(CH3NH2)6]2+ [hexakis(methylamine-κN)nickel(II) dication] to find 54 possible conformers. …
NAID 130004677831

EFFICIENT SYNTHESIS OF N-METHYLAMIDES AND AMINES VIA 4-(ALKYLAMINO)BENZYL-N-METHYLAMINE AS A NEW PROTECTING GROUP

Lee Sang-Hak,Mu Yu,Kim Gun-Woo [他]
Heterocycles : an international journal for reviews and communications in heterocyclic chemistry 87(8), 1749-1764, 2013-08-01
NAID 40019710681

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★リンクテーブル★

リンク元	「メチルアミン」「aminomethane」
拡張検索	「monomethylamine」「nitrosodimethylamine」

「メチルアミン」

Methylamine
	IUPAC name aminomethane, methanamine
	Other names monomethylamine; MMA; glycamine;
Identifiers
Abbreviations	MMA
CAS number	74-89-5
PubChem	6329
ChemSpider	6089
EC number	200-820-0
UN number	1061
DrugBank	DB01828
KEGG	C00218
MeSH	methylamine
ChEBI	CHEBI:16830
ChEMBL	CHEMBL43280
RTECS number	PF6300000
Beilstein Reference	741851
Gmelin Reference	145
3DMet	B00060
Jmol-3D images	Image 1
	SMILES CN ;
	InChI InChI=1S/CH5N/c1-2/h2H2,1H3 ; Key: BAVYZALUXZFZLV-UHFFFAOYSA-N ;
Properties
Molecular formula	CH5N
Molar mass	31.06 g mol−1
Appearance	Colorless gas
Odor	Fishy, ammoniacal
Melting point	−93.10 °C; −135.58 °F; 180.05 K
Boiling point	−6.6 to −6.0 °C; 20.0 to 21.1 °F; 266.5 to 267.1 K
Solubility in water	1.08 kg L−1 (at 20 °C)
log P	−0.472
Vapor pressure	186.10 kPa (at 20 °C)
kH	1.4 mmol Pa−1 kg−1
Basicity (pKb)	3.36
Viscosity	230 μPa s (at 0 °C)
Dipole moment	1.31 D
Thermochemistry
Std enthalpy of; formation ΔfHo298	−23.5 kJ mol−1
Hazards
MSDS	emdchemicals.com
GHS pictograms
GHS signal word	DANGER
GHS hazard statements	H220, H315, H318, H332, H335
GHS precautionary statements	P210, P261, P280, P305+351+338, P410+403
EU Index	612-001-00-9
EU classification	F+ Xn
R-phrases	R12, R20, R37/38, R41
S-phrases	(S2), S16, S26, S39
NFPA 704	4 3 0
Flash point	<−30 °C
Autoignition temperature	430 °C; 806 °F; 703 K
Explosive limits	4.9–20.8%
LD50	100 mg kg−1 (oral, rat)
Related compounds
Related alkanamines	ethylamine, dimethylamine, trimethylamine
Related compounds	ammonia
	(verify) (what is: /?); Except where noted otherwise, data are given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
	Infobox references

　　[★]

英: methylamine
関: アミノメタン、モノメチルアミン

「aminomethane」

　　[★]

アミノメタン

関: methylamine、monomethylamine

「monomethylamine」

　　[★]

モノメチルアミン

関: aminomethane、methylamine

「nitrosodimethylamine」

　　[★]

ニトロソジメチルアミン

関: dimethylnitrosamine

[CEH-1] S.N. Bizzari (November 2008). "CEH Marketing Research Report: ALKYLAMINES (C1-C6)". Chemical Economics Handbook. SRI consulting. Retrieved July 2011.

[2] Corbin D.R.; Schwarz S.; Sonnichsen G.C. (1997). "Methylamines synthesis: A review". Catalysis Today 37 (2): 71–102. doi:10.1016/S0920-5861(97)00003-5.

[Ullmann-3] Karsten Eller, Erhard Henkes, Roland Rossbacher, Hartmut Höke "Amines, Aliphatic" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2005. doi:10.1002/14356007.a02_001

[4] Charles-Adolphe Wurtz (1849) "Sur une série d'alcalis organiques homologues avec l'ammoniaque" (On a series of homologous organic alkalis containing ammonia), Comptes rendus … , 28 : 223-226. Note: Wurtz's empirical formula for methylamine is incorrect because chemists in that era used an incorrect atomic mass for carbon (6 instead of 12).

[5] Mann, F. G.; Saunders, B. C. (1960). Practical Organic Chemistry, 4th Ed.. London: Longman. p. 128. ISBN 9780582444072.

[6] Cohen, Julius (1900). Practical Organic Chemistry 2nd Ed.. London: Macmillan and Co., Limited. p. 72.

[7] Marvel, C. S.; Jenkins, R. L. (1941), "Methylamine Hydrochloride", Org. Synth. ; Coll. Vol. 1: 347

[8] Gatterman, Ludwig; and Wieland, Heinrich (1937). Laboratory Methods of Organic Chemistry. Edinburgh, UK: R & R Clark, Limited. p. 157-158.

[9] M. G. DeBacker, El B. Mkadmi, F. X. Sauvage, J.-P. Lelieur, M. J. Wagner, R. Concepcion. J. Kim, L. E. H. McMills, J. L. Dye "The Lithium−Sodium−Methylamine System: Does a Low-Melting Sodide Become a Liquid Metal?" J. Am. Chem. Soc., 1996, vol. 118, pp 1997–2003. doi:10.1021/ja952634p

[10] Thauer, R. K., "Biochemistry of Methanogenesis: a Tribute to Marjory Stephenson", Microbiology, 1998, 144, 2377-2406.

[11] The Merck Index, 10th Ed. (1983), p.864, Rahway: Merck & Co.

[12] CDC - NIOSH Pocket Guide to Chemical Hazards

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methylamine