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Amines are organic compounds which contain and are often actually based on one or more atoms of nitrogen. Structurally amines resemble ammonia in that the nitrogen can bond up to three hydrogens, but amines also have additional properties based on their carbon connectivity. In an amine, one or more of the hydrogen atoms from ammonia are replaced by organic substituents like alkyl (alkane chain) and aryl (aromatic ring) groups. Another type of organic molecule contains nitrogen without being, strictly speaking, an amine: carboxylic acid derivatives containing a trivalent (three-bond) ammonia in ground state are actually amides instead of amines. Amides and amines have different structures and properties, so the distinction is actually very important. Organicnitrogen compounds containing metals are also called amides, so if you see a molecule that has a nitrogen and either a carbonyl group or a metal next to that nitrogen, then you know that molecule should be an amide instead of an amine.

Contents

1 Preparation o 1.1 The Gabriel synthesis o 1.2 Hofmann degradation of amides o 1.3 Hofmann elimination of quaternary ammonium salts o 1.4 Reduction of nitriles and amides o 1.5 Nucleophilic substitution of haloalkanes 2 Properties o 2.1 Types of Amines o 2.2 Aromatic amines o 2.3 Naming conventions o 2.4 Physical properties 2.4.1 General properties 2.4.2 Chirality 2.4.3 Properties as bases 3 Reactions o 3.1 Amide formation o 3.2 Salt formation o 3.3 Neutralization o 3.4 Reaction with nitrous acid o 3.5 Reactions with ketones and aldehydes 4 Use of amines o 4.1 As dyes o 4.2 As drugs 5 See also

Preparation
The following laboratory methods can be considered to be in common use for purpose of the preparation of amine compounds:

The Gabriel synthesis

via azides by the Staudinger reduction. Allylic amines can be prepared from imines in the Aza-Baylis-Hillman reaction.

used for prepration of primary amines. aromatic primary amines cant b prepared by this method. cos aryl hallides do not undergo nueleophilic substitution with pottasium pthlimide

Hofmann degradation of amides

This reaction is valid for preparation of primary amines only, and it gives good yields of primary amines uncontaminated with other amines.

Hofmann elimination of quaternary ammonium salts

R3N+CH2CH2R' + OH- R3N + H2C=CHR' + H2O

Quaternary ammonium salts, upon treatment with a strong base, undergo the Hofmann Elimination.

Reduction of nitriles and amides

File:Nitrile.gif

Nitriles are reduced to amines using hydrogen in the presence of a nickel catalyst, although acidic or alkaline conditions should be avoided to avoid the possible hydrolysis of the -CN group. LiAlH4 is more commonly employed for the reduction of nitriles on the laboratory scale.

Similarly, LiAlH4 reduces amides to amines.

Nucleophilic substitution of haloalkanes

Primary amines can also be synthesized by alkylation of ammonia. Haloalkanes react with amines to give a corresponding alkyl-substituted amine, with the release of a halogen acid. Such reactions, which are most useful for alkyl iodides and bromides, are rarely employed because the degree of alkylation is difficult to control. If the reacting amine is tertiary, a quaternary ammonium cation results. Many quaternary ammonium salts can be prepared by this route with diverse R groups and many halide and pseudohalide anions.

Properties

Types of Amines
Amines can be either primary, secondary or tertiary, depending on the number of carbon-containg groups that are attached to them. If there is only one carboncontaining group (such as in the molecule CH3NH2) then that amine is considered primary. Two carbon-containing groups makes an amine secondary, and three groups makes it tertiary. Utilizing the lone electron pair of nitrogen, it is sometimes energetically favored to use the nitrogen as a nucleophile and thus bind a fourth carbon-containing group to the amine. In this case, it could be called a quaternary ammonium ion.
Primary Amine: Secondary Amine: Tertiary Amine:

An organic compound with multiple amine groups is called a diamine, triamine, tetraamine and so forth, based on the number of amine groups (also called amino groups) attached to the molecule. The chemical formula for methylene diamine (also called diaminomethane), for example, would be as follows: H2N-CH2-NH2

Aromatic amines
Aromatic amines have the nitrogen atom directly connected to an aromatic ring structure. Due to its electron withdrawing properties, the aromatic ring greatly decreases the basicity of the amine - and this effect can be either strengthened or offset depending on what substituents are on the ring and on the nitrogen. The presence of the lone electron pair from the nitrogen has the opposite effect on the aromatic ring itself; because the nitrogen atom can "loan" electron density to the ring, the ring itself becomes much more reactive to other types of chemistry.

Naming conventions
For primary amines, where the amine is not the principal characteristic group, the the prefix "amino-" is used. For example: 4-aminobenzoic acid where the carboxylic acid is the principal characteristic. Otherwise, the suffix "-amine" is used with with either the parent hybride or the R group substituent name. Example: ethanamine or ethylamine. Alternatively, the suffix "-azane" can be appended to the R group substituent name: Example: propylazane. For secondary, tertiary, and quarternary amines, the naming convention is a bit different, but the suffixes are the same. For symmetrical amines, the "di" or "tri" prefix is used depending on whether there are 2 or 3 substituents. For example, dipropylamine is a secondary amine, and triphenylamine is a tertiary amine. For asymmetric amines, the parent chain gets the "-amine" suffix. This name is then prefixed with "N-" (indicating the nitrogen bond) and the substituent group name, for

each substituent, using alphabetic order for tertiary amides. For example, N-ethyl-Nmethyl-propylamine, not N-methyl-N-ethyl-propylamine. To sum up:

as prefix: "amino-" as suffix: "-amine" the prefix "N-" shows substitution on the nitrogen atom (in the case of secondary, tertiary and quaternary amines)

Systematic names for some common amines:

methylamine

Primary amines: ethanamine or ethylamine. Secondary amines: dimethylamine Tertiary amines: trimethylamine

Physical properties
As one might readily guess, the inclusion of a heteroatom such as nitrogen in otherwise exclusively carbon and hydrogen molecules has quite an effect on the properties of amines as compared to alkanes.

General properties
Hydrogen bonding significantly influences the properties of primary and secondary amines as well as the protonated derivatives of all amines. Thus the boiling point of amines is higher than those for the corresponding phosphines (compounds containing phosphorus), but generally lower than the corresponding alcohols. Alcohols, or alkanols, resemble amines but feature an -OH group in place of NR2. Since oxygen is more electronegative than nitrogen, RO-H is typically more acidic than the related R2N-H compound. Methyl, dimethyl, trimethyl, and ethyl amines are gases under standard conditions. Most common alkyl amines are liquids, and high molecular weight amines are, quite naturally, solids at standard temperatures. Additionally, gaseous amines possess a characteristic ammonia smell, while liquid amines have a distinctive "fishy" smell. Most aliphatic amines display some solubility in water, reflecting their ability to form hydrogen bonds. Solubility decreases relatively proportionally with the increase in the

number of carbon atoms in the molecule - especially when the carbon atom number is greater than six. Aliphatic amines also display significant solubility in organic solvents, especially in polar organic solvents. Primary amines react readily with ketone compounds (such as acetone), however, and most amines are incompatible with chloroform and also with carbon tetrachloride as solvent solutions. Aromatic amines have their lone pair electrons conjugated ("shared") into the benzene ring, so their tendency to engage in hydrogen bonding is somewhat diminished. The boiling points of these molecules are therefore usually somewhat higher than other, smaller amines due to their typically larger size. They also often have relatively diminished solubility in water, although they retain their solubility in other organic solvents. Aromatically conjugated amines are often quite toxic and have the potential to be easily absorbed through the skin, so should always be treated as "hazardous".

Chirality
Tertiary amines of the type NHRR' and NRR'R" are not chiral: although the nitrogen atom bears four distinct substituents counting the lone pair, the lone pair of electrons can "flip" across the nitrogen atom and invert the other molecules. The energy barrier for just such a Walden inversion of the stereocenter with a lone pair of electrons is relatively low, e.g. ~7 kcal/mol for a trialkylamine, therefore it is difficult to obtain reliably chiral products using tertiary amines. Because of this low barrier, amines such as NHRR' cannot be resolved optically and NRR'R" can only be resolved when the R, R', and R" groups are constrained in cyclic structures. Quaternary amine structures, e.g. H3C-N+-RR'R", are chiral and are readily optically resolved.

Properties as bases
Like ammonia, amines act as bases and are reasonably strong (see the provided table for some examples of conjugate acid Ka values). The basicity of amines varies by molecule, and it largely depends on:

The availability of the lone pair of electrons from nitrogen The electronic properties of the attached substituent groups (e.g., alkyl groups enhance the basicity, aryl groups diminish it, etc.) The degree of solvation of the protonated amine, which depends mostly on the solvent used in the reaction

The nitrogen atom of a typical amine features a lone electron pair which can bind a hydrogen ion (H+) in order to form an ammonium ion -- R3NH+. The water solubility

of simple amines is largely due to the capability for hydrogen bonding that can occur between protons on the water molecules and these lone pairs of electrons.

Inductive effect of alkyl groups Ions of compound Kb 1.810-5 M 4.410-4 M

ammonia NH3 methylamine CH3NH2

propylamine CH3CH2CH2NH2 4.710-4 M 2-propylamine (CH3)2CHNH2 5.310-4 M diethylamine (CH3)2NH2 9.610-4 M

+I effect of alkyl groups raises the energy of the lone pair of electrons, thus elevating the basicity.

Mesomeric effect of aromatic systems Ions of compound Kb 1.810-5 M 3.810-10 M

ammonia NH3 aniline C6H5NH2

4-methylphenylamine 4-CH3C6H4NH2 1.210-9 M

+M effect of aromatic ring delocalizes the lone pair electron into the ring, resulting in decreased basicity. The degree of protonation of protonated amines:
Ions of compound Maximum number of H-bond NH4+ RNH3+ R2NH2+ R3NH+ 4 Very Soluble in H2O 3 2 1 Least Soluble in H2O

Reactions
Amide formation
Acyl chlorides and acid anhydrides react with primary and secondary amines without the presence of heat to form amides. Tertiary amines cannot be acylated due to the absence of a replaceable hydrogen atom. With the much less active benzoyl chloride, acylation can still be performed by the use of excess aqueous base to facilitate the reaction.

Salt formation
Because amines are basic, they neutralize carboxylic acids to form the corresponding ammonium carboxylate salts. Upon heating to 200C, the primary and secondary amine salts dehydrate to form the corresponding amides.

Neutralization
Amines R3N react with strong acids such as hydroiodic acid (HI), hydrobromic acid (HBr) and hydrochloric acid (HCl) to give ammonium salts R3NH+.

Reaction with nitrous acid

Nitrous acid with the chemical formula HNO2 is unstable. Usually it is produced indirectly in a mixture of NaNO2 and a strong acid such as HCl or H2SO4 in dilute concentration, so that the H+ ions will associate with the NO2- ions in solution. Primary aliphatic amines with nitrous acid give very unstable diazonium salts which spontaneously decompose by losing N2 to form a carbenium ion. The carbenium ion goes on to produce a mixture of alkenes, alkanols or alkyl halides, with alkanols as the major product. This reaction is of little synthetic importance because the diazonium salt formed is too unstable, even under quite cold conditions.
NaNO2 + HCl HNO2 + NaCl

Primary aromatic amines, such as aniline (phenylamine) forms a more stable diazonium ion at 05C. Above 5C, it will decompose to give phenol and N2. Diazonium salts can be isolated in the crystalline form but are usually used in solution and immediately after preparation, due to rapid decomposition on standing even with little ambient heat. Solid diazonium salts can be explosive on shock or on mild warming.

Reactions with ketones and aldehydes

Primary amines react with carbonyl compounds to form imines. Specifically, aldehydes become aldimines, and ketones become ketimines. In the case of formaldehyde (R' = H), the imine products are typically cyclic trimers. RNH2 + R'2C=O R'2C=NR + H2O

Secondary amines react with ketones and aldehydes to form enamines. An enamine contains a C=C double bond, where the second C is singly bonded to N as part of an amine ligand. R2NH + R'(R"CH2)C=O R"CH=C(NR2)R' + H2O

Ethanolamine
From Wikipedia, the free encyclopedia Jump to: navigation, search

Ethanolamine

IUPAC name[hide] 2-Aminoethanol Other names[hide] 2-Amino-l-Ethanol, Ethanolamine, Monoethanolamine, Aminoethanol, -hydroxyethylamine, -Aminoethyl alcohol, Glycinol, Olamine, MEA

Identifiers CAS number PubChem ChemSpider UNII EC number 141-43-5 700 13835336 5KV86114PT 205-483-3

DrugBank KEGG ChEBI ChEMBL RTECS number Jmol-3D images

DB03994 D05074 CHEBI:16000 CHEMBL104943 KJ5775000 Image 1 SMILES

[show]

InChI
[show]

Properties Molecular formula Molar mass C2H7NO 61.08 g mol1 Viscous colourless liquid with ammonia odour 1.012 g/cm3

Appearance

Density Melting point Boiling point Solubility in water Vapor pressure

10.3 C, 283 K, 51 F 170 C, 443 K, 338 F Miscible 64 Pa (20 C)[1]

Acidity (pKa) Refractive index (nD)

9.50[2]

1.4539 (20 C)[3]

Hazards MSDS R-phrases S-phrases JT Baker R20, R34, R36/37/38 S26, S27, S36/37, S39, S45

NFPA 704

2 3 0

Flash point Autoignition temperature Explosive limits U.S. Permissible exposure limit (PEL)

85 C (closed cup)

410 C

5.5 - 17%

3 ppm

Related compounds N-Methylethanolamine Related compounds diethanolamine triethanolamine (verify) (what is: / ?) Except where noted otherwise, data are given for materials

in their standard state (at 25 C, 100 kPa) Infobox references

Ethanolamine, also called 2-aminoethanol or monoethanolamine (often abbreviated as ETA or MEA), is an organic chemical compound that is both a primary amine and a primary alcohol (due to a hydroxyl group). Like other amines, monoethanolamine acts as a weak base. Ethanolamine is a toxic, flammable, corrosive, colorless, viscous liquid with an odor similar to that of ammonia. Ethanolamine is commonly called monoethanolamine or MEA in order to be distinguished from diethanolamine (DEA) and triethanolamine (TEA). Ethanolamine is the second-most-abundant head group for phospholipids, substances found in biological membranes, and is also used in messenger molecules such as palmitoylethanolamide which has an effect on CB1 receptors.[4] The term ethanolamines (plural) is a group of amino alcohols. A class of antihistamines is identified as ethanolamines which includes carbinoxamine, clemastine, dimenhydrinate, diphenhydramine, and doxylamine.[5]

Contents
[hide]

1 Production 2 Applications o 2.1 Gas stream scrubbing o 2.2 pH-control amine 3 References

Production [edit]
Monoethanolamine is produced by reacting ethylene oxide with aqueous ammonia; the reaction also produces diethanolamine and triethanolamine. The ratio of the products can be controlled by changing the stoichiometry of the reactants.[6]

Note that this reaction is exothermic and that controls are needed to prevent a runaway reaction.

Applications [edit]
MEA is used in aqueous solutions for scrubbing certain acidic gases. It is used as feedstock in the production of detergents, emulsifiers, polishes, pharmaceuticals, corrosion inhibitors, chemical intermediates.[6][7] For example, reacting ethanolamine with ammonia gives the commonly used chelating agent, ethylenediamine:[6]

In pharmaceutical formulations, MEA is primarily used for buffering or preparation of emulsions. MEA can be used as pH regulator in cosmetics.[8]

Gas stream scrubbing [edit]

See also: carbon dioxide scrubber

Aqueous solutions of MEA (solutions of MEA in water) are used as a gas stream scrubbing liquid in amine treaters. For example, aqueous MEA is used to remove carbon dioxide (CO2) from flue gas. Aqueous solutions can weakly dissolve certain kinds of gases from a mixed gas stream. The MEA in such solutions, acting as a weak base, then neutralizes acidic compounds dissolved in the solution to turn the molecules into an ionic form, making them polar and considerably more soluble in a cold MEA solution, and thus keeping such acidic gases dissolved in this gasscrubbing solution. Therefore, large surface area contact with such a cold scrubbing solution in a scrubber unit can selectively remove such acidic components as hydrogen sulfide (H2S) and CO2 from some mixed gas streams. For example, basic solutions such as aqueous MEA or aqueous potassium carbonate can neutralize H2S into hydrosulfide ion (HS-) or CO2 into bicarbonate ion (HCO3-).

H2S and CO2 are only weakly acidic gases. An aqueous solution of a strong base such as sodium hydroxide (NaOH) will not readily release these gases once they have dissolved. However, MEA is rather weak base and will re-release H2S or CO2 when the scrubbing solution is heated. Therefore, the MEA scrubbing solution is recycled through a regeneration unit, which heats the MEA solution from the scrubber unit to release these only slightly acidic gases into a purer form and returns the regenerated MEA solution to the scrubber unit again for reuse.

pH-control amine [edit]

Ethanolamine is often used for alkalinization of water in steam cycles of power plants, including nuclear power plants with pressurized water reactors. This alkalinization is performed to control corrosion of metal components. ETA (or sometimes a similar organic amine, e.g., morpholine) is selected because it does not accumulate in steam generators (boilers) and crevices due to its volatility, but rather distributes relatively uniformly throughout the entire steam cycle. In such application, ETA is a key ingredient of so-called "all-volatile treatment" of water (AVT).

References [edit]
1. ^ "Ethanolamine MSDS". Acros Organics. 2. ^ Hall, H.K., J. Am. Chem. Soc., 1957, 79, 5441. 3. ^ R. E. Reitmeier; V. Sivertz; H. V. Tartar (1940). "Some Properties of Monoethanolamine and its Aqueous Solutions". Journal of the American Chemical Society 62 (8): 19431944. doi:10.1021/ja01865a009. 4. ^ Calignano, A; La Rana, G; Piomelli, D (2001). "Antinociceptive activity of the endogenous fatty acid amide, palmitylethanolamide". European Journal of Pharmacology 419 (23): 1918. doi:10.1016/S0014-2999(01)00988-8. PMID 11426841. 5. ^ http://emedicine.medscape.com/article/812828-overview#showall 6. ^ a b c Klaus Weissermel, Hans-Jrgen Arpe, Charlet R. Lindley, Stephen Hawkins (2003). "Chap. 7. Oxidation Products of Ethylene". Industrial Organic Chemistry. Wiley-VCH. pp. 159161. ISBN 3-527-30578-5. 7. ^ "Ethanolamine". Occupational Safety & Health Administration. 8. ^ Carrasco, F. (2009). "Ingredientes Cosmticos". Diccionario de Ingredientes Cosmticos 4 Ed. www.imagenpersonal.net. p. 306. ISBN 978-84-613-4979-1.

Dimethylamine
From Wikipedia, the free encyclopedia Jump to: navigation, search

Dimethylamine

Other names[hide] N-Methylmethanamine

[1]

Identifiers CAS number PubChem ChemSpider UNII EC number UN number KEGG MeSH ChEBI ChEMBL 124-40-3 674 654 ARQ8157E0Q 204-697-4 1032 C00543 dimethylamine CHEBI:17170 CHEMBL120433

RTECS number Beilstein Reference Gmelin Reference 3DMet Jmol-3D images

IP8750000 605257 849 B00125 Image 1 SMILES

[show]

InChI
[show]

Properties[3][4] Molecular formula Appearance Odor Melting point Boiling point Solubility in water log P Vapor pressure kH (CH3)2NH Colorless gas Ichtyal, ammoniacal

-93 C, 180.15 K, -135 F 7-9 C, 280-282 K, 44-48 F 3.540 kg L1 0.362 170.3 kPa (at 20 C) 310 mol Pa1 kg1

Acidity (pKa) Basicity (pKb)

10.64[2] 3.36 Thermochemistry

Std enthalpy of formation fHo298

2117 kJ mol1

Hazards

GHS pictograms

GHS signal word GHS hazard statements GHS precautionary statements EU Index

DANGER

H220, H302, H315, H318, H332, H335

P210, P261, P280, P305+351+338

612-001-00-9

EU classification

F+

Xn

R-phrases S-phrases

R12, R20, R37/38, R41 (S2), S16, S26, S39

NFPA 704

4 3 0

Flash point Autoignition temperature Explosive limits

6 C

401 C

2.814.4% Related compounds

Trimethylamine Diethylamine Triethylamine Diisopropylamine Dimethylaminopropylamine Triisopropylamine Unsymmetrical dimethylhydrazine (verify) (what is: / ?)

Related amines

Related compounds

Except where noted otherwise, data are given for materials in their standard state (at 25 C, 100 kPa) Infobox references

Dimethylamine is an organic compound with the formula (CH3)2NH. This secondary amine is a colorless, flammable gas with an ammonia-like odor. Dimethylamine is commonly encountered commercially as a solution in water at concentrations up to around 40%. In 2005, an estimated 270,000 tons were produced industrially,[5] but it is also found as a natural product.

Contents
[hide]

1 Structure and properties 2 Natural Occurrence 3 Uses 4 Biochemistry 5 Toxicology 6 See also 7 References 8 External links

Structure and properties [edit]

The molecule consists of a nitrogen atom with two methyl substituents and one proton. Dimethylamine is a weak base and the pKa of the ammonium salt CH3-NH2+CH3 is 10.73, a value above methylamine (10.64) and trimethylamine (9.79). Dimethylamine reacts with acids to form salts, such as dimethylamine hydrochloride, an odorless white solid with a melting point of 171.5 C. Dimethylamine is produced by catalytic reaction of methanol and ammonia at elevated temperatures and high pressure:[6]
2 CH3OH + NH3 (CH3)2NH + 2 H2O

Natural Occurrence [edit]

Dimethylamine is found quite widely distributed in animals and plants, and is present in many foods at the level of a few mg/kg.[7]

Uses [edit]
Dimethylamine is a precursor to several industrially significant compounds.[5][8] It reacts with carbon disulfide to give dimethyl dithiocarbamate, a precursor to a family of chemicals widely used in the vulcanization of rubber. The solvents dimethylformamide and dimethylacetamide are derived from dimethylamine. It is raw material for the production of many agrichemicals and pharmaceuticals, such as dimefox and diphenhydramine, respectively. The chemical weapon tabun is derived from dimethylamine. The surfactant lauryl dimethylamine oxide is found in soaps and cleaning compounds. Unsymmetrical dimethylhydrazine, a rocket fuel, is prepared from dimethylamine.

Biochemistry [edit]
The German cockroach utilizes dimethylamine as a pheromone for communication.[9] It is an attractant for boll weevils.[10] Dimethylamine undergoes nitrosation under weak acid conditions to give dimethylnitrosamine. This animal carcinogen has been detected and quantified in human urine samples and it may also arise from nitrosation of dimethylamine by nitrogen oxides present in acid rain in highly industrialized countries.[citation needed]

Toxicology [edit]
The toxicology of dimethylamine is discussed as part of a NIH monograph concerning dimethylamine borane. LD50: 736 mg/kg (mouse, i.p.); 316 mg/kg (mouse, p.o.); 698 mg/kg (rat, p.o.); 3900 mg/kg (rat, dermal); 240 mg/kg (guinea pig or rabbit, p.o.). [11]

The unattributed LD (lethal dose) given in the Merck index for i.v. administration to rabbits, 4000 mg/kg, is unexpectedly high, and appears to be inconsistent with values given above.[10]

See also [edit]

Methylamine Trimethylamine

References [edit]
1. ^ "dimethylamine - Compound Summary". PubChem Compound. USA: National Center for Biotechnology Information. 16 September 2004. Identification. Retrieved 21 October 2011. 2. ^ Hall, H.K. (1957). J. Am. Chem. Soc. 79: 5441. doi:10.1021/ja01577a030. 3. ^ "Dimethylamine". NIST Chemistry WebBook. USA: National Institute of Standards and Technology. Retrieved 21 October 2011. 4. ^ "Dimethylamine 38931 - 99.0%". Aldrich. Sigma-Aldrich Co. Retrieved 21 October 2011. Unknown parameter |BRAND_KEY&F= ignored (help) 5. ^ a b A. B. van Gysel, W. Musin "Methylamines" in Ullmann's Encyclopedia of Industrial Chemistry, 2005 Wiley-VCH Verlag, Weinheim. doi:10.1002/14356007.a16 535 6. ^ Corbin D.R.; Schwarz S.; Sonnichsen G.C. (1997). "Methylamines synthesis: A review". Catalysis Today 37 (2): 71102. doi:10.1016/S0920-5861(97)00003-5. 7. ^ G. B. Neurath et al. (1977). "Primary and secondary amines in the human environment." Fd. Cosmet. Toxicol. 15 275-282. 8. ^ Ashford's Dictionary of Industrial Chemicals, 3rd edition, 2011, pages 3284-3286 9. ^ Zhang AQ, Mitchell SC, Smith RL (November 1998). "Dimethylamine formation in the rat from various related amine precursors". Food Chem. Toxicol. 36 (11): 9237. doi:10.1016/S0278-6915(98)00074-X. PMID 9771553. 10. ^ a b The Merck Index, 10th Ed. (1983), p.470, Rahway: Merck & Co. 11. ^ Chemical Information Profile for Dimethylamine Borane, National Toxicology Program, NIEHS, NIH (2008), p.4: http://ntp.niehs.nih.gov/ntp/htdocs/Chem_Background/ExSumPdf/DimethylamineB orane508.pdf

External links [edit]

International Chemical Safety Card 0260 (gas) International Chemical Safety Card 1485 (aqueous solution) NIOSH Pocket Guide to Chemical Hazards 0219 Properties from Air Liquide MSDS at airliquide.com

Trimethylamine
From Wikipedia, the free encyclopedia Jump to: navigation, search

Trimethylamine[1]

Identifiers CAS number PubChem ChemSpider UNII EC number UN number KEGG ChEBI ChEMBL RTECS number 75-50-3 1146 1114 LHH7G8O305 200-875-0 1083 C00565 CHEBI:18139 CHEMBL439723 PA0350000

Beilstein Reference 3DMet Jmol-3D images

956566 B00133 Image 1 SMILES

[show]

InChI
[show]

Properties Molecular formula Molar mass Appearance Odor Density Melting point Boiling point Solubility in water log P Vapor pressure kH C3H9N 59.11 g mol1 Colorless gas Fishy, ammoniacal 670 mg mL1 (at 0 C)

-117 C, 155.95 K, -179 F 3 C, 276 K, 37 F Miscible 0.119 91.74 kPa (at 21 C) 95 mol Pa1 kg1

Thermochemistry Std enthalpy of formation fH

o 298

24.523.0 kJ mol1

Hazards

GHS pictograms

GHS signal word GHS hazard statements GHS precautionary statements EU Index

DANGER

H220, H315, H318, H332, H335

P210, P261, P280, P305+351+338

612-001-00-9

EU classification

F+

Xn

R-phrases S-phrases

R12, R20, R37/38, R41 (S2), S16, S26, S29

NFPA 704

4 2 0

Flash point

7 C 190 C

Autoignition

temperature Explosive limits LD50 211.6% 500 mg kg1 (oral, rat) Related compounds

Dimethylamine N-Nitrosodimethylamine Diethylamine Triethylamine Diisopropylamine Dimethylaminopropylamine Diethylenetriamine N,N-Diisopropylethylamine Triisopropylamine Tris(2-aminoethyl)amine Mechlorethamine HN1 (nitrogen mustard) HN3 (nitrogen mustard) Unsymmetrical dimethylhydrazine Biguanide Dithiobiuret

Related amines

Related compounds

(verify) (what is: / ?) Except where noted otherwise, data are given for materials in their standard state (at 25 C, 100 kPa) Infobox references

Trimethylamine is an organic compound with the formula N(CH3)3. This colorless, hygroscopic, and flammable tertiary amine has a strong "fishy" odor in low concentrations and an ammonia-like odor at higher concentrations. It is a gas at room temperature but is usually sold in pressurized gas cylinders or as a 40% solution in water. Trimethylamine is a product of decomposition of plants and animals. It is the substance mainly responsible for the odor often associated with rotting fish, some infections, bad breath and can be a cause of vaginal odor due to bacterial vaginosis. It is also associated with taking large doses of choline and carnitine.

Trimethylamine is a nitrogenous base and can be readily protonated to give trimethylammonium cation. Trimethylammonium chloride is a hygroscopic colorless solid prepared from hydrochloric acid. Trimethylamine is a good nucleophile, and this reaction is the basis of most of its applications.

Contents
[hide]

1 Production 2 Applications 3 Trimethylaminuria 4 See also 5 References 6 External links

Production [edit]
Trimethylamine is prepared by the reaction of ammonia and methanol employing a catalyst:[2]
3 CH3OH + NH3 (CH3)3N + 3 H2O

This reaction coproduces the other methylamines, dimethylamine (CH3)2NH and methylamine CH3NH2. Trimethylamine has also been prepared via a reaction of ammonium chloride and paraformaldehyde,[3] according to the following equation:
9 (CH2=O)n + 2n NH4Cl 2n (CH3)3NHCl + 3n H2O + 3n CO2

Applications [edit]
Trimethylamine is used in the synthesis of choline, tetramethylammonium hydroxide, plant growth regulators, strongly basic anion exchange resins, dye leveling agents and a number of basic dyes.[2][4] Gas sensors to test for fish freshness detect trimethylamine.

Trimethylaminuria [edit]
Main article: Trimethylaminuria

Trimethylaminuria is a genetic disorder in which the body is unable to metabolize trimethylamine from food sources. Patients develop a characteristic fish odour of their sweat, urine, and breath after the consumption of choline-rich foods. Trimethylaminuria is an autosomal recessive disorder involving a trimethylamine

oxidase deficiency. A condition similar to trimethylaminuria has also been observed in a certain breed of Rhode Island Red chicken that produces eggs with a fishy smell, especially after eating food containing a high proportion of rapeseed.[citation needed]

See also [edit]

Ammonia, NH3 Ammonium, NH4+ Methylamine (CH3)NH2 Triethylamine (TEA)

References [edit]
1. ^ Merck Index, 11th Edition, 9625. 2. ^ a b A. B. van Gysel, W. Musin "Methylamines" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. doi:10.1002/14356007.a16_535 3. ^ Roger Adams, B. K. Brown, "Trimethylamine", Org. Synth.; Coll. Vol. 1: 75 4. ^ Ashford's Dictionary of Industrial Chemicals (3rd ed.). 2011. p. 9362. ISBN 978-09522674-3-0.

External links [edit]

Molecule of the Month: Trimethylamine NIST Webbook data

Trimethylamine
(and 'fish breath' syndrome)

Simon Cotton Uppingham School, Rutland, UK

Also available: Chime Enhanced, JMol, and VRML versions.

James Ward (1769-1859) Miranda and Caliban. (the Royal Shakespeare Theatre Collection, Stratfordupon-Avon)

"What have we here? a man or a fish? dead or alive? A fish: he smells like a fish; a very ancient and fish-like smell; a kind of not of the newest Poor-John. A strange fish! Were I in England now, as once I was, and had but this fish painted, not a holiday fool there but would give a piece of silver: there would this monster make a man; any strange beast there makes a man: when they will not give a doit to relieve a lame beggar, they will lazy out ten to see a dead Indian. Legged like a man and his fins like arms! Warm o' my troth! I do now let loose my opinion; hold it no longer: this is no fish, but an islander, that hath lately suffered by a thunderbolt."
William Shakespeare, The Tempest, Act 2.Scene 2. (Trinculo's monologue)

What was Trinculo on about when talking about Caliban?

Modern thinking inclines to the view that in describing Caliban, he was giving an early documented example of trimethylaminuria.

Which is?
People having a fish odour

Is it common?
No

And it is caused by?

Trimethylamine (TMA), (CH3)3N

How?

Fish contain a compound called trimethylamine N-oxide (TMAO). They are believed to use it to increase osmotic concentration and thus depress the freezing point of body fluids, an important detail in cold-water fish. It is also reckoned to counteract the perturbing effects of urea on proteins in enzyme systems.

So how does trimethylamine get formed?

The body contains enzymes called flavinmonoxygenases (FMOs) which are thought to break down environmental toxins in the body. One of these, FMO3, removes nitrogen compounds obtained from the diet. Mutated copies of FMO3 lose the ability to oxidise Me3N to Me3NO. One source of trimethylamine is the compound choline (Me3N+CH2CH2OH), which is found in eggs, liver, legumes and some grains; it is broken down by bacteria to form Me3N.

In turn, Me3N is normally oxidised in the liver to odourless TMAO, which is excreted from the body.

However, when the ability to oxidize trimethylamine is impaired, large amounts of the unchanged amine are excreted, producing of a highly unpleasant, fishy body odour which has led to the colloquial term "fish odour syndrome" to describe the condition.

What is trimethylamine like (apart from the fishy smell) ?

It's a colourless liquid with a boiling point around 3.5C, compared with the higher melting point of 224-226C for the more polar Me3NO, which presumably has dipole-dipole intermolecular forces. Trimethylamine is a base, like ammonia. Also like ammonia, it has a trigonal pyramidal structure. The C-N-C bond angle is 110.9, compared with 107.2 in NH3, presumably due to greater repulsions between the methyl groups. This angle is reduced to 109.0 in Me3NO.

How widespread is the complaint?

Pharmacogenetic screening has indicated that the complaint is inherited as an autosomal recessive trait. Up to 1% of people are believed to contain a defective copy of the FMO3 gene, of which everyone has two copies, one inherited from each parent. The problem arises when both copies are defective. This means that possibly one person in 10,000 could suffer from fish-breath syndrome, making it about as common as PKU (Phenylketonuria), another genetic defect about which much more is known.

What can sufferers from fish breath syndrome do about it?

It is obviously a very unpleasant thing to live with. Sufferers get ostracised, children get called names at school. People start smoking to disguise the smell. At present, no cure is known. Taking antibiotics can help (metronidazole, neomycin and lactulose have been used) and trying to control the amount of protein (and hence choline) in the diet, by eating less fish, eggs and liver, may be a good idea, though ingesting too little choline may lead to liver problems. A compound called indole-3-carbinole, found in broccoli and other dark green vegetables, can block the enzyme FMO3, so avoiding broccoli may also help. Things are complicated by the fact that indole-3-carbinole is now believed to help prevent cervical cancer.

Are humans the only sufferers?

It seems that dogs sometimes smell of trimethylamine, whilst Swedish scientists have discovered the mutation in the FMO3 gene causing some Swedish cows to produce fish-smelling milk. The plant called Stinking Goosefoot (Chenopodium olidum), shown right, also produces trimethylamine.

Bibliography

R.J. Gillespie and I. Hargittai, The VSEPR Model of Molecular Geometry, Allyn and Bacon, Boston, 1991, pp80-81 (shape). Dictionary of Natural Products, J.Buckingham ed., Chapman and Hall/CRC Press, London, 1994, Compounds T-02783 (trimethylamine) and T-02784 (trimethylamine N-oxide). M.Al-Waiz, R.Ayesh, S.C.Mitchell, J.R.Idle, and R.L.Smith, Lancet, 1987, i, 634-635 R.Ayesh, S.C.Mitchell, A.Q.Zhang, and R.L.Smith, Brit. Med. J., 1993, 307, 655-657. S.C.Mitchell, Perspec. Biol. Med., 1996, 39, 223-235. S.C.Mitchell and R.L.Smith, Drug Metab. Dispos., 2001, 29,517-521. B.A.Seibel. and P.J.Walsh, Journal of Experimental Biology, 2002, 205 (3), 297 (Me3NO in fish) A.Lunden, S.Marklund, V.Gustafsson and L.Andersson, Genome Res. 2002, 12(12):1885 (cows) H.U.Rehman, Postgrad. Med. J., 1999, 75(886), 451. (treatment) J.R.Cashman, K.Camp, S.S.Fakharzadeh , P.V.Fennessey, R.N.Hines, O.A.Mamer, S.C.Mitchell, G.P.Nguyen, D.Schlenk, R.L.Smith, S.S.Tjoa, D.E.Williams and S. Yannicelli, Curr. Drug Metab. 2003 Apr;4(2):151. (review) E.A.Fraser-Andrews, N.J.Manning, P.Eldridge, J.McGrath and H.du P.Menage, Clin Exp Dermatol. 2003, 28(2):203 (diagnosis) http://www.botanical.com/botanical/mgmh/a/arrac059.html (Stinking Goosefoot)

J.R.Cashman, Current Drug Metabolism, 2000, 1, 181. (FMO3) J.R.Cashman, B.R.Akerman, S.M.Forrest, and E.P.Treacy, Drug Metabolism and Disposition, 2000, 28, 169 (FMO3)