Methoxyamine is the organic compound with the formula CH3ONH2. Also called O-methylhydroxylamine, it is a colourless volatile liquid that is soluble in polar organic solvent and in water. It is a derivative of hydroxylamine with the hydroxyl hydrogen replaced by a methyl group. Alternatively, it can be viewed as a derivative of methanol with the hydroxyl hydrogen replaced by an amino group. It is an isomer of N-methylhydroxylamine and aminomethanol. It decomposes in an exothermic reaction (-56 kJ/mol) to methane and azanone unless stored as a hydrochloride salt.[2]
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| Names | |
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| Preferred IUPAC name
O-Methylhydroxylamine[1] | |
| Other names
Methoxylamine; (Aminooxy)methane
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| Identifiers | |
3D model (JSmol)
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| ChEMBL | |
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| DrugBank | |
| ECHA InfoCard | 100.000.600 |
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PubChem CID
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| UNII | |
CompTox Dashboard (EPA)
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| Properties | |
| CH5NO | |
| Molar mass | 47.057 g·mol−1 |
| Appearance | Colorless liquid |
| Odor | Ammoniacal |
| Melting point | −86.4[2] °C (−123.5 °F; 186.8 K) |
| Boiling point | 48.1[2] °C (118.6 °F; 321.2 K) |
| Miscible | |
| Vapor pressure | 297.5 mmHg at 25°C |
Refractive index (nD)
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1.4164 |
| Hazards | |
| GHS labelling:[3] | |
 
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| Danger | |
| H302, H312, H314, H332 | |
| P260, P261, P264, P264+P265, P270, P271, P280, P301+P317, P301+P330+P331, P302+P352, P302+P361+P354, P304+P340, P305+P354+P338, P316, P317, P321, P330, P362+P364, P363, P405, P501 | |
| NFPA 704 (fire diamond) | |
| Safety data sheet (SDS) | Santa Cruz (HCl) |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Synthesis
editMethoxyamine is prepared via O-alkylation of hydroxylamine derivatives. For example, it is obtained by O-methylation of acetone oxime followed by hydrolysis of the O-methylated oxime:[4]
- (CH3)2CNOCH3 + H2O → (CH3)2CO + H2NOCH3
The other broad method involves methanolysis of hydroxylamine sulfonates:
- H2NOSO3− + CH3OH → H2NOCH3 + HSO4−
Reactions
editAnalogous to the behavior of hydroxylamine, methoxyamine condenses with ketones and aldehydes to give imines.
Methoxyamine is used as a synthon for NH2+. It undergoes deprotonation by methyl lithium to give CH3ONHLi. This N-lithio derivative is attacked by organolithium compounds to give, after hydrolysis, amines:[5]
- H2NOCH3 + CH3Li → LiHNOCH3 + CH4
- LiHNOCH3 + RLi → RNHLi + LiOCH3
- RNHLi + H2O → RNH2 + LiOH
Uses
editMethoxyamine has potential medicinal uses. It covalently binds to apurinic/apyrimidinic (AP) DNA damage sites and inhibits base excision repair (BER), which may result in an increase in DNA strand breaks and apoptosis.This agent may potentiate the anti-tumor activity of alkylating agents.[6]
Examples of drugs incorporating the methoxyamine unit are brasofensine and gemifloxacin.
References
edit- ^ International Union of Pure and Applied Chemistry (2014). Nomenclature of Organic Chemistry: IUPAC Recommendations and Preferred Names 2013. The Royal Society of Chemistry. p. 994. doi:10.1039/9781849733069. ISBN 978-0-85404-182-4.
- ^ a b c Kokko, Bruce J.; Edmondson, Scott D. (14 March 2008). "O -Methylhydroxylamine". Encyclopedia of Reagents for Organic Synthesis: rm192m.pub2. doi:10.1002/047084289X.rm192m.pub2. ISBN 978-0471936237.
- ^ "O-Methylhydroxylamine". pubchem.ncbi.nlm.nih.gov.
- ^ Review: Houben-Weyl, Methoden der organische Chemie, vol 10.1, p 1186. Patent: Klein, Ulrich; Buschmann, Ernst; Keil, Michael; Goetz, Norbert; Hartmann, Horst "Process for preparing O-substituted hydroxylammonium salts." Ger. Offen. to BASF, (1994), DE 4233333 A1 19940407.
- ^ Kokko, Bruce J.; Edmondson, Scott D. (2008). "O-Methylhydroxylamine". Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289X.rm192m.pub2. ISBN 978-0471936237.
- ^ NCI