Methoxyamine
{{Chembox
| ImageFile = Methoxyamine.svg
| ImageSize = 150px
| ImageName = Methoxyamine
| ImageFile1 = Methoxyamine-3D.jpg
| ImageSize1 = 200px
| ImageName1 = Methoxyamine
| PIN = O-Methylhydroxylamine{{cite book |author=International Union of Pure and Applied Chemistry |date=2014 |title=Nomenclature of Organic Chemistry: IUPAC Recommendations and Preferred Names 2013 |publisher=The Royal Society of Chemistry |pages=994 |doi=10.1039/9781849733069 |isbn=978-0-85404-182-4}}
| OtherNames = Methoxylamine; (Aminooxy)methane
|Section1={{Chembox Identifiers
| CASNo = 67-62-9
| CASNo_Ref = {{cascite|correct|CAS}}
| ChEMBL = 1213633
| ChemSpiderID = 3970
| EC_number = 200-660-1
| DrugBank = DB06328
| PubChem = 4113
| UNII_Ref = {{fdacite|correct|FDA}}
| UNII = 9TZH4WY30J
| InChI = 1S/CH5NO/c1-3-2/h2H2,1H3
| InChIKey = GMPKIPWJBDOURN-UHFFFAOYSA-N
| SMILES = CON
}}
|Section2={{Chembox Properties
| C=1 | N=1 | O=1 | H=5
| Appearance = Colorless liquid
| Odor = Ammoniacal
| Solubility = Miscible
| RefractIndex = 1.4164
| VaporPressure = 297.5 mmHg at 25°C
}}
|Section7={{Chembox Hazards
| GHSPictograms = {{GHS05}}{{GHS07}}
| GHSSignalWord = Danger
| HPhrases = {{H-phrases|302|312|314|332}}
| PPhrases = {{P-phrases|260|261|264|264+265|270|271|280|301+317|301+330+331|302+352|302+361+354|304+340|305+354+338|316|317|321|330|362+364|363|405|501}}
| ExternalSDS = [http://datasheets.scbt.com/sc-257710.pdf Santa Cruz] (HCl)
| NFPA-H = 3
| NFPA-F = 1
| NFPA-R = 1
| NFPA-S =
}}
}}
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.
Synthesis
Methoxyamine 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: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.
:(CH3)2CNOCH3 + H2O → (CH3)2CO + H2NOCH3
The other broad method involves methanolysis of hydroxylamine sulfonates:
:H2NOSO3− + CH3OH → H2NOCH3 + HSO4−
Reactions
Analogous 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:{{cite book|doi=10.1002/047084289X.rm192m.pub2|chapter=O-Methylhydroxylamine |title=Encyclopedia of Reagents for Organic Synthesis |year=2008 |last1=Kokko |first1=Bruce J. |last2=Edmondson |first2=Scott D. |isbn=978-0471936237 }}
: H2NOCH3 + CH3Li → LiHNOCH3 + CH4
: LiHNOCH3 + RLi → RNHLi + LiOCH3
: RNHLi + H2O → RNH2 + LiOH
Uses
Methoxyamine 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.[http://www.cancer.gov/drugdictionary?cdrid=599836 NCI]
Examples of drugs incorporating the methoxyamine unit are brasofensine and gemifloxacin.
References
{{reflist}}
External links
- [http://www.sigmaaldrich.com/catalog/product/aldrich/226904 Sigma-Aldrich Methoxyamine Hydrochloride]