Methoxyamine: Difference between revisions
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| ImageFile = Methoxyamine. |
| ImageFile = Methoxyamine.svg |
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| ImageSize = 150px |
| ImageSize = 150px |
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| ImageName = Methoxyamine |
| ImageName = Methoxyamine |
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| ImageFile1 = Methoxyamine-3D.jpg |
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| ImageSize1 = 200px |
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| ImageName1 = Methoxyamine |
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| PIN = ''O''-Methylhydroxylamine<ref>{{cite book |author=[[International Union of Pure and Applied Chemistry]] |date=2014 |title=Nomenclature of Organic Chemistry: IUPAC Recommendations and Preferred Names 2013 |publisher=[[Royal Society of Chemistry|The Royal Society of Chemistry]] |pages=994 |doi=10.1039/9781849733069 |isbn=978-0-85404-182-4}}</ref> |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| ChEMBL = 1213633 |
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| ChemSpiderID = 3970 |
| ChemSpiderID = 3970 |
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| EC_number = 200-660-1 |
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| DrugBank = DB06328 |
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| PubChem = 4113 |
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| UNII_Ref = {{fdacite|correct|FDA}} |
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| UNII = 9TZH4WY30J |
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| InChI = 1S/CH5NO/c1-3-2/h2H2,1H3 |
| InChI = 1S/CH5NO/c1-3-2/h2H2,1H3 |
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| InChIKey = GMPKIPWJBDOURN-UHFFFAOYSA-N |
| InChIKey = GMPKIPWJBDOURN-UHFFFAOYSA-N |
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| SMILES = CON |
| SMILES = CON |
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| EINECSID = 200-660-1 |
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| NCI = TRC102 |
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| CASNo = 593-56-6 |
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|Section2={{Chembox Properties |
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| C = 1 |
| C=1 | N=1 | O=1 | H=5 |
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| N = 1 |
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| O = 1 |
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| H = 5 |
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| Appearance = Colorless liquid |
| Appearance = Colorless liquid |
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| Odor = Ammoniacal |
| Odor = Ammoniacal |
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| BoilingPtC = 48.1 <ref name=Kokko>{{cite journal |last1=Kokko |first1=Bruce J. |last2=Edmondson |first2=Scott D. |title=O -Methylhydroxylamine |journal=Encyclopedia of Reagents for Organic Synthesis |date=14 March 2008 |pages=rm192m.pub2 |doi=10.1002/047084289X.rm192m.pub2|isbn=978-0471936237 }}</ref> |
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| Density = 1.0003 g/mL |
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| BoilingPtC = 50 |
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| Solubility = Miscible |
| Solubility = Miscible |
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| RefractIndex = 1.4164 |
| RefractIndex = 1.4164 |
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| VaporPressure = 297.5 mmHg at 25°C |
| VaporPressure = 297.5 mmHg at 25°C |
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|Section7={{Chembox Hazards |
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| GHS_ref=<ref>{{cite web |title=O-Methylhydroxylamine |url=https://pubchem.ncbi.nlm.nih.gov/compound/4113#section=Safety-and-Hazards |website=pubchem.ncbi.nlm.nih.gov |language=en}}</ref> |
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| GHSPictograms = {{GHS05}}{{GHS07}} |
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| GHSSignalWord = Danger |
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| HPhrases = {{H-phrases|302|312|314|332}} |
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| 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}} |
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| NFPA-H = 3 |
| NFPA-H = 3 |
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| NFPA-F = 1 |
| NFPA-F = 1 |
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| NFPA-R = 1 |
| NFPA-R = 1 |
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| NFPA- |
| NFPA-S = |
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'''Methoxyamine''' |
'''Methoxyamine''' is the [[organic compound]] with the formula CH<sub>3</sub>ONH<sub>2</sub>. 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.<ref name=Kokko/> |
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==Synthesis== |
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:hydroxylamine + methane ⇌ hydrogen + methoxyamine / [[N-Methylhydroxylamine|''N''-methylhydroxylamine]] |
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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:<ref>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.</ref> |
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The other broad method involves [[methanol]]ysis of hydroxylamine sulfonates: |
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:HONH<sub>2</sub> + CH<sub>4</sub> ⇌ H<sub>2</sub> + H<sub>3</sub>CONH<sub>2</sub> / HONHCH<sub>3</sub> |
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==Reactions== |
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:methanol + ammonia ⇌ hydrogen + methoxyamine / [[aminomethanol]] |
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Analogous to the behavior of hydroxylamine, methoxyamine condenses with ketones and aldehydes to give imines. |
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Methoxyamine is used as a [[synthon]] for NH<sub>2</sub><sup>+</sup>. It undergoes deprotonation by [[methyl lithium]] to give CH<sub>3</sub>ONHLi. This ''N''-lithio derivative is attacked by organolithium compounds to give, after hydrolysis, amines:<ref>{{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 }}</ref> |
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: H<sub>2</sub>NOCH<sub>3</sub> + CH<sub>3</sub>Li → LiHNOCH<sub>3</sub> + CH<sub>4</sub> |
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: LiHNOCH<sub>3</sub> + RLi → RNHLi + LiOCH<sub>3</sub> |
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: RNHLi + H<sub>2</sub>O → RNH<sub>2</sub> + LiOH |
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==Uses== |
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Methoxyamine is soluble in water and most alcohols and ethers. |
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⚫ | 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.<ref name=NCI>[http://www.cancer.gov/drugdictionary?cdrid=599836 NCI]</ref> |
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Examples of drugs incorporating the methoxyamine unit are [[brasofensine]] and [[gemifloxacin]]. |
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⚫ | Methoxyamine |
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==References== |
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{{reflist}} |
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[http://pubchem.ncbi.nlm.nih.gov/summary/summary.cgi?cid=4113 Pubchem] |
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[http://www.chemspider.com/Chemical-Structure.3970.html ChemSpider] |
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[http://datasheets.scbt.com/sc-257710.pdf MSDS] |
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==External links== |
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{{Amine-stub}} |
Latest revision as of 01:28, 17 August 2023
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 | |
ChemSpider | |
DrugBank | |
ECHA InfoCard | 100.000.600 |
EC Number |
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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] | |
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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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]
Synthesis
[edit]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:[4]
- (CH3)2CNOCH3 + H2O → (CH3)2CO + H2NOCH3
The other broad method involves methanolysis of hydroxylamine sulfonates:
- H2NOSO3− + CH3OH → H2NOCH3 + HSO4−
Reactions
[edit]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:[5]
- H2NOCH3 + CH3Li → LiHNOCH3 + CH4
- LiHNOCH3 + RLi → RNHLi + LiOCH3
- RNHLi + H2O → RNH2 + LiOH
Uses
[edit]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.[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