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| ImageName = Methoxyamine
| ImageName = Methoxyamine
| ImageFile1 = Methoxyamine-3D.jpg
| ImageFile1 = Methoxyamine-3D.jpg
| ImageSize1 = 150px
| ImageSize1 = 200px
| ImageName1 = Methoxyamine
| ImageName1 = Methoxyamine
| 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>
| IUPACName = Methoxyamine
| OtherNames = Methoxylamine; (Aminooxy)methane; ''O''-Methylhydroxylamine
| OtherNames = Methoxylamine; (Aminooxy)methane
|Section1={{Chembox Identifiers
|Section1={{Chembox Identifiers
⚫
| CASNo = 67-62-9
| CASNo_Ref = {{cascite|correct|CAS}}
| ChEMBL = 1213633
| ChemSpiderID = 3970
| ChemSpiderID = 3970
| EC_number = 200-660-1
| DrugBank = DB06328
| PubChem = 4113
| PubChem = 4113
| UNII_Ref = {{fdacite|correct|FDA}}
| UNII = 9TZH4WY30J
| InChI = 1S/CH5NO/c1-3-2/h2H2,1H3
| InChI = 1S/CH5NO/c1-3-2/h2H2,1H3
| InChIKey = GMPKIPWJBDOURN-UHFFFAOYSA-N
| InChIKey = GMPKIPWJBDOURN-UHFFFAOYSA-N
| SMILES = CON
| SMILES = CON
⚫
| CASNo = 593-56-6
}}
}}
|Section2={{Chembox Properties
|Section2={{Chembox Properties
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| Appearance = Colorless liquid
| Appearance = Colorless liquid
| Odor = Ammoniacal
| Odor = Ammoniacal
| 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>
| Density = 1.0003 g/mL{{citation needed|date=August 2014}}
⚫
| MeltingPtC = -86.4<ref name=Kokko/>
| BoilingPtC = 50
| BoilingPt_notes ={{citation needed|date=August 2014}}
⚫
| MeltingPtC = 42
| MeltingPt_notes ={{citation needed|date=August 2014}}
| Solubility = Miscible
| Solubility = Miscible
| RefractIndex = 1.4164
| RefractIndex = 1.4164
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}}
}}
|Section7={{Chembox Hazards
|Section7={{Chembox Hazards
| 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>
| 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)
| ExternalSDS = [http://datasheets.scbt.com/sc-257710.pdf Santa Cruz] (HCl)
| NFPA-H = 3
| NFPA-H = 3
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}}
}}


'''Methoxyamine''' is the [[organic compound]] with the formula CH<sub>3</sub>ONH<sub>2</sub>. Also called '''''O''-methylhydroxylamine''', it a colourless volatile liquid that is soluble in polar organic solvents 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.
'''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/>


==Synthesis==
==Synthesis==
Methoxyamine is prepared via ''O''-alkylation of hydroxylamine derivatives. For example, it is obtained by ''O''-methylation of [[acetone oxime]] followed by hydrolysis or 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>
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>
:(CH<sub>3</sub>)<sub>2</sub>CNOCH<sub>3</sub> + H<sub>2</sub>O → (CH<sub>3</sub>)<sub>2</sub>CO + H<sub>2</sub>NOCH<sub>3</sub>
:(CH<sub>3</sub>)<sub>2</sub>CNOCH<sub>3</sub> + H<sub>2</sub>O → (CH<sub>3</sub>)<sub>2</sub>CO + H<sub>2</sub>NOCH<sub>3</sub>


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==Reactions==
==Reactions==
Like hydroxylamine, methoxyamine forms oximes upon treatment with ketones and aldehydes.
Analogous to the behavior of hydroxylamine, methoxyamine condenses with ketones and aldehydes to give imines.


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>Bruce J. Kokko, Scott D. Edmondson "O-Methylhydroxylamine" in eEROS, 2008. {{DOI|10.1002/047084289X.rm192m.pub2}}</ref>
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>
: H<sub>2</sub>NOCH<sub>3</sub> + CH<sub>3</sub>Li → LiHNOCH<sub>3</sub> + CH<sub>4</sub>
: H<sub>2</sub>NOCH<sub>3</sub> + CH<sub>3</sub>Li → LiHNOCH<sub>3</sub> + CH<sub>4</sub>
: LiHNOCH<sub>3</sub> + RLi → RNHLi + LiOCH<sub>3</sub>
: LiHNOCH<sub>3</sub> + RLi → RNHLi + LiOCH<sub>3</sub>
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==Uses==
==Uses==
Methoxyamine is an orally bioavailable small molecule inhibitor with potential adjuvant activity.<ref name=NCI>[http://www.cancer.gov/drugdictionary?cdrid=599836 NCI]</ref> Methoxyamine 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.<ref name=NCI/> This agent may potentiate the anti-tumor activity of alkylating agents.
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>


Drugs include [[brasofensine]] as well as [[Gemifloxacin]],..
Examples of drugs incorporating the methoxyamine unit are [[brasofensine]] and [[gemifloxacin]].


==References==
==References==
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* [http://www.sigmaaldrich.com/catalog/product/aldrich/226904 Sigma-Aldrich Methoxyamine Hydrochloride]
* [http://www.sigmaaldrich.com/catalog/product/aldrich/226904 Sigma-Aldrich Methoxyamine Hydrochloride]


[[Category:Amines]]
[[Category:Hydroxylamines]]

Latest revision as of 01:28, 17 August 2023

Methoxyamine
Methoxyamine
Methoxyamine
Names
Preferred IUPAC name
O-Methylhydroxylamine[1]
Other names
Methoxylamine; (Aminooxy)methane
Identifiers
3D model (JSmol)
ChEMBL
ChemSpider
DrugBank
ECHA InfoCard 100.000.600 Edit this at Wikidata
EC Number
  • 200-660-1
UNII
  • InChI=1S/CH5NO/c1-3-2/h2H2,1H3
    Key: GMPKIPWJBDOURN-UHFFFAOYSA-N
  • CON
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
1.4164
Hazards
GHS labelling:[3]
GHS05: CorrosiveGHS07: Exclamation mark
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)
NFPA 704 four-colored diamondHealth 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasFlammability 1: Must be pre-heated before ignition can occur. Flash point over 93 °C (200 °F). E.g. canola oilInstability 1: Normally stable, but can become unstable at elevated temperatures and pressures. E.g. calciumSpecial hazards (white): no code
3
1
1
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).

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]
  1. ^ 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.
  2. ^ 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.
  3. ^ "O-Methylhydroxylamine". pubchem.ncbi.nlm.nih.gov.
  4. ^ 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.
  5. ^ Kokko, Bruce J.; Edmondson, Scott D. (2008). "O-Methylhydroxylamine". Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289X.rm192m.pub2. ISBN 978-0471936237.
  6. ^ NCI
[edit]
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