| Identification | Back Directory | [Name]
O-(2,4-dinitrophenyl)hydroxylamine | [CAS]
17508-17-7 | [Synonyms]
NSC 148499
2,4-NitrophenoxyaMine
2,4-DinitrophenoxyaMine
4-dinitrophenyl)hydroxylamine
2,4-Dinitrophenylhydroxylamine
1-aMinooxy-2,4-dinitro-benzene
O-(2,4-dinitrophenyl)hydroxylamine
HydroxylaMine,O-(2,4-dinitrophenyl)- | [EINECS(EC#)]
241-512-6 | [Molecular Formula]
C6H5N3O5 | [MDL Number]
MFCD00075001 | [MOL File]
17508-17-7.mol | [Molecular Weight]
199.121 |
| Chemical Properties | Back Directory | [Melting point ]
112.5°C | [Boiling point ]
336.62°C (rough estimate) | [density ]
1.6937 (rough estimate) | [refractive index ]
1.6910 (estimate) | [storage temp. ]
Keep in dark place,Sealed in dry,2-8°C | [solubility ]
DMSO (Sparingly), Methanol (Slightly) | [form ]
solid | [pka]
-1.07±0.70(Predicted) | [color ]
yellow |
| Questions And Answer(Q&A) | Back Directory | [Preparation]
To a stirred solution of 13.3 gm (0.1 mole) of t-butyl JV-hydroxycar-bamate and 5.6 gm (0.1 mole) of potassium hydroxide in 200 ml of absolute ethanol is added 20.2 gm (0.1 mole) of 2,4-dinitrochlorobenzene. The resultant deep red solution is stirred at room temperature for 1 hr; then enough glacial acetic acid is added dropwise to produce a light yellow solution. The solution is poured into 1.5 liters of cold water. The yellow oil which separates is gradually converted to crystals. The solid ί-butyl JV-(2,4-dinitrophenoxy)carbamate is separated, dried, and recrystallized from an ethyl acetate-hexane mixture to afford 16.4 gm (53%), m.p. 74-75°C. To 15 ml of trifluoroacetic acid is added 4 gm (0.0133 mole) of the i-butyl J/V-(2,4-dinitrophenoxy)carbamate. After the evolution of carbon dioxide has subsided, the solution is poured into 100 ml of ice water. The resultant oily layer crystallizes on standing to afford 2.5 gm (95%), m.p. 112°C (from ethanol).
Recently it was discovered that the alkylation of ethyl JV-hydroxy-carbamate under alkaline conditions, particularly in a DMF medium at 60°C in the presence of sodium bicarbonate, leads to the ultimate formation of O-alkylated hydroxylamines. On the other hand, at 80-85°C, the direct alkylation without the presence of a base ultimately leads to N-alkylhydrox-ylamines (see Table I) [59]. The reaction of ethylazidoformate with an alcohol, while perhaps hazardous, may have some merit (Eqs. 31-33). The overall yield, based on ethyl chloroformate, is said to be on the order of 60%.
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| Hazard Information | Back Directory | [Chemical Properties]
Light yellow solid | [Uses]
Efficient agent for metal-free amination of arylboronic acids leading to primary anilines. Reagents used in Rhodium-catalyzed aziridines formation. | [Uses]
O-(2,4-Dinitrophenyl)hydroxylamine is a rapid active-site-directed inhibitor of D-amino acid oxidase; modification results in specific incorporation of an amine group into an accessible nucleophilic r
esidue with concomitant release of 2,4-dinitrophenol. | [Preparation]
To a stirred solution of 13.3 gm (0.1 mole) of t-butyl JV-hydroxycar-bamate and 5.6 gm (0.1 mole) of potassium hydroxide in 200 ml of absolute ethanol is added 20.2 gm (0.1 mole) of 2,4-dinitrochlorobenzene. The resultant deep red solution is stirred at room temperature for 1 hr; then enough glacial acetic acid is added dropwise to produce a light yellow solution. The solution is poured into 1.5 liters of cold water. The yellow oil which separates is gradually converted to crystals. The solid ?-butyl JV-(2,4-dinitrophenoxy)carbamate is separated, dried, and recrystallized from an ethyl acetate-hexane mixture to afford 16.4 gm (53%), m.p. 74-75°C. To 15 ml of trifluoroacetic acid is added 4 gm (0.0133 mole) of the i-butyl J/V-(2,4-dinitrophenoxy)carbamate. After the evolution of carbon dioxide has subsided, the solution is poured into 100 ml of ice water. The resultant oily layer crystallizes on standing to afford 2.5 gm (95%), m.p. 112°C (from ethanol).
Recently it was discovered that the alkylation of ethyl JV-hydroxy-carbamate under alkaline conditions, particularly in a DMF medium at 60°C in the presence of sodium bicarbonate, leads to the ultimate formation of O-alkylated hydroxylamines. On the other hand, at 80-85°C, the direct alkylation without the presence of a base ultimately leads to N-alkylhydrox-ylamines (see Table I) [59]. The reaction of ethylazidoformate with an alcohol, while perhaps hazardous, may have some merit (Eqs. 31-33). The overall yield, based on ethyl chloroformate, is said to be on the order of 60%.
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