O-(4-NITROBENZYL)HYDROXYLAMINE HYDROCHLORIDE Property

Melting point:

215 °C (dec.)(lit.)

Boiling point:

226°C

storage temp. 

Keep in dark place,Inert atmosphere,Room temperature

solubility 

DMSO (Slightly), Methanol (Slightly)

form 

Solid

color 

White to Off-White

Sensitive 

Moisture & Light Sensitive

BRN 

3709565

CAS DataBase Reference

2086-26-2(CAS DataBase Reference)

EPA Substance Registry System

Hydroxylamine, O-[(4-nitrophenyl)methyl]-, monohydrochloride (2086-26-2)

Safety

Risk Statements 

36/37/38

Safety Statements 

22-24/25

WGK Germany 

3

RTECS 

NC4400050

F 

3-8-9

TSCA 

Yes

HazardClass 

IRRITANT

HS Code 

29280000

Hazard and Precautionary Statements (GHS)

Symbol(GHS)

Signal word

Warning

Hazard statements

H315Causes skin irritation

H319Causes serious eye irritation

H335May cause respiratory irritation

Precautionary statements

P264Wash hands thoroughly after handling.

P264Wash skin thouroughly after handling.

P280Wear protective gloves/protective clothing/eye protection/face protection.

P302+P352IF ON SKIN: wash with plenty of soap and water.

P305+P351+P338IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continuerinsing.

P321Specific treatment (see … on this label).

P332+P313IF SKIN irritation occurs: Get medical advice/attention.

P362Take off contaminated clothing and wash before reuse.

O-(4-NITROBENZYL)HYDROXYLAMINE HYDROCHLORIDE Chemical Properties,Usage,Production

Chemical Properties

LIGHT YELLOW POWDER

Uses

A strong UV chromophore used in derivatization of reducing sugars for ultraviolet absorption detection in HPLC analyses.

Uses

As a strong UV chromophore, O-(4-Nitrobenzyl)hydroxylamine hydrochloride can be used in derivatization of reducing sugars for ultraviolet absorption detection in HPLC analyses.

Preparation

To a solution of 25 gm (0.183 mole) of benzohydroxamic acid in 28 ml of ethanol and 10.2 gm (0.184 mole) of potassium hydroxide in 40 ml of water is added a hot solution of 39.4 gm (0.184 mole) of p-nitrobenzyl bromide in ethanol. The mixture is then heated under a reflux condenser for 45 min and cooled. The precipitated crystals are separated and crystallized from ethanol. (No yield reported.) A solution of 15 gm (0.055 mole) of the above o-p-nitrobenzylbenzohy-droxamic acid (p-nitrobenzyl benzohydroxamate) in 125 ml of hot ethanol is heated to reflux for 25 min with 150 ml of cone, hydrochloric acid. To prevent the precipitation of the final product during the work-up, the following steps are carried out rapidly. The clear solution is diluted with 150 ml of water and while still warm benzoic acid and other by-products are separated by extraction with 200 ml of chloroform. The aqueous layer is evaporated to dryness under reduced pressure to afford a crude yield of 10.75 gm (96%). The residue is recrys­tallized from hot 2 Ν hydrochloric acid and washed in turn with ethanol and with ether to afford a solid, m.p. 217°C.
The free base may be produced by neutralizing the salt with sodium carbonate solution; O-p-nitrobenzylhydroxylamine, m.p. 56°C (recrystal­lized from petroleum ether). By a similar technique, O-allylhydroxylamine hydrochloride, m.p. 172°C (dec.) was also prepared.

An examination of the product of butylating benzohydroxamic acid showed that a nonacidic fraction and an equal weight of an acidic fraction were readily isolated. The nonacidic fraction contained mainly Ο, Ο '-dibutyl benzohydroxi-mate (b.p. 175-180°C/13 mm Hg) and some aniline (probably formed during the reaction by a Lossen rearrangement). On hydrolysis with eth-anolic hydrochloric acid, the hydroximate produced ethyl benzoate and O-butylhydroxylamine hydrobromide (m.p. 159-161°C; hydrochloride, m.p. 156-157°C).
The acidic fraction contained mainly O-butylbenzohydroxamic acid (butyl benzohydroxamate) which on hydrolysis formed O-butylhydrox­ylamine hydrochloride and benzoic acid. It has been contended that in this particular work, the presence of an Ν,Ο-dibutylbenzohy-droxamic acid had been overlooked. The major source of O-butylhy­droxylamine hydrochloride is from the acidic fraction, although the yield is not particularly high. The initial preparation of the butylated benzohydroxamic acid deriva­tives has been repeated recently. The analysis of the reaction products by vapor-phase chromatography showed it to contain 43% of O-butyl­benzohydroxamic acid (butyl benzohydroxamate), 17% of iV,0-dibutyl-benzohydroxamic acid, and 8% of n-butyl(Z)-0-n-butylbenzohydroximate:

The nature of the remaining 32% of the crude reaction product was not determined. The use of benzohydroxamic acid has been extended to the preparation of a variety of O-substituted hydroxylamines. For example, halocarboxylic acids have been used as alkylating agents to produce α-aminooxy acids of the type, NH20(CH2)„C02H.
A variety of O-benzylhydroxylamines, O-aralkylhydroxylamines, as well as simpler O-substituted hydroxylamines have also been prepared. In some of these prepara­tions, the hydrolysis of the O-substituted benzohydroxamic acid was car­ried out with hot alcoholic hydrogen chloride. This treatment evidently prevented the O-N cleavage which had been observed during the aqueous hydrolysis of the substituted benzohydroxamic acids.