Org. Synth. 1943, 23, 65
DOI: 10.15227/orgsyn.023.0065
p-NITROBENZOYL PEROXIDE
[Peroxide, bis(p-nitrobenzoyl)]
Submitted by Charles C. Price and Edwin Krebs.
Checked by R. L. Shriner and C. H. Tilford.
1. Procedure
A 600-ml. beaker containing 100 ml. of water and equipped with an efficient stirrer, a thermometer, and a 200-ml. separatory funnel is immersed in an ice-water bath. When the temperature of the water has fallen to 0–5°, 10 g. (0.13 mole) of sodium peroxide (Note 1) is added. Then, with vigorous stirring, a solution of 37 g. (0.2 mole) of p-nitrobenzoyl chloride in 100 ml. of dry toluene is added dropwise over a period of about 30 minutes. After the mixture has been stirred for an additional 1.5 hours, the precipitate is filtered and washed with 200 ml. of cold water (Note 2). The yield of p-nitrobenzoyl peroxide is 28.5–29 g. (86–88%). It melts at 155–156°.
The product may be recrystallized most conveniently by dissolving it as rapidly as possible (Note 3) in 500 ml. of dry toluene which has been preheated to 80–85°. As soon as the solid is completely dissolved (2–3 minutes of stirring), the solution is filtered through a warm Büchner funnel and the filtrate is immediately cooled in an ice-water bath. The yield of very pale yellow glistening needles is 25 to 26 g. (86–89% recovery); they melt at 156° with vigorous decomposition (Note 4).
2. Notes
1.
In a parallel experiment in which
25 g. of sodium peroxide was used, the precipitate was not the peroxide but evidently consisted of
sodium p-nitroperbenzoate.
2.
p-Nitrobenzoic acid may be recovered by acidification of the filtrate.
3.
Excessive heating during recrystallization leads to extensive decomposition of the peroxide.
4.
By a procedure similar to that described for
p-nitrobenzoyl peroxide, the following peroxides have been prepared:
m-nitrobenzoyl peroxide (m.p.
136–137°) in
90% yield;
anisoyl peroxide (m.p.
126–127°) in
86–89% yields;
p-bromobenzoyl peroxide (m.p.
144°) in
73% yield; and
3,4,5-tribromobenzoyl peroxide (m.p.
186°) in
40% yield.
1 The procedure is not satisfactory for preparation of
acetylsalicylyl peroxide, which is more conveniently prepared by action of
hydrogen peroxide upon an
acetone solution of the acid chloride.
3. Discussion
p-Nitrobenzoyl peroxide,
2 as well as
m-nitrobenzoyl peroxide2 and
anisoyl peroxide,
3 have been prepared in about 50% yields from the acid chlorides and an
acetone solution of
hydrogen peroxide, in the presence of a basic substance such as
pyridine,
sodium acetate, or
sodium hydroxide.
m-Nitrobenzoyl peroxide has also been prepared by nitration of
benzoyl peroxide with cold concentrated
nitric acid,
4 or with a cold
5 or hot
2 mixture of nitric and sulfuric acids.
Appendix
Chemical Abstracts Nomenclature (Collective Index Number);
(Registry Number)
sodium p-nitroperbenzoate
sodium acetate (127-09-3)
sodium hydroxide (1310-73-2)
nitric acid (7697-37-2)
acetone (67-64-1)
pyridine (110-86-1)
toluene (108-88-3)
hydrogen peroxide (7722-84-1)
sodium peroxide
benzoyl peroxide (94-36-0)
anisoyl peroxide
3,4,5-tribromobenzoyl peroxide
acetylsalicylyl peroxide
p-NITROBENZOIC ACID (62-23-7)
p-Nitrobenzoyl chloride (122-04-3)
p-Nitrobenzoyl peroxide,
Peroxide, bis(p-nitrobenzoyl) (1712-84-1)
m-nitrobenzoyl peroxide
p-bromobenzoyl peroxide
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