Organic Syntheses, CV 5, 1029
Submitted by Melvin S. Newman and H. Boden
1.
Checked by William E. Parham, Peter Delvigs, and E. Leete.
1. Procedure
A
5-l. three-necked flask fitted with an
all-glass addition funnel and two
condensers is charged with
770 ml. of concentrated sulfuric acid and
1.3 l. of 90% fuming nitric acid (Note
1). The solution is heated under gentle reflux, and a solution of
73 g. (0.4 mole) of 9-fluorenone (Note
2) in
840 ml. of concentrated sulfuric acid (Note
3) is added from the
dropping funnel over a 1-hour period. After the
fluorenone addition is complete, a solution of
950 ml. of fuming nitric acid in
1120 ml. of concentrated sulfuric acid is added dropwise during 8.5 hours to the gently refluxing reaction mixture. The heating jacket is turned off and the solution is allowed to stand for 10 hours. The reaction mixture is poured into 5 gallons of water in two
5-gal. crocks (Note
4). The light yellow precipitate is washed with water, twice by decantation, filtered, washed several times with water and sucked dry, and finally is dried in a vacuum
oven at 80° for 10 hours (Note
5). The yield of crude
2,4,5,7-tetranitrofluorenone, m.p.
249–253°, is
105–117 g. (
72–80%). This solid is recrystallized from
1.6 l. of acetic acid containing
100 ml. of acetic anhydride. The hot solution is filtered through a
fluted filter and cooled rapidly to yield
80–86 g. (
51–54%) of
2,4,5,7-tetranitrofluorenone, m.p.
253.0–254.5° cor. (Note
6) and (Note
7).
2. Notes
1.
Baker Analyzed reagent grade fuming nitric acid may be added to the
sulfuric acid without special precautions, since the heat effect is not large.
2.
Eastman white label 9-fluorenone, m.p.
82–84°, was used. The checkers used material, m.p.
83.5–84.5°, prepared from
fluorene.
2
3. The deep purple-brown solution may have to be warmed in order to dissolve all the
fluorenone.
4. This operation must be carried out in the
hood.
5. The product may be dried under reduced pressure over
calcium chloride for several days.
6. Additional product amounting to 15–17% may be obtained by recrystallization of further crops from the mother liquor.
3. Discussion
The procedure described here is essentially that of Newman and Lutz.
3 2,4,5,7-Tetranitrofluorenone has been prepared by nitration of
fluorenone,
4 2,4,7-trinitrofluorenone,
5,6 and
4,5-dinitrofluorenone.
6 The preparation by Schmidt et al.,
4,5 which supposedly yielded the 2,3,6,7-isomer, has been shown
6 to yield the 2,4,5,7-isomer.
4. Merits of Preparation
This preparation is referenced from:
Appendix
Compounds Referenced (Chemical Abstracts Registry Number)
calcium chloride (10043-52-4)
sulfuric acid (7664-93-9)
acetic acid (64-19-7)
acetic anhydride (108-24-7)
nitric acid (7697-37-2)
fluorene (86-73-7)
2,4,7-Trinitrofluorenone (129-79-3)
fluorenone,
9-fluorenone (486-25-9)
2,4,5,7-Tetranitrofluorenone,
9-Fluorenone, 2,4,5,7-tetranitro- (746-53-2)
Tetranitrofluorenone
4,5-dinitrofluorenone
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