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Org. Synth. 1962, 42, 95
DOI: 10.15227/orgsyn.042.0095
2,4,5,7-TETRANITROFLUORENONE
[9-Fluorenone, 2,4,5,7-tetranitro-]
Submitted by Melvin S. Newman and H. Boden1.
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.
7. Tetranitrofluorenone crystallizes with 0.5 mole of acetic acid which is readily lost on heating under reduced pressure.
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 shown6 to yield the 2,4,5,7-isomer.
4. Merits of Preparation
The complexes which 2,4,5,7-tetranitrofluorenone forms with aromatic compounds are in general higher melting and less soluble than are the corresponding complexes of 2,4,7-trinitrofluorenone.3,7
This preparation is referenced from:

References and Notes
  1. Department of Chemistry, Ohio State University, Columbus, Ohio.
  2. E. B. Hershberg and I. S. Cliff, J. Am. Chem. Soc., 53, 2720 (1931).
  3. M. S. Newman and W. B. Lutz, J. Am. Chem. Soc., 78, 2469 (1956).
  4. J. Schmidt, F. Retzlaff and A. Haid, Ann., 390, 210 (1912).
  5. J. Schmidt and K. Bauer, Ber., 38, 3758 (1905).
  6. F. E. Ray and W. C. Francis, J. Org. Chem., 8, 52 (1943).
  7. M. Orchin, L. Reggel, and E. O. Woolfolk, J. Am. Chem. Soc., 69, 1225 (1947).

Appendix
Chemical Abstracts Nomenclature (Collective Index Number);
(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