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Org. Synth. 1941, 21, 105
DOI: 10.15227/orgsyn.021.0105
TETRANITROMETHANE
[Methane, tetranitro-]
Submitted by Poe Liang
Checked by Nathan L. Drake and Ralph Mozingo.
1. Procedure
Caution! The product is toxic. The reaction should be carried out in a hood.
In a 250-ml. Erlenmeyer flask provided with a two-holed stopper which has a slit cut in one edge to serve as an air vent and which holds a thermometer, the bulb of which reaches almost to the bottom of the flask, is placed 31.5 g. (0.5 mole) of anhydrous nitric acid (Note 1). The flask is cooled below 10° in ice water, and 51 g. (0.5 mole) of acetic anhydride (Note 2) is slowly added from a buret through the second hole in the stopper in portions of about 0.5 ml. at a time. The temperature of the reaction mixture is never allowed to rise above 10° (Note 3). After about 5 ml. of the acetic anhydride has been added the reaction becomes less violent, and larger portions, increasing gradually from 1 to 5 ml., may be introduced at a time with constant shaking. After all the acetic anhydride has been added, the stopper and the thermometer are removed. The neck of the flask is wiped clean with a towel, and the flask is then covered with an inverted beaker and allowed to come up to room temperature in the original ice bath (Note 4).
The mixture is allowed to stand at room temperature for 7 days (Note 5), and the tetranitromethane is separated by pouring the mixture into 300 ml. of water in a 500-ml. round-bottomed flask and steam distilling (Note 6). The tetranitromethane passes over with the first 20 ml. of the distillate. The heavy product is separated from the upper layer of water, washed first with dilute alkali, finally with water, and dried over anhydrous sodium sulfate. The yield of tetranitromethane is 14–16 g. (57–65%). The product should not be distilled, as it may decompose with explosive violence. Tetranitromethane must be kept out of contact with aromatic compounds except in very small test portions, since violently explosive reactions can occur (Note 7).
2. Notes
1. The anhydrous nitric acid (sp. gr. > 1.53) is most easily obtained by slowly distilling ordinary fuming nitric acid from its own bulk of concentrated sulfuric acid. If ordinary concentrated nitric acid (sp. gr. 1.42) is used, it is advisable to distil twice from equal volumes of sulfuric acid. A technical grade of fuming nitric acid having a specific gravity of 1.60 was found to give satisfactory yields when used without further treatment; but an equivalent amount of a weaker commercial acid, corresponding to 98% nitric acid by gravity, gave considerably lower yields. The use of more than the calculated amount of nitric acid decreases the yield of tetranitromethane.
2. According to the submitter, the purity of acetic anhydride is not so important as that of the nitric acid. Equivalent amounts of 99–100% and 94–95% acetic anhydride gave practically the same yield of tetranitromethane.
3. If the flask is not cooled, the reaction proceeds more and more vigorously as the temperature rises and may, if unchecked, become violent.
4. If the flask is removed from the ice bath after the addition of the anhydride, and allowed to stand at room temperature, the reaction may become violent with great loss of product.
5. The yield is only 35% after 2 days and no greater than 65% after 10–15 days. If it should be necessary to obtain the product in shorter time, the reaction mixture may be allowed to stand at room temperature for 48 hours and then slowly heated to 70° during an interval of 3 hours and maintained at 70° for 1 hour longer before pouring into water. The yield of a run carried out in this way was, according to the submitter, 40%.
6. It is most convenient to use a 50-ml. graduated separatory funnel as the receiver during the steam distillation, if it is desired to estimate roughly the yield of tetranitromethane, the density of which is 1.65 at 15°.
7. Tetranitromethane is a valuable reagent for detecting the presence of double bonds, especially those which do not give the ordinary reactions of such linkages.1
3. Discussion
The procedure described is essentially that of Chattaway.2 Tetranitromethane has also been prepared by nitrating nitroform,3 from acetic anhydride by the action of diacetylorthonitric acid,4 from iodopicrin and silver nitrite,5 from acetyl nitrate by heating with acetic anhydride or glacial acetic acid,6 from nitrobenzene by distilling with a mixture of nitric acid and fuming sulfuric acid,7 by adding acetic anhydride to nitrogen pentoxide or a mixture of nitrogen pentoxide and nitrogen peroxide,8 by the action of acetic anhydride on highly concentrated nitric acid,9 from toluene by nitration,10 from acetylene by the action of nitric acid,11 from nitrobenzene and a mixture of nitric and fuming nitric acids,12 and from acetylene and ethylene by the action of nitric acid in the presence of a catalyst.13

References and Notes
  1. Meyer, H., Analyse und Konstitutionsermittlung organischer Verbindungen, 6th ed., p. 773, Julius Springer, Vienna, 1938; Ruzicka, Huyser, Pfeiffer, and Seidel, Ann., 471, 21 (1929).
  2. Chattaway, J. Chem. Soc., 1910, 2099; Chem, News, 102, 307 (1910).
  3. Schischkoff, Ann., 119, 247 (1861).
  4. Pictet and Genequand, Ber., 36, 2225 (1903).
  5. Hantzsch, Ber., 39, 2478 (1906).
  6. Pictet and Khotinsky, Compt. rend., 144, 210 (1907); Ber., 40, 1163 (1907).
  7. Claessen, Ger. pat. 184,229 [C. A., 1, 2524 (1907)].
  8. Schenck, Ger. pats, 211,198, 211,199 [C. A., 3, 2205 (1909)].
  9. Bayer and Co., Brit. pat. 24,299 [C. A., 5, 2305 (1911)] and Ger. pat. 224,057; Berger, Compt. rend., 151, 813 (1910); Bull. soc. chim. France, (4) 9, 26 (1911).
  10. Will, Ber., 47, 704 (1914).
  11. Orton, Brit. pat. 125,000; Orton and McKie, J. Chem. Soc., 1920, 283.
  12. McKie, J. Soc. Chem. Ind., 44, 430T (1925).
  13. McKie, J. Chem. Soc., 1927, 962.

Appendix
Chemical Abstracts Nomenclature (Collective Index Number);
(Registry Number)

diacetylorthonitric acid

iodopicrin

sulfuric acid (7664-93-9)

acetylene (74-86-2)

acetic acid (64-19-7)

acetic anhydride (108-24-7)

nitric acid (7697-37-2)

sodium sulfate (7757-82-6)

toluene (108-88-3)

Nitrobenzene (98-95-3)

ethylene (9002-88-4)

silver nitrite (7783-99-5)

tetranitromethane,
Methane, tetranitro- (509-14-8)

nitrogen peroxide

nitrogen pentoxide

nitroform

acetyl nitrate (591-09-3)