Org. Synth. 1952, 32, 95
DOI: 10.15227/orgsyn.032.0095
SODIUM NITROMALONALDEHYDE MONOHYDRATE
[Malonaldehyde, nitro-, sodium derivative]
Submitted by Paul E. Fanta
1
Checked by Cliff S. Hamilton and Philip J. Vanderhorst.
1. Procedure
See the discussion in Org. Synth. 1973, Coll. Vol. 5, 1004 with regard to potential hazards associated with this procedure.
Caution! The sodium salt of nitromalonaldehyde is impact-sensitive and thermally unstable and should be handled as a potentially explosive material.
In a
2-l. three-necked round-bottomed flask, equipped with a
thermometer, a
dropping funnel, a
mechanical stirrer and a gas vent
(Note 1), are placed
258 g. (3.74 moles) of sodium nitrite and 250 ml. of water. The contents of the flask are heated and stirred to dissolve the solid. A solution of
258 g. (1 mole) of mucobromic acid (
p. 688) in
250 ml. of warm 95% ethanol is placed in the dropping funnel and added dropwise with constant stirring over a period of 70–80 minutes. A mildly exothermic reaction occurs; the solution in the flask becomes deep red, and gas is evolved. During the addition, the temperature is kept at 54 ± 1° by intermittent application of an
ice bath to the flask
(Note 2). The mixture is stirred for an additional 10 minutes at 54 ± 1°. While being stirred continuously, it is then cooled to 0–5° by application of an ice bath. The fine, yellow precipitate is collected on a previously chilled
Büchner funnel.
The slightly moist cake of crude product is transferred to a 1-l. flask and heated to boiling with a mixture of 400 ml. of 95% ethanol and 100 ml. of water. The hot solution is filtered to remove a fine yellow solid, and the clear red filtrate is cooled to 0–5°. The recrystallized product is collected on a Büchner funnel and dried in air at room temperature. The yield is 57–65 g. (36–41%) of pink or tan needles of sodium nitromalonaldehyde monohydrate (Note 3).
2. Notes
1.
The gases evolved are slightly irritating; they should be vented to a
trap,
2 or the apparatus should be set up in a
hood.
2.
The yield is not increased and a darker, less pure product is obtained if the reaction is run at a higher temperature or for a longer time.
3.
The checkers found the product to be quite pure. An almost quantitative yield of
2-amino-5-nitropyrimidine was obtained by reaction of the product with
guanidine.
Working with Hazardous Chemicals
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In some articles in Organic Syntheses, chemical-specific hazards are highlighted in red "Caution Notes" within a procedure. It is important to recognize that the absence of a caution note does not imply that no significant hazards are associated with the chemicals involved in that procedure. Prior to performing a reaction, a thorough risk assessment should be carried out that includes a review of the potential hazards associated with each chemical and experimental operation on the scale that is planned for the procedure. Guidelines for carrying out a risk assessment and for analyzing the hazards associated with chemicals can be found in Chapter 4 of Prudent Practices.
The procedures described in Organic Syntheses are provided as published and are conducted at one's own risk. Organic Syntheses, Inc., its Editors, and its Board of Directors do not warrant or guarantee the safety of individuals using these procedures and hereby disclaim any liability for any injuries or damages claimed to have resulted from or related in any way to the procedures herein.
The paragraphs above were added in September, 2014. The statements above do not supersede any specific hazard caution notes and safety instructions included in the procedure.
3. Discussion
The procedure above is a modification of the method of Hill and Torrey,
3 which was also studied by Johnson
4 and others.
5,6This preparation is referenced from:
Appendix
Chemical Abstracts Nomenclature (Collective Index Number);
(Registry Number)
SODIUM NITROMALONALDEHYDE MONOHYDRATE
Malonaldehyde, nitro-, sodium derivative
sodium salt of nitromalonaldehyde
ethanol (64-17-5)
sodium nitrite (7632-00-0)
guanidine (113-00-8)
Mucobromic acid (488-11-9)
2-amino-5-nitropyrimidine (3073-77-6)
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