A Publication
of Reliable Methods
for the Preparation
of Organic Compounds
Annual Volume
Org. Synth. 1936, 16, 51
DOI: 10.15227/orgsyn.016.0051
[Hydrazine, methyl-, sulfate]
Submitted by H. H. Hatt
Checked by W. W. Hartman and W. D. Peterson.
1. Procedure
(A) Benzalazine.—In a 5-l. round-bottomed flask, provided with a stout glass mechanical stirrer, are placed 240 g. (1.85 moles) of powdered hydrazine sulfate (Org. Syn. Coll. Vol. I, 1941, 309), 1.8 l. of water, and 230 cc. (207 g., 3.4 moles) of 28 per cent aqueous ammonia (sp. gr. 0.90). The mixture is stirred, and, when the hydrazine sulfate has dissolved, 440 cc. (460 g., 4.35 moles) of benzaldehyde (Note 1) is added from a separatory funnel during the course of four to five hours (Note 2). After the mixture has been stirred for a further two hours, the precipitated benzalazine is filtered with suction, washed with water, and pressed thoroughly on a Büchner funnel. The product is dissolved in 800 cc. of boiling 95 per cent ethyl alcohol, and, on cooling, the azine separates in yellow needles melting at 92–93°. The yield is 350–360 g. (91–94 per cent of the theoretical amount); an additional 10–15 g. of less pure material can be isolated from the mother liquors. The azine is freed of ethyl alcohol by drying in a vacuum desiccator over calcium chloride.
(B) Methylhydrazine Sulfate.—Two hundred grams (0.96 mole) of benzalazine, 350 cc. of dry, thiophene-free benzene, and 100 cc. (133 g., 1.05 moles) of methyl sulfate (Note 3) are mixed in a 3-l. round-bottomed flask, provided with a reflux condenser bearing a calcium chloride tube. The mixture is heated continuously, with occasional shaking, on a water bath to gentle refluxing for five hours. The mixture is cooled, and the solid addition product is decomposed by adding 600 cc. of water and shaking until all the solid material has disappeared. The benzene and benzaldehyde are removed by steam distillation; the residual liquor, after cooling, is treated with 15–20 cc. of benzaldehyde and left overnight. The resin and benzalazine are separated by filtration (Note 4).
The filtrate is evaporated under reduced pressure on a water bath until a semi-crystalline mass remains; this is further desiccated by evaporating twice under reduced pressure with 50-cc. portions of absolute ethyl alcohol. The resulting crystalline cake is crushed with 50 cc. of absolute ethyl alcohol, filtered, and the process repeated. The white, crystalline product is almost pure methylhydrazine sulfate and contains very little hydrazine sulfate. After drying in a vacuum desiccator over calcium chloride, the yield is 105–110 g. (76–80 per cent of the theoretical amount). For purification, the sulfate is dissolved in about 250 cc. of boiling 80 per cent ethyl alcohol, and any undissolved material (chiefly hydrazine sulfate) is filtered. On cooling, the methylhydrazine sulfate separates in white plates, which are filtered with suction and washed with a little absolute alcohol. After drying over calcium chloride, the first fraction, m.p. 141–142°, weighs 70–75 g. (51–54 per cent of the theoretical amount) (Note 5).
2. Notes
1. The benzaldehyde should be freed of benzoic acid by shaking with aqueous sodium carbonate solution.
2. The mixture is stirred vigorously during the reaction, and one or two stout glass rods are clamped in the flask to act as baffles and to break up the lumps of benzalazine.
3. Methyl sulfate is extremely toxic. It should not be spilled; neither should the vapor be inhaled. Ammonia is a specific antidote.
4. Unreacted hydrazine sulfate is removed by conversion to benzalazine. The filtrate should not give an appreciable precipitate when mixed with 5 cc. of benzaldehyde and left for four hours.
5. From the mother liquors about 12 g. of less pure material, m.p. 133–136°, can be recovered.
3. Discussion
The procedure given above is essentially the method of Thiele.1 Methylhydrazine has also been prepared by reduction and subsequent hydrolysis of nitrosomethylurea,2 nitromethylurethane,3 and nitrosomethylamine sulfonic acid;4 and by methylation of hydrazine hydrate with methyl iodide5 or diazomethane.6

References and Notes
  1. Thiele, Ann. 376, 244 (1910).
  2. Brüning, ibid. 253, 7 (1889).
  3. Backer, Rec. trav. chim. 31, 193 (1912).
  4. Traube and Brehmer, Ber. 52, 1286 (1919).
  5. Harries and Haga, ibid. 31, 56 (1898).
  6. Staudinger and Kupfer, ibid. 45, 501 (1912).

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


ethyl alcohol,
alcohol (64-17-5)

calcium chloride (10043-52-4)

ammonia (7664-41-7)

Benzene (71-43-2)

sodium carbonate (497-19-8)

Benzoic acid (65-85-0)

benzaldehyde (100-52-7)

Methyl iodide (74-88-4)

methyl sulfate (75-93-4)

hydrazine hydrate (7803-57-8)

Hydrazine sulfate (10034-93-2)

Diazomethane (334-88-3)


Methylhydrazine sulfate,
Hydrazine, methyl-, sulfate (302-15-8)

Methylhydrazine (60-34-4)


nitrosomethylamine sulfonic acid