Organic Syntheses, CV 5, 43
Submitted by R. Gösl and A. Meuwsen
1.
Checked by N. A. Fedoruk and V. Boekelheide.
1. Procedure
To a freshly prepared solution of
11.3 g. (0.10 mole) of hydroxylamine-O-sulfonic acid (Note
1) in 64 ml. of cold water there is added
24 ml. (24 g., 0.30 mole) of pyridine (Note
2). The mixture is heated at about 90° on a
steam bath for 20 minutes. It is then cooled to room temperature with stirring, and
13.8 g. (0.10 mole) of potassium carbonate is added. The water and excess
pyridine are removed from the mixture by heating it at 30–40° in a rotatory evaporator in conjunction with a
water aspirator. The residue is treated with
120 ml. of ethanol, and the insoluble precipitate of
potassium sulfate is removed by filtration.
Fourteen milliliters (22 g., 0.10 mole) of 57% hydriodic acid is added to the filtrate, and the resulting solution is stored at −20° for 1 hour (Note
3). The solid that separates is collected; weight
15.5–17.5 g. Recrystallization of this solid from about
100 ml. of absolute ethanol gives
14–16 g. (
63–72%) of
1-aminopyridinium iodide as almost-white crystals, m.p.
160–162° (Note
4).
2. Notes
2. The
pyridine was distilled before use. When the conversion is carried out in the presence of
potassium carbonate using an equimolar amount of
pyridine instead of an excess, the yields obtained are
20–30% lower.
3
3. The temperature is kept at −20° or lower by a
bath of dry ice and methanol. If the temperature rises above −20°, an appreciable quantity of
1-aminopyridinium iodide may redissolve and be lost.
3. Discussion
The formation of
1-aminopyridinium chloride has been accomplished by the acid hydrolysis of
N-(p-acetaminobenzenesulfonimido) pyridine.
4 Also, the rearrangement of a substituted diazepine has been observed to give a 1-aminopyridine derivative.
5 The present procedure is an adaptation of that described by Gösl and Meuwsen.
3
4. Merits of the Preparation
This procedure is a convenient and general method for preparing asymmetrically substituted hydrazines.
3 This is illustrated by the following examples reported by the submitters
3 (% yields in parentheses):
methylamine to
methylhydrazinium hydrogen sulfate (
49–53%);
ethylamine to
ethylhydrazinium hydrogen oxalate (
51%);
butylamine to
butylhydrazinium hydrogen sulfate (
49–56%);
piperidine to
1-aminopiperidinium hydrogen oxalate (
32%);
dibutylamine to
1,1-dibutylhydrazinium hydrogen oxalate (
34%);
trimethylamine to
1,1,1-trimethylhydrazinium hydrogen oxalate (
79–85%);
2-picoline to
1-amino-2-methylpyridinium iodide (
57%);
2,4-lutidine to
1-amino-2,4-dimethylpyridinium iodide (
40%);
2,6-lutidine to
1-amino-2,6-dimethylpyridinium iodide (
34%);
2,4,6-collidine to
1-amino-2,4,6-trimethylpyridinium iodide (
30%); and
quinoline to
1-aminoquinolinium iodide (
32%).
Appendix
Compounds Referenced (Chemical Abstracts Registry Number)
N-(p-acetaminobenzenesulfonimido) pyridine
ethanol (64-17-5)
potassium carbonate (584-08-7)
acetic acid (64-19-7)
potassium sulfate (37222-66-5)
pyridine (110-86-1)
piperidine (110-89-4)
hydriodic acid (10034-85-2)
Quinoline (91-22-5)
methylamine (74-89-5)
Trimethylamine (75-50-3)
2,6-Lutidine (108-48-5)
chloramine (10599-90-3)
2,4,6-collidine (108-75-8)
2-picoline (109-06-8)
Butylamine (109-73-9)
Dimethyl acetylenedicarboxylate (762-42-5)
ethylamine (75-04-7)
1-Aminopyridinium iodide,
Pyridinium, 1-amino-, iodide (6295-87-0)
Hydroxylamine-O-sulfonic acid (2950-43-8)
1-aminopyridinium chloride
ethylhydrazinium hydrogen oxalate
butylhydrazinium hydrogen sulfate
1-aminopiperidinium hydrogen oxalate
Dibutylamine (111-92-2)
1,1-dibutylhydrazinium hydrogen oxalate
1,1,1-trimethylhydrazinium hydrogen oxalate
1-amino-2-methylpyridinium iodide
2,4-lutidine (108-47-4)
1-amino-2,4-dimethylpyridinium iodide
1-amino-2,6-dimethylpyridinium iodide
1-amino-2,4,6-trimethylpyridinium iodide
1-aminoquinolinium iodide
ethyl propiolate (623-47-2)
methylhydrazinium hydrogen sulfate
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