7
16
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 3, March, 2004
Agafonov et al.
Table 1. Yields and characteristics of Nꢀmonoalkylꢀ (8a—d) and N,N´ꢀdialkylhydrazines (9a—d, 11, 12)
a
M.p./°Cb
Proꢀ
duct
Yield (%)
MS,
m/z ([M]+)
from 1b
from 1c
CH Cl2 Dioxane
CH Cl2 Dioxane
MeCN
91
MeCN
0
I
II
2
2
8
8
8
8
9
9
9
9
1
1
a
b
c
d
a
b
c
d
1
2
0
0
0
0
0
0
0
0
89
95
83
79
0
81
85
77
75
0
0
0
142—144
sulfate)
110—113
1427
46
122
74
(
93
85
85
0
0
0
1118
1759
(
(
(
monohydrochloride)
177—178
0
(
oxalate)
165—166
oxalate)
0
0
1659
88
(
92
87
83
84
88
90
82
81
167—170
dihydrochloride)
223—227
monohydrochloride)
157—160
1687
60
(
0
0
0
220—22510
16011
212
116
144
136
102
0
0
0
(
(
(
dihydrochloride)
145—147
dihydrochloride)
142—144
0
0
0
—c
82
72
14013
dihydrochloride)
113—117
114—11514
monohydrochloride)
a
b
c
The yields of 8a—d and 9a—d were determined from the GLC data for the hydrolyzed reaction mixtures.
I refers to the data of the present study; II refers to the literature data.
Ref. 12: b.p. 85 °C (15 Torr).
ether (2×5 mL). The aqueous phase was evaporated to dryness in
vacuo, the residue was dissolved in EtOH (1 mL), and AcONa
2. H. Taylor, J. Chem. Phys., 1940, 8, 1.
3. C. D. Harries and E. Klamt, Ber., 1895, 28, 503.
4. R. Wegler, J. Prakt. Chem. [2], 1937, 148, 135.
5. F. Sommer, O. F. Schulz, and M. Nassau, Z. Anorg. Chem.,
1925, 147, 154.
6. N. E. Agafonov, A. V. Dudin, A. A. Preobrazhenskii, and
V. M. Zhulin, Izv. Akad. Nauk, Ser. Khim., 2003, 259 [Russ.
Chem. Bull., Int. Ed., 2003, 52].
(
2 mmol) and a solution of picric acid (2.5 mmol) in 2 mL of
EtOH were added. The precipitates of hydrazinium picrates that
formed were filtered off, washed with EtOH (2 mL), dried, and
eluted with CHCl through a filter with Al O (h = 1 cm) (picric
3
2
3
acid was retained by the filter); the eluate was analyzed
by GLC.18 Bases 8a—d and 9a—d were characterized in the
form of sulfates, hydrochlorides, or oxalates obtained according
to known procedures.7
7. J. Thiele, Ber., 1909, 42, 2575.
8. T. Curtius, Ber., 1900, 33, 2459.
—12
Synthesis of 1ꢀbenzylꢀ2ꢀmethylhydrazine (11) and 1ꢀbutylꢀ2ꢀ
methylhydrazine (12). A solution of azine 1c (1 mmol) and MeI
9. G. Gever and K. Hayes, J. Org. Chem., 1949, 14, 813.
10. T. Curtius, J. Prakt. Chem. [2], 1900, 62, 83.
11. B. W. Langley, B. Lythgoe, and L. S. Rayner, J. Chem. Soc.,
1952, 4191.
(
2) (2.2 mmol) in 1 mL of CH Cl was kept in a Teflon tube at
2 2
5
0 °C and a pressure of 10 kbar for 5 h. The reaction mixture was
cooled, volatile components were removed in vacuo, and comꢀ
pound 3 or 5 (2.2 mmol) and dioxane (1 mL) were added. The
mixture was placed again in a Teflon tube and kept at p =
12. H. Feuer, G. B. Silverman, H. P. Angstadt, and A. R. Fauke,
J. Org. Chem., 1962, 27, 2081.
13. J. Thiele, Ann., 1910, 376, 239.
1
0 kbar as described above. On cooling, volatile components
14. G. H. Coleman, H. Gilman, C. E. Adams, and P. E. Pratt,
J. Org. Chem., 1938, 3, 99.
15. D. Vorlander, Ber., 1906, 39, 803.
were removed in vacuo and 20% HCl (3 mL) was added. The
mixture was refluxed for 10 min and cooled, pꢀMeOC H CHO
6
4
was extracted with ether (2×5 mL), the aqueous phase was
alkalified with NaOH, and the product was extracted with ether
16. T. Curtius and R. Jay, J. Prakt. Chem. [2], 1889, 39, 27.
17. T. Curtius, J. Prakt. Chem. [2], 1912, 85, 393.
18. N. E. Agafonov, A. V. Dudin, A. A. Preobrazhenskii, and
V. M. Zhulin, Izv. Akad. Nauk, Ser. Khim., 1999, 1014 [Russ.
Chem. Bull., 1999, 48, 1005 (Engl. Transl.)].
(
2×5 mL). The extracts were treated with a solution of gaseous
HCl in ether to give hydrochlorides 11 and 12 in 82 and 72%
yields, respectively (see Table 1).
References
Received December 23, 2003;
1
. C. Harries and T. Haga, Ber., 1898, 31, 56.
in revised form February 16, 2004