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An efficient and simple procedure for conversion of different classes of aldehydes and ketones into
the corresponding semicarbazones with semicarbazide hydrochloride using basic alumina is studied.
Scheme I
1338 J. Chin. Chem. Soc., Vol. 54, No. 5, 2007 Kiasat et al.
Table 1. Protection of carbonyl compounds as semicarbazones using basic alumina under solvent free
conditionsa,b
M.P.
Time Yield
No Substrate Product Found
(min) (%)
(lit.9)
221
1 CHO CH=NNHCONH2 5 89
(222)
H3C
219
2 CHO H3C CH=NNHCONH2 6 85
(221)
H3CO 212
3 CHO H3CO CH=NNHCONH2 5 83
(210)
227
4 Cl CHO Cl CH=NNHCONH2 4 88
(230)
OH OH
229
5 4 76
CHO CH=NNHCONH2 (231)
NO2 NO2
242
6 8 74
CHO CH=NNHCONH2 (246)
215
7 CH=CHCHO CH=CHCH=NNHCONH2 5 90
(215)
200
8 CHO CH=NNHCONH2 5 77
(202)
O O
198
9 COCH3 C(CH3)=NNHCONH2 10 74
(198)
195
10 CH2COCH3 CH2C(CH3)=NNHCONH2 8 87
(198)
165
11 O NNHCONH2 6 80
(166)
O NNHCONH2
120
12 4 85
(122)
a.
Yields refer to isolated products. b Products were characterized by comparison of their physical
data, IR, and NMR spectra with known samples.
clean conversion of carbonyl compounds to semicarba- reaction media is essential. It can be emphasized that the re-
zones, addition of a few drops of t-BuOH and water in the action is clean, the work-up is straightforward and, from
Preparation of Semicarbazones J. Chin. Chem. Soc., Vol. 54, No. 5, 2007 1339
economical and environmental points of view, use of sol- vent evaporated under reduced pressure to give the product
vent free conditions is favorable. which was recrystallized from a suitable solvent and af-
In conclusion, we have demonstrated an efficient, forded the TLC and 1H NMR pure products in 74-90% iso-
mild and novel protection methodology of carbonyl group lated yields.
using semicarbazide hydrochloride in the presence of basic
alumina under solvent free conditions. We believe that the
present procedure provides an easy, mild, efficient, versa- Received January 29, 2007.
tile and general methodology for the protection of different
classes of carbonyl compounds, and we feel that it may be a
suitable addition to methodologies already present in the ACKNOWLEDGEMENT
literature.
Partial support for this work by Chamran University
Research Council is gratefully acknowledged.
EXPERIMENTAL
General REFERENCES
Chemicals such as carbonyl compounds, semicarba-
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products are known compounds and are identified by com- Catal. 2004, 226, 54.
3. (a) Kabalka, G. W.; Pagni, R. M. Tetrahedron 1997, 53,
parison of their physical and spectral data with those of au-
7999. (b) Parks, G. A. Chem. Rev. 1965, 65, 177.
thentic samples.8 The purity determination of the products
4. Fieser, L. F.; Fieser, M. Reagents for Organic Synthesis;
and reaction monitoring were accomplished by TLC on sil- John Wiley & Sons: New York, 1967; p 1000.
ica gel polygram SILG/UV 254 plates. 5. Vogel, A. I. Textbook of Practical Organic Chemistry; 4 th
ed.; ELBS and Longman: London, 1978.
General procedure for the protection of carbonyl 6. Hajipour, A. R.; Mohammadpoor-Baltork, I.; Bigdeli, M. J.
compounds as semicarbazones Chem. Res. 1999, 570 and references cited therein.
Protection was carried out by mixing the carbonyl 7. Kiasat, A. R.; Kazemi, F.; Mehrjardi, M. F. Asian J. Chem.
2005, 17, 2830.
compound (1 mmol), semicarbazide hydrochloride (1.5
8. Shriner, R. L.; Fuson, R. C. The Systematic Identification of
mmol), basic alumina (2 g) and a few drops of t-BuOH and
Organic Compounds; 5th ed.; John Wiley & Sons: New York,
water. The reaction mixture was ground for the time speci- 1964.
fied in the Table 1. The progress of the reaction was moni- 9. Shriner, R. L.; Fuson, R. C.; Curtin, D. Y. The Systematic
tored by TLC using ether-CCl4. On completion of the reac- Identification of Organic Compounds; 5th ed.; John Wiley &
tion, the reaction mixture was poured into methanol (20 Sons: New York, 1980.
mL). The solid was filtered off by sinter glass and the sol-