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DOI: 10.1055/s-2008-1077973
Copper-Catalyzed Mild and Efficient Entry to 1-Substituted Indazolones
Publication History
Publication Date:
15 July 2008 (online)
Abstract
A variety of 1-alkyl- and aryl-substituted indazolones were synthesized easily starting from commercially available 2-halobenzoic acids and hydrazines via the copper-catalyzed intramolecular C-N bond formation of 2-halobenzohydrazides under mild conditions.
Key words
indazolone - copper - proline - coupling - hydrazide
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Mills AD.Nazer MZ.Haddadin MJ.Kurth MJ. J. Org. Chem. 2006, 71: 2687MissingFormLabel - For some other references for the synthesis of indazolone analogues, see:
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a recent example for copper-catalyzed intramolecular C-N
coupling reaction, see:
Lu H.Li C. Org. Lett. 2006, 8: 5365MissingFormLabel - 12b During the preparation
of this manuscript, Zhu and co-workers disclosed their studies on
the synthesis of 2-aryl-2H-indazoles
via copper(I)-catalyzed intramolecular amination reaction of N′-aryl-N′-(o-bromobenzyl) acetyl-hydrazines, but
the reaction need higher reaction tempera-ture (100-105 ˚C)
and long reaction time (20 h) in a pressure tube. See:
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C-N coupling reactions at room temperature, see:
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References and Notes
The acid hydrazides were synthesized
from corresponding acid chloride with hydrazine or the condensation
of
2-halobenzoic acid with hydrazine using EDC.
Typical Experimental
Procedure - Synthesis of 1-
tert
-butyl-1,2-dihydroindazol-3-one
The
mixture of 2-iodobenzoic acid N′-tert-butylhydrazide (0.32 g, 1.0 mmol),
CuI (19 mg, 0.10 mmol, 10 mol%), l-proline
(23 mg, 0.20 mmol, 20 mol%), and K2CO3 (0.28
g, 2.0 mmol) in DMSO (10 mL) was stirred at r.t. for 3 h under nitrogen
atmosphere. The mixture was treated with H2O and the
mixture was extracted three times with EtOAc. The combined organic
layer was washed with H2O and brine, and dried over MgSO4.
After filtration, solvent was evaporated in vacuo to ca. 1 mL and
crystallization afforded 1-tert-butyl-1,2-dihydroindazole-3-one
(0.19 g, 97%) as white crystals. R
f
= 0.36
(hexane-EtOAc, 1:1); mp 115-117 ˚C. IR (KBr):
2979 (NH), 1648 (C=O), 1538, 1209, 748 cm-¹. ¹H NMR
(400 MHz, DMSO): δ = 10.47 (br s, 1 H, NH), 7.61
(d, 1 H, J = 8.5
Hz, C-4), 7.59 (d, 1 H, J = 7.8
Hz, C-7), 7.26 (dd, 1 H, J = 6.8,
8.5, Hz, C-5), 6.96 (dd, 1 H, J = 6.8,
7.8 Hz, C-6), 1.60 (s, 9 H, t-Bu). ¹³C
NMR (136 MHz, DMSO): δ = 152.8, 139.5, 126.4,
120.1, 118.2, 113.9, 111.9, 58.3, 29.3 (3 × C).
ESI-HRMS: m/z calcd for C11H14N2O 191.1179;
found: 191.1182.
Acid hydrazide derived from 2,4,6-trichlorophenyl-hydrazine, tert-butylcarbazide, benzoylhydrazine,
and
p-toluenesulfonylhydrazine
did not afford the corresponding indazolone to recover the starting
material even at heating conditions (>100 ˚C).
A variety of compounds possessing pharmaceutical profile have been prepared from indazolone derivatives, see ref. 15.