L
C. Glas, F. Bracher
Paper
Synthesis
6,7-Dichloro-N-methoxy-N-methyl-1H-indole-2-carboxamide (5l-
1) and 5,6-Dichloro-N-methoxy-N-methyl-1H-indole-2-carboxam-
ide (5l-2)
(7) Gao, W.-C.; Jiang, S.; Wang, R.-L.; Zhang, C. Chem. Commun.
2013, 49, 4890; and references cited therein.
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Marinelli, F. J. Org. Chem. 2018, 83, 6354.
Prepared according to General Procedure C from (Z)-2-azido-3-(3,4-
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Med. Chem. Lett. 1995, 5, 491. (d) Nakao, K.; Stevens, R. W.;
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WO99/35130, 1999.
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dichlorophenyl)-N-methoxy-N-methylacrylamide
(4l;
267 mg,
1.00 mmol). FCC (100 % CH2Cl2) gave the pure compound 5l-1 as a
reddish oil; yield: 53.0 mg (0.194 mmol, 20%); Rf = 0.43 (100%
CH2Cl2); HPLC purity (method a): >95% (210 nm), >95% (254 nm) and
5l-2 as an orange solid; yield: 26.0 mg (0.0952 mmol, 10%); mp 188
°C; Rf = 0.35 (100% CH2Cl2); HPLC purity (method a): >95% (210 nm),
>95% (254 nm).
6,7-Dichloro-N-methoxy-N-methyl-1H-indole-2-carboxamide (5l-1)
IR (ATR): 3158, 3034, 2938, 1880, 1626, 1470, 1375, 1333, 1154, 1031,
1004, 969, 817, 757, 733 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 9.37 (s, 1 H, NH), 7.52 (dd, J = 8.5, 0.8
Hz, 1 H, 4-H), 7.22 (d, J = 2.2 Hz, 1 H, 3-H), 7.20 (d, J = 8.5 Hz, 1 H, 5-H),
3.85 (s, 3 H, OCH3), 3.43 (s, 3 H, NCH3).
13C NMR (126 MHz, CDCl3): δ = 160.9 (C-1′), 134.1 (C-7a), 129.5 (C-2),
128.5 (C-6), 127.9 (C-3a), 122.8 (C-5), 121.6 (C-4), 115.7 (C-7), 108.9
(C-3), 61.6 (OCH3), 33.4 (NCH3).
HRMS (ESI): m/z [M]·+ calcd for C11H1035Cl2N2O2·+: 272.0119; found:
272.0133.
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1740.
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Perkin Trans. 1 1984, 2189.
5,6-Dichloro-N-methoxy-N-methyl-1H-indole-2-carboxamide (5l-2)
IR (ATR): 3290, 1615, 1564, 1522, 1444, 1330, 1201, 999, 957, 865,
750, 725 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 9.49 (s, 1 H, NH), 7.78 (s, 1 H, 4-H), 7.56
(d, J = 1.0 Hz, 1 H, 7-H), 7.14 (dd, J = 2.1, 1.0 Hz, 1 H, 3-H), 3.85 (s, 3 H,
OCH3), 3.44 (s, 3 H, NCH3).
13C NMR (126 MHz, CDCl3): δ = 161.01 (C-1′), 134.50 (C-7a), 129.95
(C-2), 129.02 (C-6), 128.00 (C-5), 124.83 (C-3a), 123.49 (C-4), 113.34
(C-7), 107.36 (C-3), 61.60 (OCH3), 33.40 (NCH3).
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Int. Ed. 2015, 54, 6236.
HRMS (EI): m/z [M]·+ calcd for C11H1035Cl2N2O2·+: 272.0119; found:
272.0119.
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Algarra, M.; Santos, J. P.; Costa, M. L.; Rodrigues, P.; Andrade, M.
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Acknowledgment
We thank Anna Niedrig and Salvatore Geraci for technical support.
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Supporting Information
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Supporting information for this article is available online at
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© Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–L