E
Synthesis
Q. Zhang et al.
Special Topic
1
HRMS (ESI): m/z [M – 2 H]2– calcd for C H N O : 197.9924; found:
H NMR (500 MHz, CDCl ): δ = 8.32 (s, 2 H), 11.32 (s, 1 H).
3
6
2
2
6
13
197.9924.
C NMR (125 MHz, CDCl ): δ = 124.5, 131.2, 137.8, 148.0.
3
HRMS (ESI): m/z [M – H]– calcd for C H ClN O : 216.9658; found:
6
2
2
5
216.9658.
Funding Information
4-Bromo-2,3,6-trinitrophenol (2i)
This work was supported by the NSFC (21522202, 21502017,
Yellow solid; yield: 71 mg (46%); mp 160–161 °C.
21702028).
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H NMR (500 MHz, CDCl ): δ = 9.20 (s, 1 H).
3
13
C NMR (125 MHz, CDCl ): δ = 126.26, 126.27, 129.7, 137.1, 138.2,
3
Supporting Information
153.2.
HRMS (ESI): m/z [M – H]– calcd for C HBrN O : 305.9003; found:
Supporting information for this article is available online at
6
3
7
305.9008.
https://doi.org/10.1055/s-0037-1610038.
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References
Yellow solid; yield: 63 mg (49%); mp 115–116 °C.
1
H NMR (500 MHz, CDCl ): δ = 1.44 (t, J = 7.0 Hz, 3 H), 4.47 (q, J = 7.0
(1) (a) Ciamician, G. Science 1912, 36, 385. (b) Yoon, T. P.; Ischay, M.
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D.; Moore, T. A.; Moore, A. L. Acc. Chem. Res. 1993, 26, 198.
3
Hz, 2 H), 8.95 (s, 2 H), 11.78 (s, 1 H).
13
C NMR (125 MHz, CDCl ): δ = 14.2, 62.6, 122.0, 132.0, 137.4, 152.0,
3
1
62.4.
(
2) Narayanam, J. M. R.; Stephenson, C. R. J. Chem. Soc. Rev. 2011, 40,
02.
3) (a) Prier, C. K.; Rankic, D. A.; MacMillan, D. W. C. Chem. Rev.
013, 113, 5322. (b) Hopkinson, M. N.; Sahoo, B.; Li, J. L.;
HRMS (ESI): m/z [M – H]– calcd for C H N O : 255.0259; found:
2
9
7
2
7
1
55.0263.
(
2
2
,6-Dinitro-4-(trifluoromethyl)phenol (2k)
Glorius, F. Chem. Eur. J. 2014, 20, 3874. (c) Shaw, M. H.; Twilton,
J.; MacMillan, D. W. C. J. Org. Chem. 2016, 81, 6898.
Yellow solid; yield: 74 mg (59%); mp 47–48 °C.
1
(4) (a) Noble, A.; MacMillan, D. W. C. J. Am. Chem. Soc. 2014, 136,
1602. (b) Terrett, J. A.; Clift, M. D.; MacMillan, D. W. C. J. Am.
H NMR (500 MHz, CDCl ): δ = 8.59 (s, 2 H), 11.70 (s, 1 H).
3
1
13
C NMR (125 MHz, CDCl ): δ = 121.8 (q, J = 270.0 Hz), 122.0 (q, J =
3
Chem. Soc. 2014, 136, 6858. (c) Pirnot, M. T.; Rankic, D. A.;
Martin, D. B. C.; MacMillan, D. W. C. Science 2013, 339, 1593.
(d) Nagib, D. A.; Scott, M. E.; MacMillan, D. W. C. J. Am. Chem.
Soc. 2009, 131, 10875. (e) Nicewicz, D. A.; MacMillan, D. W. C.
Science 2008, 322, 77.
3
6.3 Hz), 128.4 (q, J = 3.0 Hz), 137.7, 151.5.
19
F NMR (564 MHz, CDCl ): δ = –62.77.
3
HRMS (ESI): m/z [M – H]– calcd for C H F N O : 250.9921; found:
2
7
2
3
2
5
50.9917.
(5) (a) Du, J.; Yoon, T. P. J. Am. Chem. Soc. 2009, 131, 14604.
(
b) Ischay, M. A.; Anzovino, M. E.; Du, J.; Yoon, T. P. J. Am. Chem.
4
-Methyl-2,6-dinitrophenol (2l)
Soc. 2008, 130, 12886.
Yellow solid; yield: 54 mg (55%); mp 84–85 °C.
(
6) (a) Konieczynska, M. D.; Dai, C.; Stephenson, C. R. J. Org. Biomol.
Chem. 2012, 10, 4509. (b) Dai, C.; Narayanam, J. M. R.;
Stephenson, C. R. J. Nat. Chem. 2011, 3, 140. (c) Condie, A. G.;
González-Gómez, J. C.; Stephenson, C. R. J. J. Am. Chem. Soc.
1
H NMR (500 MHz, CDCl ): δ = 2.46 (s, 3 H), 8.15 (s, 2 H), 11.29 (s,
3
1
H).
13
C NMR (125 MHz, CDCl ): δ = 20.2, 129.4, 131.7, 137.2, 147.4.
3
2
010, 132, 1464. (d) Tucker, J. W.; Narayanam, J. M. R.; Krabbe, S.
HRMS (ESI): m/z [M – H]– calcd for C H N O : 197.0204; found:
7
5
2
5
W.; Stephenson, C. R. J. Org. Lett. 2010, 12, 368. (e) Narayanam, J.
M. R.; Tucker, J. W.; Stephenson, C. R. J. J. Am. Chem. Soc. 2009,
197.0213.
131, 8756.
2,6-Dinitro-4-(trifluoromethoxy)phenol (2m)
(
7) (a) Booth, G. Nitro Compounds, Aromatic, In Ullmann’s Encyclo-
pedia of Industial Chemistry; Wiley-VCH: Weinheim, 2000.
(b) Heaney, F. Synthesis 2001, 2528. (c) Schlosser, M.; Ruzziconi,
R. Synthesis 2010, 2111. (d) Schofield, K. Aromatic Nitration;
Cambridge University Press: Cambridge, 1980. (e) Chu, W.;
Zhou, D.; Gaba, V.; Liu, J.; Li, S.; Peng, X.; Xu, J.; Dhavale, D.;
Bagchi, D. P.; d’Avignon, A.; Shakerdge, N. B.; Bacskai, B. J.; Tu, Z.;
Kotzbauer, P. T.; Mach, R. H. J. Med. Chem. 2015, 58, 6002.
Yellow oil; yield: 68 mg (51%).
1
H NMR (600 MHz, CDCl ): δ = 8.24 (s, 2 H), 11.12 (s, 1 H).
3
13
C NMR (150 MHz, CDCl ): δ = 120.2 (q, J = 260.2 Hz), 124.7, 137.6,
3
139.1, 148.2.
19
F NMR (564 MHz, CDCl ): δ = –58.69.
3
HRMS (ESI): m/z [M – H]– calcd for C H F N O : 266.9932; found:
7
2
3
2
6
(f) Ikeda, S.; Toganoh, M.; Easwaramoorthi, S.; Lim, J. M.; Kim,
266.9943.
D.; Furuta, H. J. Org. Chem. 2010, 75, 8637.
(
8) (a) Esakkidurai, T.; Kumarraja, M.; Pitchumani, K. J. Chem. Sci.
2
,5-Dinitrobenzene-1,4-diol (2n)
2003, 115, 113. (b) Olah, G. A.; Malhotra, R.; Narang, S. C. Nitra-
Yellow solid; yield: 69 mg (69%); mp 207–208 °C.
tion: Methods and Mechanisms; Wiley-VCH: Weinheim, 1989.
(c) Crampton, M. R.; Cropper, E. L.; Gibbons, L. M.; Millar, R. W.
Green Chem. 2002, 4, 275.
1
H NMR (500 MHz, CDCl ): δ = 9.20 (s, 2 H).
3
13
C NMR (125 MHz, CDCl ): δ = 126.3, 137.1, 153.2.
3
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Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–F