10.1002/ejoc.201701399
European Journal of Organic Chemistry
COMMUNICATION
4-chloro-3-hydroxy-2-phenylnaphthalen-1-yl
acetate (19). The
1279, 1077, 844, 791, 697. 1H NMR (500 MHz, CDCl3) δ 7.95 (s, 1H),
7.87 (s, 1H), 7.47 (d, J = 8.7 Hz, 1H), 7.41 (s, 1H), 7.33 (d, J = 8.7 Hz,
1H), 4.19 (s, 1H). 13C NMR (126 MHz, CDCl3) δ 140.7, 135.3, 127.8,
127.4, 125.64, 125.60, 124.7, 122.7, 120.2, 118.9, 116.8, 110.3, 32.3.
The spectroscopic data match with those previously described.[59]
following compound was obtained according to the general procedure for
chlorination by using 3-hydroxy-2-phenylnaphthalen-1-yl acetate in 51%
yield as slightly yellow oil. 1H NMR (400 MHz, CDCl3): δ 8.16 (d, J = 8.5
Hz, 1H), 7.79 (d, J = 8.4 Hz, 1H), 7.63 (t, J = 7.7 Hz, 1H). 13C NMR (101
MHz, CDCl3): δ 169.1, 147.5, 143.9, 132.3, 130.8, 130.1, 128.6, 128.5,
128.3, 125.1, 123.6, 123.3, 123.2, 122.1, 112.1, 20.47. HRMS (ESI+)
calcd. for C18H14ClO3 [M+H]: 311.0480, found 311.0553.
1,3,6,8-tetrachloro-9-methyl-9H-carbazole (25a). IR (KBr, cm-1) 2922,
1556, 1453, 1264, 1043, 835, 715. 1H NMR (500 MHz, CDCl3) δ 7.81 (s,
1H), 7.42 (s, 1H), 4.49 (s, 1H); 13C NMR (126 MHz, CDCl3) δ 136.8,
129.0, 125.7, 125.6, 118.7, 117.6, 35.1. The spectroscopic data match
with those previously described.[60]
4-chloro-2-phenylnaphtalene-1,3-diyl acetate (20). The following
compound was obtained according to the general procedure for
chlorination by using 2-phenylnaphtalene-1,3-diyl acetate in 20% yield as
pale yellow oil. 1H RMN (500 MHz, CDCl3): δ 8.32 (d, J = 8.5 Hz, 2H),
7.84 (d, J = 8.4 Hz, 2H), 7.67 (t, J = 7.1 Hz, 2H), 7.59 (t, J = 7.1 Hz, 2H),
7.45 – 7.37 (m, 6H), 7.32 (d, J = 8.2 Hz, 4H), 2.07 (s, 6H), 2.03 (s, 6H).
13C RMN (126 MHz, CDCl3): δ 168.7, 168.2, 143.81, 143.3, 132.6, 130.9,
130.0, 129.9, 128.3, 128.2, 127.4, 126.5, 124.9, 122.3, 122.2, 115.5,
29.9, 20.4. HRMS (ESI+) calcd. for C20H16ClO4 [M+H]: 355.0737, found
355.0726.
3-bromo-1-chloro-4-(phenethylamino)naphthalen-2-ol (26). A 25 ml
dry round bottom flask was charged with compound 23 (1.0 equiv),
phenylethylamine (1.2 equiv) and dissolved in methanol [0.3 M]. The
reaction was stirred by 2 h. Then reaction mixture was evaporated and
purified by chromatography column by using ethylacetate/hexane to yield
24 in 45% yield as grey solid. m.p. 66-68°C. IR (KBr, cm-1) 3496, 2926,
1578, 1496, 1453, 1387, 1344, 1217, 1145, 1105, 1029, 942, 813, 755,
699. 1H NMR (400 MHz, CDCl3): δ 8.04 (d, J = 8.2 Hz, 1H), 7.98 (d, J =
8.0 Hz, 1H), 7.54 (t, J = 7.1 Hz, 1H), 7.35 (d, J = 8.9 Hz, 1H), 7.31 (d, J =
7.1 Hz, 2H), 7.28 -7.22 (m, 3H), 6.16 (s, 1H), 3.51 (t, J = 6.9 Hz, 2H),
2.98 (t, J = 6.6 Hz, 2H). 13C NMR (101 MHz, CDCl3): δ 146.0, 144.3,
139.0, 130.7, 128.9, 128.7, 128.0, 126.6, 124.6, 124.2, 124.0, 123.5,
108.3, 105.3, 51.9, 37.4.
3-chloro-4-methoxybenzaldehyde (21). The following compound was
obtained according to the general procedure for chlorination by using 4-
methoxybenzaldehyde in 88% yield as faint yellow solid. m.p. 42-44 °C.
IR (KBr, cm-1) 1697, 1597, 1568, 1504, 1315, 1276, 1256, 1199, 1059,
1013, 894, 818, 714, 687, 638, 616. 556. 1H NMR (500 MHz, CDCl3): δ
9.85 (s, 1H), 7.91 (d, J = 2.0 Hz, 1H), 7.78 (dd, J = 8.5, 2.0 Hz, 1H), 7.05
(d, J = 8.5 Hz, 1H), 4.00 (s, 1H). 13C NMR (126 MHz, CDCl3): δ 189.8,
160.0, 131.4, 130.6 130.5, 123.9, 111.8, 56.6. The spectroscopic data
match with those previously described.[57]
Acknowledgements
A We gratefully thank to CONACyT (CB-2013/220836), FOMIX
(CONACyT-CONCyTEG GTO-2012-C03-194610) and University
of Guanajuato through project 962/2016 for financial support.
We acknowledge the facilities from the DCNyE, Chemistry
2-chlorodibenzo[b, d]furan (22). The following compound was obtained
according to the general procedure for chlorination by using dibenzofuran
in 63% yield as withe solid. m.p. 99-101 ºC. 1H NMR (500 MHz, CDCl3):
δ 7.94 – 7.89 (m, 4H), 7.57 (d, J = 8.3 Hz, 2H), 7.51 – 7.47 (m, 4H), 7.41
(dd, J = 8.3, 1.7 Hz, 2H), 7.36 (t, J = 7.5 Hz, 2H). 13C NMR (126 MHz,
CDCl3): δ 156.9, 154.6, 128.4, 128.1, 128.0, 127.30, 123.2, 120.1, 120.6,
113.1, 112.8, 112.0. The spectroscopic data match with those previously
described.[58]
Department,
the
National
Laboratory
UG-CONACyT
(LACAPFEM) in Guanajuato University for full characterization.
We thank to CONACyT for the fellowship to P. D. Nahide, V.
Ramadoss, Y. Satkar and K. Juárez. We especially thank to A.D.
Galván and I.J Arroyo for preliminary experimentation..
6-bromo-1,1-dichloronaphthalen-2(1H)-one
(23).
The
following
compound was obtained according to the general procedure for
chlorination by using 6-Bromo-2-napthol in 72% yield as orange solid.
m.p. 40-42 °C. IR (KBr, cm-1) 1688, 1582, 1553, 1481, 1308, 1281, 1236,
1198, 1080, 926, 890, 792, 790, 693, 646, 563. 1H NMR (400 MHz,
CDCl3): δ 7.94 (d, J = 8.1 Hz, 1H), 7.66 (d, J = 8.2 Hz, 1H), 7.48 (s, 1H),
7.36 (d, J = 9.8 Hz, 1H), 6.39 (d, J = 9.9 Hz, 1H). 13C NMR (101 MHz,
CDCl3): δ 185.3, 143.3, 139.5, 134.1, 132.1, 131.2, 128.7, 124.9, 124.0,
79.9. HRMS (ESI-): calcd. for C10H5BrCl2O [M-H]: 288.8823, found
288.2923.
Keywords: Electrophilic chlorination of phenols • PIFA/AlCl3
system • Iodine (III) reagents • New chlorinating reagent •
Chlorophenols
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3-bromo-1,1-dichloronaphthalen-2(1H)-one
(24).
The
following
compound was obtained according to the general procedure for
chlorination by using 6-Bromo-2-napthol in 72% yield as orange solid.
m.p. 46-48 °C. IR (KBr, cm-1) 1705, 1604, 1562, 1343, 1227, 1147, 955,
923, 826, 813, 759, 746, 681, 656, 621. 580. 530. 1H NMR (400 MHz,
CDCl3): δ 8.05 (d, J = 7.6 Hz, 1H), 7.85 (s, 1H), 7.56 (d, J = 14.3 Hz, 1H),
7.46 (t, J = 7.2 Hz, 1H), 7.29 (d, J = 7.2 Hz, 1H). 13C NMR (101 MHz,
CDCl3): δ 180.5, 146.1, 140.1, 131.6, 131.1, 129.7, 129.2, 127.1, 118.4,
80.6. HRMS (ESI-): calcd. for C10H6BrClO [M-H]: 288.8823, found
288.2921.
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Med. Chem. 2008, 51, 3841-3855.
1,3,6-trichloro-9-methyl-9H-carbazole (25). The following compound
was obtained according to the general procedure for chlorination by
using N-methylcarbazole, 4 equiv of PIFA and 6 equiv of AlCl3 in 61%
yield as white solid. m.p. 136-138 ºC. IR (KBr, cm-1) 2921, 1315, 1448,
[4]
[5]
Tang, M. L.; Bao, Z. Chem. Mater. 2011, 23, 446-455.
Regina, G. L.; D´Auria, F. D.; Tafi, A.; Piscitelli, F.; Olla, S.; Caporuscio,
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