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P.K. Pramanick et al. / Tetrahedron xxx (2017) 1e10
4.3.4. 3-Bromo-4-methoxybenzaldehyde (2d)
4.3.11. (3-Bromo-4-methoxyphenyl) (morpholino)methanone (2k)
59.4 mg, 99% yield. White solid; mp. 110e112 ꢀC. 1H NMR
37.4 mg, 87% yield from the reaction of 1d with 1.0 equiv NBS
under N2 atmosphere. 1H NMR (400 MHz, CDCl3)
d
9.85 (s, 1H), 8.09
(400 MHz, CDCl3)
d
7.63 (d, J ¼ 2.1 Hz, 1H), 7.37 (dd, J ¼ 8.4, 2.1 Hz,
(d, J ¼ 1.9 Hz, 1H), 7.83 (dd, J ¼ 8.5, 1.9 Hz, 1H), 7.02 (d, J ¼ 8.5 Hz,
1H), 3.99 (s, 3H). The NMR data is in good agreement with that
reported in the literature.31
1H), 6.91 (d, J ¼ 8.5 Hz,1H), 3.92 (s, 3H), 3.72e3.60 (m, 8H). 13C NMR
(101 MHz, CDCl3)
d 169.0, 157.3, 132.8, 128.8, 128.3, 111.9, 111.6, 67.0
(two peaks overlap), 56.5. IR (neat) 2924(s), 2857(w), 1705(s),
1599(s),1497(w),1362(w),1271(s),1250(s),1111(s),1014(s), 901(w),
844(w), 757(w). HRMS (APCI) calcd for C12H15BrNOþ3 [MþH]þ
300.0230; found 300.0225.
4.3.5. 1-(3-Bromo-4-methoxyphenyl)ethanone (2e)
44.4 mg, 97% yield. 1H NMR (400 MHz, CDCl3)
d 8.17 (s, 1H), 7.92
(d, J ¼ 8.6 Hz, 1H), 6.94 (d, J ¼ 8.6 Hz, 1H), 3.97 (s, 3H), 2.56 (s, 3H).
The NMR data is in good agreement with that reported in the
literature.32
4.3.12. 4-Bromo-2-nitroanisole (4a)
44.0 mg, 95% yield from the reaction of 3a with NBS at 50 ꢀC for
48 h. White solid; mp. 84e86 ꢀC. 1H NMR (400 MHz, CDCl3)
d
7.98
(s, 1H), 7.64 (d, J ¼ 8.9 Hz, 1H), 6.99 (d, J ¼ 8.9 Hz, 1H), 3.96 (s, 3H).
13C NMR (101 MHz, CDCl3)
152.3, 137.0 (two peaks overlap), 128.5,
4.3.6. 1-(3-Bromo-4-methoxyphenyl)-1-propanone (2f)
43.7 mg, 90% yield. White solid; mp. 98e101 ꢀC. 1H NMR
d
(400 MHz, CDCl3)
d
8.17 (d, J ¼ 2.1 Hz, 1H), 7.93 (dd, J ¼ 8.6, 2.1 Hz,
115.3, 112.0, 56.9. IR (neat) 2922(m), 2853(w), 1601(m), 1513(s),
1468(w), 1342(m), 1264(s), 1154(w), 1101(w), 1009(s), 875(m),
814(s), 528(w). HRMS (APCI) calcd for C7H7BrNOþ3 [MþH]þ
231.9526; found 230.9524.
1H), 6.93 (d, J ¼ 8.6 Hz, 1H), 3.96 (s, 3H), 2.94 (q, J ¼ 7.2 Hz, 2H), 1.21
(t, J ¼ 7.2 Hz, 3H). 13C NMR (101 MHz, CDCl3)
d 198.5, 159.5, 133.7,
131.1, 129.2, 112.0, 111.2, 56.6, 31.6, 8.4. IR (neat) 2971(w), 2931(w),
1676(s), 1591(s), 1405(m), 1254(s), 1189(s), 1009(w), 795(w),
673(w). HRMS (APCI) calcd for C10H12BrOþ2 [MþH]þ 243.0015;
found 243.0014.
4.3.13. 2-(Benzyloxy)-5-bromobenzonitrile (4b)
55.9 mg, 97% yield. 1H NMR (400 MHz, CDCl3)
d 7.67 (d,
J ¼ 2.5 Hz, 1H), 7.57 (dd, J ¼ 9.0, 2.5 Hz, 1H), 7.48e7.31 (m, 5H), 6.88
(d, J ¼ 9.0 Hz, 1H), 5.20 (s, 2H). The NMR data is in good agreement
with that reported in the literature.33
4.3.7. 1-(4-(Benzyloxy)-3-bromophenyl)-1-propanone (2g)
49.8 mg, 78% yield. White solid; mp. 91e93 ꢀC. 1H NMR
(400 MHz, CDCl3)
d
8.20 (d, J ¼ 1.8 Hz, 1H), 7.88 (dd, J ¼ 8.6, 1.8 Hz,
1H), 7.53e7.30 (m, 5H), 6.96 (d, J ¼ 8.6 Hz, 1H), 5.23 (s, 2H), 2.93 (q,
4.3.14. 5-Bromo-2-(methyloxy)benzonitrile (4c)
J ¼ 7.2 Hz, 2H), 1.20 (t, J ¼ 7.2 Hz, 3H). 13C NMR (101 MHz, CDCl3)
40.7 mg, 96% yield. 1H NMR (400 MHz, CDCl3)
d 7.66 (d,
d
198.4, 158.6, 135.8, 133.7, 131.3, 129.0, 128.8, 128.3, 127.0, 112.8,
J ¼ 2.4 Hz, 1H), 7.63 (dd, J ¼ 8.9, 2.5 Hz, 1H), 6.87 (d, J ¼ 8.9 Hz, 1H),
3.93 (s, 3H). The NMR data is in good agreement with that reported
in the literature.34
112.6, 71.0, 31.6, 8.4. IR (neat) 2955(w), 2855(w), 1676(s), 1591(m),
1499(w), 1452(w), 1405(w), 1254(s), 1203(s), 1046(w), 1016(w),
797(w), 726(w), 679(w). HRMS (APCI) calcd for
C
16H16BrOþ2
[MþH]þ 319.0328; found 319.0322.
4.3.15. 50-Bromo-20-methoxyacetophenone (4d)
45.3 mg, 99% yield. White solid, mp. 35e37 ꢀC. 1H NMR
4.3.8. 1-(3-Bromo-4-(hexyloxy)phenyl) -1-propanone (2h)
55.7 mg, 89% yield. White solid; mp. 37e38 ꢀC. 1H NMR
(400 MHz, CDCl3)
d
7.83 (d, J ¼ 2.6 Hz, 1H), 7.54 (dd, J ¼ 8.8, 2.6 Hz,
1H), 6.86 (d, J ¼ 8.8 Hz, 1H), 3.90 (s, 3H), 2.59 (s, 3H). 13C NMR
(400 MHz, CDCl3)
d
8.17 (d, J ¼ 1.9 Hz, 1H), 7.89 (dd, J ¼ 8.6, 1.9 Hz,
(101 MHz, CDCl3) d 198.4, 158.1, 136.2, 133.1, 129.8, 113.7, 113.3, 56.0,
1H), 6.90 (d, J ¼ 8.6 Hz, 1H), 4.09 (t, J ¼ 6.5 Hz, 2H), 2.93 (q,
J ¼ 7.2 Hz, 2H), 1.91e1.80 (m, 2H), 1.56e1.46 (m, 2H), 1.39e1.32 (m,
4H), 1.21 (t, J ¼ 7.2 Hz, 3H), 0.91 (t, J ¼ 6.8 Hz, 3H). 13C NMR
31.9. IR(neat) 2916 (w), 2846 (w), 1672 (s), 1586 (m), 1478 (s), 1393
(s), 1354 (m), 1268 (s), 1221 (s), 1178 (w), 1144 (w), 1020 (m), 899
(w), 807 (m), 718 (w), 626 (w), 565 (w), 522 (w) HRMS (APCI) calcd
for C9H10O2Brþ [MþH]þ 228.9859; found 228.9857.
(101 MHz, CDCl3) d 198.5,159.2,133.7, 130.8,129.1,112.4,112.0, 69.5,
31.6 (two peaks overlap), 29.0, 25.7, 23.0, 14.1, 8.4. IR (neat)
2935(w), 2859(w), 1678(s), 1593(m), 1499(m), 1405(w), 1254(s),
1205(s), 1046(w), 1016(w), 797(w), 728(w), 679(w). HRMS (APCI)
calcd for C15H22BrOþ2 [MþH]þ 313.0798; found 313.0794.
4.3.16. Ethyl 5-bromo-2-methoxybenzoate (4e)
47.1 mg, 91% yield. Liquid. 1H NMR (400 MHz, CDCl3)
d 7.88 (d,
J ¼ 2.6 Hz, 1H), 7.54 (dd, J ¼ 8.9, 2.6 Hz, 1H), 6.86 (d, J ¼ 8.9 Hz, 1H),
4.35 (q, J ¼ 7.1 Hz, 2H), 3.88 (s, 3H), 1.38 (t, J ¼ 7.1 Hz, 3H). 13C NMR
4.3.9. 3-Bromo-4-methoxybenzoic acid (2i)
43.4 mg, 94% yield. White solid; mp. 219e221 ꢀC. 1H NMR
(101 MHz, CDCl3) d 164.9, 158.4, 136.0, 134.2, 122.3, 114.1, 112.4, 61.3,
56.4, 14.4. IR(neat) 2979 (w), 2840 (w), 1731 (s), 1592 (m), 1488 (s),
1403 (w), 1364 (w), 1297 (m), 1274 (m), 1099 (m), 1079 (m), 1023
(m), 813 (m), 675 (w), 626 (w), 530 (w). HRMS (APCI) for C8H6O2Brþ
[MþH]þ 212.9546; found 212.9544.
(400 MHz, DMSO-d6)
d
8.07 (d, J ¼ 2.1 Hz, 1H), 7.95 (dd, J ¼ 8.6,
2.1 Hz, 1H), 7.21 (d, J ¼ 8.7 Hz, 1H), 3.94 (s, 3H). 13C NMR (101 MHz,
DMSO-d6)
d 165.9, 158.9, 133.8, 130.7, 124.3, 112.3, 110.4, 56.7. IR
(neat) 2926(w), 2847(w), 1664(s), 1593(m), 1501(w), 1430(w),
1273(s), 1250(s), 1126(w), 1054(m), 899(w), 763(m). HRMS (APCI)
calcd for C8H6BrOꢁ3 [M-H]- 228.9506; found 228.9501.
4.3.17. 4-Bromo-2-fluoro-1-(hexyloxy)benzene (4f)
54.4 mg, 99% yield. Liquid. 1H NMR (400 MHz, CDCl3)
d 7.22 (dd,
4.3.10. Ethyl 3-bromo-4-methoxybenzoate (2j)
J ¼ 10.6, 2.4 Hz,1H), 7.19e7.13 (m,1H), 6.82 (t, J ¼ 8.7 Hz,1H), 3.99 (t,
50.8 mg, 98% yield. White solid; mp. 70e71 ꢀC. 1H NMR
J ¼ 6.6 Hz, 2H), 1.86e1.73 (m, 2H), 1.52e1.41 (m, 2H), 1.39e1.29 (m,
(400 MHz, CDCl3)
d
8.22 (d, J ¼ 2.1 Hz, 1H), 7.98 (dd, J ¼ 8.6, 2.1 Hz,
4H), 0.91 (t, J ¼ 9.2, 4.7 Hz, 3H). 13C NMR (101 MHz, CDCl3)
d 152.8
1H), 6.91 (d, J ¼ 8.6 Hz, 1H), 4.35 (q, J ¼ 7.1 Hz, 2H), 3.95 (s, 3H), 1.38
(d, J ¼ 250.6 Hz), 146.8 (d, J ¼ 10.5 Hz), 127.3 (d, J ¼ 4.0 Hz), 119.8 (d,
J ¼ 21.4 Hz), 116.1 (d, J ¼ 2.4 Hz), 111.9 (d, J ¼ 8.3 Hz), 69.8, 31.7, 29.2,
25.7, 22.7, 14.2. IR (neat) 2930 (w), 2859 (w), 1582 (w), 1505 (s),
1409 (w),1305 (m),1266 (m),1207 (m),1129 (m),1019 (m), 876 (m),
858 (m), 799 (m), 638 (w), 575 (w). HRMS (APCI) for C12H16BrFOþ
[M]þ 274.0363; found 274.0363.
(t, J ¼ 7.1 Hz, 3H). 13C NMR (101 MHz, CDCl3)
d 165.3, 159.5, 134.8,
130.7, 124.3, 111.5, 111.1, 61.2, 56.5, 14.5. IR (neat) 2924(w), 2845(w),
1705(s), 1599(m), 1497(m), 1362(m), 1268(s), 1246(s), 1126(s),
1016(m), 901(w), 842(w), 763(s). HRMS (APCI) calcd for C10H12BrO3þ
[MþH]þ 258.9964; found 258.9963.
Please cite this article in press as: Pramanick PK, et al., Mechanistic study on iodine-catalyzed aromatic bromination of aryl ethers by N-