Verma et al.
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(dd, J = 6.6 and 1.8 Hz, 2H), 4.04 (s, 3H), 1.34 (s, 9H); 13C NMR
(CDCl3) δ 165.8, 152.7, 149.0, 141.8, 139.7, 132.7, 132.2, 129.1,
128.5, 127.8, 125.7, 125.6, 125.5, 119.3, 93.9, 88.0, 55.6, 34.9,
31.1; HRMS (ESI) calcd for C23H21NO2 (M þ Hþ) 343.1572,
found 343.1569.
Methyl 2-((6-Methoxynaphthalen-2-yl)ethynyl)quinoline-3-
carboxylate (5i). The product was obtained as an orange solid,
mp 126-128 °C: 1H NMR (300 MHz, [D]CHCl3) δ 8.81 (s, 1H),
8.17(d, J = 7.2 Hz, 2H), 7.90-7.80(m, 3H), 7.77-7.73(m, 2H),
7.60(t, J = 6.9 Hz, 1H), 7.16 (td, J = 9.0 and 2.4 Hz, 2H), 4.07
(s, 3H), 3.93 (s, 3H); 13C NMR (CDCl3) δ 165.7, 158.7, 149.1,
141.8, 139.8, 134.8, 132.7, 132.2, 129.7, 129.3, 129.1, 128.6,
128.4, 127.8, 126.9, 125.8, 125.4, 119.5, 117.2, 105.9, 94.4,
88.4, 55.4, 52.7; HRMS (ESI) calcd for C24H17NO3 (M þ Hþ)
367.1208, found 367.1210.
NMR (CDCl3) δ 165.2, 152.4, 138.2, 132.0, 128.4, 122.5, 93.3,
83.7, 52.6, 51.3; HRMS (ESI) calcd for C10H9NO3 (M þ Hþ)
191.0582, found 191.0588.
Ethyl 2-(3-Hydroxyprop-1-ynyl)nicotinate (5u). The product
was obtained as a yellow oil: 1H NMR (400 MHz, [D]CHCl3 þ
(CD3)2SO) δ 8.48 (t, J = 4.8 Hz, 1H), 8.15 (d, J = 8.4 Hz, 1H),
7.36-7.34 (m, 1H), 4.30 (s, 2H), 4.16-4.13 (m, 2H), 1.24-1.21
(m, 3H); 13C NMR (CDCl3 þ (CD3)2SO): 165.0, 151.5, 138.1,
131.8, 128.4, 122.3, 93.8, 82.9, 61.6, 50.7, 14.1; HRMS (ESI)
calcd for C11H11NO3 (M þ Hþ) 205.0739, found 205.0742.
Methyl 2-(Phenylethynyl)nicotinate (5v). The product was
obtained as a yellow oil: 1H NMR (300 MHz, [D]CHCl3) δ
8.75 (t, J = 4.8 Hz, 1H), 8.27 (d, J = 7.8 Hz, 1H), 7.68-7.65 (m,
2H), 7.39-7.37 (m, 3H), 7.35-7.26 4.67 (m, 1H), 4.0 (s, 3H); 13
C
NMR (CDCl3) δ 165.6, 152.6, 142.8, 142.6, 138.2, 132.3, 129.3,
128.4, 122.3, 122.2, 94.2, 87.9, 52.6; HRMS (ESI) calcd for
C15H11NO2 (M þ Hþ) 237.0790, found 237.0792.
Methyl 2-((3,5-Dimethoxyphenyl)ethynyl)quinoline-3-carbox-
ylate (5j). The product was obtained as an orange solid, mp
1
118-120 °C: H NMR (300 MHz, [D]CHCl3) δ 8.81 (s, 1H),
Methyl 2-(Cyclohexylethynyl)nicotinate (5w). The product
1
was obtained as a yellow oil: H NMR (300 MHz, [D]CHCl3)
8.16 (d, J = 9.0 Hz, 1H), 7.91-7.81(m, 2H), 7.61(t, J = 6.9 Hz,
1H), 6.88 (s, 2H), 6.52 (s, 1H), 4.05 (s, 3H), 3.82 (s, 6H); 13C
NMR (CDCl3) δ 165.6, 160.5, 149.0, 141.4, 139.8, 132.2, 129.1,
128.5, 127.9, 125.8, 125.5, 123.6, 110.0, 102.9, 93.3, 87.9, 55.5,
52.6; HRMS (ESI) calcd for C21H17NO4 (M þ Hþ) 347.1158,
found 347.1160.
δ 8.67 (dd, J = 1.8, 4.8 Hz, 1H), 8.18 (dd, J = 1.8, 8.1 Hz, 1H),
7.28-7.24 (m, 1H), 3.94 (s, 3H), 2.78-2.69 (m, 1H), 1.95-1.91
(m, 2H), 1.83-1.77 (m, 2H), 1.64-1.56 (m, 3H), 1.40-1.34 (m,
3H); 13C NMR (CDCl3) δ 166.0, 152.3, 143.1, 138.0, 128.4,
121.6, 100.3, 79.4, 52.4, 32.1, 29.9, 25.8, 24.8; HRMS (ESI) calcd
for C15H17NO2 (M þ Hþ) 243.1259, found 243.1256.
Methyl 2-((4-Methoxyphenyl)ethynyl)quinoline-3-carboxylate
(5k). The product was obtained as an orange solid, mp 82-
84 °C: 1H NMR (300 MHz, [D]CHCl3) δ 8.80 (s, 1H), 8.15
(d, J = 6.5 Hz, 1H), 7.90-7.81 (m, 2H), 7.68-7.60 (m, 3H), 6.92
(d, J = 6.8 Hz, 2H), 4.05 (s, 3H), 3.85 (s, 3H); 13C NMR (CDCl3)
δ 165.7, 160.5, 149.0, 141.9, 139.7, 134.0, 132.1, 129.1, 128.5,
127.7, 125.6, 125.4, 114.4, 114.1, 94.0, 87.6, 55.3, 52.6; HRMS
(ESI) calcd for C20H15NO3 (M þ Hþ) 317.1052, found 317.1050.
Methyl 2-((1-Hydroxycyclohexyl)ethynyl)quinoline-3-carbox-
ylate (5p). The product was obtained as a yellow solid, mp
Methyl 2-(m-Tolylethynyl)nicotinate (5x). The product was
obtained as a yellow oil: 1H NMR (300 MHz, [D]CHCl3) δ 8.747
(d, J = 4.5 Hz, 1H), 8.26 (d, J = 8.1 Hz, 1H), 7.47 (d, J = 8.4 Hz,
2H), 7.34-7.29 (m, 1H), 7.24-7.18 (m, 2H), 4.00 (s, 3H), 2.36 (s,
3H); 13C NMR (CDCl3) δ 165.5, 152.5, 142.8, 138.1, 138.1,
132.8, 130.2, 129.3, 128.3, 128.3, 122.1, 122.0, 94.4, 87.5, 52.5,
21.2; HRMS (ESI) calcd for C16H13NO2 (M þ Hþ) 251.0946,
found 251.0950.
Methyl 2-(Cyclohexylethynyl)benzoate (5y). The product was
obtained as a yellow oil: 1H NMR (300 MHz, [D]CHCl3) δ 7.47
(d, J = 7.5, 1H), 7.33 (d, J = 6.9, 1H), 7.24-7.17 (m, 2H), 3.33
(s, 3H), 2.60-2.57 (m, 1H), 1.62-1.89 (m, 4H), 1.60-1.19 (m,
6H); 13C NMR (CDCl3) δ 138.3, 131.2, 127.2, 126.5, 124.8,
122.0, 101.9, 98.1, 76.9, 53.5, 31.7, 28.8, 24.9, 23.8; HRMS (ESI)
calcd for C16H18O2 (M þ Hþ) 242.1307, found 242.1310.
Methyl 2-Chloroquinoline-3-carboxylate (5z). The product
was obtained as white solid: mp 70-72 °C: 1H NMR (300
MHz, [D]CHCl3) δ 8.69(s, 1H), 8.04 (d, J = 8.4 Hz, 1H),
7.90-7.80 (m, 2H), 7.62 (t, J = 7.2 Hz, 1H), 4.01 (s, 3H); 13C
NMR (CDCl3) δ 165.0, 148.3, 147.6, 141.7, 132.7, 128.5, 128.2,
127.9, 125.8, 124.1, 52.9; HRMS (ESI) calcd for C11H8ClNO2
(M þ Hþ) 221.0244, found 221.0248.
1
122-124 °C: H NMR (300 MHz, [D]CHCl3) δ 8.74 (s, 1H),
8.13 (d, J = 8.4 Hz, 1H), 7.87-7.77 (m, 2H), 7.61-7.56 (m, 1H),
3.98 (s, 3H), 2.98 (s, 1H), 2.14 (d, J = 6.3 Hz, 3H), 1.80-1.60
(m, 7H); 13C NMR (CDCl3) δ 165.7, 148.8, 141.2, 139.6, 132.1,
129.1, 128.5, 127.9, 125.8, 125.6, 97.7, 83.1, 69.0, 52.6, 39.6, 25.2,
23.1; HRMS (ESI) calcd for C19H19NO3 (M þ Hþ) 309.1365,
found 309.1370.
Methyl 2-(3-Hydroxyprop-1-ynyl)quinoline-3-carboxylate (5q).
The product was obtained as a yellow solid, mp 100-102 °C: 1H
NMR (300 MHz, [D]CHCl3) δ 8.75 (s, 1H), 8.09 (d, J = 8.4 Hz,
1H), 7.92-7.78 (m, 2H), 7.60 (t, J = 8.1 Hz, 1H), 4.67
(s, 2H), 3.99 (s, 3H), 3.51 (s, 1H); 13C NMR (CDCl3) δ 165.3,
148.7, 141.0, 139.8, 132.4, 128.8, 128.5, 128.0, 125.8, 124.9, 94.5,
92.5, 52.6, 51.4; HRMS (ESI) calcd for C14H11NO3 (M þ Hþ)
241.0739, found 241.0740.
Methyl 2-Bromonicotinate (5aa). The product was obtained as
a yellow oil: 1H NMR (300 MHz, [D]CHCl3) δ 8.49 (dd, J = 1.8,
4.8 Hz, 1H), 8.08 (dd, J = 1.8, 4.8 Hz, 1H), 7.38-7.34 (m, 1H),
3.96 (s, 3H); 13C NMR (CDCl3) δ 165.4, 152.1, 140.7, 139.6,
129.6, 122.3, 53.0; HRMS (ESI) calcd for C7H6BrNO2 (M þ
Hþ) 214.9582, found 214.9588.
Methyl 2,5-Dibromobenzoate (5bb). The product was ob-
tained as an orange solid, mp 46-48 °C: 1H NMR (300 MHz,
[D]CHCl3) δ 8.00 (d, J = 1.8 Hz, 1H), 7.54-7.4 (m, 2H), 3.94 (s,
3H); 13C NMR (CDCl3) δ 165.2, 135.8, 135.5, 134.2, 134.1,
121.0, 120.5, 52.8; HRMS (ESI) calcd for C8H6Br2O2 (M þ Hþ)
291.8735, found 291.8732.
Ethyl 2-(3-Hydroxyprop-1-ynyl)quinoline-3-carboxylate (5r).
1
The product was obtained as brown solid, mp 80-82 °C: H
NMR (300 MHz, (CD3)2SO) δ 8.89 (s, 1H), 8.18 (dd, J = 7.8, 1.4
Hz, 1H), 8.05-7.97 (m, 1H), 7.94-7.87 (m, 1H), 7.74-7.67
(m, 1H), 4.45-4.34 (m, 4H), 1.36 (t, J = 6.9 Hz, 3H); HRMS
(ESI) calcd for C15H13NO3 (M þ Hþ) 255.0895, found 255.0898.
Methyl 2-(3-Hydroxyprop-1-ynyl)-6-methoxyquinoline-3-car-
boxylate (5s). The product was obtained as a yellow solid, mp
1
116-118 °C: H NMR (400 MHz, [D]CHCl3) δ 8.65 (s, 1H),
8.02 (d, J = 9.1 Hz, 1H), 7.42 (dd, J = 9.1, 2.7 Hz, 1H), 7.65
(d, J = 2.7 Hz, 1H), 4.55 (s, 2H), 3.94 (s, 3H), 3.88 (s, 3H), 2.47
(s, 1H); 13C NMR (CDCl3) δ 165.4, 159.10, 144.7, 138.6, 138.2,
130.2, 127.3, 125.8, 125.3, 105.5, 92.3, 84.2, 55.8, 52.7, 51.7;
HRMS (ESI) calcd for C15H13NO4 (M þ Hþ) 271.0845, found
271.0849.
Methyl 4-Methoxybenzoate (5cc). The product was obtained
as white solid: 1H NMR (300 MHz, [D]CHCl3) δ 7.99 (d, J = 7.2
Hz, 2H), 6.91 (d, J = 9.0 Hz, 2H), 3.88 (s, 3H), 3.85 (s, 3H); 13
C
NMR (CDCl3) δ 166.9, 163.4, 131.2, 122.6, 113.6, 55.5, 51.9;
HRMS (ESI) calcd for C9H10O3 (M þ Hþ) 166.0630, found
166.0634.
Methyl 4-Nitrobenzoate (5dd). The product was obtained as a
yellow solid: 1H NMR (300 MHz, CDCl3) δ 8.35-8.20 (m, 4H),
3.98 (s, 3H); 13C NMR (CDCl3) δ 165.2, 150.5, 135.5, 130.8,
Methyl 2-(3-Hydroxyprop-1-ynyl)nicotinate (5t). The product
was obtained as a yellow oil: H NMR (400 MHz, [D]CHCl3)
1
δ 8.63 (dd, J = 1.2, 3.2 Hz, 1H), 8.18 (dd, J = 1.8, 5.9 Hz, 1H),
7.61-7.56 (m, 1H), 4.50 (s, 2H), 3.87 (s, 3H), 2.88 (s, 1H); 13
7702 J. Org. Chem. Vol. 75, No. 22, 2010
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