The Journal of Organic Chemistry
Article
1
1
1
4
23−124 °C; H NMR (400 MHz, chloroform-d) δ 8.11 (dd, J = 8.4,
.4 Hz, 2H), 7.99−7.94 (m, 2H), 7.64−7.55 (m, 2H), 7.54−7.44 (m,
H), 7.01−6.95 (m, 1H), 6.70−6.59 (m, 2H), 5.39 (dt, J = 9.2, 0.9
(1,6-Dimethyl-1,2,3,4-tetrahydroquinoline-3,4-diyl)bis((4-
methoxyphenyl)methanone) (3f). Purified using column chromatog-
raphy (SiO , 5% ethyl acetate in hexane), off-white solid, 53.3 mg
2
1
Hz, 1H), 4.49 (td, J = 9.6, 4.8 Hz, 1H), 3.49 (dd, J = 11.3, 4.9 Hz,
H), 3.30 (dd, J = 11.3, 9.8 Hz, 1H), 2.90 (s, 3H), 2.11 (s, 3H) ppm;
C{ H} NMR (101 MHz, chloroform-d) δ 202.5, 200.5, 144.0,
38.0, 136.1, 133.53, 133.48, 129.1 (2C), 129.0 (2C), 128.9 (2C),
28.65 (2C), 128.6, 128.2, 126.9, 122.5, 112.2, 53.2, 46.2, 45.5, 39.5,
0.5 ppm; ATR-FTIR ν = 1687, 1669, 1511, 1213, 967, 774, 690
cm ; HRMS (ESI) m/z calcd C H NO [M + H] 370.1807,
found 370.1825.
(50%); mp 139−140 °C; H NMR (400 MHz, chloroform-d) δ 8.08
(d, J = 9.0 Hz, 2H), 7.95 (d, J = 8.9 Hz, 2H), 7.08−6.86 (m, 5H),
6.70−6.56 (m, 2H), 5.32 (dt, J = 9.7, 1.0 Hz, 1H), 4.44 (td, J = 10.0,
1
13
1
4
1
.8 Hz, 1H), 3.88 (s, 3H), 3.86 (s, 3H), 3.44 (dd, J = 11.2, 4.8 Hz,
H), 3.28 (dd, J = 11.2, 10.2 Hz, 1H), 2.90 (s, 3H), 2.09 (s, 3H)
1
1
2
1
3
1
ppm; C{ H} NMR (101 MHz, chloroform-d) δ 200.9, 199.0, 163.9,
max
−
1
+
163.8, 144.0, 131.5 (2C), 131.2, 131.0 (2C), 129.1, 128.5, 128.4,
26.8, 123.1, 114.1 (2C), 114.0 (2C), 112.2, 55.59, 55.58, 53.6, 46.0,
2
5
24
2
1
4
1
+
5.0, 39.6, 20.5 ppm; ATR-FTIR ν = 1661, 1598, 1572, 1509,
(
1,6-Dimethyl-1,2,3,4-tetrahydroquinoline-3,4-diyl)bis(p-tolyl-
methanone) (3b). Purified using column chromatography (SiO , 5%
max
−
1
316, 1255, 1170, 845 cm ; HRMS (ESI) m/z calcd C H NO [M
27 28
4
2
+
H] 430.2018, found 430.2024.
1,6-Dimethyl-1,2,3,4-tetrahydroquinoline-3,4-diyl)bis((4-
trifluoromethyl)phenyl)methanone) (3g). Purified using column
ethyl acetate in hexane), yellow solid, 63 mg (63%); mp 150−153 °C;
1
(
H NMR (400 MHz, chloroform-d) δ 8.03−7.96 (m, 2H), 7.88−7.81
(
(
m, 2H), 7.32−7.21 (m, 4H), 6.95 (ddd, J = 8.3, 1.4, 0.8 Hz, 1H),
chromatography (SiO , 5% ethyl acetate in hexane), thick yellow-
2
6
1
2
.67−6.58 (m, 2H), 5.34 (d, J = 9.3 Hz, 1H), 4.44 (td, J = 9.7, 4.8 Hz,
1
orange oil, 35 mg (28%); H NMR (400 MHz, chloroform-d) δ
H), 3.45 (dd, J = 11.2, 4.8 Hz, 1H), 3.27 (dd, J = 11.3, 9.9 Hz, 1H),
1
3
1
8.25−8.13 (m, 2H), 8.08−8.01 (m, 2H), 7.83−7.71 (m, 4H), 6.99
.89 (s, 3H), 2.43 (s, 3H), 2.40 (s, 3H), 2.09 (s, 3H) ppm; C{ H}
NMR (101 MHz, chloroform-d) δ 202.1, 200.1, 144.44, 144.35,
44.1, 135.6, 133.6, 129.7 (2C), 129.6 (2C), 129.3 (2C), 128.9 (2C),
28.6, 128.5, 126.8, 122.9, 112.1, 53.4, 46.0, 45.36, 39.60, 21.9, 21.8,
0.5 ppm; ATR-FTIR ν = 1665, 1604, 1515, 1271, 1182, 828, 789
cm ; HRMS (ESI) m/z calcd C H NO [M + H] 398.2120,
found 398.2132.
1,6-Dimethyl-1,2,3,4-tetrahydroquinoline-3,4-diyl)bis((4-
isobutylphenyl)methanone) (3c). Purified using column chromatog-
raphy (SiO , 5% ethyl acetate in hexane), yellow solid, 61.9 mg
52%); mp 113−114 °C; H NMR (400 MHz, chloroform-d) δ 8.00
d, J = 8.3 Hz, 2H), 7.87 (d, J = 8.3 Hz, 2H), 7.29−7.19 (m, 4H),
.95 (ddt, J = 8.3, 2.1, 0.8 Hz, 1H), 6.66−6.60 (m, 2H), 5.35 (d, J =
.4 Hz, 1H), 4.46 (td, J = 9.7, 4.8 Hz, 1H), 3.47 (dd, J = 11.2, 4.8 Hz,
H), 3.29 (dd, J = 11.2, 9.9 Hz, 1H), 2.90 (s, 3H), 2.54 (dd, J = 11.1,
.2 Hz, 4H), 2.10 (s, 3H), 1.99−1.82 (m, 2H), 0.96−0.87 (m, 12H)
ppm; C{ H} NMR (101 MHz, chloroform-d) δ 202.0, 200.1, 148.0,
47.9, 143.9, 135.8, 133.8, 129.5 (2C), 129.4 (2C), 128.9 (2C), 128.6
2C), 128.50, 128.3, 126.6, 122.8, 112.0, 53.3, 46.1, 45.5, 45.4, 45.2,
9.5, 30.1, 22.4, 22.4, 22.3, 20.4 ppm; ATR-FTIR ν = 1668, 1603,
514, 1270, 1181, 860, 799 cm ; HRMS (ESI) m/z calcd
C H NO [M + H] 482.3059, found 482.3070.
1,6-Dimethyl-1,2,3,4-tetrahydroquinoline-3,4-diyl)bis((4-(tert-
butyl)phenyl)methanone) (3d). Purified using column chromatog-
raphy (SiO , 5% ethyl acetate in hexane), yellow solid, 54.5 mg
45%); mp 179−181 °C; H NMR (400 MHz, chloroform-d) δ 8.02
d, J = 8.6 Hz, 2H), 7.89 (d, J = 8.6 Hz, 2H), 7.47 (dd, J = 15.8, 8.6
Hz, 3H), 6.99−6.92 (m, 1H), 6.67−6.59 (m, 2H), 5.35 (d, J = 9.4 Hz,
H), 4.46 (td, J = 9.7, 4.8 Hz, 1H), 3.47 (dd, J = 11.3, 4.8 Hz, 1H),
.28 (dd, J = 11.3, 9.9 Hz, 1H), 2.90 (s, 3H), 2.10 (s, 3H), 1.36 (s,
H), 1.33 (s, 9H) ppm; C{ H} NMR (101 MHz, chloroform-d) δ
02.0, 199.9, 157.2, 157.0, 143.9, 135.4, 133.4, 128.9 (2C), 128.6
2C), 128.5, 128.3, 126.7, 125.8 (2C), 125.7 (2C), 122.8, 111.9, 53.2,
(
dq, J = 8.2, 0.9 Hz, 1H), 6.66 (d, J = 8.4 Hz, 1H), 6.54−6.48 (m,
1
3
3
H), 5.32 (d, J = 9.5 Hz, 1H), 4.46 (td, J = 9.7, 5.1 Hz, 1H), 3.55−
1
1
2
.44 (m, 1H), 3.29 (dd, J = 11.2, 10.1 Hz, 1H), 2.90 (d, J = 0.7 Hz,
1
3
1
H), 2.10 (s, 3H) ppm; C{ H} NMR (101 MHz, chloroform-d) δ
max
2
−
1
+
201.6, 199.8, 143.8, 140.5, 138.7, 134.8 (q, C−F, JC−F = 33 Hz),
2
7
28
2
2
1
1
(
2
34.7 (q, C−F, J
= 33 Hz), 129.4 (2C), 129.0 (2C), 128.2, 127.3,
C−F
1
26.4−125.8 (m, C−F, 4C), 123.7 (q, C−F, J
= 272.6 Hz), 123.6
C−F
(
1
q, C−F, J
= 272.6 Hz), 121.9, 121.2, 112.4, 52.9, 46.6, 46.2, 39.5,
C−F
1
9
0.46 ppm; F NMR (470 MHz, chloroform-d) δ −63.16(s, 3F),
2
1
−63.23(s, 3F) ppm; ATR-FTIR ν = 1683, 1512, 1322, 1170, 1128,
max
(
(
6
9
1
7
−
1
1
5
067 cm ; HRMS (ESI) m/z calcd C H F NO [M + H]+
27 22 6 2
06.1555, found 506.1548.
(
1,6-Dimethyl-1,2,3,4-tetrahydroquinoline-3,4-diyl)bis((4-
bromophenyl)methanone) (3h). Purified using column chromatog-
raphy (SiO , 5% ethyl acetate in hexane), yellow solid, 113.4 mg
2
1
13
1
(84%); mp 128−130 °C; H NMR (400 MHz, chloroform-d) δ
8
(
2
3
.00−7.88 (m, 2H), 7.85−7.77 (m, 2H), 7.71−7.56 (m, 4H), 6.97
1
(
3
1
ddt, J = 8.3, 2.2, 0.8 Hz, 1H), 6.65 (d, J = 8.3 Hz, 1H), 6.52 (dt, J =
.0, 0.9 Hz, 1H), 5.30−5.16 (m, 1H), 4.39 (td, J = 9.9, 5.0 Hz, 1H),
max
.44 (dd, J = 11.3, 5.0 Hz, 1H), 3.26 (dd, J = 11.3, 10.1 Hz, 1H), 2.90
−
1
13
1
(
s, 3H), 2.09 (s, 3H) ppm; C{ H} NMR (101 MHz, chloroform-d)
δ 201.4, 199.6, 143.8, 136.67, 134.7, 132.34 (2C), 132.28 (2C), 130.6
2C), 130.2 (2C), 128.99, 128.98, 128.8, 128.3, 127.1, 122.3, 112.3,
+
33
40
2
(
(
5
3.2, 46.3, 45.6, 39.5, 20.5 ppm; ATR-FTIR ν = 2856, 1670, 1654,
max
2
−1
1
1582, 1507, 1067, 1005, 816 cm ; HRMS (ESI) m/z calcd
C H Br NO [M + H] 526.0017, found 526.0025.
(
(
+
2
5
22
2
2
(
1,6-Dimethyl-1,2,3,4-tetrahydroquinoline-3,4-diyl)bis((4-
chlorophenyl)methanone) (3i). Purified using column chromatog-
1
3
9
2
(
4
raphy (SiO , 5% ethyl acetate in hexane), yellow solid, 83.1 mg
2
1
(
(
72%); mp 149−150 °C; H NMR (400 MHz, chloroform-d) δ 8.03
d, J = 8.6 Hz, 2H), 7.89 (d, J = 8.7 Hz, 2H), 7.46 (dd, J = 16.1, 8.6
1
3
1
Hz, 4H), 6.97 (ddt, J = 8.3, 2.1, 0.8 Hz, 1H), 6.65 (d, J = 8.4 Hz, 1H),
.54 (dt, J = 2.0, 0.9 Hz, 1H), 5.28 (dd, J = 9.6, 1.1 Hz, 1H), 4.41 (td,
J = 9.9, 5.0 Hz, 1H), 3.45 (dd, J = 11.3, 5.0 Hz, 1H), 3.27 (dd, J =
6
5.9, 45.2, 39.5, 35.1, 35.1, 31.1, 31.0, 20.4 ppm; ATR-FTIR ν
668, 1604, 1514, 1270, 1188, 803 cm ; HRMS (ESI) m/z calcd
C H NO [M + H] 482.3059, found 482.3069.
1,6-Dimethyl-1,2,3,4-tetrahydroquinoline-3,4-diyl)bis((3,4-
dimethylphenyl)methanone) (3e). Purified using column chroma-
=
max
−
1
1
13
1
1
(
1
1
1.2, 10.1 Hz, 1H), 2.90 (s, 3H), 2.10 (s, 3H) ppm; C{ H} NMR
+
33
40
2
101 MHz, chloroform-d) δ 201.2, 199.4, 143.8, 140.2, 140.2, 136.3,
34.3, 130.5 (2C), 130.1 (2C), 129.34 (2C), 129.28 (2C), 128.8,
(
28.3, 127.0, 122.3, 112.2, 53.2, 46.3, 45.6, 39.5, 20.5 ppm; ATR-
tography (SiO , 5% ethyl acetate in hexane), yellow solid, 43.4 mg
−1
2
FTIR νmax = 2859, 1673, 1587, 1512, 1399, 1204, 1090, 818 cm ;
1
(
(
(
46%); mp 129−130 °C; H NMR (400 MHz, chloroform-d) δ 7.85
dd, J = 10.2, 2.4 Hz, 2H), 7.70 (dd, J = 10.2, 2.5 Hz, 2H), 7.25−7.18
m, 2H), 6.95 (dd, J = 8.3, 2.2 Hz, 1H), 6.67−6.59 (m, 2H), 5.34 (d,
J = 9.4 Hz, 1H), 4.45 (td, J = 9.7, 4.7 Hz, 1H), 3.49−3.41 (m, 1H),
.28 (dd, J = 11.2, 10.0 Hz, 1H), 2.90 (d, J = 1.1 Hz, 3H), 2.34 (s,
H), 2.32 (s, 3H), 2.31 (s, 3H), 2.29 (s, 3H), 2.09 (s, 3H) ppm;
C{ H} NMR (101 MHz, chloroform-d) δ 202.4, 200.4, 144.0,
+
HRMS (ESI) m/z calcd C H Cl NO [M + H] 438.1028, found
2
5
22
2
2
4
38.1028.
3-Benzoyl-1,6-dimethyl-1,2,3,4-tetrahydroquinolin-4-yl)(4-
methoxyphenyl)methanone (3ja) and (4-benzoyl-1,6-Dimethyl-
(
3
3
1
,2,3,4-tetrahydroquinolin-3-yl)(4-methoxyphenyl)methanone
(3jb). Purified using column chromatography (SiO , 1% ethyl acetate
2
13
1
1
in hexane), thick yellow oil, 66 mg (64%); H NMR (400 MHz,
1
1
3
1
43.2, 143.1, 137.23, 137.20, 136.1, 134.1, 130.2, 130.14, 130.08,
29.9, 128.6, 128.5, 127.0, 126.8, 126.5, 123.1, 112.0, 53.5, 46.0, 45.3,
chloroform-d) δ 8.11−8.06 (m, overlapping 3ja and 3jb, 4H), 7.98−
7.92 (m, overlapping 3ja and 3jb, 4H), 7.62−7.53 (m, overlapping 3ja
and 3jb, 2H), 7.52−7.42 (m, overlapping 3ja and 3jb, 4H), 7.00−6.90
(m, overlapping 3ja and 3jb, 6H), 6.67−6.57 (m, overlapping 3ja and
3jb, 4H), 5.38−5.31 (m, overlapping 3ja and 3jb, 2H), 4.52−4.40 (m,
9.6, 20.5, 20.22, 20.18, 20.0, 19.9 ppm; ATR-FTIR ν = 1662,
max
−
1
603, 1518, 1267, 1208, 794 cm ; HRMS (ESI) m/z calcd
+
C H NO [M + H] 426.2433, found 426.2436.
29
32
2
1
906
J. Org. Chem. 2021, 86, 1901−1910