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The Journal of Organic Chemistry
29.8, 20.1. HRMS (ESI): m/z calcd for C11H14NO [M + H]+
176.1070, found 176.1066.
51.5, 43.0, 37.5, 16.8, 15.5, 14.2. HRMS (ESI): m/z calcd for
C14H19ClNO2 [M + H]+ 268.1099, found 268.1100.
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5a,6,7,8,9,10,10a,11ꢀoctahydrobenzo[b]cyclohepta[e][1,4]ꢀ
oxazine (2f). White solid. Yield: 81% (165 mg); mp: 80ꢀ81
oC.1H NMR (400 MHz, Chloroformꢀd) (major diastereomer)
δ 6.81 – 6.72 (m, 2H), 6.68 – 6.55 (m, 2H), 4.32ꢀ4.28 (m, 1H),
3.47 (dt, J = 8.8, 3.0 Hz, 1H), 1.92 – 1.44 (m, 10H). 13C NMR
(151 MHz, Chloroformꢀd) (major diastereomer) δ 143.2,
132.9, 121.0, 118.1, 116.3, 114.5, 76.2, 53.4, 31.4, 30.6, 27.9,
23.0, 21.4. HRMS (ESI): m/z calcd for C13H18NO [M + H]+
204.1383, found 204.1380.
Ethyl
5,7,8,9,10,10aꢀhexahydroacridineꢀ8a(6H)ꢀ
1
carboxylate (4f). Pale yellow wax. Yield: 93% (241 mg). H
NMR (400 MHz, Chloroformꢀd) δ 7.01 – 6.95 (m, 2H), 6.60
(td, J = 7.4, 1.1 Hz, 1H), 6.48 (dd, J = 7.8, 1.0 Hz, 1H), 4.18
(q, J = 7.1 Hz, 2H), 3.82 (dd, J = 6.8, 3.2 Hz, 1H), 3.71 (s,
1H), 3.02 – 2.79 (m, 2H), 1.84 – 1.40 (m, 8H), 1.24 (t, J = 7.2
Hz, 3H). 13C NMR (151 MHz, Chloroformꢀd) δ 176.2, 142.6,
129.3, 126.9, 118.0, 116.5, 113.3, 60.5, 51.1, 44.1, 34.2, 30.0,
29.8, 22.2, 21.2, 14.2. HRMS (ESI): m/z calcd for C16H22NO2
[M + H]+ 260.1645, found 260.1644.
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Ethyl
2,3ꢀdimethylꢀ1,2,3,4ꢀtetrahydroquinolineꢀ3ꢀ
1
Ethyl 2ꢀmethylꢀ5,7,8,9,10,10aꢀhexahydroacridineꢀ8a(6H)ꢀ
carboxylate (4g). Reddishꢀbrown oil. Yield: 87% (238 mg). 1H
NMR (500 MHz, Chloroformꢀd) δ 6.81 – 6.79 (m, 2H), 6.41
(d, J = 8.0 Hz, 1H), 4.18 (q, J = 7.2 Hz, 2H), 3.79 – 3.78 (m,
1H), 3.49 (s, 1H), 3.00ꢀ2.76 (m, 2H), 2.22 (s, 3H), 1.84 – 1.43
(m, 8H), 1.25 (t, J = 7.0 Hz, 3H). 13C NMR (151 MHz, Chloꢀ
roformꢀd) δ 176.2, 140.2, 129.8, 127.5, 125.7, 118.0, 113.5,
60.5, 51.2, 44.3, 34.0, 30.1, 29.7, 22.1, 21.3, 20.5, 14.2.
HRMS (ESI): m/z calcd for C17H24NO2 [M + H]+ 274.1802,
found 274.1800
carboxylate (4a). Yellow oil. Yield: 86% (201 mg). H NMR
(400 MHz, Chloroformꢀd) (major diastereomer) δ 7.06 – 6.97
(m, 2H), 6.65 (t, J = 7.4 Hz, 1H), 6.51 (d, J = 8.0 Hz, 1H),
4.22 – 4.16 (m, 2H), 3.70 (q, J = 6.5 Hz, 1H), 3.55 (s, 1H),
3.27 (d, J = 15.6 Hz, 1H), 2.61 (d, J = 16.0 Hz, 1H), 1.29 –
1.24 (m, 3H), 1.14ꢀ1.11 (m, 3H), 1.11 – 1.09 (m, 3H). 13C
NMR (151 MHz, Chloroformꢀd) (major diastereomer) δ
176.4, 142.8, 129.5, 126.8, 119.1, 117.3, 113.7, 60.7, 51.4,
43.3, 38.1, 17.0, 15.1, 14.2. HRMS (ESI): m/z calcd for
C14H20NO2 [M + H]+ 234.1489, found 234.1489.
Ethyl 2ꢀmethoxyꢀ5,7,8,9,10,10aꢀhexahydroacridineꢀ8a(6H)ꢀ
Ethyl
2,3,6ꢀtrimethylꢀ1,2,3,4ꢀtetrahydroquinolineꢀ3ꢀ
1
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carboxylate (4h). Brown oil. Yield: 90% (260 mg). H NMR
carboxylate (4b). Pale yellow oil. Yield: 87% (215 mg). H
NMR (400 MHz, Chloroformꢀd) (major diastereomer) δ 6.84ꢀ
6.79 (m, 2H), 6.46ꢀ6.42 (m, 1H), 4.20ꢀ4.14 (m, 2H), 3.65 (q, J
= 6.4 Hz, 1H), 3.60 (s, 1H), 3.23 (d, J = 16.0 Hz, 1H), 2.55 (d,
J = 16.0 Hz, 1H), 2.21 (s, 3H), 1.28 – 1.23 (m, 4H), 1.11 –
1.09 (m, 3H), 1.08 (s, 3H). 13C NMR (151 MHz, Chloroformꢀ
d) (major diastereomer) δ 176.5, 140.4, 130.0, 127.5, 126.5,
119.3, 114.0, 60.6, 51.6, 43.4, 38.1, 20.5, 16.9, 15.1, 14.2.
HRMS (ESI): m/z calcd for C15H22NO2 [M + H]+ 248.1645,
found 248.1643.
(400 MHz, Chloroformꢀd) δ 6.60 (dd, J = 8.6, 3.0 Hz, 1H),
6.56 (d, J = 2.8 Hz, 1H), 6.44ꢀ6.42 (m, 1H), 4.15 (q, J = 7.1
Hz, 2H), 3.72 (s, 3H), 3.28 (s, 1H), 3.00ꢀ2.78 (m, 2H), 1.84–
1.36 (m, 8H), 1.22 (t, J = 7.2 Hz, 3H). 13C NMR (151 MHz,
Chloroformꢀd) δ 176.2, 151.5, 136.6, 119.3, 114.7, 114.5,
113.2, 60.5, 55.8, 51.5, 44.4, 33.7, 30.4, 29.6, 22.0, 21.6, 14.1.
HRMS (ESI): m/z calcd for C17H24NO3 [M + H]+ 290.1751,
found 290.1752
Ethyl 2ꢀbromoꢀ5,7,8,9,10,10aꢀhexahydroacridineꢀ8a(6H)ꢀ
carboxylate (4i). Brown solid. Yield: 81% (274 mg); mp: 80ꢀ
Ethyl 6ꢀmethoxyꢀ2,3ꢀdimethylꢀ1,2,3,4ꢀtetrahydroquinolineꢀ
3ꢀcarboxylate (4c). Yellow oil. Yield: 85% (224 mg). 1H
NMR (400 MHz, Chloroformꢀd) (major diastereomer) δ 6.62
(dd, J = 8.4, 2.8 Hz, 1H), 6.57 (d, J = 2.4 Hz, 1H), 6.49ꢀ6.47
(m, 1H), 4.20ꢀ4.13 (m, 2H), 3.72 (s, 3H), 3.61 (q, J = 6.4 Hz,
1H), 3.27 (d, J = 16.0 Hz, 1H), 2.56 (d, J = 16.0Hz, 1H), 1.26
(t, J = 7.0 Hz, 3H), 1.10ꢀ1.08 (m, 6H). 13C NMR (151 MHz,
Chloroformꢀd) (major diastereomer) δ 176.4, 152.0, 136.7,
120.7, 115.3, 114.6, 113.1, 60.6, 55.7, 51.8, 43.5, 38.2, 16.8,
15.1, 14.2. HRMS (ESI): m/z calcd for C15H22NO3 [M + H]+
264.1594, found 264.1597.
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81 C. 1H NMR (400 MHz, Chloroformꢀd) (major diastereꢀ
omer) δ 7.05 – 7.01 (m, 2H), 6.32 (d, J = 8.4 Hz, 1H), 4.14 (q,
J = 7.2 Hz, 2H), 3.75 (dd, J = 7.2, 3.4 Hz, 1H), 3.70 (s, 1H),
2.95 – 2.75 (m, 2H), 1.83 – 1.36 (m, 8H), 1.21 (t, J = 7.0 Hz,
3H). 13C NMR (151 MHz, Chloroformꢀd) (major diastereꢀ
omer) δ 175.8, 141.6, 131.6, 129.6, 120.1, 114.8, 107.8, 60.7,
51.3, 43.8, 33.2, 30.3, 29.8, 21.9, 21.5, 14.1. HRMS (ESI):
m/z calcd for C16H21BrNO2 [M + H]+ 338.0750, found
338.0756.
Ethyl 2ꢀchloroꢀ5,7,8,9,10,10aꢀhexahydroacridineꢀ8a(6H)ꢀ
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Ethyl 6ꢀbromoꢀ2,3ꢀdimethylꢀ1,2,3,4ꢀtetrahydroquinolineꢀ3ꢀ
carboxylate (4j). Brown oil. Yield: 85% (250 mg). H NMR
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carboxylate (4d). Green oil. Yield: 79% (247 mg). H NMR
(400 MHz, Chloroformꢀd) (major diastereomer) δ 6.91 – 6.88
(m, 2H), 6.36 (d, J = 8.2 Hz, 1H), 4.14 (q, J = 7.1 Hz, 2H),
3.75 (dd, J = 7.2, 3.2 Hz, 1H), 3.68 (s, 1H), 2.95 – 2.75 (m,
2H), 1.85 – 1.35 (m, 8H), 1.21 (t, J = 7.0 Hz, 3H). 13C NMR
(151 MHz, Chloroformꢀd) (major diastereomer) δ 175.8,
141.2, 128.8, 126.7, 120.7, 119.6, 114.4, 60.7, 51.4, 43.9,
33.2, 30.3, 29.8, 21.9, 21.6, 14.1. HRMS (ESI): m/z calcd for
C16H21ClNO2 [M + H]+ 294.1255, found 294.1256.
(400 MHz, Chloroformꢀd) (major diastereomer) δ 7.11ꢀ7.04
(m, 2H), 6.38ꢀ6.35(m, 1H), 4.19ꢀ4.13 (m, 2H), 3.75 (s, 1H),
3.66 (q, J = 6.5 Hz, 1H), 3.42 (q, J = 6.9 Hz, 0H), 3.20 (d, J =
16.0 Hz, 1H), 2.54 (d, J = 16.0 Hz, 1H), 1.26 – 1.23 (m, 3H),
1.09 (d, J = 6.4 Hz, 3H), 1.06 (s, 3H). 13C NMR (151 MHz,
Chloroformꢀd) (major diastereomer) δ 176.0, 141.8, 131.8,
129.5, 121.2, 115.2, 108.6, 60.8, 51.4, 43.0, 37.5, 16.8, 15.5,
14.2. HRMS (ESI): m/z calcd for C14H19BrNO2 [M + H]+
312.0594, found 312.0598.
Ethyl 1,2,3,3a,4,9ꢀhexahydroꢀ9aHꢀcyclopenta[b]quinolineꢀ
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9aꢀcarboxylate (4k). Orange oil. Yield: 82% (201 mg). H
Ethyl 6ꢀchloroꢀ2,3ꢀdimethylꢀ1,2,3,4ꢀtetrahydroquinolineꢀ3ꢀ
NMR (400 MHz, Chloroformꢀd) δ 7.03ꢀ6.99 (m, 2H), 6.66 –
6.62 (m, 1H), 6.53ꢀ6.51 (m, 1H), 4.12ꢀ4.07 (m, 3H), 3.84 (s,
1H), 3.12ꢀ2.66 (m, 2H), 2.18 – 2.00 (m, 2H), 1.81 – 1.53 (m,
4H), 1.18 (t, J = 7.0 Hz, 3H). 13C NMR (151 MHz, Chloroꢀ
formꢀd) δ 176.1, 143.6, 128.8, 127.1, 120.1, 117.2, 113.6,
60.7, 58.3, 51.0, 35.0, 34.3, 33.2, 21.0, 14.0. HRMS (ESI):
m/z calcd for C15H20NO2 [M + H]+ 246.1489, found 246.1489.
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carboxylate (4e). Green oil. Yield: 84% (225 mg). H NMR
(400 MHz, Chloroformꢀd) (major diastereomer) δ 6.98 – 6.91
(m, 2H), 6.43 – 6.39 (m, 1H), 4.20ꢀ4.13 (m, 2H), 3.80 (s, 1H),
3.66 (q, J = 6.5 Hz, 1H), 3.20 (d, J = 16.4 Hz, 1H), 2.54 (s,
1H), 1.25(t, J = 7.2 Hz, 3H), 1.10 (d, J = 6.8 Hz, 3H), 1.07 (s,
3H). 13C NMR (151 MHz, Chloroformꢀd) (major diastereꢀ
omer) δ 176.0, 141.3, 129.0, 126.7, 121.6, 120.7, 114.8, 60.8,
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