ˇ
90 R. Bukšnaitiene˙ and I. Cikotiene˙
75.0, 62.3. Anal. Calcd for C20H15Cl3N2: C, 61.64; H, 3.88; N, 7.19.
Found: C, 61.55; H, 4.00; N, 7.23.
CH(CH2)2], 0.83–0.91 [m, 2H, CH(CH2)2], 0.52–0.58 [m, 1H,
CH(CH2)2]; 13C NMR: δ 152.8, 148.1, 138.3, 137.4, 130.3, 128.6,
127.8, 127.6, 127.2, 126.0, 125.9, 124.4, 117.9, 104.7, 101.8, 76.4,
57.1, 14.2, 8.6, 4.5. Anal. Calcd for C23H19Cl3N2: C, 64.28; H, 4.46;
N, 6.52. Found: C, 64.16; H, 4.49; N, 6.88.
1-(Trichloromethyl)-2-(phenylethyl)-1,2-dihydrobenzo[b][1,6]
naphthyridine (2g) Yield 76% (method B); yellow solid; mp
110–112°C; 1H NMR (300 MHz, CDCl3) δ8.07 (1H, d, J= 8.4 Hz,ArH),
7.70–7.77 (3H, m, ArH), 7.42–7.48 (1H, m, ArH), 6.98–7.05 (5H, m,
ArH), 6.79 [1H, dd, J = 7.3, 0.9 Hz, C(3)H], 6.14 [1H, d, J = 7.3 Hz, C(4)
H], 4.78 [1H, d, J = 0.9 Hz, C(1)H], 3.91–3.99 (2H, m, PhCH2CH2N),
2.73–2.92 (2H, m, PhCH2CH2N); 13C NMR: δ 152.4, 141.1, 138.7,
138.2, 130.8, 129.2, 128.8, 128.2, 126.8, 126.5, 125.8, 125.1, 124.2,
117.8, 104.7, 103.7, 76.7, 60.1, 37.7. Anal. Calcd for C21H17Cl3N2: C,
62.47; H, 4.24; N, 6.94. Found: C, 62.55; H, 4.15; N, 7.09.
3-Cyclopropyl-1-(trichloromethyl)-2-(phenylethyl)-1,2-di-
hydrobenzo[b][1,6]-naphthyridine (2l) Yield 71% (method
1
B); yellow oil; H NMR: δ 8.02 (dd, 1H, J = 8.25, 1.2 Hz, ArH),
7.65–7.73 (m, 3H, ArH), 7.37–7.43 (m, 1H, ArH), 6.95–7.05 (m, 5H,
ArH), 6.05 [s, 1H, C(4)H], 4.80 [s, 1H, C(1)H], 4.58–4.67 (m, 1H,
PhCH2CH2N), 3.67–3.77 [m, 1H, PhCH2CH2N], 2.76–2.80 (m, 2H,
PhCH2CH2N), 1.72–1.79 [m, 1H, CH(CH2)2], 1.05–1.10 [m, 1H,
CH(CH2)2], 0.89–0.94 [m, 2H, CH(CH2)2], 0.78–0.82 [m, 1H,
CH(CH2)2]; 13C NMR: δ 153.1, 152.9, 148.2, 137.9, 137.2, 130.0,
128.7, 128.3, 127.8, 127.7, 126.3, 124.3, 118.1, 104.6, 102.7, 77.1,
56.5, 36.1, 13.8, 9.3, 4.9. Anal. Calcd for C24H21Cl3N2: C, 64.95; H,
4.77; N, 6.31. Found: C, 65.09; H, 4.96; N, 6.49.
2-Allyl-1-(trichloromethyl)-1,2-dihydrobenzo[b][1,6]naph-
thyridine (2h) Yield 16% (method A), 75% (method B); yellow
solid; mp 124–126°C; 1H NMR: δ 8.13 [s, 1H, C(10)H], 8.00 (d, 1H,
J = 8.25 Hz, ArH), 7.78 (dd, 1H, J = 8.1, 1.2 Hz, ArH), 7.65–7.71
(m, 1H, ArH), 7.38–7.43 (m, 1H, ArH), 6.72 [dd, 1H, J = 7.5, 1.2
Hz, C(3)H], 6.02 [d, 1H, J = 7.5 Hz, C(4)H], 5.71–5.83 (m, 1H,
CH2CH = CH2), 5.23 [d, 1H, J = 1.2 Hz, C(1)H], 5.07–5.16 (m, 2H,
CH2CH = CH2), 4.28–4.36 (m, 1H, CH2CH = CH2), 4.11–4.19
(m, 1H, CH2CH = CH2); 13C NMR: δ 152.4, 148.3, 141.3, 138.3,
133.5, 130.5, 128.0, 127.9, 126.4, 124.7, 118.4, 117.3, 104.7, 103.2,
74.9, 60.2. Anal. Calcd for C16H13Cl3N2: C, 56.58; H, 3.86; N, 8.25.
Found: C, 56.71; H, 4.00; N, 8.33.
2-Allyl-1-(trichloromethyl)-3-cyclopropyl-1,2-dihydrobenzo[b]
1
[1,6]naphthyridine (2m) Yield 64% (method B); yellow oil; H
NMR: δ 8.13 [s, 1H, C(10)H], 8.03 (d, 1H, J = 8.4 Hz, ArH), 7.79
(dd, 1H, J = 8.1, 1.2 Hz, ArH), 7.66–7.71 (m, 1H, ArH), 7.38–7.44
(m, 1H, ArH), 6.04 [s, 1H, C(4)H], 5.64–5.76 (m, 1H, CH2CH =
CH2), 5.19 [s, 1H, C(1)H], 4.92–5.05 (m, 3H, CH2CH = CH2 and
CH2CH = CH2), 4.18 (ddt, 1H, J = 18, 4.8, 1.2 Hz, CH2CH = CH2),
1.63–1.73 [m, 1H, CH(CH2)2], 0.84–1.06 [m, 3H, CH(CH2)2], 0.64–
0.72 [m, 1H, CH(CH2)2]; 13C NMR: δ 154.1, 152.9, 148.0, 137.7,
133.8, 130.4, 127.9, 127.6, 124.6, 118.2, 116.6, 104.7, 101.9, 75.6,
56.0, 14.2, 8.7, 4.4. Anal. Calcd for C19H17Cl3N2: C, 60.10; H, 4.51;
N, 7.38. Found: C, 59.87; H, 4.45; N, 7.40.
2-Butyl-1-(trichloromethyl)-1,2-dihydrobenzo[b][1,6]naph-
thyridine (2i) Yield 45% (method A), 85% (method B); yellow
solid; mp 102–104°C; 1H NMR: δ 8.14 [s, 1H, C(10)H], 8.02 (d, 1H,
J = 8.4 Hz, ArH), 7.78 (dd, 1H, J = 8.1, 0.9 Hz, ArH), 7.64–7.70 (m,
1H, ArH), 7.37–7.43 (m, 1H, ArH), 6.73 [dd, 1H, J = 7.5, 1.2 Hz,
C(3)H], 6.03 [d, 1H, J = 7.5 Hz, C(4)H], 5.21 [d, 1H, J = 1.2 Hz,
C(1)H], 3.53–3.73 (m, 2H, CH2CH2CH2CH3), 1.47–1.57 (m, 2H,
CH2CH2CH2CH3), 1.16–1.28 (m, 2H, CH2CH2CH2 CH3), 0.85 (t, 3H,
J = 7.5 Hz, CH2CH2CH2CH3); 13C NMR (75 MHz, CDCl3) δ 152.4,
147.9, 141.5, 138.3, 130.6, 127.9, 127.7, 126.3, 124.7, 117.5, 104.7,
102.5, 75.7, 57.8, 32.4, 19.8, 13.7. Anal. Calcd for C17H17Cl3N2:
C, 57.40; H, 4.82; N, 7.88. Found: C, 57.66; H, 4.75; N, 7.99.
2-Butyl-1-(trichloromethyl)-3-cyclopropyl-1,2-dihydro-
benzo[b][1,6]naphthyridine (2n) Yield 57% (method B); yel-
1
low solid; mp 112–114°C; H NMR: δ 8.17 [s, 1H, C(10)H], 8.04
(d, 1H, J = 8.4 Hz, ArH), 7.80 (dd, 1H, J = 7.8, 1.2 Hz, ArH),
7.67–7.72 (m, 1H,ArH), 7.39–7.45 (m, 4H,ArH), 6.03 [s, 1H, C(4)H],
5.19 [s, 1H, C(1)H], 4.26–4.36 (m, 1H, CH2CH2CH2CH3), 3.45–3.55
(m, 1H, CH2CH2CH2CH3), 1.68–1.77 [m, 1H, CH(CH2)2], 1.40–1.50
(m, 2H, CH2CH2CH2CH3), 1.22–1.29 (m, 2H, CH2CH2CH2CH3),
1.01–1.08 [m, 2H, CH(CH2)2], 0.89–0.93 [m, 1H, CH(CH2)2], 0.87
(t, 3H, J = 7.5 Hz, CH2CH2CH2CH3), 0.72–0.84 [m, 1H, CH(CH2)2];
13C NMR: δ 152.9, 147.6, 137.9, 130.6, 127.9, 127.2, 126.1, 124.6,
118.3, 104.6, 101.3, 76.2, 54.4, 31.5, 19.9, 14.1, 13.8, 9.3, 5.0. Anal.
Calcd for C20H21Cl3N2: C, 60.70; H, 5.35; N, 7.08. Found: C, 60.64;
H, 5.48; N, 6.99.
1-(Trichloromethyl)-2-cyclopentyl-1,2-dihydrobenzo[b][1,6]
naphthyridine (2j) Yield 75% (method B); yellow solid; mp
137–138°C; 1H NMR (300 MHz, CDCl3) δ 8.18 [s, 1H, C(10)
H], 8.05 (d, 1H, J = 8.7 Hz, ArH), 7.79 (dd, 1H, J = 7.95, 0.9 Hz,
ArH), 7.68–7.74 (m, 1H, ArH), 7.41–7.47 (m, 1H, ArH), 6.90
[dd, 1H, J = 7.8, 1.2 C(3)H], 6.12 [d, 1H, J = 7.8 Hz, C(4)H],
5.31 [d, 1H, J = 1.2 Hz, C(1)H], 4.09 [pent., 1H, J = 7.8 Hz,
CH(CH2CH2)2], 2.21–2.30 [m, 1H, CH(CH2CH2)2], 1.91–2.00 [m,
2H, CH(CH2CH2)2], 1.69–1.85 [m, 4H, CH(CH2CH2)2], 1.36–1.46
[m, 1H, CH(CH2CH2)2]; 13C NMR: δ 152.3, 147.4, 138.8, 137.6,
130.7, 127.9, 127.3, 126.3, 124.7, 117.6, 104.3, 102.9, 77.3, 68.7,
33.5, 29.7, 24.0, 23.9. Anal. Calcd for C18H17Cl3N2: C, 58.80; H,
4.66; N, 7.62. Found: C, 59.01; H, 4.75; N, 7.49.
1-(Trichloromethyl)-2-cyclopentyl-3-cyclopropyl-1,2-dihyd-
robenzo[b][1,6]naphthyridine (2o) Yield 72% (method B); yel-
low oil; 1H NMR: δ 8.17 [s, 1H, C(10)H], 8.00 (dd, 1H, J = 8.4, 0.6
Hz, ArH), 7.80 (dd, 1H, J = 8.1, 1.2 Hz, ArH), 7.64–7.68 (m, 1H,
ArH), 7.39–7.44 (m, 1H, ArH), 6.14 [s, 1H, C(4)H], 5.18 [s, 1H,
C(1)H], 4.51–4.62 [m, 1H, CH(CH2CH2)2], 2.12–2.16 [m, 1H,
CH(CH2)2], 1.45–1.74(m, 6H), 1.92–2.00(m, 1H), 0.96–1.17(m, 3H)
[CH(CH2)2, and CH(CH2CH2)2], 0.83–0.92 [m, 1H, CH(CH2)2],
0.64–0.73 [m, 1H, CH(CH2)2]; 13C NMR: δ 155.7, 153.2, 148.3,
136.9, 130.0, 128.0, 127.8, 126.5, 124.6, 119.9, 105.8, 70.3, 62.9,
30.2, 30.0, 23.1, 22.5, 14.5, 10.0, 5.0. Anal. Calcd for C21H21Cl3N2:
C, 61.86; H, 5.19; N, 6.87. Found: C, 62.00; H, 5.22; N, 6.90.
3-Cyclopropyl-1-(trichloromethyl)-2-(phenylmethyl)-1,2-
dihydrobenzo[b][1,6]-naphthyridine (2k) Yield 65% (method
1
B); yellow solid; mp 146–148°C; H NMR: δ 8.05 (d, 1H, J = 8.4
Hz, ArH), 8.04 [s, 1H, C(10)H], 7.76 (dd, 1H, J = 8.25, 1.2 Hz, ArH),
7.67–7.71 (m, 1H, ArH), 7.38–7.44 (m, 1H, ArH), 7.17–7.20 (m, 3H,
ArH), 6.97–7.00 (m, 2H, ArH), 6.08 [s, 1H, C(4)H], 5.64 (d, 1H,
J2 = 17.4 Hz, PhCH), 5.25 [s, 1H, C(1)H], 4.88 (d, 1H, J2 = 17.4
Hz, PhCH), 1.62–1.73 [m, 1H, CH(CH2)2], 1.02–1.09 [m, 1H,
3-Butyl-1-(trichloromethyl)-2-(phenylmethyl)-1,2-dihydro-
benzo[b][1,6]naphthyridine (2p) Yield 64% (method B); yellow
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