10.1002/ejoc.201801037
European Journal of Organic Chemistry
FULL PAPER
obtained as a brown solid, 95%; mp 149-151 °C; 1H NMR δ 8.00
(d, J = 1.8 Hz, 1H), 7.55 (dd, J = 1.7, 7.4 Hz, 1H), 7.42-7.33 (m,
4H), 7.81 (dd, J = 1.4, 7.7 Hz, 1H), 7.09-7.02 (m, 4H), 6.91 (d, J
= 8.2 Hz, 2H), 6.80 (dd, J = 7.4 Hz, 1H), 6.39 (d, J = 7.8 Hz, 2H),
5.36 (s, 1H), 5.19 (s, 1H), 4.56 (s, 2H), 2.28 (s, 3H); 13C NMR δ
147.3, 144.1, 144.0, 140.3, 140.2, 140.0, 139.2, 135.3, 130.9,
130.8, 129.8, 129.7, 129.5, 129.2, 128.0, 127.7, 124.7 (q, J = 21.5
Hz), 123.7 (q, J = 272.7 Hz), 123.5 (q, J = 4.5 Hz), 123.0 (q, J =
3.9 Hz), 119.9, 116.5, 115.4, 54.7, 21.6; HRMS (ESI, positive): m/z
calcd. For C29H23F3N2NaO2S ([M+Na]+) 543.1325, found
543.1326.
= 7.7 Hz, 1H), 4.69 (brs, 1H), 4.26 (brs, 1H), 3.81 (s, 3H), 2.29 (s,
3H); 13C NMR δ 157.6, 147.8, 144.0, 143.1, 140.2, 137.8, 136.6,
136.2, 133.9, 132.7, 131.6, 130.2, 129.8, 129.5, 129.2, 128.8,
128.5, 127.7, 127.4, 127.1, 126.6, 125.9, 124.4, 120.0, 119.8,
116.9, 110.4, 56.8, 55.5, 21.6 (a pair of peaks at the aromatic
region was overlapped); HRMS (ESI, positive): m/z calcd for
C35H30N2NaO3S ([M+Na]+) 581.1868, found 581.1869.
(E)-12-Phenyl-5-tosyl-7-(4-(trifluoromethyl)benzylidene)-
5,6,7,12-tetrahydrodibenzo[b,e][1,4]diazocine (2j)
Isolated by PTLC (hexane/dichloromethane = 1/2). The title
compound is obtained as a white solid, 85%; mp 172 °C; 1H NMR
δ 7.64 (dd, J = 1.5, 8.2 Hz, 1H), 7.31 (d, J = 8.2 Hz, 2H), 7.31-
7.23 (m, 4H), 7.20-7.01 (m, 6H), 6.86-6.98 (m, 5H), 6.83 (dd, J =
7.3, 7.3 Hz, 1H), 6.58 (d, J = 8.1 Hz, 2H), 6.52 (s, 1H), 4.54 (brs,
1H), 4.51 (brs, 1H), 2.30 (s, 3H); 13C NMR δ 147.8, 143.7, 143.5,
140.4, 139.7, 138.2, 137.7, 136.2, 136.1, 133.0, 130.7, 130.1,
129.5, 129.5, 129.2, 129.2, 129.0 (q, J = 32.2 Hz), 128.1, 127.8,
127.7, 127.0, 126.9, 125.3, 125.1 (q, J = 3.9 Hz), 124.6 (q, J =
237.5 Hz), 120.2, 116.9, 56.9, 21.6 HRMS (ESI, positive): m/z
(E)-7-Benzylidene-12-phenyl-5-tosyl-5,6,7,12-
tetrahydrodibenzo[b,e][1,4]diazocine (2f)
Isolated by PTLC (hexane/dichloromethane = 1/2). The title
compound is obtained as a yellow solid, 94%; mp 196 °C; 1H NMR
δ 7,71-7.62 (m, 1H), 7.32-7.24 (m, 2H), 7.23-7.13 (m, 4H), 7.13-
7.03 (m, 7H), 6.97-6.86 (m, 3H), 6.85-6.74 (m, 3H), 6.60 (d, J =
8.6 Hz, 2H), 6.53 (s, 1H), 4.54 (brs, 1H), 4.43 (brs, 1H), 2.28 (s,
3H); 13C NMR 147.8, 143.5, 143.3, 139.7, 137.7, 136.7, 136.1,
135.1, 135.1, 133.0, 132.3, 130.8, 129.5, 129.2, 129.0, 128.9,
128.0, 128.0, 127.7, 127.6, 127.2, 126.9, 126.8, 124.9, 119.9,
116.8, 57.0, 21.6; HRMS (ESI, positive):m/z calcd for
C34H28N2NaO2S ([M+Na]+) 551.1764, found 551.1764.
calcd
for
C35H27F3N2NaO2S ([M+Na]+) 619.1635,
found
619.1638.
(E)-7-(4-Fluorobenzylidene)-12-phenyl-5-tosyl-5,6,7,12-
tetrahydrodibenzo[b,e][1,4]diazocine (2k)
(E)-7-(4-Methoxybenzylidene)-12-phenyl-5-tosyl-5,6,7,12-
tetrahydrodibenzo[b,e][1,4]diazocine (2g)
Isolated by PTLC (hexane/dichloromethane = 1/2). The title
compound is obtained as a yellow solid, 87%; mp 193 °C; 1H NMR
δ 7.65 (dd, J = 1.4, 8.0 H, 1H), 7.30-7.20 (m, 4H), 7.20-7.11 (m,
3H), 7.08 (dd, J = 7.7, 7.7 Hz, 3H), 6.97-6.88 (m, 3H), 6.82 (dd, J
= 7.4, 7.4 Hz, 1H), 6.76 (d, J = 7.2 Hz, 4H), 6.58 (d, J = 8.0 Hz,
2H), 6.47 (s, 1H), 4.52 (brs, 1H), 4.42 (brs, 1H), 2.29 (s, 3H); 13C
NMR δ 162.0 (d, J = 217.8 Hz), 147.8, 143.7, 143.4, 139.8, 137.7,
136.1, 136.5, 135.3 (d, J = 1.2 Hz), 132.9, 132.8, 132.8, 131.0,
130.8, 130.6 (d, J = 8.1 Hz), 129.5, 129.2, 129.1, 128.0, 127.8,
126.9 (d, J = 4.2 Hz), 125.0, 120.0, 116.9, 115.1 (d, J = 21.5 Hz),
57.0, 21.6 (a pair of peaks at the aromatic region was
overlapped.); HRMS (ESI, positive): m/z calcd for
C34H27FN2NaO2S ([M+Na]+) 569.1669, found 569.1669.
Isolated by PTLC (hexane/dichloromethane = 1/2). The title
1
compound is obtained as colorless oil, 41%; H NMR δ 8.24 (s,
1H), 7.78 (dd, J = 1.4, 7.9 Hz, 1H), 7.65 (dd, J = 1.5, 8.2 Hz, 1H),
7.40 (dd, J = 1.5, 7.9 Hz, 1H), 7.36 (d, J = 8.6 Hz, 2H), 7.22-7.18
(m, 2H), 7.18-7.12 (m, 4H), 7.12-7.00 (m, 5H), 6.91-6.88 (m, 2H),
6.82 (s, 1H), 6.79 (d, J = 8.2 Hz, 2H), 4.08 (s, 2H), 3.81 (s, 3H),
2.20 (s, 3H); 13C NMR δ 158.3, 148.7, 148.1, 143.2, 142.8, 136.6,
136.0, 135.8, 134.6, 132.6, 132.2, 130.5, 129.9, 129.3, 129.2,
128.6, 128.0, 127.4, 126.9, 125.3, 125.0, 124.8, 123.6, 123.4,
120.1, 114.2, 55.4, 42.8, 21.5; HRMS (ESI, positive): m/z calcd
for C35H30N2NaO3S ([M+Na]+) 581.1870, found 581.1869.
(E)-7-(3-Methoxybenzylidene)-12-phenyl-5-tosyl-5,6,7,12-
tetrahydrodibenzo[b,e][1,4]diazocine (2h)
(E)-7-(4-Chlorobenzylidene)-12-phenyl-5-tosyl-5,6,7,12-
tetrahydrodibenzo[b,e][1,4]diazocine (2l)
Isolated by PTLC (hexane/dichloromethane = 1/2). The title
compound is obtained as a yellow solid, 53%; mp 91 °C; 1H NMR
δ 7.66 (dd, J = 1.6, 8.8 Hz, 1H), 7.30-7.26 (m, 1H), 7.25-7.04 (m,
9H), 7.00 (dd, J = 7.9, 7.9 Hz, 1H), 6.96-6.89 (m, 3H), 6.82 (dd, J
= 7.3, 7.3 Hz, 1H), 6.63 (dd, J = 2.4, 8.4 Hz, 1H), 6.59 (d, J = 4.0
Hz, 2H), 6.51 (s, 1H), 6.43 (d, J = 4.0 Hz, 1H), 6.27 (s, 1H), 4.54
(brs, 1H), 4.42 (brs, 1H), 3.54 (s, 3H), 2.29 (s, 3H); 13C NMR δ
159.2, 147.9, 143.5, 143.3, 139.8, 138.1, 137.8, 136.7, 136.2,
135.4, 133.1, 132.4, 130.8, 129.5, 129.2, 129.1, 129.0, 128.1,
127.8, 127.6, 126.9, 126.9, 124.9, 121.7, 120.0, 116.9, 113.8,
113.6, 57.0, 55.1, 21.6; HRMS (ESI, positive): m/z calcd for
C35H30N2NaO3S ([M+Na]+) 581.1869, found 581.1869.
Isolated by pTLC (hexane/dichloromethane = 1/2). The title
compound is obtained as a yellow solid, 89%; mp 210 °C; 1H NMR
δ 7.64 (d, J = 8.0 Hz, 1H), 7.32-7.21 (m, 4H), 7.20-7.10 (m, 3H),
7.08 (t, J = 7.3 Hz, 3H), 7.04 (d, J = 8.4 Hz, 2H), 6.96-6.89 (m,
3H), 6.82 (dd, J = 7.2, 7.2 Hz, 1H), 6.72 (d, J = 8.3 Hz, 2H), 6.57
(d, J = 8.2 Hz, 2H), 6.45 (s, 1H), 4.52 (brs, 1H), .4.44 (brs, 1H),
2.29 (s, 3H); 13C NMR δ 147.8, 143.6, 143.4, 139.7, 137.7, 136.4,
136.2, 136.1, 135.2, 133.0, 132.9, 130.8, 130.7, 130.3, 129.5,
129.5, 129.2, 128.3, 127.9, 127.9, 127.7, 126.9, 126.9, 125.1,
120.1, 116.9, 57.0, 21.6; HRMS (ESI, positive): m/z calcd for
C34H27O2ClNaO2S ([M+Na]+) 585.1373, found 585.1374.
Ethyl
(E)-2-(12-phenyl-5-tosyl-5,12-
(E)-7-(2-Methoxybenzylidene)-12-phenyl-5-tosyl-5,6,7,12-
tetrahydrodibenzo[b,e][1,4]diazocine (2i)
dihydrodibenzo[b,e][1,4]diazocin-7(6H)-ylidene)acetate (2m)
Isolated by PTLC (dichloromethane). The title compound is
obtained as yellow oil, 98%; 1H NMR δ 7.62 (dd, J = 1.5, 7.7 Hz,
1H),7.31-7.51 (m, 4H), 7.17 (dd, J = 1.1, 8.0 Hz, 1H), 6.99-7.14
(m, 8H), 6.76 (dd, J = 7.3, 7.3 Hz, 1H), 6.51 (d, J = 7.8 Hz, 2H),
5.73 (s, 1H), 4.88 (brs, 1H), 4.20 (brs, 1H), 4.02 (q, J = 7.1 Hz,
2H), 2.31 (s, 3H), 1.13 (t, J = 7.1 Hz, 3H); 13C NMR δ 165.1, 154.6,
147.4, 143.9, 140.8, 139.2, 137.4, 137.1, 136.3, 134.0, 130.8,
Isolated by pTLC (hexane/dichloromethane = 1/2). The title
1
compound is obtained as brown oil, 50%; H NMR δ 7.70 (d, J =
8.2 Hz, 1H), 7.32 (d, J = 8.2 Hz, 1H), 7.25-7.11 (m, 6H), 7.06 (dd,
J = 8.0, 8.0 Hz, 3H), 7.00 (d, J = 7.8 Hz, 1H), 6.91 (d, J = 8.1 Hz,
2H), 6.81 (q, J = 8.2 Hz, 2H), 6.77 (d, J = 4.3 Hz, 1H), 6.68 (s, 1H),
6.58 (d, J = 8.1 Hz, 2H), 6.45 (dd, J = 7.6, 7.6 Hz, 1H), 6.04 (d, J
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