The Journal of Organic Chemistry
Note
6.22 (s, 0.29H), 5.94 (d, J = 6.0 Hz, 0.29H), 5.86 (d, J = 6.0 Hz,
0.71H), 3.97 (s, 2.13H), 3.92 (s, 3H), 3.90 (s, 0.87H), 3.82 (s, 2.13H),
3.80 (s, 0.87H), 3.78−3.72 (m, 2H), 1.31−1.26 (m, 3H); 13C NMR
(100 MHz, CDCl3) δ 174.2, 155.8, 155.8, 152.0, 152.0, 143.6, 140.2,
138.4, 138.3, 138.12, 137.6, 135.6, 134.6, 133.8, 131.2, 128.8, 128.5,
128.3, 128.2, 128.0, 120.8, 116.5, 111.5, 111.2, 90.1, 90.0, 68.6, 66.8,
61.4, 61.3, 61.1, 61.1, 56.6, 35.6, 35.6, 12.9, 12.8; Ion-trap-HRMS
(ESI) calcd for C23H23ClNO4S [M + H]+ 444.1036, found 444.1027.
5′-(Chloro(phenyl)methylene)-1-ethyl-4,6-dimethoxy-5′H-spiro-
[indoline-3,2′-thiophen]-2-one (10ab). Brown syrup (84 mg, 68%,
Z/E = 1:4): IR (KBr) 2938, 1721, 1617, 1460, 1345, 1282, 1209, 1150,
0.67H), 6.21 (s, 0.33H), 5.97−5.95 (m, 1H), 3.98 (s, 2.0H), 3.93 (s,
1.0H), 3.92 (s, 2.0H), 3.89 (s, 1.0H), 3.82 (s, 2.0H), 3.80 (s, 1.0H),
3.75 (q, J = 7.2 Hz, 2H), 1.29 (t, J = 7.2 Hz, 3H); 13C NMR (100
MHz, CDCl3) δ 174.1, 155.8, 155.8, 152.0, 152.0, 146.7, 142.2, 140.0,
139.2, 138.4, 138.3, 138.2, 138.1, 136.0, 135.8, 135.4, 130.9, 129.4,
128.8, 128.5, 128.4, 128.3, 128.2, 111.4, 111.2, 111.1, 105.2, 90.1, 90.0,
68.7, 66.4, 61.3, 61.3, 61.1, 61.1, 56.6, 56.6, 35.6, 35.6, 12.9, 12.8; Ion-
trap-HRMS (ESI) calcd for C23H23BrNO4S [M + H]+ 488.0531, found
488.0518.
5′-(Bromo(phenyl)methylene)-1-ethyl-4,6-dimethoxy-5′H-spiro-
[indoline-3,2′-thiophen]-2-one (11ab). Brown syrup (97 mg, 71%,
Z/E = 1:1.2): IR (KBr) 2925, 1717, 1616, 1458, 1237, 911, 811, 693
1
1080, 902, 816, 756, 628 cm−1; H NMR (400 MHz, CDCl3) δ 7.50
1
(d, J = 8.0 Hz, 1.6H), 7.45 (d, J = 8.0 Hz, 0.4H), 7.39−7.29 (m, 3H),
6.69−6.66 (m, 1H), 6.16 (s, 0.8H), 6.14 (s, 0.2H), 6.12 (s, 1H), 5.82
(d, J = 6.0 Hz, 0.8H), 5.78 (d, J = 6.0 Hz, 0.2H), 3.84 (s, 3H), 3.82 (s,
2.4H), 3.75 (s, 0.6H), 3.74 (q, J = 7.2 Hz, 3H), 1.28 (t, J = 7.2 Hz,
3H); 13C NMR (100 MHz, CDCl3) δ 174.5, 162.9, 157.9, 144.2,
144.1, 143.9, 143.6, 137.7, 137.5, 135.8, 131.2, 128.8, 128.3, 128.2,
128.1, 120.2, 119.9, 105.4, 92.7, 92.6, 89.0, 88.9, 66.7, 55.9, 55.8, 55.7,
35.7, 35.7, 12.8; Ion-trap-HRMS (ESI) calcd for C22H21ClNO3S [M +
H]+ 414.0931, found 414.0923.
5′-(Chloro(phenyl)methylene)-1-ethyl-5,6-dimethoxy-5′H-spiro-
[indoline-3,2′-thiophen]-2-one (10ac). Brown syrup (82 mg, 66%, Z/
E = 1:4): IR (KBr) 2933, 1716, 1616, 1503, 1462, 1376, 1345, 1216,
1033, 783, 756, 698 cm−1; 1H NMR (400 MHz, CDCl3) δ 7.71 (d, J =
7.2 Hz, 0.4H), 7.51 (d, J = 7.2 Hz, 1.6H), 7.41−7.33 (m, 3H), 7.11 (d,
J = 6.0 Hz, 0.2H), 6.93 (s, 0.8H), 6.89 (s, 0.2H), 6.69 (d, J = 6.0 Hz,
0.8H), 6.48 (s, 0.8H), 6.45 (s, 0.2H), 5.92 (d, J = 6.0 Hz, 0.2H), 5.83
(d, J = 6.0 Hz, 0.8H), 3.94 (s, 2.4H), 3.92 (s, 0.6H), 3.87 (s, 2.4H),
3.85 (s, 0.6H), 3.78 (q, J = 7.2 Hz, 3H), 1.31 (t, J = 7.2 Hz, 3H); 13C
NMR (100 MHz, CDCl3) δ 174.0, 150.9, 145.9, 143.3, 137.5, 136.7,
135.9, 135.5, 130.9, 128.8, 128.5, 128.4, 128.2, 128.0 121.4, 119.0,
109.8, 109.7, 94.5, 94.4, 68.1, 56.8, 56.5, 35.6, 35.5, 12.8; Ion-trap-
HRMS (ESI) calcd for C22H21ClNO3S [M + H]+ 414.0931, found
414.0922.
5′-(Chloro(naphthalen-2-yl)methylene)-1-ethyl-4,5,6-trimethoxy-
5′H-spiro[indoline-3,2′-thiophen]-2-one (10ca). Brown syrup (100
mg, 68%, Z/E = 1:2.5): IR (KBr) 2932, 1718, 1610, 1470, 1340, 1225,
1132, 1097, 798 cm−1; 1H NMR (400 MHz, CDCl3) δ 8.16 (s,
0.29H), 7.95 (s, 0.71H), 7.86−7.80 (m, 3H), 7.62−7.60 (m, 0.87H),
7.53−7.45 (m, 2.13H), 7.19 (d, J = 6.0 Hz, 0.29H), 6.79 (d, J = 6.0 Hz,
0.71H), 6.26 (s, 0.71H), 6.22 (s, 0.29H), 5.97 (d, J = 6.0 Hz, 0.29H),
5.89 (d, J = 6.0 Hz, 0.71H), 4.00 (s, 2.13H), 3.92 (s, 3H), 3.89 (s,
0.87H), 3.83 (s, 2.13H), 3.80 (s, 0.87H), 3.77 (q, J = 7.2 Hz, 2H), 1.30
(t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 174.1, 155.8,
152.0, 144.0, 138.4, 138.3, 135.8, 134.9, 134.6, 133.8, 133.0, 132.9,
132.8, 132.7, 131.3, 128.3, 128.2, 128.1, 127.9, 127.6, 127.6, 127.5,
126.7, 126.6, 126.4, 126.3, 125.4, 120.9, 111.4, 90.1, 90.0, 66.9, 61.4,
61.3, 61.1, 56.6, 56.5, 35.6, 35.6, 12.9, 12.8. Ion-trap-HRMS (ESI)
calcd for C27H25BrClNO4S [M + H]+ 494.1193, found 494.1185.
5′-(Chloro(4-chlorophenyl)methylene)-1-ethyl-4,5,6-trimethoxy-
5′H-spiro[indoline-3,2′-thiophen]-2-one (10da). Brown syrup (103
mg, 72%, Z/E = 1:2.3): IR (KBr) 2932, 1721, 1611, 1474, 1343, 1229,
1130, 1090, 1040, 797 cm−1; 1H NMR (400 MHz, CDCl3) δ 7.64 (d, J
= 8.4 Hz, 0.6H), 7.43 (d, J = 8.4 Hz, 1.4H), 7.35 (d, J = 8.4 Hz, 1.4H),
7.30 (d, J = 8.4 Hz, 0.6H), 7.11 (d, J = 6.0 Hz, 0.3H), 6.67 (d, J = 6.0
Hz, 0.7H), 6.25 (s, 0.7H), 6.22 (s, 0.3H), 5.96 (d, J = 6.0 Hz, 0.3H),
5.89 (d, J = 6.0 Hz, 0.7H), 3.96 (s, 2.1H), 3.92 (s, 2.1H), 3.91 (s,
1.8H), 3.82 (s, 2.1H), 3.80(s, 0.9H), 3.76 (q, J = 7.2 Hz, 2H), 1.30 (t, J
= 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 173.9, 155.9, 152.0,
144.3, 138.3, 136.7, 136.3, 136.0, 135.1, 135.0, 134.3, 133.7, 130.8,
130.0, 129.4, 128.6, 128.4, 119.3, 111.1, 90.1, 90.0, 68.8, 66.9, 61.4,
61.3, 61.1, 61.1, 56.6, 35.6, 12.9, 12.8; Ion-trap-HRMS (ESI) calcd for
C23H22Cl2NO4S [M + H]+ 478.0647, found 478.0638.
cm−1; H NMR (400 MHz, CDCl3) δ 7.48−7.44 (m, 2H), 7.37−
7.29(m, 3H), 6.69−6.66 (m, 1H), 6.16−6.12 (m, 2H), 5.93 (d, J = 6.0
Hz, 0.55H), 5.78 (d, J = 6.0 Hz, 0.45H), 3.84−3.81 (br, 4.55H), 3.75
(s, 1.45H), 3.74 (q, J = 7.2 Hz, 2H), 1.28 (t, J = 7.2 Hz, 3H); 13C
NMR (100 MHz, CDCl3) δ 175.0, 174.4, 163.0, 162.9, 157.9, 144.1,
143.5, 137.5, 137.1, 136.1, 135.9, 131.4, 131.0, 129.4, 128.8, 128.3,
128.2, 128.2, 128.1, 126.3, 119.9, 105.8, 105.3, 92.7, 92.7, 88.9, 88.9,
68.8, 68.3, 55.9, 55.8, 55.6, 35.7, 35.7, 12.8; Ion-trap-HRMS (ESI)
calcd for C22H21BrNO3S [M + H]+ 458.0426, found 458.0413.
5′-(Bromo(phenyl)methylene)-1-ethyl-5,6-dimethoxy-5′H-spiro-
[indoline-3,2′-thiophen]-2-one (11ac). Brown syrup (97 mg, 71%, Z/
E = 1:5.6): IR (KBr) 2927, 1713, 1617, 1503, 1374, 1214, 1103, 1032,
1
782, 749, 696 cm−1; H NMR (400 MHz, CDCl3) δ 7.67 (d, J = 7.6
Hz, 0.3H), 7.49 (d, J = 7.6 Hz, 1.7H), 7.37−7.31(m, 3H), 7.06 (d, J =
6.0 Hz, 0.15H), 6.94 (s, 0.85H), 6.73 (s, 0.15H), 6.61 (d, J = 6.0 Hz,
0.85H), 6.48 (s, 1H), 5.94 (d, J = 6.0 Hz, 0.85H), 5.80 (d, J = 6.0 Hz,
0.15H), 3.94 (s, 3H), 3.88 (s, 2.55H), 3.85 (s, 0.45H), 3.80 (q, J = 7.2
Hz, 2H), 1.30 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ
174.1, 173.9, 150.9, 146.4, 145.8, 139.0, 137.1, 135.9, 130.7, 129.3,
128.4, 128.3, 128.1, 118.9, 111.7, 109.8, 94.5, 94.4, 67.7, 56.8, 56.8,
56.5, 35.6, 35.5, 12.9; Ion-trap-HRMS (ESI) calcd for C22H21BrNO3S
[M + H]+ 458.0426, found 458.0420.
5′-(Bromo(4-fluorophenyl)methylene)-1-ethyl-4,5,6-trimethoxy-
5′H-spiro[indoline-3,2′-thiophen]-2-one (11ba). Brown syrup (91
mg, 60%, Z/E = 1:1.5): IR (KBr) ν3749, 2936, 1714, 1502, 1460,
1375, 1217, 782 cm−1; 1H NMR (400 MHz, CDCl3) δ 7.63−7.60 (m,
0.8H), 7.46−7.43 (m, 1.2H), 7.07−6.97 (m, 2.4H), 6.56 (d, J = 6.0 Hz,
0.6H), 6.25 (s, 0.6H), 6.21 (s, 0.4H), 5.97 (d, J = 6.0 Hz, 1H), 3.97 (s,
1.8H), 3.92 (s, 1.2H), 3.92 (s, 1.8H), 3.89 (s, 1.2H), 3.81 (s, 1.8H),
3.79 (s, 1.2H), 3.77−3.70 (m, 2H), 1.30−1.25 (m, 3H); 13C NMR
(100 MHz, CDCl3) δ 174.0, 155.9, 155.8, 152.0, 152.0, 147.0, 142.2,
138.3, 138.3, 138.1, 136.3, 135.6, 135.4, 135.3, 131.2, 131.1, 130.9,
130.8, 130.6, 115.4, 115.3, 115.2, 115.1, 111.2, 111.0, 109.1, 103.8,
90.1, 90.0, 68.8, 66.5, 61.4, 61.3, 61.1, 56.6, 56.5, 35.6, 35.6, 12.9, 12.8;
Ion-trap-HRMS (ESI) calcd for C23H22BrFNO4S [M + H]+ 506.0437,
found 506.0423.
5′-(Bromo(4-fluorophenyl)methylene)-1-ethyl-5,6-dimethoxy-
5′H-spiro[indoline-3,2′-thiophen]-2-one (11bd). Brown syrup (92
mg, 65%, Z/E = 1:1.2): IR (KBr) 3749, 2929, 1717, 1614, 1341, 1228,
1037, 794 cm−1; 1H NMR (400 MHz, CDCl3) δ 7.65−7.62 (m,
0.9H), 7.48−7.44 (m, 1.1H), 7.07−6.99 (m, 2.45H), 6.92 (s, 0.55H),
6.88 (s, 0.45H), 6.54 (d, J = 6.0 Hz, 0.55H), 6.47 (s, 0.55H), 6.44 (s,
0.45H), 6.95 (d, J = 6.0 Hz, 1H), 3.93 (s, 1.65H), 3.91 (s, 1.35H), 3.86
(s, 1.65H), 3.85 (s, 1.35H), 3.79−3.72 (m, 2H), 1.31−1.28 (m, 3H);
13C NMR (100 MHz, CDCl3) δ 174.0,173.9, 161.3, 161.1, 151.0,
150.9, 146.7, 145.8, 141.9, 137.4, 136.6, 135.9, 135.6, 135.5, 131.2,
131.1, 130.9, 130.8, 130.4, 118.7, 118.6, 115.5, 115.4, 115.3, 115.2,
110.3, 109.8, 109.7, 104.6, 94.5, 94.5, 94.5, 70.0, 67.8, 56.8, 56.8, 56.5,
56.5, 35.6, 35.6, 12.9, 12.8; Ion-trap-HRMS (ESI) calcd for
C22H20BrFNO3S [M + H]+ 476.0331, found 476.0315.
5′-(Bromo(naphthalen-2-yl)methylene)-1-ethyl-4,5,6-trimethoxy-
5′H-spiro[indoline-3,2′-thiophen]-2-one (11ca). Brown syrup (88
mg, 55%, Z/E = 1:2.3): IR (KBr) 2935, 1720, 1611, 1472, 1342, 1229,
1130, 1099, 796 cm−1; 1H NMR (400 MHz, CDCl3) δ 8.11 (s, 0.3H),
7.92 (s, 0.7H), 7.86−7.76 (m, 3H), 7.60−7.44 (m, 3H), 7.14 (d, J =
6.0 Hz, 0.3H), 6.70 (d, J = 6.0 Hz, 0.7H), 6.26 (s, 0.7H), 6.21 (s,
0.3H), 6.01 (d, J = 6.0 Hz, 0.3H), 5.99 (d, J = 6.0 Hz, 0.7H), 4.02 (s,
2.1H), 3.94 (s, 0.9H), 3.92 (s, 2.1H), 3.88 (s, 0.9H), 3.83 (s, 2.1H),
5′-(Bromo(phenyl)methylene)-1-ethyl-4,5,6-trimethoxy-5′H-
spiro[indoline-3,2′-thiophen]-2-one (11aa). Brown syrup, (114 mg,
78%, Z/E = 1:2): IR (KBr) 2932, 1718, 1610, 1471, 1341, 1227, 1129,
1082, 1038, 793, 749, 695 cm−1; 1H NMR (400 MHz, CDCl3) δ 7.63
(d, J = 8.0 Hz, 0.66H), 7.43 (d, J = 8.0 Hz, 1.34H), 7.38−7.24 (m,
3H), 7.08 (d, J = 6.0 Hz, 0.33H), 6.63 (d, J = 6.0 Hz, 0.67H), 6.25 (s,
6369
dx.doi.org/10.1021/jo301039y | J. Org. Chem. 2012, 77, 6365−6370