The Journal of Organic Chemistry
Article
−
1
−1
1
+
709, 1469, 1217, 754 cm ; HRMS (m/z): calcd for C H OS [M
2924, 2850, 1476, 1261,738, 638 cm ; HRMS (m/z): calcd for
23
19
2
+
+
H] , 375.0877; found, 375.0910.
C H OS Na [M + Na] , 373.0696; found, 373.0692.
2
1
18
2
2
,3-Bis((2-methoxyphenyl)thio)-1H-inden-1-one (5f). Red liquid;
2,3-Bis((2-methoxyphenyl)thio)-1H-inden-1-ol (5g′). Colorless
1
1
(
44 mg; 70% yield; R 0.50 (20% ethyl acetate in hexanes); H NMR
CDCl , 500 MHz): δ 3.62 (s, 3H), 3.72 (s, 3H), 6.61 (d, J = 7.1 Hz,
liquid; 85 mg; 83% yield; R 0.30 (20% ethyl acetate in hexanes);
f
f
1
H NMR (CDCl , 500 MHz): δ 3.87 (s, 3H), 3.89 (s, 3H), 5.00 (s,
3
3
1
H), 6.68 (d, J = 8.5 Hz, 1H), 6.70−6.75 (m, 2H), 6.78 (t, J = 7.7 Hz,
1H), 6.77 (t, J = 7.5 Hz, 1H), 6.86 (d, J = 8.4 Hz, 1H), 6.90−6.95 (m,
2H), 6.98−7.01 (m, 1H), 7.03 (dd, J = 7.7, 1.3 Hz, 1H), 7.10−7.18
(m, 3H), 7.31 (td, J = 7.8, 1.6 Hz, 1H), 7.37−7.41 (m, 1H), 7.49 (dd,
1
H), 6.94 (dd, J = 7.9, 1.2 Hz, 1H), 6.97−7.04 (m, 1H), 7.06−7.20
(m, 2H), 7.23−7.29 (m, 1H), 7.31 (dd, J = 7.7, 1.3 Hz, 1H), 7.35 (d,
13 1
13
1
J = 6.9 Hz, 1H); C{ H}NMR (CDCl3, 125 MHz): δ 55.8, 55.9,
J = 7.9, 1.8 Hz, 1H); C{ H} NMR (CDCl , 125 MHz): δ 56.0, 56.2,
3
1
1
1
10.7, 111.3, 116.5, 120.6, 120.9, 121.1, 121.9, 123.5, 124.6, 126.8,
28.5, 129.5, 131.2, 131.4, 133.3, 135.1, 142.5, 156.5, 159.4, 164.7,
90.6; FTIR (neat): 3055, 2917, 1708, 1478, 1228, 746 cm ; HRMS
76.9, 110.8, 111.7, 120.4, 120.5, 121.2, 121.6, 122.4, 123.6, 126.2,
127.2, 128.8, 129.2, 130.4, 132.8, 135.4, 141.9, 143.7, 151.5, 156.7,
−
1
−1
158.9; ATR (neat): 3451, 3065, 2932, 1578, 1241, 763,750 cm ;
+
+
(m/z): calcd for C H O S Na [M + Na] , 429.0595; found,
HRMS (m/z): calcd for C H O S Na [M + Na] , 431.0751; found,
2
3
18
3
2
23 20
3 2
4
29.0579.
431.0742.
7
-Methoxy-2,3-bis(o-tolylthio)-1H-inden-1-one (5g). Red liquid;
7-Methoxy-2-((4-methoxyphenyl)thio)naphthalen-1-ol (5aa).
1
1
20 mg; 59% yield; R 0.40 (20% ethyl acetate in hexanes); H NMR
Colorless liquid; 122 mg; 78% yield; R 0.60 (10% ethyl acetate in
f
f
1
(
(
6
1
1
1
CDCl , 400 MHz): δ 2.11 (s, 3H), 2.37 (s, 3H), 3.77 (s, 3H), 6.31
hexanes); H NMR (CDCl , 400 MHz): δ 3.60 (s, 3H), 3.82 (s, 3H),
3
3
d, J = 8.4 Hz, 1H), 6.57 (dd, J = 8.4, 2.4 Hz, 1H), 7.00−7.15 (m,
6.65 (d, J = 7.6 Hz, 2H), 7.01 (d, J = 8.4 Hz, 2H), 7.05−7.15 (m,
H), 7.20−7.28 (m, 1H), 7.32 (t, J = 7.6 Hz, 1H), 7.44 (d, J = 7.6 Hz,
2H), 7.16−7.30 (m, 2H), 7.43 (s, 1H), 7.56 (d, J = 8.8 Hz, 1H);
H); 13C{ H} NMR (CDCl , 100 MHz): δ 20.3, 21.0, 55.8, 109.6,
1
13
1
3
C{ H} NMR (CDCl , 100 MHz): δ 55.4, 55.5, 101.2, 111.7, 115.0,
3
16.3, 121.9, 122.1, 125.8, 126.3, 126.8, 127.6, 127.8, 130.3, 130.4,
30.9, 133.7, 133.8, 134.6, 135.4, 136.5, 142.3, 161.7, 167.5, 190.2;
1
1
1
20.4, 120.5, 124.7, 126.6, 129.2, 129.3, 129.9, 130.8, 152.8, 157.8,
58.7; FTIR (ATR): 3394, 2938, 2838, 1577, 1492, 1430, 1245, 1168,
025, 825, 728 cm .
−
1
−
1
FTIR (KBr): 3059, 2918, 1701, 1476, 1223, 745 cm ; HRMS (m/z):
calcd for C H O S [M + H]+, 405.0983; found, 405.1017.
24
21
2
2
2-((4-Fluorophenyl)thio)-7-methoxynaphthalen-1-ol (5ab). Col-
7
-Methoxy-2,3-bis(p-tolylthio)-1H-inden-1-one (5h). Red liquid;
orless liquid; 121 mg; 82% yield; R 0.80 (10% ethyl acetate in
f
1
1
163 mg; 81% yield; R 0.75 (20% ethyl acetate in hexanes); H NMR
f
hexanes); H NMR (CDCl , 400 MHz): δ 3.82 (s, 3H), 6.73−6.85
3
(
(
3
CDCl , 500 MHz): δ 2.28 (s, 3H), 2.38 (s, 3H), 3.75 (s, 3H), 6.24
d, J = 8.3 Hz, 1H), 6.53 (dd, J = 8.4, 2.5 Hz, 1H), 7.00−7.07 (m,
H), 7.12−7.20 (m, 4H), 7.41 (d, J = 8.1 Hz, 2H); C{ H} NMR
3
(m, 2H), 6.92−7.00 (m, 2H), 7.04 (s, 1H), 7.07−7.15 (m, 1H),
7
1
.19−7.26 (m, 2H), 7.43 (d, J = 1.2 Hz, 1H), 7.57 (d, J = 9.2 Hz,
1
3
1
13 1
H); C{ H} NMR (CDCl , 100 MHz): δ 55.5, 102.3, 110.2, 116.3
3
(CDCl , 125 MHz): δ 21.1, 21.5, 55.8, 109.6, 116.2, 123.0, 123.9,
3
(d, J = 22.0 Hz), 120.7, 120.8, 124.8, 129.0, 129.1, 129.3 (d, J = 9.3
Hz), 131.1, 131.2 (d, J = 3.6 Hz), 153.2, 157.9, 161.6 (d, J = 244.6
Hz); FTIR (ATR): 3405, 2927, 2846, 1577, 1488, 1218, 1025, 821,
1
1
25.6, 129.0, 129.7, 130.2, 131.6, 133.5, 133.8, 133.9, 136.2, 140.0,
61.4, 166.9, 190.1; ATR (neat): 2919, 2854, 1697, 1473, 1222, 771
−
1
−
1
cm ; HRMS (m/z): calcd for C H O S [M + H]+, 405.0983;
found, 405.0964.
Z)-1-Phenyl-2,3-bis(p-tolylthio)prop-2-en-1-one (5i). Red liquid;
2
4
21
2
2
728 cm .
7
-Methoxy-2-((3-methoxyphenyl)thio)naphthalen-1-ol (5ac).
(
Colorless liquid; 113 mg; 72% yield; R 0.55 (10% ethyl acetate in
f
1
1
1
41 mg; 66% yield; R 0.65 (10% ethyl acetate in hexanes); H NMR
f
hexanes); H NMR (CDCl , 400 MHz): δ 3.61 (s, 3H), 3.86 (s, 3H),
3
(
7
CDCl , 400 MHz): δ 6.63 (d, J = 1.2 Hz, 1H), 7.16−7.20 (m, 1H),
3
6.55−6.68 (m, 3H), 6.99−7.07 (m, 2H), 7.10−7.15 (m, 1H), 7.25−
1
3
1
.21−7.24 (m, 4H), 7.28−7.31 (m, 1H), 7.35−7.40 (m, 3H), 7.40−
.44 (m, 1H), 7.45−7.48 (m, 2H); C{ H} NMR (CDCl , 100
7
.30 (m, 2H), 7.46 (s, 1H), 7.62 (d, J = 8.8 Hz, 1H); C{ H} NMR
13 1
7
3
(CDCl , 100 MHz): δ 55.3, 55.5, 101.3, 109.4, 111.6, 112.6, 119.1,
3
MHz): δ 123.3, 124.9, 126.8, 128.2, 128.3, 128.6, 129.1, 129.4, 129.6,
120.6, 124.8, 129.3, 129.7, 130.1, 131.2, 137.6, 153.5, 157.8, 160.2;
1
3
29.7, 129.8, 132.2, 133.6, 133.9, 144.0, 160.7, 189.3; FTIR (KBr):
FTIR (ATR): 3401, 2923, 2850, 1577, 1461, 1218,1033, 836, 767
−
1
−
1
058, 2925, 1708, 1596, 1576, 1476, 759 cm ; HRMS (m/z): calcd
cm .
+
for C H BrOS [M + H] , 424.9669; found, 424.9668.
21
13
2
7-Methoxy-2,3-bis(phenylthio)naphthalen-1-ol (6aa). Colorless
1
2
,3-Bis(benzylthio)-1H-inden-1-one (5j). Red liquid; 80 mg; 43%
liquid; 138 mg; 70% yield; R 0.70 (10% ethyl acetate in hexanes); H
f
1
yield; R 0.43 (5% ethyl acetate in hexanes); H NMR (CDCl , 500
MHz): δ 4.03 (s, 2H), 4.30 (s, 2H), 7.07 (d, J = 7.2 Hz, 1H), 7.10−
f
3
NMR (CDCl , 400 MHz): δ 3.82 (s, 3H), 6.92−6.99 (m, 3H), 7.00−
3
7
1
.08 (m, 5H), 7.09−7.15 (m, 3H), 7.22 (s, 1H), 7.51 (s, 1H), 7.70 (s,
13 1
7
6
1
1
1
.15 (m, 3H), 7.16−7.24 (m, 8H), 7.26−7.30 (m, 1H), 7.40 (d, J =
H), 8.15 (d, J = 9.2 Hz, 1H); C{ H} NMR (CDCl , 100 MHz): δ
3
.9 Hz, 1H); 13C{ H} NMR (CDCl , 125 MHz): δ 36.5, 36.8, 119.6,
1
3
55.6, 102.1, 110.2, 121.2, 121.4, 125.4, 125.8, 126.4, 126.9, 127.2,
28.0, 129.0, 129.3, 131.8, 135.6, 138.5, 138.6, 155.1, 158.2; FTIR
ATR): 3397, 3058, 2923, 1577, 1423, 1268, 1172, 1029, 829, 744
21.8, 127.1, 127.3, 128.0, 128.7, 128.9, 129.0, 129.3, 129.6, 130.2,
33.5, 135.8, 138.4, 143.5, 162.2, 192.5; FTIR (neat): 3059, 2987,
718, 1476, 1223, 745 cm ; HRMS (m/z): calcd for C H OS Na
1
(
−
1
−
1
2
3
18
2
cm .
+
[
M + Na] , 397.0696; found, 397.0687.
7
-Methoxy-2,3-bis(p-tolylthio)naphthalen-1-ol (6ab). Colorless
1
2
,3-Bis(naphthalen-2-ylthio)-1H-inden-1-one (5k). Red liquid;
liquid; 140 mg; 67% yield; R 0.50 (5% ethyl acetate in hexanes); H
f
1
108 mg; 48% yield; R 0.31 (5% ethyl acetate in hexanes); H
f
NMR (CDCl , 500 MHz): δ 2.24 (s, 3H), 2.27 (s, 3H), 3.93 (s, 3H),
3
NMR (CDCl , 500 MHz): δ 6.64 (d, J = 7.2 Hz, 1H), 7.07−7.12 (m,
3
6.97 (s, 4H), 7.03 (s, 4H), 7.20 (dd, J = 9.1, 2.6 Hz, 1H), 7.28 (br s,
1
3
1
1
7
H), 7.13−7.20 (m, 2H), 7.31−7.50 (m, 7H), 7.54−7.58 (m, 3H),
1
2
1
H), 7.58 (d, J = 2.6 Hz, 1H); C{ H} NMR (CDCl , 125 MHz): δ
3
13 1
.63−7.69 (m, 2H), 7.72−7.77 (m, 1H), 7.81 (s, 1H); C{ H} NMR
1.0, 21.1, 55.6, 102.1, 111.1, 121.2, 122.0, 125.8, 127.6, 127.8, 128.0,
29.8, 130.2, 131.6, 132.0, 134.6, 135.5, 136.6, 137.8, 154.6, 158.1;
(CDCl3, 100 MHz): δ 121.4, 122.4, 125.9, 126.2, 126.6, 126.8, 127.1,
1
1
1
27.3, 127.4, 127.8, 127.9, 128.0, 128.3, 128.5, 128.9, 129.7, 129.9,
31.1, 131.5, 132.0, 132.7, 133.1, 133.4, 133.6, 133.7, 142.6, 162.3,
90.8; FTIR (neat): 3057, 2978, 1704, 1477, 1223, 741 cm ; HRMS
FTIR (ATR): 3343, 2936, 2833, 1592, 1568, 1398,1026, 885, 769,
−
1
6
59 cm .
−
1
7
-Methoxy-2,3-bis((2-methoxyphenyl)thio)naphthalen-1-yl 2-Io-
+
(m/z): calcd for C H OS Na [M + Na] , 469.0696; found,
dobenzoate (6ba). Colorless liquid; 213 mg; 63% yield; R 0.50 (5%
2
9
18
2
f
1
4
69.0674.
ethyl acetate in hexanes); H NMR (CDCl , 400 MHz): δ 3.84−4.03
3
(
Z)-1-Phenyl-2,3-bis(phenylthio)prop-2-en-1-ol (3a′). Colorless
(m, 9H), 6.45 (d, J = 8.0 Hz, 1H), 6.64 (t, J = 7.6, 1H), 6.78−6.90
(m, 3H), 6.98−7.10 (m, 2H), 7.18−7.23 (m, 3H), 7.43 (t, J = 7.6,
1H), 7.61 (s, 1H), 7.82 (s, 1H), 7.96−8.10 (m, 2H), 8.19 (d, J = 9.2,
liquid; 154 mg; 85% yield; R 0.59 (20% ethyl acetate in hexanes);
f
1
H NMR (CDCl , 400 MHz): δ 5.15 (s, 1H), 7.07−7.14 (m, 2H),
3
1
3
1
13
1
7
1
1
.15−7.28 (m, 12H), 7.29−7.34 (m, 2H); C{ H} NMR (CDCl ,
1H); C{ H} NMR (CDCl , 100 MHz): δ 55.6, 56.0, 56.1, 94.8,
3
3
00 MHz): δ 76.7, 126.6, 126.8, 127.5, 128.2, 128.5, 129.2, 129.3,
30.3, 131.8, 133.9, 135.0, 136.7, 141.2; ATR (neat): 3431, 3063,
102.0, 110.3, 110.9, 111.0, 119.4, 121.2, 121.3, 121.7, 123.5, 125.9,
126.1, 127.1, 127.2, 128.0, 128.1, 128.7, 130.6, 132.0, 132.1, 133.3,
J
J. Org. Chem. XXXX, XXX, XXX−XXX