Advanced Synthesis & Catalysis
10.1002/adsc.201801535
1
17.6, 52.3; HRMS (FD) m/z calcd for C18
H
14Br
2
O
4
5-(Phenylethynyl)benzo[d][1,3]dioxole (333 mg, 1.5
+
(
M ): 451.9259, found: 451.9256.
mmol) afforded 5c (209 mg, 0.82 mmol, 55% yield);
1
yellow oil; H NMR (500 MHz, CDCl
3
) δ 7.96 (dt, J
(
E)-4,4'-(1,2-Dibromoethene-1,2-
= 8.5, 1.4 Hz, 2H), 7.65 (m, 1H), 7.51 (m, 2H), 7.48
13
diyl)dibenzonitrile (4r)
(m, 2H), 6.86 (d, J = 8.6 Hz, 1H), 6.08 (m, 2H); C
) δ 194.5, 192.8, 153.4, 148.6,
mmol) afforded 4r (378 mg, 0.97 mmol, 65% yield); 134.7, 133.0, 129.9, 128.9, 127.9, 127.8, 108.4, 108.3,
4
,4'-(Ethyne-1,2-diyl)dibenzonitrile (342 mg, 1.5 NMR (126 MHz, CDCl
3
1
+
white solid, mp 218-219 ℃; H NMR (500 MHz, 102.2; MS (EI) m/z = 254 (M ).
CDCl
3
) δ 7.74 (ddd, J = 8.6, 2.0, 1.5 Hz, 4H), 7.63
13
(
ddd, J = 8.6, 2.0, 1.5 Hz, 4H); C NMR (126 MHz, 1-(4-Fluorophenyl)-2-phenylethane-1,2-dione (5d)
[32]
CDCl
3
) δ 144.2, 132.3, 129.8, 118.0, 117.3, 113.0;
+
HRMS (FD) m/z calcd for C16
H
8
Br
2
N
2
(M ): 1-Fluoro-4-(phenylethynyl)benzene (294 mg, 1.5
3
85.9055, found: 385.9043.
mmol) afforded 5d (222 mg, 0.97 mmol, 65% yield);
1
pale yellow oil; H NMR (500 MHz, CDCl
3
) δ 8.02
(
E)-1,2-Dibromo-1,2-di(pyridin-2-yl)ethane (4s)
(ddt, J = 8.9, 5.3, 2.1 Hz, 2H), 7.98 (m, 2H), 7.67 (tt,
,2-Di(pyridin-2-yl)ethyne (270 mg, 1.5 mmol) J = 7.5, 1.3 Hz, 1H), 7.53 (m, 2H), 7.20 (ddt, J = 9.0,
1
1
3
afforded 4s (321 mg, 0.94 mmol, 63% yield); white 7.4, 2.1 Hz, 2H); C NMR (126 MHz, CDCl
solid, mp 177-178 ℃; H NMR (500 MHz, CDCl
3
) δ
1
3
) δ 194.0, 192.7, 166.7 (d, JC-F = 259.5 Hz), 135.0, 132.8,
8
1
.73 (ddd, J = 4.8, 1.8, 0.9 Hz, 2H), 7.80 (td, J = 7.7, 132.7 (d, JC-F = 10.0 Hz), 129.9, 129.4 (d, JC-F = 3.78
.8 Hz, 2H), 7.64 (dt, J = 7.8, 1.1 Hz, 2H), 7.31 (ddd, Hz), 129.0, 116.4 (d, JC-F = 22.6 Hz); MS (EI) m/z =
13
+
J = 7.6, 4.8, 1.1 Hz, 2H); C NMR (126 MHz, 228 (M ).
CDCl ) δ 156.9, 149.7, 136.7, 124.4, 123.7, 118.4;
HRMS (FD) m/z calcd for C12
85.9055, found: 385.9052.
3
+
H
8
Br
2
N
2
(M ): 1-(4-Chlorophenyl)-2-phenylethane-1,2-dione (5e)
[7c]
3
1
-Chloro-4-(phenylethynyl)benzene (319 mg, 1.5
(
E)-1,2-Dibromo-1,2-di(pyridin-3-yl)ethane (4t)
,2-Di(pyridin-3-yl)ethyne (270 mg, 1.5 mmol) yellow solid; mp 70-72 ℃ (lit. 70 ℃); H NMR (500
afforded 4t (362 mg, 1.06 mmol, 71% yield); white MHz, CDCl ) δ 7.97 (m, 2H), 7.93 (m, 2H), 7.68 (m,
mmol) afforded 5e (293 mg, 1.2 mmol, 80% yield);
1
1
3
1
13
solid, mp 167-168 ℃; H NMR (400 MHz, CDCl
3
) δ 1H), 7.53 (m, 2H), 7.50 (m, 2H); C NMR (126 MHz,
.82 (d, J = 1.6 Hz, 2H), 8.63 (dd, J = 4.6, 1.0 Hz, CDCl ) δ 193.8, 193.0, 141.6, 135.0, 132.7, 131.3,
H), 7.85 (dt, J = 7.9, 2.0 Hz, 2H), 7.39 (dd, J = 7.9, 131.2, 129.9, 129.4, 129.0; MS (EI) m/z = 244 (M ).
.8 Hz, 2H); 13C NMR (100 MHz, CDCl
) δ 149.9,
49.8, 136.5, 136.4, 123.2, 116.5; HRMS (FD) m/z 1,1-Dibromo-1-phenylheptan-2-one (7a)
8
2
4
1
3
+
3
+
calcd for C12
3
H
8
Br
2
N
2
(M ): 337.9054, found: Hept-1-yn-1-ylbenzene (258 mg, 1.5 mmol) afforded
1
37.9050.
7a (375 mg, 1.08 mmol, 72% yield); colorless oil; H
NMR (500 MHz, CDCl ) δ 8.34 (m, 2H), 7.56 (tt, J =
3
1
-Phenyl-2-(p-tolyl)ethane-1,2-dione (5a) [7c]
7.4, 1.2, 1H), 7.45 (m, 2H), 2.66 (m, 2H), 1.72 (m,
1
-Methyl-4-(phenylethynyl)benzene (288 mg, 1.5 2H), 1.41 (m, 2H), 1.38 (m, 2H), 0.92 (t, J = 7.1, 3H);
1
3
mmol) afforded 5a (235 mg, 1.05 mmol, 70% yield);
C NMR (126 MHz, CDCl ) δ 188.6, 133.1, 132.6,
) δ 7.97(m, 131.0, 127.8, 66.9, 46.7, 31.1, 27.0, 22.4, 13.9;
3
1
yellow oil; H NMR (500 MHz, CDCl
3
+
2
1
H), 7.86 (dt, J = 8.3, 1.8 Hz, 2H), 7.65 (tt, J = 7.5, HRMS (FD) m/z calcd for C13
.3 Hz, 1H), 7.51(m, 2H), 7.31 (m, 2H), 2.43 (s, 3H); 345.9568, found: 345.9572.
H
16Br O (M ):
2
1
3
C NMR (126 MHz, CDCl ) δ 194.7, 194.2, 146.2,
3
1
34.7, 133.1, 130.5, 130.0, 129.8, 129.7, 128.9, 21.9; 1,1-Dibromo-1-phenylpentan-2-one (7b)
+
MS (EI) m/z = 224 (M ).
Pent-1-yn-1-ylbenzene (216 mg, 1.5 mmol) afforded
b (312 mg, 0.97 mmol, 65% yield); pale yellow oil;
H NMR (500 MHz, CDCl
J = 7.4, 1.2, 1H), 7.45 (m, 2H), 2.65 (m, 2H), 1.76 (m,
7
1
1
-(3,4-Dimethylphenyl)-2-phenylethane-1,2-dione
3
) δ 8.34 (m, 2H), 7.56 (tt,
5b) [
7c]
(
1
3
1
,2-Dimethyl-4-(phenylethynyl)benzene (309 mg, 1.5 2H), 1.05 (t, J = 7.4, 3H); C NMR (126 MHz,
mmol) afforded 5b (257 mg, 1.08 mmol, 72% yield); CDCl
3
) δ 188.5, 133.1, 132.6, 131.0, 127.8, 66.6, 48.7,
1
pale yellow solid; mp: 61-62 °C (lit. 63 ℃); H NMR 20.8, 13.5; HRMS (FD) m/z calcd for C11
H
12Br O
2
+
(
400 MHz, CDCl
3
) δ 7.66 (dt, J = 8.5, 1.5 Hz, 2H), (M ): 317.9255, found: 317.9264.
.73 (s, 1H), 7.69 (dd, J = 7.8, 1.5 Hz, 1H), 7.64 (m,
H), 7.49 (m, 2H), 7.25 (d, J = 7.8 Hz, 1H), 2.33 (s, 6,6-Dibromodecan-5-one (7c)
H), 2.30 (s, 3H); 13C NMR (100 MHz, CDCl
) δ Dec-5-yne (207 mg, 1.5 mmol) afforded 7c (371 mg,
94.8, 194.6, 145.0, 137.6, 134.7,133.2, 130.9, 130.7, 1.18 mmol, 79% yield); colorless oil; H NMR (500
7
1
3
1
1
2
3
1
30.3, 129.9, 128.9, 127.7, 20.3, 19.7; MS (EI) m/z = MHz, CDCl
3
) δ 3.09 (m, 2H), 2.46 (m, 2H), 1.68 (m,
+
38 (M ).
2H), 1.62 (m, 2H), 1.47 – 1.35 (m, 4H), 0.96 (td, J =
1
3
7
.3, 2.2 Hz, 6H); C NMR (126 MHz, CDCl
3
) δ
1
-(Benzo[d][1,3]dioxol-5-yl)-2-phenylethane-1,2-
198.2, 71.9, 44.6, 36.1, 29.7, 27.5, 22.2, 22.1, 13.9,
[
32]
+
dione (5c)
13.9; HRMS (FD) m/z calcd for C10
14.9724, found: 314.9726.
H
18Br O (M ):
2
3
1
1
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