Ni(0)-CATALYZED DIMERIZATION OF o-KETO CARBOXYLIC ACID PSEUDOCHLORIDES
675
8
5
Mixture of diastereomers, separated by fractional
crystallization from chloroform–methanol, 3 : 1. meso-
H , J 7.6 Hz), 7.57 d (2H, H , J 7.6 Hz), 7.79 s (2H,
1
5
13
17
H ). C NMR spectrum, δ, ppm: 21.29 (C ), 21.85
1
6
3
5
8
3
a, colorless crystals, mp 269–271°C (270–271°C [6]).
(C ), 94.16 (C ), 126.44 (C ), 124.38 (C ), 126.83
–
1
9
13
7
15
IR spectrum, ν, cm : 1778.44 (C=O), 1448.60,
(C ), 128.95 (C ), 129.60 (C ), 130.08 (C ), 135.15
1
4
6
12
10
1
7
7
228.54, 1244.14, 1220.99, 1069.57, 999.17, 731.05,
(C ), 134.42 (C ), 133.04 (C ), 134.23 (C ), 133.38
1
13
11
4
1
10.80. Н NMR spectrum, δ, ppm: 7.12 m (2H, H ),
(C ), 148.38 (C ), 170.02 (C ). Found, %: C 81.19; Н
5.72. C Н O . Calculated, %: C 80.99; Н 5.52.
1
2,12'
7
.12 m (4H, H
), 7.42 t (2H, H , J 7.6 Hz), 7.59 d
3
2
26
4
8
11,11'
6
(
2H, H , J 7.6 Hz), 7.63 m (4H, H
), 7.74 t (2H, H ,
3
-(Diphenyl-4-yl)-3-[1-(diphenyl-4-yl)-3-oxo-1H-
5
13
J 7.6 Hz), 8.37 d (2H, H , J 7.8 Hz). C NMR
spectrum, δ, ppm: 90.13 (C ), 125.18 (C ), 125.59
2
-benzofuran-1-yl]-2-benzofuran-1(3H)-one (3c).
Yield 79%. Mixture of diastereomers; the racemate
was extracted with hot toluene, and the residue was the
meso form. meso-3c, colorless crystals, mp 285–286°C
DMF, decomp.). IR spectrum, ν, cm : 1772.66
C=O), 1488.15, 1366.62, 1284.65, 1241.25, 1216.17,
069.57, 1022.32, 1009.78, 993.38, 765.77, 759.02,
36.84, 717.55, 701.15. Н NMR spectrum, δ, ppm:
.32 t (2H, H , J 7.7 Hz), 7.37 d (4H, H
3
5
8
9
11,11'
12,12'
10
(
C ), 126.25 (C ), 126.89 (C
), 127.89 (C
),
1
3
7
6
1
1
2
1
1
28.57 (C ), 129.78 (C ), 134.27 (C ), 135.01 (C ),
49.12 (C ), 168.78 (C ). (±)-3a, colorless crystals, mp
73–275°C (275–278°C [6]). IR spectrum, ν, cm :
4
1
–1
(
–
1
(
772.66 (C=O), 1446.67, 1286.58, 1248.96, 1224.95,
1
7
7
8
7
7
7
1
068.61, 1007.85, 997.24, 973.13, 738.77, 714.66. Н
1
1
3
NMR spectrum, δ, ppm: 7.21 m (2H, H ), 7.21 m (4H,
H
7
7
9
1
17
12,12'
, J
1
2,12'
7
8
), 7.34 t (2H, H , J 7.8 Hz), 7.62 d (2H, H , J
16,16'
7
.5 Hz), 7.38 t (2H, H
.6 Hz), 7.47 d (4H, H
.6 Hz), 7.71 d (4H, H , J 8.5 Hz), 7.77 t (2H H , J
, J 7.8 Hz), 7.43 t (2H, H , J
, J 7.8 Hz), 7.62 d (2H, H , J
11,11'
6
.8 Hz), 7.73 m (4H, H
.96 d (2H, H , J 7.8 Hz). C NMR spectrum, δ, ppm:
0.93 (C ), 124.57 (C ), 125.72 (C ), 129.88 (C ),
), 7.57 t (2H, H , J 7.8 Hz),
15,15'
8
5
13
11,11'
6
3
5
8
9
5
13
.7 Hz), 8.43 d (2H, H , J 7.8 Hz). C NMR spectrum,
11,11'
12,12'
13
26.42 (C
), 128.18 (C
), 128.46 (C ), 129.86
3
5
8
δ, ppm: 90.24 (C ), 125.16 (C ), 125.81 (C ), 126.30
7
6
10
4
(
C ), 134.72 (C ), 136.70 (C ), 149.26 (C ), 169.36
9
12,12'
15,15'
11,11'
(
1
(
(
3
1
1
7
C ), 126.47 (C
), 127.02 (C
), 127.40 (C
),
1
(
C ). Found, %: C 80.18; Н 4.13. C Н O .
17
16,16'
7
28
18
4
27.74 (C ), 128.86 (C
), 129.91 (C ), 134.06
Calculated, %: C 80.37; Н 4.34.
10
6
14
13
C ), 134.39 (C ), 139.85 (C ), 141.18 (C ), 149.16
4
1
C ), 168.85 (C ). (±)-3c, colorless crystals, mp 295–
3
-(2,5-Dimethylphenyl)-3-[1-(2,5-dimethylphe-
nyl)-3-oxo-1H-2-benzofuran-1-yl]-2-benzofuran-1-
3H)-one (3b). Yield 33%. Mixture of diastereomers,
–
1
00°C (toluene, decomp.). IR spectrum, ν, cm :
768.80 (C=O), 1489.11, 1449.57, 1286.58, 1246.07,
230.64, 1084.04, 993.38, 975.06, 823.64, 758.06,
(
separated by fractional crystallization from chloro-
form–methanol, 3 : 1. meso-3b, colorless crystals, mp
1
35.87, 697.30. Н NMR spectrum, δ, ppm: 7.32 t (2H,
1
7
7
–
1
H , J 7.7 Hz), 7.37 t (2H, H , J 7.7 Hz), 7.40 t (4H,
2
1
1
1
16–220°C (224–226°C [7]). IR spectrum, ν, cm :
776.52 (C=O), 1496.83, 1465.96. 1366.62, 1285.61,
244.14, 1232.57, 1109.12, 1076.33, 1036.78,
1
6,16'
12,12'
H
, J 7.8 Hz), 7.48 d (4H, H
, J 8.5 Hz), 7.52 d
1
8
5,15'
6
(
4H, H
, J 8.5 Hz), 7.60 t (2H, H , J 7.8 Hz), 7.65 d
11,11'
1
(2H, H , J 7.7 Hz), 7.83 d (4H, H
, J 8.5 Hz), 8.00 d
025.21, 820.75, 746.48, 738.77, 686.69. Н NMR
spectrum, δ, ppm: 2.25 s (6H, H C ), 2.27 s (6H,
H C ), 6.90 d (2H, H , J 8.6 Hz), 6.95 d (2H, H , J
.6 Hz), 7.39 s (2H, H ), 7.51 t (2H, H , J 7.6 Hz),
5
13
17
(2H, H , J 7.8 Hz). C NMR spectrum, δ, ppm: 90.99
3
3
5
8
12,12'
1
6
12
13
(C ), 124.56 (C ), 125.81 (C ), 126.84 (C
), 126.97
3
11,11'
9
15,15'
17
1
5
7
(C
), 127.03 (C ), 127.06 (C
), 127.66 (C ),
8
7
7
2
1
1
1
16,16'
7
6
10
8
6
128.85 (C
), 129.92 (C ), 134.79 (C ), 135.67 (C ),
.56 d (2H, H , J 7.6 Hz), 7.61 t (2H, H , J 7.6 Hz),
1
3
14
4
1
5
13
140.06 (C ), 141.16 (C ), 149.11 (C ), 169.37 (C ).
Found, %: C 84.05; Н 4.35. C40
C 84.19; Н 4.59.
.77 d (2H, H , J 7.6 Hz). C NMR spectrum, δ, ppm:
1
7
16
3
5
Н O . Calculated, %:
26 4
1.00 (C ), 23.75 (C ), 93.92 (C ), 125.64 (C ),
8
9
13
7
25.65 (C ), 127.58 (C ), 129.37 (C ), 129.89 (C ),
1
5
14
6
12
30.19 (C ), 132.67 (C ), 133.40 (C ), 133.59 (C ),
3-[3-Oxo-1-(4-phenoxyphenyl)-1H-2-benzofu-
ran-1-yl]-3-(4-phenoxyphenyl)-2-benzofuran-1(3H)-
one (3d). Yield 72%. Mixture of diastereomers,
separed by semipreparative HPLC. meso-3d, colorless
crystals, mp 220.5–221°C. Retention time 12.02 min.
IR spectrum, ν, cm : 1774.59 (C=O), 1587.48,
1505.51, 1489.11, 1456.32, 1288.50, 1241.25,
1202.67, 1167.95, 1098.51, 1073.47, 1022.32,
10
11
4
1
34.07 (C ), 135.72 (C ), 149.50 (C ), 168.62 (C ).
±)-3b, colorless crystals, mp 204–206°C (206–209°C
(
[
–
1
7]). IR spectrum, ν, cm : 1771.69 (C=O), 1500.68,
1
1
7
2
366.62, 1284.65, 1244.14, 1219.06, 1105.26,
090.79, 1073.43, 980.84, 964.45, 811.10, 742.63,
–
1
1
16
31.05. Н NMR spectrum, δ, ppm: 2.03 s (6H, H C ),
3
1
7
12
13
.19 s (6H, H C ), 6.92 s (4H, H , H ), 7.31 t (2H,
3
7
6
1
H , J 7.6 Hz), 7.50 t (2H, H , J 7.6 Hz), 7.53 d (2H,
1003.03, 994.35, 869.93, 742.63. Н NMR spectrum,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 5 2019