UPDATES
tion (acetone); 1HNMR (400 MHz, DMSO-d6): d(1H)=10.10
(1H, s, -CHO) 9.69 (1H, s. -OH), 8.05 (2H, m), 8.00 (2H, m),
7.87 (2H, m), 7.77 (2H, m), 7.62 (2H, m), 6.93 (2H, m);
13CNMR (100.6 MHz, DMSO-d6): d(13C)=192.8 (1H, s,
-CHO), 157.6, 145.5, 140.5, 136.6, 135.1, 130.1 (all C), 130.3
(2C), 127.9 (2C), 127.7 (2C), 127.1 (2C), 126.6 (2C), 115.9
(2C), (all =CH-); HRMS (MALDI): m/z calcd. for C19H14O2
(M+), 274.0988; found: 274.0990; Anal. calcd. for C19H14O2: C
83.19, H 5.14; found C 82.91, H 5.22.
127.9 (2C), 127.5 (2C), 126.6 (4C), 116.0 (2C), (all =CH-);
HRMS (MALDI): m/z calcd. for C19H14O3 (M+), 290.0938;
found: 290.0940; Anal. calcd. for C19H14O3: C 78.61, H 4.86;
found C 78.43, H 4.89.
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4’’-(Diphenylamino)-1,1’:4’,1’’-terphenyl-4-ol (3i): White crys-
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tals; yield: 2.96 g (89%); mp 211–2128C (EtOH); HNMR
(400 MHz, DMSO-d6): d(1H)=9.65 (1H, s. -OH), 7.65–7.74
(6H, m), 7.58 (2H, m), 7.37 (4H, m), 7.08–7.14 (8H, m), 6.90
(2H, m); 13CNMR (100.6 MHz, DMSO-d6): d(13C)=157.3,
147.2 (2C), 146.8, 138.8, 137.6, 133.8, 130.5, (all C), 129.8
(4C), 127.7 (2C), 127.5 (2C), 126.7 (2C), 126.5 (2C), 124.3
(4C), 123.5 (2C), 123.5 (2C), 115.9 (2C), (all =CH-); HRMS
(MALDI): m/z calcd. for C30H23NO (M+), 413.1774; found:
413.1775; Anal. calcd. for C30H23NO: C 87.14, H 5.61, N 3.39;
found C 87.20, H 5.65, N 3.31.
4’’-(Trifluoromethyl)-1,1’:4’,1’’-terphenyl-4-ol (3d):
White
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23
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27
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crystals; yield: 2.33 g (92%); mp 259–2618C (EtOAc);
1HNMR (400 MHz, DMSO-d6): d(1H)=9.70 (1H, s. -OH),
7.98 (2H, m), 7.86 (2H, m), 7.84 (2H, m), 7.77 (2H, m), 7.62
(2H, m), 6.92 (2H, m); 13CNMR (100.6 MHz, DMSO-d6):
d(13C)=157.6, 143.9, 140.4, 136.5, 130.1, 128.2 (all C), 124.3
(CF3, q, J(F,C)=271.8 Hz) 127.9 (2C), 127.6 (2C), 127.3 (2C)
126.7 (2C), 125.9 (2C, q, J(F,C)=3.6 Hz)), 116.0 (2C), (all =
CH-); HRMS (MALDI): m/z calcd. for C19H13F3O (M+),
314.0913; found: 314.0916; Anal. calcd. for C19H13F3O: C
72.61, H 4.17; found C 72.69, H 4.12.
Tert–butyl (4’’-hydroxy-1,1’:4’,1’’-terphenyl-4-yl)carbamate
(3j): White crystals; yield: 2.67 g (92%); mp 340–3508C,
decomposition (EtOAc); 1HNMR (400 MHz, DMSO-d6):
d(1H)=9.62 (1H, s. -OH), 9.50 (1H, s. –NH-), 7.55–7.67 (8H,
m), 7.52 (2H, m), 6.86 (2H, m), 1.50 (9H, s, (CH3)3);
13CNMR (100.6 MHz, DMSO-d6): d(13C)=157.3, 152.9,
139.2, 138.7, 137.8, 133.4, 130.5, (all C), 127.7 (2C), 126.8
(2C), 126.6 (2C), 126.5 (2C), 118.6 (2C), 115.9 (2C), (all =
CH-), 79.3 (CH), 28.3 (CH3)3); HRMS (MALDI): m/z calcd.
for C23H23NO3 (M+), 361.1673; found: 361.1677; Anal. calcd.
for C23H23NO3: C 76.43, H 6.41, N 3.88; found C 76.51, H
6.42, N 3.86.
2’’,4’’,6’’-Trimethyl-1,1’:4’,1’’-terphenyl-4-ol (3e): White crys-
tals; yield: 1.83 g (94%); mp 154–1558C (60% EtOH);
1HNMR (400 MHz, DMSO-d6): d(1H)=9.63 (1H, s, -OH),
7.67 (2H, m), 7.59 (2H, m), 7.17 (2H, m), 6.97 (2H, s), 6.92
(2H, m), 2.30 (1x3H, s), 2.01 (2x3H, s); 13CNMR (100.6
MHz, DMSO-d6): d(13C)=157.2, 138.6, 138.5, 138.3, 135.9,
135.2 (2C), 130.7, (all C), 129.6 (2C), 128.1 (2C), 127.7 (2C),
126.0 (2C), 115.9 (2C), (all =CH-), 20.7 (CH3), 20.6 (2xCH3);
HRMS (MALDI): m/z calcd. for C21H20O (M+), 288.1509;
found: 288.1512; Anal. calcd. for C21H20O: C 87.46, H 6.99;
found C 87.47, H 7.09.
4’’-(Methylsulfanyl)-1,1’:4’,1’’-terphenyl-4-ol (3k): White crys-
1
tals; yield: 2.02 g (86%); mp 299–3028C (acetone); HNMR
(400 MHz, DMSO-d6): d(1H)=9.63 (1H, s. -OH), 7.66 (6H,
m), 7.54 (2H, m), 7.34 (2H, m), 6.86 (2H, m), 3.40 (SCH3);
13CNMR (100.6 MHz, DMSO-d6): d(13C)=157.3, 139.1,
137.5, 137.4, 136.2, (all C), 127.7 (2C), 126.9 (2C), 126.8 (2C),
126.5 (2C), 126.4 (2C), 115.8 (2C), (all =CH-), 14.7 (SCH3);
HRMS (MALDI): m/z calcd. for C19H16OS (M+), 292.0916;
found: 292.0918; Anal. calcd. for C19H16OS: C 78.05, H 5.52,
S 10.97; found C 78.11, H 5.53, S 10.91.
4’’-Methoxy-1,1’:4’,1’’-terphenyl-4-ol (3f):[31] White crystals;
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yield: 2.01 g (91%); mp 284–2858C (EtOAc); HNMR (400
MHz, DMSO-d6): d(1H)=9.62 (1H, s, -OH), 7.72 (2H, m),
7.70 (2H, m), 7.66 (2H, m), 7.58 (2H, m), 7.08 (2H, m), 6.92
(2H, m), 3.41 (3H, s, -OCH3); 13CNMR (100.6 MHz, DMSO-
d6): d(13C)=158.9, 157.2, 138.6, 137.8, 132.2, 130.5, (all C),
127.6 (4C), 126.6 (2C), 126.4 (2C), 115.9 (2C), 114.5 (2C) (all
=CH-), 55.3 (s, -OCH3); HRMS (MALDI): m/z calcd. for
C19H16O2 (M+), 276.1145; found: 276.1146; Anal. calcd. for
C19H16O2: C 82.58, H 5.84; found C 82.62, H 5.87.
4’’-Nitro-1,1’:4’,1’’-terphenyl-4-ol (3l):[33] Yellow crystals;
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yield: 2.07 g (88%); mp 276–2788C (EtOAc); HNMR (400
MHz, DMSO-d6): d(1H)=9.69 (1H, s. -OH), 8.30 (2H, m),
8.00 (2H, m), 7.84 (2H, m), 7.75 (2H, m), 7.59 (2H, m), 6.87
(2H, m); 13CNMR (100.6 MHz, DMSO-d6): d(13C)=157.6,
146.5, 146.2, 140.8, 135.6, 129.9, (all C), 127.9 (2C), 127.8
(2C), 127.5 (2C) 126.7 (2C), 124.3 (2C), 115.9 (2C), (all =
CH-); HRMS (MALDI): m/z calcd. for C18H13NO3 (M+),
291.0889; found: 291.0895; Anal. calcd. for C18H13NO3: C
74.22, H 4.50, N 4.81; found C 74.10, H 4.53, N 4.79.
4’’-Chloro-1,1’:4’,1’’-terphenyl-4-ol (3g): White crystals; yield:
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2.03 g (90%); mp 269–2718C (EtOAc); HNMR (400 MHz,
DMSO-d6): d(1H)=9.65 (1H, s. -OH), 7.78 (2H, m), 7.76
(2H, m), 7.72 (2H, m), 7.59 (2H, m), 7.56 (2H, m), 6.92 (2H,
m); 13CNMR (100.6 MHz, DMSO-d6): d(13C)=157.4, 139.7,
138.6, 136.7, 132.3, 130.2 (all C), 129.0 (2C), 128.3 (2C), 127.8
(2C) 127.1 (2C), 126.6 (2C), 115.9 (2C), (all =CH-); HRMS
(MALDI): m/z calcd. for C18H13ClO (M+), 280.0649; found:
280.0652; Anal. calcd. for C18H13ClO: C 77.01, H 4.67, Cl
12.63; found C 76.95, H 4.71, Cl 12.64.
3’’-(Hydroxymethyl)-1,1’:4’,1’’-terphenyl-4-ol (3m):
White
crystals; yield: 1.93 g (87%); mp 230–2328C (EtOAc);
1HNMR (400 MHz, DMSO-d6): d(1H)=9.75 (1H, s. -OH),
7.70–7.78 (5H, m), 7.56–7.66 (3H, m), 7.39–7.51 (2H, m), 7.01
(2H, m), 5.44 (1H, t, OH), 4.71 (2H, d); 13CNMR (100.6
MHz, DMSO-d6): d(13C)=157.5, 143.5, 139.8, 139.4, 138.4,
130.6, (all C), 129.0, 127.9 (2C), 127.2 (2C), 126.6 (2C), 125.8,
125.0, 124.7, 116.1 (2C), (all =CH-), 63.3 (CH2); HRMS
(MALDI): m/z calcd. for C19H16O2 (M+), 276.1145; found:
276.1147; Anal. calcd. for C19H16O2: C 82.58, H 5.84; found C
82.56, H 5.87.
4’’-Hydroxy-1,1’:4’,1’’-terphenyl-4-carboxylic acid (3h): White
crystals; yield: 2.07 g (89%); mp 342–3448C (DMF/water
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4:1); HNMR (400 MHz, DMSO-d6): d(1H)=12.80 (1H, s,
-COOH) 9.68 (1H, s. -OH), 8.08 (2H, m), 7.85 (2H, m), 7.79
(2H, m), 7.72 (2H, m), 7.60 (2H, m), 6.93 (2H, m); 13CNMR
(100.6 MHz, DMSO-d6): d(13C)=167.4 (1H, s, -COOH),
157.6, 144.0, 140.2, 136.9, 130.2, 129.6 (all C), 130.2 (2C),
Adv. Synth. Catal. 2016, 358, 1–13
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ꢂ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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These are not the final page numbers!