L.B. Jimenez et al. / Tetrahedron 70 (2014) 3614e3620
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4.3. Photoinduced reactions in DMSO
4.7. 1-([1,10-Biphenyl]-4-yl)naphthalen-2-ol (16)
Into a previously dried 25 mL two-neck round-bottomed flask
Isolated by column chromatography and eluted with petroleum
equipped with nitrogen inlet and magnetic stirrer, 10 mL of dried
ether/diethyl ether (95:5). Mp 202.0e203.1 ꢃC. 1H NMR (400 MHz,
ꢁ
DMSO stored under molecular sieves (4 A) was added. The solvent
(CD3)2CO):
d
7.29e7.42 (m, 4H), 7.47e7.53 (m, 5H), 7.77e7.86 (m,
119.3, 122.3,
was degassed three times under vacuum and stirring, interspersed
with N2. Afterward, potassium tert-butoxide and the anion source
(aromatic amines or alcohols) were added and 5 min later, the
corresponding amount of substrate. After irradiation, the reaction
was quenched by the addition of ammonium nitrate and Milli-Q
water. The workup was done adding to the reaction mixture an
excess (20 ml) of Milli-Q water and then extraction with CH2Cl2
(3ꢂ20 mL). The CH2Cl2 extract was water washed twice to elimi-
nate the residual DMSO. The organic extract thus obtained was
dried with MgSO4. After filtration, the organic solvent was elimi-
nated under reduced pressure. In those reactions where 2-naphthol
was employed as nucleophilic precursor in both solvents, the re-
action crude was washed with an excess of acidic aqueous solution
until an acid pH is obtained. Afterward, the workup followed as it
was described before. When substrates are 4 or 5 the crude is
extracted twice using ethyl acetate.
6H), 8.13 (s, 1H, OH). 13C NMR(100 MHz, (CD3)2CO):
d
123.8, 125.4, 127.2, 127.9, 127.9, 128.4, 129.0, 129.9, 129.9, 130.1,
132.8, 135.0, 136.4, 140.8, 141.8, 152.6. HRMS (ESI): m/z calcd for
C
22H16OꢀHþ: 295.1117, [MꢀH]þ found: 295.1144.
4.8. 1,10-([1,10-Biphenyl]-4,40-di-yl)bis(naphthalen-2-ol) (17)
Isolated by column chromatography and eluted using a gradient
of petroleum ether/diethyl ether from 5% of diethyl ether to 80%.
Mp 191.0e191.8. 1H NMR (400 MHz, (CD3)2CO):
d
7.30e7.39 (m, 6H),
7.54 (d, 6H, J¼8.24 Hz), 7.84e7.87 (m, 4H), 7.94 (d, 4H, J¼8.24 Hz),
8.25 (s, 2H, OH). 13C NMR(100 MHz, (CD3)2CO):
119.2, 122.2, 123.7,
d
125.3, 127.1, 127.8, 128.9, 129.8, 130.0, 132.8, 134.9, 136.4, 140.5,
152.6. For more details in the assignment and 2D-NMR experi-
ments, see Supplementary data. HRMS (ESI): m/z calcd for
C
32H22O2ꢀHþ: 437.1620 [MꢀH]þ, found: 437.1611.
4.4. 1,10-(1,4-Phenylene)dinaphthalen-2-amine (7)
4.9. 10,100-([1,10-Biphenyl]-4,40-di-yl)bis(phenanthren-9-
amine) (18)
It was isolated by column chromatography, employing a linear
gradient of eluent composed by petroleum ether and ethyl acetate,
from 0% to 40% of ethyl acetate. Melting point: 240 ꢃC with de-
Isolated by precipitation during the workup and washed several
times with acetone. Decomposed when heated (ca. 360 ꢃC), mp not
composition. 1H NMR (400 MHz, acetone-d6):
d
4.64 (s, 4H, NH2),
7.18e7.24 (m, 4H), 7.45e7.47 (m, 3H), 7.55e7.56 (ds, 4H), 7.72e7.77
(m, 5H). 13C NMR (acetone-d6)
118.8 (Cq), 119.3 (CH), 122.2 (CH),
determined. 1H NMR (400 MHz, DMSO-d6):
d 5.10 (s, 4H, NH2),
7.20e7.22 (m, 2H), 7.36e7.42 (m, 4H), 7.50 (d, 4H, J¼8.2 Hz),
d
7.68e7.76 (m, 4H), 8.08 (d, 4H, J¼8.2 Hz), 8.31e8.33 (m; 2H),
124.5 (CH), 127.0 (CH), 128.5 (Cq), 128.8 (CH), 128.9 (CH), 129.4 (CH),
129.4 (CH), 132.8 (CH), 135.1 (Cq), 137.6 (Cq), 143.9(Cq). HRMS (ESI):
m/z calcd for C26H20N2þHþ: 361.1699 [MþH]þ, found: 361.1677.
8.73e8.75 (m, 2H), 8.86e8.88 (m, 2H). 13C NMR (DMSO-d6):
d115.0
(q), 122.8 (CH), 123.2 (q), 123.6 (CH), 124.8 (q), 125.0 (CH), 125.1
(CH), 126.9 (CH), 127.3 (CH), 128.2 (CH), 130.7 (q), 132.3 (CH), 133.5
(q), 137.5 (q), 138.8 (q), 139.3 (q). HRMS (ESI): m/z calcd for
4.5. 1,10-(1,4-Phenylene)bis(naphthalen-2-ol) (11)
C
40H28N2þHþ: 537.2253, [MþH]þ¼found: 537.2335.
Isolated by column chromatography and eluted with petroleum
ether/ethyl ether in a polarity gradient starting from 0 to 30 % of
4.10. 1-([1,10-Biphenyl]-4-yl)naphthalen-2-amine (19)
diethyl ether. Mp 239.6e240.3 ꢃC; 1H NMR (400 MHz, CDCl3):
d
5.31
It was isolated by column chromatography, employing a linear
gradient of eluent composed by petroleum ether and ethyl acetate,
from 0% to 15% of ethyl acetate. 1H NMR ((CD3)2CO, 400 MHz):
(s, 2H, OH), 7.31 (d, 1H, J¼8.8), 7.33 (d, 1H, J¼8.8), 7.36e7.48 (m, 4H),
7.53 (d, 1H, J¼8.37), 7.58 (d, 1H, J¼8.37), 7.68 (d, 4H, J¼3.34), 7.88
(br d, 4H, J¼8.52). 13C NMR(100 MHz, CDCl3):
d
117.7, 120.5, 120.6,
d 4.485 (s, 2H, NH2), 7.162e7.184 (m, 1H), 7.224e7.243 (m, 1H),
123.7, 124.6, 124.7, 126.9, 128.3, 129.2, 130.0, 130.0, 132.6, 132.6,
7.330e7.382 (m, 2H), 7.410e7.431 (m, 2H), 7.478e7.516 (m, 2H),
133.3, 133.4, 134.7, 134.7, 150.4. HRMS (ESI): m/z calcd for
7.70e7.78 (m, 6H), 7.842e7.863 (m, 2H). 13C NMR ((CD3)2CO,
C
26H18O2þHþ: 363.1380 [MþH]þ, found: 363.1376.
100 MHz) d 121.3 (CH), 123.8 (q), 125.9 (CH), 126.7 (CH), 127.3 (CH),
127.5 (CH), 127.8 (CH), 128.4 (CH), 128.8 (CH), 131.4 (CH), 133.9 (Cq),
136.7 (Cq), 139.8 (Cq), 140.5 (Cq), 142.6 (Cq). HRMS (ESI): m/z calcd
for C22H17NþHþ: 296.1361, [MþH]þ found: 296.1355.
4.6. 10,100-(1,4-Phenylene)diphenanthren-9-amine (14)
Isolated by column chromatography, employing a linear gradi-
ent of eluent composed by petroleum ether and diethyl ether, from
0% to 50 % of diethyl ether. Mp: 300 ꢃC with decomposition. 1H NMR
4.11. [1,10:40,100-Ternaphthalene]-2,200-diol (20c)
(400 MHz, DMSO-d6 after sonication):
d
5.20 (s, 2H, NH2), 5.41 (s,
Isolated as a white solid from reaction crude by silica gel column
chromatography. It was eluted in ether petroleum/ethyl acetate at
increased polarity from 0% to 60% of ethyl acetate. Mp: 264.3e265.2 ꢃC.
2H, NH2), 7.34e7.46 (m,10H), 7.68e7.73 (m, 4H), 8.34e8.39 (m, 2H),
8.74 (d, J¼8.1, 2H), 8.87 (d, J¼7.9,1H). 1He1H COSY NMR (DMSO-d6):
dH
/dH 7.36/7.34, 7.45/7.35, 7.45/7.44, 7.47/7.35, 7.49/7.35, 8.37/7.72,
1H NMR ((CD3)2CO, 400 MHz)
d 7.273e7.369 (m, 8H), 7.40 (d, 2H,
8.39/7.71, 8.73/7.36, 8.73/7.40, 8.75/7.59, 8.87, 7.72, 8.89/7.72.
1He13C HSQC NMR (DMSO-d6): dH
dC 7.37/122.5, 7.35/124.3, 7.44/
127.2, 7.51/132.6, 7.56/132.6, 7.72/127.0, 8.36/123.5, 8.74/123.0,
8.88/123.5. 1He13C HMBC NMR (DMSO-d6): dH
dC 5.20/115.4, 5.20/
125.1, 5.40/114.9, 5.40/125.1, 7.34/114.9, 7.34/124.6, 7.35/122.4, 7.36/
114.9, 7.36/122.4, 7.36/124.6, 7.38/125.1, 7.39/124.6, 7.47/123.1, 7.47/
133.7, 7.51/114.9, 7.51/132.6, 7.51/137.2, 7.56/115.4, 7.56/137.2, 7.70/
123.5, 7.70/125.1, 7.75/123.7, 7.75/130.7, 8.37/127.1, 8.37/130.7, 8.37/
139.4, 8.74/127.3, 8.74/130.7, 8.74/133.7, 8.88/124.6, 8.88/125.1,
8.88/126.7. HRMS (ESI): m/z calcd for C34H24N2þNaþ: 483.1832,
found: 483.1827.
J¼8.9), 7.425e7.450 (dd, 2H, J1¼3.3, J2¼6.5), 7.679 (s, 2H), 7.699 (s, 2H,
/
OH), 7.93e7.95 (dd, 2H, J1¼2.5, J2¼6.7), 7.986 (d, 2H, J¼8.9). 13C NMR
((CD3)2CO, 100 MHz)
d 119.1 (CH), 120.2 (q), 123.9 (CH), 125.7 (CH),
/
176.0(CH),127.2(CH),127.3(CH),128.9(CH),129.7(q),130.1(CH),130.5
(CH), 134.6 (q), 134.7 (q), 135.5 (q), 153.4 (q, CeOH). HRMS (ESI): m/z
calcd for C30H20O2þNaþ: 435.1356, [MþNa]þ found: 435.1340.
4.12. [1,10:40,100-Ternaphthalene]-2,200-diol (20t)
Isolated as a pale yellow solid by silica gel column chromatog-
raphy from reaction mixture. It was eluted in ether petroleum/ethyl