V. I. Maslennikova et al. / Tetrahedron Letters 53 (2012) 886–889
889
chromatography (silica gel, benzene/hexane, 1/1. Caution! Benzene is
Supplementary data
carcinogenic. The syntheses should therefore be carried out in a well-ventilated
1
hood.). Dark-grey powder. Yield 0.085 (70%). Mp 164–165 °C.
H NMR
3 2
(400 MHz, CDCl ) d: 4.76 (s, 2H, CH ), 5.73 (br s, 2H, NH), 6.90 (d, 4H,
J = 7.8 Hz, H-oPh), 7.03 (t, 2H, J = 7.4 Hz, H-pPh), 7.06 (d, 2H, J = 8.7 Hz, H-3),
7.08 (dd, 2H, J = 8.7 Hz, J = 1.8 Hz, H-6), 7.15 (d, 2H, J = 1.9 Hz, H-8), 7.25 (dd,
4
H, J = 8.3, J = 7.8 Hz, H-mPh), 7.62 (d, 2H, J = 8.8 Hz, H-5), 7.64 (d, 2H, J = 8.7 Hz,
References and notes
13
H-4). C NMR (100.5 MHz, CDCl
3 2
), d: 24.76 (CH ), 106.44 (C-8), 116.43 (C-3),
1
18.51 (q, J = 322.5 Hz, CF ), 119.82 (C-oPh,C-6), 122.71 (C-pPh), 125.40 (C-9),
3
1
.
Maslennikova, V. I.; Sotova, T. Y.; Vasyanina, L. K.; Lyssenko, K. A.; Antipin, M.
Y.; Adamson, S. O.; Dementyev, A. I.; Habicher, W. D.; Nifantyev, E. E.
Tetrahedron 2007, 63, 4162–4171.
127.83 (C-1), 129.18 (C-4), 129.64 (C-mPh), 130.22 (C-4), 134.24 (C-10), 141.27
(C-iPh), 143.12 (C-7), 146.29 (C-2). IR (Nujol): 3415, 3396, 2937, 2850, 1462,
1435, 1374, 1229, 1216, 1135, 922, 888, 724, 640, 599, 506 cm . Anal. Calcd
ꢀ
1
2
3
4
.
.
.
Canete, A.; Melendrez, M. X.; Saitz, C.; Zanocco, A. L. Synth. Commun. 2001, 31,
for C35
3.23.
H
24
F
6 2
N O
6
2
S ⁄C
6 6
H : C, 59.70; H, 3.67; N, 3.40. Found: C, 59.31; H, 3.69; N,
2
143–2148.
(a) Yang, B. H.; Buchwald, S. L. J. Organomet. Chem. 1999, 576, 125–146; (b)
Meadows, R. E.; Woodward, S. Tetrahedron 2008, 64, 1218–1224.
2-Phenylaminonaphthalene (3): A mixture of dinaphthylmethane 1 (0.60 g,
9. Lloyd-Jones, G. C.; Moseley, J. D.; Rennya, J. S. Synthesis 2008, 661–689.
10. Oligothiocarbamates
9
and 10: N,N-Dimethylthiocarbamoyl chloride
(0.45 mmol) were added to solution of
(0.3 mmol) in acetone (6 mL). The reaction
(0.45 mmol) and Cs
dinaphthylmethane
2
CO
or
3
a
1
1
.8 mmol), aniline (1.53 g, 16.5 mmol), and aniline hydrochloride (1.32 g,
0 mmol) was heated for 2 h at 145 °C in a CEM Discover system with focused
1
2
mixture was refluxed for 48 h with stirring. Acetone was distilled off, and
1 M HCl (10 mL) was added to the residue. The resulting precipitate was
microwave radiation (Focused Microwave™ Synthesis System Discover) (50–
1
5
50 W, 2455 MHz). The reaction mixture was neutralized with NaOH (1.23 g in
0 mL of O). Excess aniline was removed by steam-distillation, the
O. The product was
filtered and washed with H
2
O (50 mL). The product was dried for 3 h at 65–
0
H
2
70 °C/1 mm Hg. 2,2 -Di(thiocarbamoyl)dinaphthylmethane (9) (Table 2). Light-
yellow powder. 1H NMR (400 MHz, CDCl
NCH ), 4.81 (s, 2H, CH ), 7.04 (d, 2H, J = 8.7 Hz, H-3), 7.48 (dd, 2H, J = 6.8 Hz,
precipitate that formed was filtered and washed with H
2
3 3
), d: 2.07 (s, 6H, NCH ), 3.08 (s, 6H,
isolated by column chromatography (silica gel, benzene). Pale-orange powder.
Yield 0.15 g (43%). Mp 107–109 °C. Lit. data: mp 107–109 °C [Louie, J.; Driver,
M. S.; Hamann, B. C.; Hartwig, J. F. J. Org. Chem. 1997, 62, 1268–1273.].
3
2
J = 8.2 Hz, H-7), 7.51 (dd, 2H, J = 6.8 Hz, J = 8.2 Hz, H-6), 7.74 (d, 2H, J = 9.2 Hz,
H-4), 7.85 (d, 2H, J = 7.8 Hz, H-8), 8.33 (d, 2H, J = 8.3 Hz, H-5). 13C NMR
0
0
5
.
Reaction of 2,2 ,7,7 -tetrahydroxydinaphthylmethane (2) with aniline: A mixture
of dinaphthylmethane 2 (0.60 g, 1.8 mmol), aniline (1.53 g, 16.5 mmol), and
aniline hydrochloride (1.32 g, 10 mmol) was heated for 2 h at 145 °C under
microwave irradiation. The reaction mixture was neutralized with NaOH
3 2 3 3
(100.5 MHz, CDCl ), d: 24.03 (CH ), 37.28 (N–CH ), 42.72 (N–CH ), 123.09 (C-
3), 124.60 (C-5), 125.32(C-7), 126.14 (C-6), 127.52 (C-4), 128.83 (C-8, C-1),
132.36 (C-10), 133.16 (C-9), 149.81 (C-2), 186.15 (C@S). IR (Nujol): 2953, 2924,
ꢀ
1
2854, 1538, 1463, 1379, 1281, 1217, 1121, 820, 746 cm . Anal. Calcd for
(
1.23 g in 50 mL of H
the precipitated products were filtered, washed with H
column chromatography (silica gel, benzene. Caution! Benzene is carcinogenic.
2
O). Excess aniline was removed by steam-distillation, and
C
27
H
26
N
2 2 2
O S : C, 68.32; H, 5.52; N, 5.90. Found: C, 68.61; H, 5.48; N, 5.68.
0
0
2
O, and separated by
2,2 ,7,7 -Tetra(thiocarbamoyl)dinaphthylmethane (10) (Table 2). Light-yellow
powder. 1H NMR (400 MHz, CDCl
3.37 (s, 6H, NCH ), 3.45 (s, 6H, NCH
), d: 2.31 (s, 6H, NCH
), 4.62 (s, 2H, CH ), 7.05 (d, 2H, J = 8.7 Hz,
3
3 3
), 3.12 (s, 6H, NCH ),
0
0
The syntheses should therefore be carried out in a well-ventilated hood.). 2,2 ,7,7 -
Tetra(phenylamino)-1,1 -binaphthyl (4). Green powder. Yield: 0.64 g (58%). Mp
1
3
3
2
0
H-3), 7.31 (dd, 2H, J = 9.2 Hz, J = 3.2 Hz, H-6), 7.73 (d, 2H, J = 9.2 Hz, H-4), 7.85
1
13
38–140 °C. H NMR (300 MHz, CDCl
3
), d: 5.81 (br s, 4H, NH), 6.99 (tt, 4H,
(d, 2H, J = 8.7 Hz, H-5), 7.90 (d, 2H, J = 2.2 Hz, H-8). C NMR (100.5 MHz,
J = 7.4 Hz, J = 2.4 Hz, H-pPh), 7.04 (dd, 4H, J = 8.8 Hz, J = 2.2 Hz, H-3,6), 7.16 (d,
H, J = 8.7 Hz, H-oPh), 7.25 (d, 2H, J = 2.2 Hz, H-8), 7.31 (dd, 8H, J = 8.7 Hz,
CDCl
3 2 3 3 3
), d: 24.96 (CH ), 37.87 (N–CH ), 39.05 (N–CH ), 42.94 (N–CH ), 43.38 (N–
8
CH ), 116.47 (C-8), 122.23 (C-6), 123.34 (C-3), 127.21 (C-4), 127.69 (C-1),
3
1
3
J = 7.4 Hz, H-mPh), 7.64 (d, 4H, J = 8.8 Hz, H-4,5). C NMR (100.5 MHz, CDCl
3
),
129.44 (C-5), 130.17 (C-10), 133.88 (C-9), 150.40 (C-7), 152.48 (C-2), 186.10
d: 110.24 (C-8), 117.55 (C-3, C-6), 118.51 (C-oPh), 121.45 (C-pPh), 124.91 (C-9),
(C@S), 187.60 (C@S). IR (Nujol): 2924, 2853, 1534, 1510, 1457, 1393, 1284,
ꢀ
1
1
1
8
28.61 (C-1), 129.05 (C-4, C-5), 129.53 (C-mPh), 135.99 (C-10), 141.56 (C-iPh),
1206, 1168, 1128, 1058, 837, 722 cm . Anal. Calcd for C33
H, 5.33; N, 8.23. Found: C, 58.02; H, 5.04; N, 8.45.
36 4 4 4
H N O S : C, 58.21;
42.97 (C-2, C-7). IR (Neat): 3412, 3395, 1628, 1597, 1501, 1304, 1165, 871,
ꢀ
1
40, 820, 731, 687 cm . Anal. Calcd for C44
H
N
34 4
: C, 85.41; H, 5.54; N, 9.05.
11. (a) Fabbri, D.; Delogu, G.; De Lucchi, O. J. Org. Chem. 1993, 58, 1748–1750; (b)
Cossu, S.; De Lucchi, O.; Fabbri, D.; Valle, G.; Painter, G. F.; Smith, R. A. J.
Tetrahedron 1997, 53, 6073–6084; (c) Cossu, S.; Delogu, G.; De Lucchi, O.;
Fabbri, D.; Fois, M. P. Synth. Commun. 1989, 20, 3431–3435.
+
+
Found: C, 85.45; H, 5.73; N, 8.82. MALDI, m/z: 618 [M ], 619 [M+H ]. 2,7-
Di(phenylamino)naphthalene (5). Violet powder. Yield: 0.03 g (5%). Mp 158–
1
1
59 °C. H NMR (400 MHz, acetone-d
6
), d: 6.88 (tt, 2H, J = 7.4 Hz, J = 2.4 Hz, H-
0
0
pPh), 7.09 (dd, 2H, J = 8.8 Hz, J = 2.2 Hz, H-3,6), 7.22–7.30 (m, 8H, H-o,mPh),
.35 (d, 2H, J = 2.2 Hz, H-1,8), 7.56 (br s, 2H, NH), 7.64 (d, 2H, J = 8.8 Hz, H-4,5).
12. 2,2 -Di(carbamoylthio)dinaphthylmethane (11) and 2,2 -(thio)dinaphthylmethane
(12). Method 1. Compound 9 (0.078 g, 0.16 mmol) was heated for 20 min at
268–270 °C. Method 2. Compound 9 (0.11 g, 0.23 mmol) was heated for 20 min
at 270 °C in a CEM Discover microwave reactor (50–150 W, 2455 MHz). In both
7
1
3
C NMR (100.5 MHz, CDCl
C-3 or C-6), 117.28 (C-3 or C-6), 117.67 (C-oPh), 117.95 (C-oPh), 120.36 (C-
pPh), 120.57 (C-pPh), 124.5 (C-9), 128.69 (C-4 or C-5), 128.79 (C-4 or C-5),
3
), d: 108.94 (C-1 or C-8), 109.19 (C-1 or C-8), 117.00
(
2 2
cases, the products were dissolved in CH Cl (2 mL) and separated by column
1
7
1
9
C
29.12 (C-mPh), 129.39 (C-mPh), 136.36 (C-10), 142.09 (C-iPh), 143.65 (C-2, C-
chromatography (silica gel, benzene:1,4-dioxane = 10:1. Caution! Benzene is
carcinogenic. The syntheses should therefore be carried out in a well-ventilated
hood.).
). IR (Nujol): 3412, 3396, 2956, 2854, 1594, 1503, 1458, 1374, 1302, 1208,
ꢀ
1
158, 874, 834, 732, 686 cm . Anal. Calcd for C22
H N : C, 85.13; H, 5.85; N,
18 2
+ +
0
.03. Found: C, 85.32; H, 5.79; N, 8.96. MALDI MS, m/z: 309 [MꢀH ], 310 [M ].
2,2 -Di(carbamoylthio)dinaphthylmethane (11) (Table 2). Light brown powder.
1
H
N
18 2
.
H NMR (400 MHz, CDCl
), 7.27 (dd, 2H, J = 6.9 Hz, J = 8.3 Hz, H-6), 7.38 (dd, 2H, J = 6.9 Hz, J = 8.7 Hz,
H-7), 7.56 (d, 2H, J = 8.2 Hz, H-3), 7.71 (d, 2H, J = 8.3 Hz, H-4), 7.76 (d, 2H,
J = 8.3 Hz, H-8), 8.03 (d, 2H, J = 8.7 Hz, H-5). 13C NMR (100.5 MHz, CDCl
), d:
33.98 (CH ), 36.86 (N–CH ), 125.80 (C-5), 126.03 (C-7), 126.41 (C-6), 126.54 (C-
3 3 3
), d: 2.83 (s, 6H, NCH ), 2.93 (s, 6H, NCH ), 5.46 (s, 2H,
22
0
6
.
2,2 -Di(trifluoromethanesulfonyl)dinaphthylmethane (6) (Table 1). Brown
CH
2
1
powder. Yield 0.16 g (78%). Mp 114–115 °C. H NMR (400 MHz, CDCl
.04 (s, 2H, CH ), 7.37 (dd, 2H, J = 8.2 Hz, J = 7.3 Hz, H-6), 7.45 (dd, 2H,
J = 8.7 Hz, J = 6.0 Hz, H-7), 7.47 (d, 2H, J = 9.2 Hz, H-3), 7.83 (d, 4H, J = 9.1 Hz, H-
3
), d:
5
2
3
2
3
1
3
4
1
1
1
1
,5), 7.84 (d, 2H, J = 9.1 Hz, H-8). C NMR (100.5 MHz, CDCl
18.71 (q, CF , J = 319.2 Hz), 119.54 (C-3), 124.36 (C-4 or C-5), 126.86 (C-7),
3
), d: 24.66 (CH
2
),
1), 127.17 (C-4), 128.51 (C-8), 133.41 (C-10), 134.25 (C-3), 134.44 (C-9), 143.78
(C-2), 166.23 (C@O). IR (Nujol): 2925, 2854, 1677, 1659, 1462, 1361, 1259,
3
ꢀ
1
27.63 (C-1), 127.71 (C-6), 129.06 (C-8), 130.04 (C-4 or C-5), 132.60 (C-10),
32.87 (C-9), 145.63 (C-2). IR (Nujol): 2925, 2850, 1462, 1429, 1377, 1248,
209, 1137, 1034, 976, 881, 833, 810, 754, 717, 653, 610, 576, 493 cm . Anal.
: C, 48.94; H, 2.50. Found: C, 48.62; H, 2.46.
,2 ,7,7 -Tetra(trifluoromethanesulfonyl)dinaphthylmethane (7) (Table 1). Light-
1095, 907, 820, 805, 742, 689 cm . Anal. Calcd for C27
H
26
N
2
O
2 2
S
: C, 68.32; H,
0
5.52; N, 5.90. Found: C, 68.83; H, 5.89; N, 5.29. 2,2 -(Thio)dinaphthylmethane
ꢀ
1
(12) (Table 2). Cherry-colored powder. 1H NMR (400 MHz, CDCl
2H, CH ), 7.49 (dd, 2H, J = 7.3 Hz, J = 7.8 Hz, H-7), 7.52 (d, 2H, J = 8.7 Hz, H-3),
7.64 (dd, 2H, J = 6.9 Hz, J = 8.3 Hz, H-6), 7.70 (d, 2H, J = 8.3 Hz, H-4), 7.85 (d, 2H,
3
), d: 4.73 (s,
Calcd for C23
2
H
14
F
6
O
S
6 2
2
0
0
1
13
yellow powder. Yield 0.20 g (67%). Mp 113–114 °C. H NMR (400 MHz, CDCl
d: 5.01 (s, 2H, CH ), 7.35 (dd, 2H, J = 9.20 Hz, J = 2.30 Hz, H-6), 7.58 (d, 2H,
J = 9.20 Hz, H-3), 7.73 (d, 2H, J = 1.80 Hz, H-8), 7.93 (d, 4H, J = 9.10 Hz, H-4,5).
3
),
J = 8.2 Hz, H-8), 8.39 (d, 2H, J = 8.7 Hz, H-5). C NMR (100.5 MHz, CDCl
3
), d:
28.16 (CH ), 122.40 (C-5), 124.73 (C-3), 125.30 (C-7), 126.87 (C-4), 126.94 (C-
2
2
6), 128.92 (C-1), 129.00 (C-8), 131.12 (C-2), 131.65 (C-10), 132.68 (C-9). IR
1
3
ꢀ1
C NMR (100.5 MHz, CDCl
3
), d: 24.48 (CH
, J = 320.52 Hz), 120.98 (C-3), 121.34 (C-6), 127.42
C-1), 130.52 (C-4), 131.93 (C-5), 132.04 (C-10), 132.86 (C-9), 146.39 (C-7),
2
), 116.32 (C-8), 118.69 (q, CF
3
,
(Nujol): 2924, 2854, 1462, 1377, 803, 743 cm . Anal. Calcd for C21
84.53; H, 4.73. Found: C, 84.60; H, 4.89.
H14S: C,
J = 320.52 Hz), 118.72 (q, CF
(
3
0
0
13. 2,2 -Thio-7,7 -di(carbamoylthio)dinaphthylmethane (13) (Table 2). Compound 10
(0.104 g, 0.15 mmol) was heated for 20 min at 250 °C. The product was isolated
by column chromatography (silica gel, EtOAc/hexane = 10:1). Cherry-colored
1
8
1
48.34 (C-2). IR (Nujol): 2937, 2850, 1460, 1432, 1377, 1229, 1213, 1136, 920,
85, 726, 637, 607, 598, 506 cm . Anal. Calcd for C25
.41. Found: C, 34.77; H, 1.08.
ꢀ
1
12 12 12 4
H F O S : C, 34.89; H,
powder. 1H NMR (400 MHz, CDCl
3.07 (s, 3H, NCH ), 3.09 (s, 3H, NCH
), d: 3.01 (s, 3H, NCH
), 5.19 (s, 2H, CH ), 7.45 (d, 2H, J = 8.2 Hz,
3
3 3
), 3.02 (s, 3H, NCH ),
7
8
.
.
Stang, P. J.; Hanack, M.; Subramanian, L. R. Synthesis 1992, 85–126.
3
3
2
0
0
2,2 -Di(trifluoromethanesulfonyl)-7,7 -(diphenylamino)-dinaphthylmethane
Table 1). A mixture of BINAP (0.012 g, 0.019 mmol) and Pd(OAc) (0.003 g,
.013 mmol) in toluene (10 mL) was heated for 5 min at 85 °C with stirring
(8)
H-3), 7.59 (dd, 2H, J = 8.2 Hz, J = 1.9 Hz, H-6), 7.70 (d, 2H, J = 8.7 Hz, H-4), 7.84
(d, 2H, J = 8.2 Hz, H-5), 8.43 (d, 2H, J = 1.9 Hz, H-8). 13C NMR (100.5 MHz,
(
0
2
3 2 3
CDCl ), d: 29.78 (CH ), 37.01 (N–CH ), 126.79 (C-4), 127.11 (C-1), 127.31 (C-2),
129.06 (C-5), 131.88 (C-8), 132.85 (C-6), 133.92 (C-10), 134.02 (C-9), 135.85 (C-
under argon, then tetratriflate
7
(0.14 g, 0.16 mmol), aniline (0.18 g,
1
.95 mmol), and Cs
2
CO
3
(0.64 g, 1.95 mmol) were added. The reaction
3), 143.93 (C-7), 166.00 (C@O), 166.76 (C@O). IR (Nujol): 2923, 2853, 1665,
ꢀ
1
mixture was kept for 5 h at 110 °C. The precipitate that formed was filtered
and the filtrate concentrated. The product was isolated by column
1460, 1376, 1364, 1257, 1092, 906, 841, 688 cm
. Anal. Calcd for
27 24 2 2 3
C H N O S : C, 64.26; H, 4.79; N, 5.55. Found: C, 64.46; H, 4.87; N, 5.70.