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S. Nagarajan et al. / Tetrahedron 68 (2012) 9371e9375
(50 mL) was added dropwise over 4 h and stirred overnight at
55 ꢀC. The suspension was filtered and 500 mL of water was added
to the filtrate, which provided the product. The filtration/dilution
operation was repeated for three more times and the precipitates
were regrouped, dried under vacuum, and recrystallized in ethanol.
9.79 (br s, 1H), 8.10 (m, 1H), 7.95 (m, 1H), 7.85 (s, 1H), 7.63 (m, 2H),
2.31 (s, 3H), 2.19 (s, 3H); 13C (75 MHz, CD2Cl2):
137.0, 135.4, 132.7,
130.9, 128.4, 127.7, 127.4, 127.4, 127.1, 123.0, 21.8; MS (CI, CH4): m/z
calcd for C17H21BO2: 268.2; found 269.2 [MHþ]. Anal. Calcd for
C17H21BO2: C, 76.14; H, 7.89. Found: C, 75.89; H, 7.82.
d
Yield: 17.8 g (85%); 1H NMR (300 MHz, DMSO-d6):
d 9.79 (br s, 1H,
NH), 8.11e8.08 (m, 1H), 7.97e7.93 (m, 1H), 7.85 (s, 1H), 7.64e7.61
(m, 2H); 13C NMR (300 MHz, DMSO-d6): 168.5, 133.8, 132.2, 131.8,
131.6, 130.0, 127.0, 126.8, 126.3, 123.8, 119.6, 22.6, 17.8; MS (CI, CH4):
m/z calcd for C13H12BrNO: 278.1; found: 278.0 [Mþ]. Anal. Calcd for
C13H12BrNO: C, 56.14; H, 4.35; N, 5.04. Found: C, 56.15; H, 4.15; N,
5.06.
3.10. 3-(4-Methylnaphthalen-1-yl)perylene 5 and 3-(3-
methylnaphthalen-1-yl)perylene 13
A solution of 3 (200 mg, 0.6 mol) and 4 (186 mg, 1 mmol)/12
(215 mg, 0.8 mmol) in toluene (25 mL) was stirred at 80 ꢀC for
20 min with argon bubbling. To this solution, Pd(PPh3)2Cl2 (12 mg,
0.18 mmol), triphenylphosphine (38 mg, 0.36 mmol), and 0.5 mL of
a 2 M aqueous potassium carbonate solution (1 mmol) were added .
The mixture was then stirred overnight at 110 ꢀC under argon and
the solvent was evaporated. The residue was stirred in 50 mL of
boiling ethanol and filtered. The precipitate was then dissolved in
100 mL of boiling toluene and the hot solution was filtered on
a small plug of silica gel. The solution was then concentrated and
cooled to ꢂ20 ꢀC to give a yellow solid.
3.7. 4-Bromo-2-methylnaphthalen-1-amine hydrochloride 9
About 15 g (53.93 mmol) of 8 was dissolved in boiling ethanol
(300 mL). After addition of concentrated HCl (80 mL), the mixture
was refluxed for 24 h, cooled to room temperature, and filtered
giving 9 g of white needles. To the filtrate was added again 80 mL of
concentrated HCl; after 24 h reflux, cooling, and filtration gave
a new crop of 5.1 g of product. The acidification sequence was re-
peated and furnished 0.2 g of product. Total yield of 4-bromo-2-
methylnaphthalen-1-amine hydrochloride 9: 14 g (95%). 1H
3.10.1. 3-(4-Methylnaphthalen-1-yl)perylene 5. Yield: 81%; 1H
(300 MHz, DMSO-d6):
7.62e7.54 (m, 3H), 4.07 (br s, 2H), 2.52 (s, 3H).
d
8.24 (d, J¼9.0 Hz, 1H), 8.0 (d, J¼9.3 Hz, 1H),
(300 MHz, CD2Cl2):
d
8.34 (d, J¼7.8 Hz, 1H), 8.26e8.31 (m, 2H), 8.22
(d, J¼8.9 Hz, 1H), 8.13 (d, J¼8.4 Hz, 1H), 7.75 (d, J¼8.3 Hz, 2H),
7.40e7.57 (m, 6H), 7.22e7.37 (m, 4H), 2.81 (s, 3H); 13C (75 MHz,
3.8. 1-Bromo-3-methylnaphthalene 10
CD2Cl2): d 136.5, 136.3, 135.6, 135.2, 134.4, 133.6, 129.4, 126.7, 126.6,
125.5, 125.0, 124.8, 124.7, 121.9, 120.9, 120.8, 120.5, 120.0, 20.4; MS
(CI, NH3): m/z calcd for C31H20: 392.1; found 392 [Mþ]. Anal. Calcd
for C31H20: C, 94.86; H, 5.14. Found: C, 94.41; H, 5.45.
9 was suspended in a mixture of acetic acid (100 mL), water
(50 mL), concentrated HCl (10 mL), and the suspension was cooled
to 2e5 ꢀC by an external ice. Then a cold solution of sodium nitrite
(4.2 g, 60.87 mmol) in water (15 mL) was added dropwise, stirred
for 30 min at 2e5 ꢀC. This cold solution was then poured in cold 50%
aqueous solution of hypophosphorous acid (120 mL) and stirred
overnight at room temperature, and then 1 h at 100 ꢀC. The sus-
pension was then extracted with ether (3ꢁ250 mL); washing of the
organic phase with water (3ꢁ250 mL), drying (MgSO4), and evap-
oration of the solvent left crude brown oil that was purified by
chromatography on silica (eluent: petroleum ether). Yield: 7.50 g,
3.10.2. 3-(3-Methylnaphthalen-1-yl)perylene 13. Yield: 72%; 1H
(300 MHz, CD2Cl2):
7.68e7.79 (m, 5H), 7.60 (dd, J¼7.6 Hz, J¼8.4 Hz, 1H), 7.46 7.53 (m,
3H), 2.12 (s, 3H); 13C (75 MHz, CD2Cl2):
138.3, 138.1, 135.3, 134.8,
d 8.17e8.27 (m, 5H), 7.96e8.12 (m, 3H),
d
134.1, 133.9, 131.2, 131.1, 130.0, 128.7, 128.6, 127.8, 127.5, 126.8, 126.7,
126.5, 126.1, 25.9, 125.1, 120.4, 120.3, 119.9, 21.4; MS (CI, NH3): m/z
calcd for C31H20: 392.1; found 392 [Mþ]. Anal. Calcd for C31H20: C,
94.86; H, 5.14. Found: C, 94.61; H, 5.58.
66%; 1H (300 MHz, CD2Cl2):
d
8.24 (d, J¼7.8 Hz, 1H), 7.78 (d,
J¼8.4 Hz, 1H), 7.69 (s, 1H, b), 7.59e7.52 (m, 3H); 13C (75 MHz,
CD2Cl2):
d
137.1, 135.4, 132.7, 130.9, 128.4, 127.7, 127.4, 127.3, 127.1,
3.11. Methylterrylenes 1 and 2
122.9, 21.8; MS (CI, CH4): m/z calcd for C11H9Br: 221; found 221
[Mþ]. Anal. Calcd for C11H9Br: C, 59.76; H, 4.10. Found: C, 60.31;
H, 4.24.
To a solution of 5 (respectively, 13) (200 mg, 0.509 mmol) in dry
chlorobenzene (25 mL) was added anhydrous aluminum chloride
(600 mg, 4.5 mmol) and the mixture was stirred at 80 ꢀC under
argon for 4 h. After cooling to room temperature, 10% HCl (50 mL)
was added; after 1 h stirring, the mixture was filtered over paper.
The filter paper and the precipitate were then extracted in a Soxhlet
apparatus with toluene for 48 h. The toluene solution was then
cooled to room temperature and centrifuged giving a dark black
colored powder. 1H NMR and 13C NMR could not be measured due
to the poor solubility of the methylterrylene.
3.9. 4,4,5,5-Tetramethyl-2-(3-methylnaphthalen-1-yl)-1,3,2-
dioxaborolane 12
A solution of 10 (880 mg, 3.98 mmol) in dry ether (20 mL) was
cooled to ꢂ78 ꢀC and then n-BuLi (1.6 M in hexane, 3 mL, 4.8 mmol)
was added dropwise. The bath was removed and the mixture was
stirred at room temperature for 2 h. The reaction mixture was then
cooled to ꢂ78 ꢀC and a solution of tri-iso-propyl borate (1.3 mL,
1.059 g, 5.76 mmol) in dry ether (10 mL) was added rapidly. The
mixture was stirred at ꢂ78 ꢀC for half an hour and then at room
temperature overnight. Then, aqueous HCl (2 M, 50 mL) was added
and milky white emulsion gradually became clear. The ethereal
layer was separated and the aqueous layer was extracted with ether
(3ꢁ100 mL). The combined ether solution was dried (MgSO4). After
filtration, the solution of 11 was rotoevaporated and the white
residue was dissolved in DCM (50 mL). Pinacol (4.5 mmol, 531 mg)
and molecular sieves were added and the mixture was stirred for 2
days at room temperature. After filtration and evaporation, the
residue was chromatographed using silica gel with cyclohexane/
dichloromethane (4:1) as eluent. Yield: 85%; 1H (300 MHz, DMSO):
3.11.1. Isomer (1). Yield: 24%; MS (CI, NH3): m/z calcd for C31H18
:
390.5; found 391.5 [MHþ]; HRMS (DCI, CH4): m/z calcd for C31H19
[MHþ]: 391.1487; found: 391.1481; UVevis: lmax (CH2Cl2)/nm 560
(
/dm3 molꢂ1 cmꢂ1 72,000), 520 (44,800), 483 (19,400), 440 sh;14
3
emission lmax (toluene)/nm (lexc: 560 nm): 578, 620. Anal. Calcd
for C31H18: C, 95.35; H, 4.65. Found: C, 94.9; H, 4.8.13
3.11.2. Isomer (2). Yield: 12%; MS (CI, NH3): m/z calcd for C31H18
:
390.5; found 391.2 [MHþ]; HRMS (DCI, CH4): m/z calcd for C31H19
[MHþ]: 391.1487; found: 391.1489; UVevis: lmax (CH2Cl2)/nm
(
/dm3 molꢂ1 cmꢂ1): 482 (59,035); 514 (87,510); 558 (88,150).14
3
Anal. Calcd for C31H18: C, 95.35; H, 4.65. Found: C, 94.8; H, 4.95.13