T. R. Linderoth, K. V. Gothelf et al.
FULL PAPER
yielded the product as a light yellow oil (1.56 g, 81%). 1H NMR
(400 MHz, CDCl3): δ = 8.97 (m, 1 H), 8.34 (m, 1 H), 7.99 (d, J =
7.9 Hz, 1 H), 7.83 (d, J = 7.9 Hz, 1 H), 7.71–7.57 (m, 2 H), 4.33
product as a yellow syrup (381 mg, 82%). 1H NMR (400 MHz,
CDCl3): δ = 9.06–9.03 (m, 1 H), 8.78–8.56 (m, 5 H), 8.21 (d, J =
7.8 Hz, 1 H), 7.92 (t, J = 7.6 Hz, 4 H), 7.78–7.58 (m, 7 H), 4.37 (d,
(d, J = 5.7 Hz, 2 H), 1.84 (sept, J = 6.0 Hz, 1 H), 1.52–1.18 (m, 40 J = 5.7 Hz, 2 H), 3.93 (q, J = 7.0 Hz, 4 H), 1.88 (sept, J = 6.0 Hz,
H), 0.89 (t, J = 6.7 Hz, 6 H) ppm. 13C NMR (100 MHz, CDCl3):
δ = 167.1, 132.5, 132.2, 129.9, 128.9, 128.6, 128.4, 127.7, 127.6,
1 H), 1.51–1.23 (m, 46 H), 0.89 (t, J = 6.9 Hz, 6 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 167.3, 147.3, 134.2, 133.6, 133.2, 133.1,
127.5, 126.3, 68.1, 37.5, 31.9, 31.5, 30.0, 29.7, 29.6, 29.4, 26.8, 22.7, 131.5, 131.4, 130.4, 129.6, 129.4, 129.2, 129.2, 128.1, 127.9, 127.5,
14.1 ppm. HRMS: calcd. for C35H55BrO2Na [M + Na]+ 609.3283; 127.4, 127.1, 127.0, 126.9, 126.8, 126.6, 126.4, 126.0, 126.0, 125.7,
found 609.3277.
124.3, 122.9, 120.7, 116.9, 111.1, 95.9, 95.2, 93.6, 92.2, 68.1, 49.4,
42.1, 37.5, 32.0, 31.5, 30.0, 29.7, 29.7, 29.6, 29.4, 26.8, 22.7, 14.7,
14.1, 11.5 ppm. HRMS: calcd. for C63H77N3O2Na [M + Na]+
930.5913; found 930.5916.
Tetradecyl Ester 15: Compounds 14 (1.00 g, 1.70 mmol) and 6
(428 mg, 1.70 mmol), bis(triphenylphosphane)palladium(II) di-
chloride (119 mg, 0.17 mmol), and copper(I) iodide (32 mg,
0.17 mmol) were placed in a flame-dried Schlenk flask. After three
successive vacuum/argon cycles, toluene (35 mL), triethylamine
(5 mL), and tri-tert-butylphosphane (0.34 mL, 1 m, 0.34 mmol)
were introduced, by syringe in each case. The reaction mixture was
stirred at 80 °C overnight. It was then poured into water (50 mL),
and the aqueous layer was extracted with diethyl ether (3ϫ 25 mL).
The combined organic phases were washed with brine and dried
with MgSO4, and the solvent was evaporated in vacuo. Purification
by flash chromatography (CH2Cl2/pentane 1:3, v/v) yielded the
product as a yellow syrup (954 mg, 74%). 1H NMR (400 MHz,
CDCl3): δ = 9.08–8.99 (m, 1 H), 8.75–8.69 (m, 2 H), 8.55 (d, J =
7.8 Hz, 1 H), 8.20 (d, J = 7.6 Hz, 1 H), 7.90 (d, J = 7.9 Hz, 2 H),
2-Decyltetradecyl Ester 18: Compound 17 (164 mg, 0.18 mmol) and
methyl iodide (7 mL) were placed in a sealed tube. The solution
was degassed, and the tube was sealed. After heating at 110 °C
overnight, the starting triazene had been completely consumed.
During this time, diethyldimethylammonium iodide precipitated
from the solution. The reaction mixture was poured into pentane
(20 mL), filtered, and concentrated onto silica. Purification by flash
chromatography (CH2Cl2/pentane 1:5, v/v) yielded the product as
1
a red powder (150 mg, 89%), m.p. 90–92 °C. H NMR (400 MHz,
CDCl3): δ = 9.02–8.98 (m, 1 H), 9.67–8.63 (m, 1 H), 9.61–8.56 (m,
2 H), 9.51 (d, J = 9.2 Hz, 1 H), 8.22–8.10 (m, 3 H), 7.93–8.87 (m,
3 H), 7.75–8.63 (m, 6 H), 7.56 (d, J = 7.6 Hz, 1 H), 4.35 (d, J =
7.75–7.54 (m, 5 H), 4.36 (d, J = 5.7 Hz, 2 H), 3.93 (q, J = 7.0 Hz, 5.6 Hz, 2 H), 1.85 (sept, J = 6.0 Hz, 1 H), 1.52–1.17 (m, 40 H),
4 H), 1.87 (sept, J = 6.0 Hz, 1 H), 1.51–1.23 (m, 46 H), 0.89 (t, J
= 6.9 Hz, 6 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 167.4,
147.4, 134.2, 133.6, 131.6, 131.4, 129.6, 129.4, 129.3, 128.8, 128.0,
127.2, 127.2, 127.0, 126.7, 126.3, 125.9, 125.7, 124.3, 116.6, 111.0,
96.4, 91.9, 68.0, 49.4, 42.1, 37.5, 31.9, 31.5, 30.0, 29.7, 29.7, 29.6,
0.87 (t, J = 7.0 Hz, 6 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
167.3, 137.0, 134.2, 133.6, 133.5, 133.1, 133.1, 132.8, 132.1, 132.0,
131.9, 131.3, 131.1, 130.2, 130.0, 129.3, 129.2, 128.5, 128.4, 128.3,
128.0, 127.8, 127.6, 127.1, 126.9, 126.7, 126.4, 125.8, 121.9, 121.5,
101.0, 94.9, 93.9, 93.8, 93.6, 68.1, 37.5, 31.9, 31.5, 30.0, 29.7, 29.4,
29.4, 26.8, 22.7, 14.7, 14.1, 11.5 ppm. HRMS: calcd. for 26.8, 22.7, 14.1 ppm. HRMS: calcd. for C59H67IO2Na [M + Na]+
C51H71N3O2Na [M + Na]+ 780.5444; found 780.5440.
957.4083; found 957.4083.
2-Decyltetradecyl Ester 16: Compound 15 (572 mg, 0.76 mmol) and
methyl iodide (7 mL) were placed in a sealed tube. The solution
was degassed, and the tube was sealed. After heating at 110 °C
overnight, the starting triazene had been completely consumed.
During this time, diethyldimethylammonium iodide precipitated
from the solution. The reaction mixture was poured into pentane
(20 mL), filtered, and concentrated onto silica. Purification by flash
chromatography (CH2Cl2/pentane 1:9, v/v) yielded the product as
a yellow oil (498 mg, 84%). 1H NMR (400 MHz, CDCl3): δ = 9.01–
8.98 (m, 1 H), 8.64–8.59 (m, 1 H), 8.53–8.47 (m, 1 H), 8.20–8.12
(m, 3 H), 7.89 (d, J = 7.6 Hz, 1 H), 7.74–7.62 (m, 4 H), 7.58 (d, J
= 7.6 Hz, 1 H), 4.35 (d, J = 5.7 Hz, 2 H), 1.85 (sept, J = 6.0 Hz, 1
1-Bromo-4-(dodec-1-yn-1-yl)naphthalene (20): 1,4-Dibromonaphth-
alene (2.00 g, 6.99 mmol), dodec-1-yne (1.28 g, 7.69 mmol), bis(tri-
phenylphosphane)palladium(II) dichloride (245 mg, 0.35 mmol),
and copper(I) iodide (66 mg, 0.35 mmol) were placed in a flame-
dried Schlenk flask. After three successive vacuum/argon cycles,
toluene (40 mL) and triethylamine (10 mL) were introduced, both
by syringe. The reaction mixture was stirred at 80 °C overnight. It
was then poured into water (50 mL), and the aqueous layer was
extracted with diethyl ether (3ϫ 25 mL). The combined organic
phases were washed with brine and dried with MgSO4, after which
the crude product was concentrated onto silica. Purification by
flash chromatography (pentane) yielded the product as a pale yel-
1
H), 1.52–1.17 (m, 40 H), 0.87 (t, J = 6.8 Hz, 6 H) ppm. 13C NMR low oil (1.25 g, 48%). H NMR (400 MHz, CDCl3): δ = 8.37 (m,
(100 MHz, CDCl3): δ = 167.3, 137.0, 134.2, 133.6, 133.5, 132.8, 1 H), 8.24 (m, 1 H), 7.71 (d, J = 7.7 Hz, 1 H), 7.65–8.58 (m, 2 H),
131.3, 131.2, 129.2, 129.2, 128.4, 128.1, 128.0, 127.9, 127.1, 126.9,
126.6, 126.4, 125.7, 121.7, 101.3, 94.2, 93.3, 68.1, 37.5, 31.9, 31.5,
30.0, 29.7, 29.4, 26.8, 22.7, 14.1 ppm. HRMS: calcd. for C47H61INa
[M + Na]+ 807.3614; found 807.3615.
7.45 (d, J = 7.7 Hz, 1 H), 2.56 (t, J = 7.1 Hz, 2 H), 1.71 (quint, J
= 7.1 Hz, 2 H), 1.53 (quint, J = 7.1 Hz, 2 H), 1.40–1.12 (m, 12 H),
0.89 (t, J = 6.9 Hz, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
134.6, 131.7, 130.0, 129.4, 127.6, 127.4, 127.2, 126.9, 122.5, 122.0,
96.8, 78.0, 31.9, 29.7, 29.6, 29.4, 29.2, 29.1, 28.8, 22.7, 19.8,
14.1 ppm. HRMS: calcd. for C22H27BrNa [M + Na]+ 393.1194;
found 393.1196.
2-Decyltetradecyl Ester 17: Compounds 16 (396 mg, 0.50 mmol)
and 6 (190 mg, 0.76 mmol), bis(triphenylphosphane)palladium(II)
dichloride (35 mg, 0.05 mmol), and copper(I) iodide (9 mg,
0.05 mmol) were placed in a flame-dried Schlenk flask. After three
successive vacuum/argon cycles, toluene (20 mL), triethylamine
(4 mL), and tri-tert-butylphosphane (0.10 mL, 1 m, 0.10 mmol)
were introduced, by syringe in each case. The reaction mixture was
stirred at 80 °C overnight. It was then poured into water (50 mL),
and the aqueous layer was extracted with diethyl ether (3ϫ 25 mL).
The combined organic phases were washed with brine and dried
with MgSO4, and the solvent was evaporated in vacuo. Purification
by flash chromatography (CH2Cl2/pentane 1:2, v/v) yielded the
Alkyne 21: Compounds 20 (300 mg, 0.81 mmol) and 6 (227 mg,
0.90 mmol),
bis(triphenylphosphane)palladium(II)
dichloride
(57 mg, 0.08 mmol), and copper(I) iodide (15 mg, 0.08 mmol) were
placed in a flame-dried Schlenk flask. After three successive vac-
uum/argon cycles, toluene (20 mL), triethylamine (10 mL), and tri-
tert-butylphosphane (0.16 mL, 1 m, 0.16 mmol) were introduced,
by syringe in each case. The reaction mixture was stirred at 80 °C
overnight. It was then poured into water (40 mL), and the aqueous
layer was extracted with diethyl ether (3ϫ 25 mL). The combined
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Eur. J. Org. Chem. 2013, 2813–2822