ARTICLE
1-(Prop-2-ynyloxy)octane
(m, AC:CACH2ACH2A, 2H), 1.38 (m, CH3ACH2A, 2H), 1.26
(m, ACH2ACH2ACH2A, 16H), 0.88 (t, CH3ACH2A, 3H).
Colorless oil, 61%. 1H NMR (CDCl3, ppm): 4.10 (s,
AC:CACH2AOA, 2H), 3.49 (t, ACH2ACH2AOA, 2H), 2.38
(s, HAC:CACH2A, 1H), 1.57 (t, ACH2ACH2AOA, 2H), 1.33
(m, CH3ACH2A, 2H), 1.26 (m, ACH2ACH2ACH2A, 8H), 0.86
(t, CH3ACH2A, 3H).
Dec-1-yne
Colorless oil, 63%. 1H NMR (CDCl3, ppm): 2.18 (m,
AC:CACH2ACH2A, 2H), 1.93 (t, HAC:CACH2A, 1H), 1.52
(m, AC:CACH2ACH2A, 2H), 1.38 (m, CH3ACH2A, 2H), 1.28
(m, ACH2ACH2ACH2A, 8H), 0.88 (t, CH3ACH2A, 3H).
General Procedure for Reaction of
Trimethylsilylacetylene with Alkylbromide
General Procedure for Synthesis of Enediyne
2-Benzyl-5,6-bis(3-(hexadecyloxy)prop-1-ynyl)
Trimethyl(octadec-1-ynyl)silane40
To a stirred solution of (trimethylsilyl)acetylene (5 mL, 35.2
mmol) in dry THF (35 mL), n-BuLi (2.5M, 29.3 mmol) in dry
hexane (11.7 mL) was added dropwise while keeping the
temperature approximately at ꢀ78 ꢁC. After 45 min, HMPA
(11.7 mL) and hexadecyl bromide (3.58 g, 11.7 mmol) were
added dropwise to the reaction mixture while maintaining
the temperature approximately at ꢀ78 ꢁC. After 24 h at
room temperature, the reaction mixture was worked up by
pouring into a large volume of water and extracting with
diethyl ether. The organic layer was washed with brine and
dried over anhydrous MgSO4. The mixture was filtered,
evaporated, and purified by silica gel column chromatogra-
phy. Elution with petroleum ether afforded the title com-
pound (3.20 g, 84%) as a colorless oil. 1H NMR (CDCl3,
ppm): 2.21 (t, AC:CACH2ACH2A, 2H), 1.52 (m,
AC:CACH2ACH2A, 2H), 1.36 (m, CH3ACH2A, 2H), 1.25 (m,
ACH2ACH2ACH2A, 24H), 0.88 (t, CH3ACH2A, 3H), 0.14 (s,
SiACH3, 9H).
isoindoline-1,3-dione
2-Benzyl-5,6-dibromoisoindoline-1,3-dione (0.55 g, 1.39
mmol), CuI (7.9 mg, 0.0417 mmol), 1-(prop-2-ynyloxy)hexa-
decane (1.01 g, 3.61 mmol), and Pd(PPh3)2Cl2 (29.3 mg,
0.0417 mmol) were mixed in a 25 mL Schlenk flask, then
added 2 mL degassed TEA, 3 mL degassed DMF under a
nitrogen atmosphere. After stirred for 16 h at 80 ꢁC, the
resulting solution was partitioned with saturated aqueous
NaCl, 1 M HCl, and dichloromethane, the organic layer was
dried over anhydrous MgSO4. After removal of the solvent
under vacuum, the residual was purified by silica chromatog-
raphy with PE/EtOAc (40/1) as eluent to yield yellow solid
product, 75%. 1H NMR (CDCl3, ppm): 7.87 (s, PhAH, 2H),
7.42–7.28 (m, PhAH, 5H), 4.83 (s, PhACH2A, 2H), 4.42 (s,
C:CACH2AOACH2ACH2A, 4H), 3.59 (t, C:CACH2A
OACH2ACH2A, 4H), 1.62 (t, C:CACH2AOACH2ACH2A, 4H),
1.35 (m, CH3ACH2A, 4H), 1.25 (m, ACH2ACH2ACH2A, 48H),
0.88 (t, CH3ACH2A, 6H). 13C NMR (CDCl3, ppm): 166.7,
136.0, 131.0, 130.8, 128.7, 128.6, 127.9, 126.7, 94.3, 83.4,
70.5, 58.6, 41.9, 31.9, 29.7, 29.6, 29.3, 26.2, 22.7, 14.1. MS:
m/z calcd. for C53H79NO4: 793.6009; found: 793.6011. Elem.
Anal.: calcd. for C53H79NO4. 2hexane. H2O: C, 79.29; H, 11.16;
N, 1.42. Found: C, 79.63; H, 11.96; N, 1.41.
Trimethyl(tetradec-1-ynyl)silane
Colorless oil, 84%. 1H NMR (CDCl3, ppm): 2.20 (t,
AC:CACH2ACH2A, 2H), 1.52 (m, AC:CACH2ACH2A, 2H),
1.36 (m, CH3ACH2A, 2H), 1.26 (m, ACH2ACH2ACH2A, 16H),
0.88 (t, CH3ACH2A, 3H), 0.14 (s, SiACH3, 9H).
5,6-Bis(3-(octyloxy)prop-1-ynyl)-2-((R)-
(Dec-1-ynyl)trimethylsilane
1-phenylethyl)isoindoline-1,3-dione (R-2a)
Colorless oil, 83%. 1H NMR (CDCl3, ppm): 2.20 (t,
AC:CACH2ACH2A, 2H), 1.51 (m, AC:CACH2ACH2A, 2H),
1.37 (m, CH3ACH2A, 2H), 1.28 (m, ACH2ACH2ACH2A, 8H),
0.88 (t, CH3ACH2A, 3H), 0.14 (s, SiACH3, 9H).
Yellow viscous liquid. 1H NMR (CDCl3, ppm): 7.83 (s, PhAH,
2H), 7.49-7.24 (m, PhAH, 5H), 5.54 (m, CH3ACHA, 1H),
4.41 (s, C:CACH2AOACH2ACH2A, 4H), 3.59 (t,
C:CACH2AOACH2ACH2A, 4H), 1.91 (d, CH3ACHA, 3H),
1.62 (t, C:CACH2AOACH2ACH2A, 4H), 1.37 (m,
CH3ACH2A, 4H), 1.27 (m, ACH2ACH2ACH2A, 16H), 0.87 (t,
CH3ACH2A, 6H). 13C NMR (CDCl3, ppm): 166.8, 140.0, 130.9,
130.7, 129.6, 128.5, 127.7, 127.4, 126.5, 94.2, 83.4, 70.5,
58.6, 49.9, 32.8, 31.8, 29.6, 29.4, 29.2, 26.1, 22.6, 17.4, 14.0.
MS: m/z calcd. for C38H49NO4: 583.3; found: 583.4. Elem.
Anal.: calcd. for C39H64NO4: C, 76.67; H, 10.56; N, 2.29.
Found: C, 76.50; H, 10.69; N, 2.36. [a]D ¼ þ25.4ꢁ (c 1.24,
CH2Cl2). S-2a was synthesized in the same manner.
General Procedure for Removal of Trimethylsilyl Group
Octadec-1-yne
A mixture of trimethyl(octadec-1-ynyl)silane (2.00 g, 6.2
mmol) in 20 mL of dry THF was stirred at 0 ꢁC, and then
tetrabutylammonium fluoride (3.24 g) in THF (12 mL) was
added dropwise to the stirred solution. After 2 h, the reac-
tion mixture was quenched with a 1 M HCl solution and
extracted with diethyl ether. The organic extracts were dried
over anhydrous MgSO4 and concentrated in vacuo to afford
the title compound as a colorless oil (1.56 g, 100%). 1H
NMR (CDCl3, ppm): 2.18 (m, AC:CACH2ACH2A, 2H), 1.93
(t, HAC:CACH2A, 1H), 1.53 (m, AC:CACH2ACH2A, 2H),
1.38 (m, CH3ACH2A, 2H), 1.26 (m, ACH2ACH2ACH2A 24H),
0.88 ( t, CH3ACH2A, 3H).
5,6-Bis(3-(dodecyloxy)prop-1-ynyl)-2-((R)-
1-phenylethyl)isoindoline-1,3-dione (R-2b)
Yellow solid. 1H NMR (CDCl3, ppm): 7.83 (s, PhAH, 2H),
7.49–7.27 (m, PhAH, 5H), 5.54 (m, CH3ACHA, 1H), 4.41 (s,
C:CACH2AOACH2ACH2A, 4H), 3.59 (t, C:CACH2AOA
CH2ACH2A, 4H), 1.91 (d, CH3ACHA, 3H), 1.62 (t,
C:CACH2AOACH2ACH2A, 4H), 1.36 (m, CH3ACH2A, 4H),
1.25 (m, ACH2ACH2ACH2A, 32H), 0.88 (t, CH3ACH2A, 6H).
13C NMR (CDCl3, ppm): 166.8, 140.0, 130.9, 130.7, 128.5,
Tetradec-1-yne
Colorless oil, 86%. 1H NMR (CDCl3, ppm): 2.18 (m,
AC:CACH2ACH2A, 2H), 1.93 (t, HAC:CACH2A, 1H), 1.52
FORMATION OF CONJUGATED POLYNAPHTHALENE, MIAO ET AL.
2191