Biradicals from Benzoenyne-Allenes
J . Org. Chem., Vol. 66, No. 20, 2001 6667
Hz), 6.30 (1 H, d, J ) 7.7 Hz), 6.06 (1 H, d, J ) 1.6 Hz), 4.97
(1 H, d, J ) 2.0 Hz), 4.76-4.69 (2 H, m), 4.21-4.05 (2 H, m);
13C δ 145.1, 142.9, 139.3, 138.4, 137.3, 135.3, 134.8, 134.0,
133.1, 130.1, 129.7, 129.2, 129.15, 129.10, 128.7, 128.2, 128.0,
127.5, 127.3, 126.8, 126.4, 125.2, 124.7, 124.4, 123.6, 121.2,
107.1, 73.2, 67.3, 62.8.
4,4-Dim eth yl-3-p h en yl-1-[2-(2-p h en yleth yn yl)p h en yl]-
1-p en tyn -3-ol (40). The same procedure was repeated as
described for 13a except that 2 derived from 0.468 g of 1-(2-
ethynylphenyl)-2-phenylethyne (2.31 mmol) and 0.341 g of 2,2-
dimethylpropiophenone (39, 2.10 mmol) were used to afford
40 (0.722 g, 1.98 mmol, 94% yield) as a viscous liquid: IR
(neat) 3562, 2215 cm-1; 1H δ 7.77-7.72 (2 H, m), 7.58-7.43 (4
H, m), 7.35-7.22 (8 H, m), 2.38 (1 H, s), 1.09 (9 H, s); 13C δ
142.0, 132.2, 132.1, 131.7, 128.4, 128.2, 128.0, 127.9, 127.8,
127.3, 127.0, 125.8, 125.1, 123.0, 96.3, 93.2, 88.3, 84.5, 79.5,
39.7, 25.6; MS m/z 364 (M+), 349, 307.
ether. The organic layer was separated, dried over sodium
sulfate, and concentrated. Purification by flash column chro-
matography (silica gel/5% diethyl ether in hexanes, Rf ) 0.64)
provided 0.230 g (0.660 mmol, 96% yield) of 51 as a yellow
liquid: IR 2215, 755, 701, 690 cm-1; 1H δ 7.56-7.51 (1 H, m),
7.49-7.40 (5 H, m), 7.34-7.18 (8 H, m), 3.70 (1 H, s), 1.05 (9
H, s); 13C δ 139.2, 132.13, 132.07, 131.7, 129.8, 128.2, 127.9,
127.6, 127.3, 126.6, 126.3, 125.6, 123.3, 95.7, 92.8, 88.6, 82.4,
50.6, 35.5, 27.8; MS m/z 348 (M+), 333, 318, 291; HRMS calcd
for C27H24 348.1878, found 348.1870.
10-(1,1-Dim e t h yle t h yl)-5-p h e n yl-11H -b e n zo[b]flu o-
r en e (55). The following procedure is representative for the
preparation of the polycyclic aromatic hydrocarbons from the
diacetylenic hydrocarbons. To 0.224 g of 51 (0.643 mmol) in
10 mL of anhydrous toluene under a nitrogen atmosphere were
added 0.70 mL of a 1.0 M solution of potassium tert-butoxide
in THF (0.70 mmol) and 0.5 mL of tert-butyl alcohol. The
reaction mixture was heated under reflux for 6 h. After the
reaction mixture was allowed to cool to room temperature, 10
mL of water and 40 mL of diethyl ether were introduced, and
the organic layer was separated, dried over sodium sulfate,
and concentrated. Purification by flash column chromatogra-
phy (silica gel/5% diethyl ether in hexanes, Rf ) 0.73) provided
0.202 g (0.580 mmol, 90% yield) of 55 as a yellow solid: mp
7-Ch lor o-1-(1,1-d im eth yleth yl)-1,2-d ip h en yl-1H-cyclo-
bu t[a ]in d en e (41) a n d 10-(1,1-Dim eth yleth yl)-5-p h en yl-
11H-ben zo[b]flu or en -11-ol (42). The same procedure was
repeated as described for 15a except that 0.431 g (1.18 mmol)
of 40 was used to afford 415 (0.379 g, 0.99 mmol, 84% yield)
as an orange solid and 42 (0.013 g, 0.036 mmol, 3% yield) as
a yellow solid. 41: mp 156-157 °C; IR 1203, 753, 691 cm-1
;
1H δ 8.01 (2 H, dd, J ) 8.1 and 1.3 Hz), 7.66 (1 H, d, J ) 7.5
Hz), 7.61-7.52 (4 H, m), 7.45 (2 H, t, J ) 7.2 Hz), 7.37 (1 H,
td, J ) 7.5 and 1.1 Hz), 7.27 (2 H, t, J ) 7.1 Hz), 7.20 (2 H, t,
J ) 7.3 Hz), 1.26 (9 H, s); 13C δ 154.0, 148.5, 145.8, 143.2,
142.5, 135.0, 129.5, 129.2, 129.1, 128.9, 128.5, 128.4, 127.6,
126.4, 124.9, 123.4, 119.7, 112.5, 77.2, 37.1, 28.7; MS m/z 382
(M+), 367, 347, 325, 289; HRMS calcd for C27H23Cl 382.1488,
found 382.1472. Anal. Calcd for C27H23Cl: C, 84.69; H, 6.05;
Cl, 9.26. Found: C, 84.65; H, 6.20; Cl, 9.18. 42: IR 3372, 768,
1
144-145 °C; IR 907, 764, 730, 702 cm-1; H δ 8.62 (1 H, d, J
) 8.7 Hz), 7.65-7.27 (9 H, m), 7.20 (1 H, td, J ) 7.3 and 0.8
Hz), 6.96 (1 H, t, J ) 7.4 Hz), 6.26 (1 H, d, J ) 7.9 Hz), 4.51
(2 H, s), 1.92 (6 H, s); 13C δ 144.2, 141.0, 140.3, 139.8, 138.1,
137.5, 134.5, 133.1, 131.3, 130.2, 129.2, 127.9, 127.6, 127.5,
126.8, 126.2, 124.1, 123.9, 123.6, 123.3, 40.2, 38.9, 34.3; MS
m/z 348 (M+), 333, 291; HRMS calcd for C27H24 348.1878, found
348.1866. Anal. Calcd for C27H24: C, 93.06; H, 6.94. Found:
C, 92.78; H, 6.93.
1
702 cm-1; H δ 8.59 (1 H, d, J ) 8.9 Hz), 7.63-7.56 (4 H, m),
Dia cetylen e 60. The same procedure was repeated as
described for 51 except that 0.409 g (1.00 mmol) of 26 was
used to afford 60 (0.382 g, 0.973 mmol, 97% yield) as a light
yellow solid: mp 45-47 °C; IR 2215, 796, 757, 690 cm-1; 1H δ
8.12 (2 H, br), 7.63 (2 H, br m), 7.49 (2 H, d, J ) 7.3 Hz), 7.40-
7.18 (11 H, m), 7.16 (2 H, s), 4.81 (1 H, s); 13C δ 137.5, 134.0,
132.2, 132.1, 131.9, 131.3, 128.7, 128.4, 128.2, 128.0, 127.9,
127.6, 126.2, 125.9, 125.8, 125.6, 123.0, 93.3, 92.1, 88.5, 86.0
7.51 (1 H, dd, J ) 8.3 and 1.6 Hz), 7.43 (1 H, td, J ) 7.7 and
1.6 Hz), 7.39-7.29 (3 H, m), 7.22 (1 H, td, J ) 7.5 and 1 Hz),
7.00 (1 H, td, J ) 7.7 and 1 Hz), 6.33 (1 H, d, J ) 10.1 Hz),
6.16 (1 H, d, J ) 7.9 Hz), 1.95 (9 H, s), 1.83 (1 H, d, J ) 10.1
Hz); 13C δ 146.3, 144.7, 140.1, 139.2, 139.1, 135.9, 135.4, 133.2,
132.4, 130.2, 129.9, 129.3, 129.1, 128.7, 128.3, 127.83, 127.76,
127.3, 125.0, 124.5, 123.7, 74.2, 38.6, 33.4; MS m/z 364 (M+),
331, 307; HRMS calcd for C27H24O 364.1827, found 364.1816.
1H -Cyclob u t [a ]in d en e 48 a n d 2,11-Dih yd r o-1,1-d i-
m eth yl-6-p h en yl-1H-in d en o[1,7-a b]flu or en -11-ol (50). The
same procedure was repeated as described for 15a except that
0.276 g of 46 (0.760 mmol) was used to afford 48 (0.017 g, 0.045
mmol, 6% yield) as an orange solid and 50 (0.213 g, 0.588
mmol, 77% yield) as a yellow solid. 48: IR 1200, 752, 738, 688
1
(br), 40.8 (br); MS m/z 392 (M+), 391, 315. The broad H NMR
signals at δ 8.12 and 7.63 and the 13C NMR signals at δ 86.0
and 40.8 suggest a relatively slow conformational inversion
of the central seven-membered ring.
Hyd r oca r bon 61. The same procedure was repeated as
described for 55 except that 0.099 g (0.25 mmol) of 60 was
used to afford 615 (0.080 g, 0.20 mmol, 81% yield) as a light
1
cm-1; H δ 7.76 (1 H, d, J ) 7.5 Hz), 7.48 (1 H, dm, J ) 7.5
1
yellow solid: mp 197-198 °C; IR 727, 703 cm-1; H δ 7.67-
and 1 Hz), 7.43 (1 H, td, J ) 7.7 and 1 Hz), 7.36-7.24 (8 H,
m), 7.20-7.10 (2 H, m), 3.23 (1 H, d, J ) 15.8 Hz), 3.02 (1 H,
d, J ) 16.0 Hz), 1.32 (3 H, s), 1.17 (3 H, s); 13C δ 153.0, 149.3,
145.8, 144.9, 141.4, 140.7, 133.9, 129.6, 129.0, 128.9, 128.1,
127.9, 127.1, 125.4, 125.1, 124.6, 123.5, 119.9, 111.1, 75.5, 47.3,
45.6, 28.7, 24.5; MS m/z 380 (M+), 365, 345, 330; HRMS calcd
for C27H21Cl 380.1332, found 380.1344. 50: mp 140-142 °C;
7.55 (3 H, m), 7.50-7.27 (8 H, m), 7.25-7.17 (3 H, m), 7.00 (1
H, t, J ) 7.7 Hz), 6.69 (1 H, d, J ) 12.1 Hz), 6.62 (1 H, d, J )
11.9 Hz), 6.38 (1 H, d, J ) 7.7 Hz), 4.63 (1 H, d, J ) 22.6 Hz),
3.88 (1 H, d, J ) 22.4 Hz); 13C δ 144.0, 142.2, 140.8, 139.1,
139.0, 138.7, 137.9, 137.7, 136.0, 134.4, 134.1, 133.8, 133.6,
132.6, 130.5, 130.4, 129.9, 129.4, 129.3, 129.1, 128.7, 128.6,
127.9, 127.8, 127.1, 126.4, 125.1, 124.7, 124.3, 123.5, 38.4; MS
m/z 392 (M+), 315; HRMS calcd for C31H20 392.1565, found
392.1571. Anal. Calcd for C31H20: C, 94.86; H, 5.14. Found:
C, 94.56; H, 5.39. The observation of the two 1H NMR signals
at δ 4.63 and 3.88 attributable to the two hydrogens on the
sp3 carbon suggests a relatively slow interconversion of the
two helical conformers of 61. The relatively large geminal
coupling constant of 22.5 Hz is consistent with the earlier
report of J ) -22.3 Hz for fluorene.14
1
IR 3389, 780, 763, 741, 703 cm-1; H δ 7.63 (1 H, d, J ) 7.5
Hz), 7.6-7.53 (3 H, m), 7.47-7.35 (3 H, m), 7.29-7.19 (3 H,
m), 7.04 (1 H, t, J ) 7.6 Hz), 6.46 (1 H, d, J ) 7.9 Hz), 5.96 (1
H, d, J ) 10.3 Hz), 3.35 (2 H, s), 1.88 (1 H, d, J ) 10.3 Hz),
1.77 (3 H, s), 1.74 (3 H, s); 13C δ 150.5, 146.5, 143.6, 140.1,
138.3, 137.3, 135.5, 132.3, 131.0, 130.1, 129.9, 129.0, 128.8,
128.2, 127.8, 127.7, 125.0, 123.6, 121.6, 119.7, 73.0, 48.9, 45.0,
31.6, 26.5; MS m/z 362 (M+), 347, 345, 329; HRMS calcd for
C
27H22O 362.1671, found 362.1657. Anal. Calcd for C27H22O:
C, 89.47; H, 6.12. Found: C, 89.32; H, 6.12.
Ack n ow led gm en t. The financial support of the
National Science Foundation (CHE-9618676) to K.K.W.
is gratefully acknowledged. J .L.P. acknowledges the
support (CHE-9120098) provided by the Chemical In-
strumentation Program of the National Science Foun-
dation for the acquisition of a Siemens P4 X-ray
4,4-Dim eth yl-3-p h en yl-1-[2-(2-p h en yleth yn yl)p h en yl]-
1-p en tyn e (51). The following procedure is representative for
the preparation of the diacetylenic hydrocarbons from the
diacetylenic propargylic alcohols. To a mixture of the alcohol
40 (0.250 g, 0.686 mmol) and triethylsilane (0.120 g, 1.03
mmol) in 6 mL of methylene chloride was added 0.21 mL of
trifluoroacetic acid (0.313 g, 2.74 mmol). After 5 min of stirring
at room temperature, 0.290 g of sodium carbonate (2.74 mmol)
was added followed by 10 mL of water and 40 mL of diethyl
(14) Cookson, R. C.; Crabb, T. A.; Frankel, J . J .; Hudec, J . Tetra-
hedron Suppl. No. 7, 1966, 355-390.