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solid (142.2 mg, 78 % yield). H NMR (400 MHz, CDCl3): δ = 8.69 (d, yellow solid (148.7 mg, 82 % yield). H NMR (400 MHz, CDCl3): δ =
J = 7.6 Hz, 1 H), 7.63 (d, J = 7.2 Hz, 1 H), 7.56 (d, J = 7.2 Hz, 1 H), 8.53 (d, J = 2.4 Hz, 1 H), 7.51–7.49 (m, 5 H), 7.42 (d, J = 8.0 Hz, 1 H),
7.42–7.38 (m, 1 H), 7.36–7.30 (m, 2 H), 7.28–7.24 (m, 3 H), 7.21–7.14 7.37–7.35 (m, 2 H), 7.21–7.19 (m, 2 H), 6.77 (dd, J = 2.4, J = 6.0 Hz,
(m, 3 H), 7.13–7.08 (m, 1 H), 7.03–6.98 (m, 1 H), 6.83 (t, J = 7.6 Hz,
1 H), 6.94 (dd, J = 2.4, J = 6.0 Hz, 1 H), 6.09 (d, J = 2.4 Hz, 1 H), 3.87
1 H), 6.41 (d, J = 8.0 Hz, 1 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
(s, 3 H), 3.47 (s, 3 H), 2.48 (s, 3 H), 2.41 (s, 3 H) ppm. 13C NMR
164.5, 163.9, 162.1, 161.4, 141.8, 141.7, 141.5, 140.8, 140.7, 138.0, (100 MHz, CDCl3): δ = 159.0, 157.9, 140.1, 139.6, 139.3, 139.1, 138.3,
137.3, 130.9, 130.8, 130.4, 130.3, 129.5, 129.1, 127.7, 127.6, 127.0, 137.1, 133.9, 133.8, 131.6, 129.8, 129.4, 129.0, 123.3, 120.2, 119.2,
125.7, 125.0, 125.0, 125.0, 120.6, 119.7, 119.7, 118.6, 118.4, 116.6, 115.2, 115.1, 110.8, 110.6, 102.9, 91.5, 55.7, 54.9, 29.8, 21.7, 21.4
116.4, 116.1, 115.8, 115.6, 100.8, 92.2 ppm. ESI-HRMS: calcd. for
ppm. ESI-HRMS: calcd. for C32H27O2 [M + H]+ 443.2006; found
443.2009.
C28H17F2 [M + H]+ 391.1293; found 391.1290.
9-[1,3-Bis(3-fluorophenyl)prop-2-yn-1-ylidene]-9H-fluorene (5i):
By the general procedure for 5a, 5i was obtained as a yellow solid
(176.0 mg, 89 % yield). 1H NMR (400 MHz, CDCl3): δ = 8.89 (m, 1 H),
7.73 (m, 1 H), 7.66 (d, J = 7.2 Hz, 1 H), 7.58–7.56 (m, 4 H), 7.51–7.50
(m, 2 H), 7.42–7.40 (m, 2 H), 7.38–7.37 (m, 2 H), 7.23–7.22 (m, 1 H),
7.15–7.05 (m, 1 H), 6.81 (d, J = 8.4 Hz, 1 H), 6.45 (d, J = 7.6 Hz, 1 H)
ppm. 13C NMR (100 MHz, CDCl3): δ = 141.1, 140.7, 140.6, 138.3,
138.1, 137.4, 135.3, 134.7, 132.9, 130.7, 129.5, 129.3, 129.1, 128.9,
127.6, 126.9, 125.7, 124.9, 121.6, 121.0, 119.7, 119.7, 101.1, 92.6 ppm.
ESI-HRMS: calcd. for C28H17Cl2 [M + H]+ 423.0702; found 423.0705.
9-(1,3-Di-p-tolylprop-2-yn-1-ylidene)-2,7-difluoro-9H-fluorene
(6c): By the general procedure for 5a, 6c was obtained as a yellow
solid (160.5 mg, 89 % yield). H NMR (400 MHz, CDCl3): δ = 8.68 (t,
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J = 12.8 Hz, 1 H), 7.58–7.47 (m, 6 H), 7.40–7.37 (m, 2 H), 7.27–7.24
(m, 2 H), 7.15–7.11 (m, 1 H), 6.98–6.92 (m, 1 H), 6.36–6.30 (m, 1 H),
2.54 (m, 3 H), 2.44 (m, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
163.7, 163.0, 162.9, 161.3, 160.5, 140.2, 140.1, 139.8, 139.5, 139.4,
139.0, 138.0, 136.2, 135.6, 135.5, 131.7, 131.4, 130.0, 129.5, 129.1,
128.8, 128.7, 126.0, 119.9, 119.8, 115.6, 115.4, 115.1, 112.8, 112.5,
112.4, 112.1, 104.3, 91.3, 21.7, 21.5 ppm. ESI-HRMS: calcd. for
C
30H21F2 [M + H]+ 419.1606; found 419.1609.
9-[1,3-Bis(3-chlorophenyl)prop-2-yn-1-ylidene]-9H-fluorene
(5j): By the general procedure for 5a, 5j was obtained as yellow
Dimethyl 9-(1,3-Di-p-tolylprop-2-yn-1-ylidene)-9H-fluorene-2,7-
dicarboxylate (6d): By the general procedure for 5a, 6d was ob-
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solid (158.2 mg, 80 % yield). H NMR (400 MHz, CDCl3): δ = 8.82 (d,
J = 8.0 Hz, 1 H), 7.74 (d, J = 7.2 Hz, 1 H), 7.67 (d, J = 7.2 Hz, 1 H),
7.60 (d, J = 12.4 Hz, 2 H), 7.51–7.26 (m, 9 H), 6.97 (t, J = 8.0 Hz, 1
H), 6.55 (d, J = 8.0 Hz, 1 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
141.6, 141.4, 140.8, 140.7, 137.9, 137.2, 135.0, 134.6, 131.5, 130.5,
129.9, 129.5, 129.3, 129.2, 129.1, 128.8, 127.7, 127.4, 127.0, 125.7,
125.0, 124.8, 120.4, 119.8, 119.7, 100.7, 92.4 ppm. ESI-HRMS: calcd.
for C28H17Cl2 [M + H]+ 423.0702; found 423.0708.
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tained as a yellow solid (162.2 mg, 89 % yield). H NMR (400 MHz,
CDCl3): δ = 9.73 (s, 1 H), 8.16 (d, J = 7.6 Hz, 1 H), 7.95 (d, J = 7.6 Hz,
1 H), 7.84 (d, J = 7.6 Hz, 1 H), 7.76 (d, J = 8.4 Hz, 1 H), 7.64 (d, J =
7.6 Hz, 2 H), 7.50–7.42 (m, 2 H), 7.42–7.34 (m, 2 H), 7.25–7.20 (m, 3
H), 3.96 (s, 3 H), 3.78 (s, 3 H), 2.53 (s, 3 H), 2.40 (s, 3 H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 167.2, 166.9, 142.8, 142.8, 139.8, 139.1,
138.9, 138.6, 137.8, 136.5, 132.1, 130.4, 129.9, 129.8, 129.7, 129.4,
129.1, 128.9, 127.1, 126.4, 126.2, 120.0, 105.0, 91.4, 52.2, 52.1, 21.8,
21.6 ppm. ESI-HRMS: calcd. for C34H27O4 [M + H]+ 499.1904; found
499.1898.
9-[1,3-Bis(4-nitrophenyl)prop-2-yn-1-ylidene]-9H-fluorene (5k):
By the general procedure for 5a, 5k was obtained as a yellow solid
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(203.4 mg, 98 % yield). H NMR (400 MHz, CDCl3): δ = 8.71 (d, J =
8.0 Hz, 1 H), 8.39 (d, J = 8.4 Hz, 2 H), 8.25 (d, J = 8.0 Hz, 2 H), 7.76
(d, J = 8.0 Hz, 2 H), 7.72 (d, J = 7.6 Hz, 1 H), 7.69–7.65 (m, 3 H), 7.54
(t, J = 8.4 Hz, 1 H), 7.46 (t, J = 7.2 Hz, 1 H), 7.39 (t, J = 7.2 Hz, 1 H),
7.32–7.26 (m, 2 H), 6.91 (t, J = 8.0 Hz, 1 H), 6.43 (d, J = 8.0 Hz, 1 H)
ppm. 13C NMR (100 MHz, CDCl3): δ = 148.1, 147.7, 145.9, 141.2,
137.6, 136.7, 134.5, 133.5, 132.4, 130.5, 130.3, 129.9, 129.4, 128.6,
127.9, 127.3, 125.6, 125.1, 124.7, 124.0, 120.1, 118.5, 100.1, 95.3 ppm.
ESI-HRMS: calcd. for C28H17N2O4 [M + H]+ 445.1188; found 445.1185.
(E)-9-[1,3-Bis(4-methoxyphenyl)prop-2-yn-1-ylidene]-1,3,7-tri-
methyl-9H-fluorene (6e): By the general procedure for 5a, 6e was
obtained as a yellow solid (161.2 mg, 83 % yield). 1H NMR (400 MHz,
CDCl3): δ = 8.69 (s, 1 H), 7.60–7.56 (m, 3 H), 7.41 (d, J = 8.8 Hz, 1
H), 7.34 (s, 1 H), 7.17 (d, J = 7.6 Hz, 1 H), 6.94 (d, J = 8.8 Hz, 2 H),
6.88 (d, J = 8.8 Hz, 2 H), 6.63 (s, 1 H), 3.86 (s, 3 H), 3.84 (s, 3 H), 2.46
(s, 3 H), 2.37 (s, 3 H), 1.45 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3):
δ = 160.2, 159.3, 141.6, 141.2, 138.3, 137.2, 136.4, 135.3, 135.1, 133.1,
133.0, 131.8, 130.9, 128.8, 124.8, 121.9, 119.0, 117.6, 115.8, 114.4,
114.2, 114.1, 114.0, 101.0, 92.5, 55.4, 22.3, 21.9, 21.5 ppm. ESI-HRMS:
calcd. for C33H29O2 [M + H]+ 457.2162; found 457.2159.
4-(9H-Fluoren-9-ylidene)pent-2-yne-1,5-diyldiacetate (5l): By
the general procedure for 5a, 5l was obtained as a yellow liquid
(87.3 mg, 54 % yield). 1H NMR (400 MHz, CDCl3): δ = 8.59 (d, J =
7.6 Hz, 1 H), 7.69–7.65 (m, 2 H), 7.57 (d, J = 8.0 Hz, 1 H), 7.37 (t, J =
7.2 Hz, 2 H), 7.30 (t, J = 18.4 Hz, 2 H), 5.31 (s, 2 H), 5.07 (s, 2 H),
2.20–2.16 (m, 6 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 170.9, 170.3,
(E)-9-(1,3-Di-p-tolylprop-2-yn-1-ylidene)-1,3,7-trimethyl-9H-
fluorene (6f): By the general procedure for 5a, 6f was obtained as
143.7, 141.0, 140.5, 137.6, 136.7, 129.5, 129.5, 127.7, 127.6, 126.2, a yellow solid (146.3 mg, 81 % yield). The structure of 6f was deter-
125.2, 120.0, 119.5, 115.9, 95.4, 86.6, 64.4, 53.0, 21.0, 20.9 ppm. ESI-
mined by X-ray crystal diffraction. 1H NMR (400 MHz, CDCl3): δ =
8.79 (s, 1 H), 7.64 (d, J = 7.6 Hz, 1 H), 7.58 (d, J = 8.0 Hz, 2 H), 7.47
(s, 1 H), 7.45 (s, 1 H), 7.40–7.39 (m, 2 H), 7.28–7.27 (m, 1 H), 7.25 (s,
1 H), 7.23 (s, 2 H), 7.21 (s, 1 H), 6.69 (s, 1 H), 2.53 (s, 3 H), 2.45 (s, 3
H), 2.44 (s, 3 H), 2.43 (s, 3 H), 1.48 (s, 3 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 142.3, 141.6, 141.4, 139.9, 139.0, 138.5, 137.7, 137.3,
136.4, 135.3, 135.2, 131.5, 131.0, 130.4, 129.5, 129.3, 129.0, 125.0,
122.1, 120.7, 119.0, 117.6, 101.0, 93.0, 22.2, 21.9, 21.7, 21.5, 21.4
ppm. ESI-HRMS: calcd. for C33H29 [M + H]+ 425.2269; found
425.2273.
HRMS: calcd. for C22H19O4 [M + H]+ 347.1278; found 347.1281.
9-(1,3-Di-p-tolylprop-2-yn-1-ylidene)-2,7-dimethyl-9H-fluorene
(6a): By the general procedure for 5a, 6a was obtained as a yellow
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solid (124.5 mg, 69 % yield). H NMR (400 MHz, CDCl3): δ = 8.63 (s,
1 H), 7.40 (d, J = 7.6 Hz, 1 H), 7.35–7.32 (m, 5 H), 7.17 (d, J = 8.0 Hz,
2 H), 7.04 (d, J = 8.0 Hz, 3 H), 6.86 (d, J = 7.6 Hz, 1 H), 6.21 (s, 1 H),
2.35 (s, 6 H), 2.24 (s, 3 H), 1.95 (s, 3 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 140.2, 139.1, 138.7, 138.2, 138.1, 138.1, 137.3, 136.5,
135.7, 131.5, 129.6, 129.4, 129.1, 126.5, 125.8, 122.8, 120.6, 118.9,
102.0, 92.2, 22.2, 21.8, 21.7, 21.5 ppm. ESI-HRMS: calcd. for C32H27
[M + H]+ 411.2113; found 411.2109.
(E)-9-(1,3-Di-p-tolylprop-2-yn-1-ylidene)-6-methoxy-1,3-di-
methyl-9H-fluorene (6g): By the general procedure for 5a, 6g was
obtained as a yellow solid (132.3 mg, 73 % yield). 1H NMR (400 MHz,
CDCl3): δ = 8.65 (d, J = 8.4 Hz, 1 H), 7.40 (d, J = 8.0 Hz, 2 H), 7.28
9-(1,3-Di-p-tolylprop-2-yn-1-ylidene)-2,7-dimethoxy-9H-fluor-
ene (6b): By the general procedure for 5a, 6b was obtained as a
Eur. J. Org. Chem. 2016, 1110–1118
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