6
Tetrahedron
1
Pale yellow sticky liquid, yield: 80%, H NMR (500 MHz,
HRMS
(ESI-TOF)
calculated[M+H]+for
C26H14F8O:
CDCl3): δ7.62 (d, J = 7.5Hz, 2H), 7.45(t, J=7.5Hz, 1H), 7.29 (t,
J=7Hz, 3H), 7.24 (s, 1H), 7.18 (s, 1H ), 7.14 (d, J=8.5Hz, 2H),
7.06 (d, J=8Hz, 2H), 6.45 (t, J=12.5Hz, 1H), 1.23 (s, 9H), 1.22 (s,
495,0995,found: 495.0990
5.23 (E)-2,2-difluoro-1-phenyl-4,6-di(thiophen-2-yl)hex-3-en-
5-yn-1-one(3u)
2
9H); 13C NMR (125MHz, CDCl3): 187.24 (t, ’JC-F=28.93Hz),
152.45, 152.36, 133.98 (t, 3JC-F=9.93Hz), 133.81, 132.70, 131.98,
Pale yellow sticky liquid , yield: 75%, 1H NMR (500 MHz,
CDCl3): δ7.77 (d, J = 10Hz, 2H), 7.50 (t, J=7.5Hz, 1H), 7.43 (s,
1H), 7.34 (t, J=8Hz, 3H), 7.22-7.20 (m, 1H ), 7.11-7.10 (m, 1H),
7.05 (d, J=5Hz, 1H), 6.93(d, J=5Hz, 1H), 6.41 (d, J=13Hz, 1H);
δ187.16 (t,2’JC-F=30Hz), 135.42, 135.30, 134.35,133.89, 133.06,
2
131.59, 129.45, 128.61, 128.22, 126.95 (t, JC-F=26.875Hz),
1
125.40, 124.94, 119.21, 114.67 (t, JC-F=245.125Hz), 93.56,
88.88, 34.86, 34.70, 31.24,31.13; 19F NMR (376 MHz, CDCl3):
δ -87.41 (d, J = 12.78Hz, 2F)ꢁHRMS (ESI-TOF) calculated
[M+H]+ for C32H32F2O: 471.2499ꢀ foundꢄ471.2498.
3
132.50 (t, JC-F=9.375Hz), 131.62, 130.11, 129.83, 128.87,
2
128.60, 128.41, 128.13 (t, JC-F=24.375Hz), 120.47, 114.71 (t,
5.19 (E)-2,2-difluoro-4,6-bis(4-fluorophenyl)-1-phenylhex-3-
en-5-yn-1-one(3q)
1JC-F=247.5Hz), 92.77, 89.81; 19F NMR (376 MHz, CDCl3): δ -
88.53 (d, J = 13.16Hz, 2F) ꢁ HRMS (ESI-TOF) calculated
[M+H]+ for C20H12F2OS2:371.0376, foundꢄ371.0372.
1
Pale yellow sticky liquid , yield: 90%, H NMR (500 MHz,
CDCl3): δ 7.75 (d, J = 7.8Hz, 2H), 7.51 (t, J = 7.4 Hz, 1H), 7.34
(t, J = 7.0 Hz, 4H), 7.18-7.15 (m , 2H), 6.95 (t, J = 7.5 Hz, 2H),
6.87 (t, J=10Hz, 2H) , 6.49 (t, J = 12.8Hz, 1H) ; 13C NMR (125
MHz, CDCl3): δ187.11 (t, 2’JC-F=30Hz), 163.12 (d, 1’’JC-
F=248.75Hz), 163.03 (d,1’’’JC-F=250Hz), 134.20, 133.85, 133.79,
5.24 (E)-4,6-di(cyclohex-1-en-1-yl)-2,2-difluoro-1-phenylhex-
3-en-5-yn-1-one(3v)
1
Pale yellow sticky liquid , Yield: 90%, H NMR (500 MHz,
CDCl3): δ8.00 (d, J = 7.5Hz, 2H), 7.59(t, J=7.5Hz, 1H), 7.45 (t,
J=8Hz, 2H), 6.21-6.16 (m, 2H), 5.72-5.70 (m, 1H ), 2.12 (d,
J=4.5Hz, 3H),1.95-1.82 (m, 2H), 1.65-1.56 (m, 5H), 1.43-1.41
(m, 2H), 1.37-1.32 (m, 2H),1.27-1.23 (m, 2H); 13C NMR
(125MHz, CDCl3): 186.61 (t, 2’JC-F=28.12Hz), 136.93, 136.57 (t,
3JC-F=12.5Hz), 134.04, 133.73, 133.14, 131.86, 129.99, 128.35,
126.68 (t, 2JC-F=30Hz), 120.25, 114.75 (t, 1JC-F=241.25Hz), 95.37,
84.94, 28.91, 25.88, 25.80, 24.67, 22.18, 21.82, 21.37, 21.06; 19F
NMR (376 MHz, CDCl3): δ -85.37 (d, J = 10.52Hz, 2F)ꢁHRMS
(ESI-TOF) calculated [M+H]+ for C24H24F2O:367.1873ꢀ foundꢄ
367.1866.
3
132.72 (t, JC-F=9.375Hz), 131.68, 130.75, 130.68, 128.50,
2
2
127.72 (t, JC-F=26.875Hz), 115.58 (d, ’’JC-F=85Hz), 115.2 (d,
2’’’JC-F=85Hz), 114.66 (t, JC-F=246.875Hz), 92.69, 88.83; 19F
1
NMR (376 MHz, CDCl3): δ -89.42 (d, J = 12.5 Hz, 2F), -109.95
(s, 1F), -112.41 (s, 1F); HRMS (ESI-TOF) calculated [M+H]+
for C24H14F4O: 395.1059,found:395.1055
5.20 (E)-4,6-bis(4-bromophenyl)-2,2-difluoro-1-phenylhex-3-
en-5-yn-1-one (3r)
Pale yellow sticky liquid ꢁ yield=79% ꢁ 1H NMR
(500MHz,CDCl3) :δ 7.84(d, J = 7.5Hz, 2H), 7.59 (t, J = 7.25Hz,
1H), 7.46-7.39 (m, 6H), 7.35(d, J = 8.5Hz, 2H), 7.14 (d, J =
8.5Hz, 2H), 6.57 (t, J=13.0Hz, 1H); 13C NMR (125MHz, CDCl3):
5.25
(E)-4,6-bis(4-ethylphenyl)-2-fluoro-2-methyl-1-
(thiophen-2-yl)hex-3-en-5-yn-1-one(3w)
3
δ187.19 (t, 2’JC-F=30.625Hz), 134.34, 133.21, 132.49 (t, JC-
1
Pale yellow sticky liquid , yield: 68%, H NMR (500 MHz,
CDCl3): δ7.77 (d, J = 3Hz, 1H), 7.69 (dd, J=4.9, 0.7Hz, 1H),
7.35 (d, J=8.5Hz, 2H), 7.256 (t, J=6Hz, 2H), 7.14 (d, J=8.5Hz,
2H ), 7.10-7.08 (m, 3H), 6.45 (t, J=13.25Hz, 1H), 2,65-2.60 (m,
4H), 1.23-1.20 (m, 6H); 13C NMR (125MHz, CDCl3): 180.95 (t,
2’JC-F=31.87Hz), 145.62, 145.31, 138.29, 135.91, 135.26,
134.57(t, 3JC-F=9.375Hz), 133.10, 131.84, 128.78, 128.37, 127.97,
F=9.375Hz), 131.92, 131.79, 131.61, 131.36, 130.31, 129.84,
2
128.59, 128.10 (t, JC-F=26.25Hz), 123.72, 123.56, 120.89,
1
114.69 (t, JC-F=247.5Hz), 92.83, 89.76; 19F NMR (376Hz,
CDCl3): -89.76 (d, J=12.74Hz, 2F); HRMS (ESI-TOF)
calculated[M+H]+for C24H16F2OBr2: 517.9339, found:517.9336
5.21 (E)-4,6-bis(4-chlorophenyl)-2,2-difluoro-1-phenylhex-3-
en-5-yn-1-one(3s)
2
1
127.51, 126.20 (t, JC-F=26.875Hz), 119.43, 114.73 (t, JC-
F=247.5Hz), 93.89, 89.07, 28.87, 28.66, 15.34, 15.26; 19F NMR
(376 MHz, CDCl3): δ -88.61 (d, J = 13.16Hz, 2F)ꢁHRMS
(ESI-TOF) calculated [M+H]+ for C26H22F2OS:421.1438 ꢀ
foundꢄ421.1437.
Pale yellow sticky liquid ꢁ yield=82% ꢁ 1H NMR
(500MHz,CDCl3) :δ 7.84(d, J = 7.5Hz, 2H), 7.58 (t, J = 7.5Hz,
1H), 7.41 (t, J = 7.75Hz, 2H), 7.35(d, J = 8.5Hz, 2H ), 7.29 (t, J =
8.5Hz, 2H), 7.25-7.19 (m, 4H), 6.57 (t, J=13.0Hz, 1H); 13C
NMR (125MHz, CDCl3): δ187.16 (t, 2’JC-F=30Hz), 135.43,
135.30, 134.35,133.89, 133.06, 132.51 (t, 3JC-F=9.375Hz), 131.62,
5.26 Ethyl (E)-2,2-difluoro-4,6-diphenylhex-3-en-5-ynoate
(3x)
2
1
130.11, 129.83, 128.87, 128.60, 128.41, 128.13 (t, JC-
Pale yellow sticky liquid , yield: 90%, H NMR (500 MHz,
1
F=24.375Hz), 120.47, 114.71 (t, JC-F=247.5Hz), 92.77, 89.81;
CDCl3): δ7.48-7.46 (m, 4H), 7.39-7.38 (m, 3H), 7.36-7.34 (m,
3H), 6.36 (t, J=12.25Hz, 1H), 3.94 (q, J=7.2Hz, 2H), 1.16(t,
J=7.2Hz, 3H); 13C NMR (125MHz, CDCl3): 162.90 (t, 2’JC-
19F NMR (376Hz,CDCl3): -88.80 (d, J=13.16Hz, 2F); HRMS
(ESI-TOF) calculated[M+H]+for C24H16F2OCl2: 427.0468,found:
427.0459.
3
F=33.43Hz), 135.55, 133.78 (t, JC-F=10Hz), 131.83, 129.17,
2
129.11, 128.66, 128.43, 128.23, 126.87 (t, JC-F=28.06Hz),
5.22
(E)-2,2-difluoro-1-phenyl-4,6-bis(4-
1
122.19, 111.90 (t, JC-F=243.81Hz), 93.61, 89.14, 63.01, 28.66,
(trifluoromethyl)phenyl)hex-3-en-5-yn-1-one(3t)
13.65; 19F NMR (376 MHz, CDCl3): δ -91.80 (s, 2F); MS (ES-
TOF) calculated [M+H]+ for C20H16F2O2: 327.1197, found:
327.3
Pale yellow sticky liquid ꢁ yield=75% ꢁ 1H NMR
(500MHz,CDCl3) :δ 7.86 (d, J = 7.5Hz, 2H), 7.61-7.53(m, 7H),
7.44-7.41 (m, 4H), 6.68 (t, J=13.25Hz, 1H); 13C NMR (125MHz,
CDCl3): δ187.20 (t, 2’JC-F=29.375Hz), 138.94, 134.48, 132.09
5.27 (E)-(5,5,6,6,7,7,8,8,9,9,10,10-dodecafluorodec-3-en-1-
yne-1,3-diyl)dibenzene (3y)
3
2
131.91 (t, JC-F=8.75Hz), 131.49, 129.86, 129.40(t, JC-
F=26.25Hz), 129.00, 128.66, 125.41(q, 2’’’JC-F=3.3Hz), 125.18 (q,
1
Pale yellow sticky liquid , yield: 70%, H NMR (500 MHz,
2’’JC-F=3.75Hz), 123.84 (q, ’’’JC-F=270.41Hz), 123.73 (q, ’’JC-
1
1
CDCl3): δ7.5 (d, J=6.1Hz, 4H), 7.42-7.41 (m, 3H), 7.38-7.33 (m,
3H), 6.25 (t, J=15.25Hz, 1H).
2
F=270.83Hz), 127.59 (t, JC-F=26.875Hz), 126.69, 122.19,
114.64 (t, JC-F=247.5Hz), 92.56, 90.50; 19F NMR (376Hz,
1
CDCl3): δ -66.82(s, 3F), -62.97(s, 3F), -89.26 (d,J=15.04Hz, 2F);