D.J. Burton, G.A. Hartgraves / Journal of Fluorine Chemistry 130 (2009) 254–258
257
1
2
3
4JHH = 2.7 Hz); 13C NMR (Neat):
d
152.6 (ddd, JCF = 285.7 Hz,
2JCF = 48.1 Hz, JCF = 17.8 Hz), 197.5 (d, JCF = 10.2 Hz), 108.5 (s),
78.8 (dd, 2JCF = 22.7 Hz, 3JCF = 3.5 Hz), 30.6 (s), 26.7 (s), 25.4 (s). GC–
MS: m/z (relative intensity): 188 (100.0). IR: 2937 (s), 1960
1JCF = 274.1 Hz, 2JCF = 45.5 Hz), 124.5 (ddd, 1JCF = 235.8 Hz,
2JCF = 53.0 Hz, JCF = 18.2 Hz), 75.2 (s), 69.1 (s), 15.6 (d,
2
2JCF = 23.7 Hz). GC–MS, m/z (relative intensity): 120 (100.0), 119
(C C C) (w), 1765 (F2C CF) (s), 1687 (F2C CF) (m), 1277 (vs),
(51.9). IR: 3317 (BC)
(s), 1804 (F2C CF) (s), 1765
1274 (vs), 1088 (vs), 1066 (s).
(F2C CF) (m), 1301 (vs), 1216 (s), 1096 (s).
3.2.5. Preparation of (E)-4,5,6,6,6-pentafluorohex-4-ene-1-yne
Similar to Section 3.2.1, a 19-ml aliquot of a 0.76-M (Z)-
pentafluoropropenylzinc reagent (14.3 mmol) in DMF, 2.1 g
Cu(I)Br) (14.3 mmol), and 3.15 g of 3-tosyl-1-propyne (15 mmol)
gave after distillation and washing with water 1.46 g (60%) of a
mixture which contained 87% (E)-4,5,6,6,6-pentafluorohex-4-ene-
1-yne and 13% (E)-4,5,6,6,6-pentafluoro-1,2,4-hexadiene (as
determined by GLPC analysis). 19F NMR: [(E)-CF3CF=CFCH2C CH]:
3.2.2. Reaction of trifluorovinylcopper with 3-tosyl-1-butyne
Similar to Section 3.2.1,
a 30-ml aliquot of a 1.45-M
trifluorovinylzinc reagent (43 mmol), 6.17 g (43 mmol) of Cu(I)Br
and 10.1 g (45 mmol) of 3-tosyl-1-butyne gave 3.67 g (64%) of a
mixture after distillation. The mixture (94% GLPC purity) contained
32% of 3-methyl-4,5,5-trifluoropent-4-ene-1-yne and 68% of 5,6,6-
trifluoro-2,3,5-hexatriene (as determined by GLPC analysis), 19F
NMR: (F2 CFCH(CH3)CBCH):
d
ꢀ105.1 (dd, 2JFF = 84.2 Hz,
d
-68.6
(dd,
4JFF = 20.9 Hz,
3JFF = 11.0 Hz),
ꢀ171.6
dqt,
3JFF = 34.1 Hz), ꢀ122.3 (ddd, 3JFF = 114.7 Hz, 2JFF = 84.2 Hz,
3JFF = 133.7 Hz, 3JFF = 11.0 Hz, 4JFH = 5.6 Hz), ꢀ139.8 (dqt,
4JFH = 3.1 Hz), ꢀ182.7 (ddd, 3JFF = 114.7 Hz, 3JFF = 34.1 Hz,
3JFF = 133.7 Hz, JFF = 20.9 Hz, JFH = 18.5 Hz); 1H NMR:
d
2.14 (t,
4
3
3JFH = 26.8 Hz); 1H NMR:
d
1.44 (d, JHH = 7.2 Hz), 2.16 (d,
4JHH = 2.7 Hz), 3.14 (dm, JFH = 18.5 Hz); GC–MS, m/z (relative
intensity): 170 (53.9), 101 (100.0). IR (mixture): 1382 (s), 1251 (s),
1217 (s), 1199 (s), 1155 (vs). GC–MS, m/z (relative intensity): [(E)
3
3
4JHH = 2.4 Hz), 3.50 (m); 13C NMR (Neat):
d 153.6 (ddd,
1JCF = 289.6 Hz, 1JCF = 280.5 Hz, 2JCF = 46.0 Hz), 128.2 (ddd,
1JCF = 239.5 Hz, 2JCF = 50.7 Hz, 2JCF = 16.1 Hz), 80.2 (d, 3JCF = 3.0 Hz),
CF3CF CFCH
C CH2]: 170 (59.3), 101 (100.0).
2
68.9 (s), 23.4 (d, JCF = 23.2 Hz), 16.6 (s). GC–MS, m/z (relative
intensity): 134 (19.4), 119 (74.8), 69 (100.0). 19F NMR:
3.2.6. Reaction of (Z)-pentafluoropropenylcopper reagent with
3-tosyl-1-butyne
(F2C CFCH
C
CHCH3):
d
ꢀ103.0 (dddd, 2JFF = 73.5 Hz,
3JFF = 30.0 Hz,
4JFH = 2 Hz,
6JFH = 2 Hz),
ꢀ121.5
(dddd,
Similar to Section 3.2.1, a 32-ml aliquot of a 0.94-M (Z)-
pentafluoropropenylzinc reagent (30 mmol) in DMF, 0.3 g
(10 mol%) Cu(I)Br and 6.7 g (30 mmol) of 3-tosyl-1-butyne gave
after distillation 4.0 g (67%), bp 40–45 8C/90 mm Hg, a mixture
(GLPC purity, 96%) which contained 23% of (E)-3-methyl-4,5,6,6,6-
pentafluorohex-4-ene-1-yne and 77% of (E)-5,6,7,7,7-pentafluoro-
2,3,5-heptatriene (as determined by GLPC analysis). 19FNMR: [(E)-
3JFF = 109.2 Hz, JFF = 73.5 Hz, JFH = 3.1 Hz, JFH = 3.1 Hz), ꢀ177.3
2
4
6
(ddd, 3JFF = 109.2 Hz, 3JFF = 30.0 Hz, 3JFH = 22.7 Hz); 1H NMR:
d 1.74
3
5
(dd, JHH = 7.0 Hz, JHH = 3.5 Hz), 5.56 (m), 5.80 (m); 13C NMR
(Neat):
150.4 (ddd, 1JCF = 286.6 Hz, 1JCF = 275.1 Hz, 2JCF = 46.2 Hz),
123.6 (ddd, JCF = 229.6 Hz, JCF = 49.3 Hz, JCF = 19.0 Hz), 203.8
d
1
2
2
3
4
2
(dd, JCF = 10.4 Hz, JCF = 3.8 Hz), 91.5 (s), 80.6 (dd, JCF = 22.6 Hz,
3JCF = 3.4 Hz), 12.4 (s), GC–MS, m/z (relative intensity): 134 (100.0),
133 (41.7). IR: Mixture of F2C=CFCH=C=CHCH3 and
F2C=CFCH(CH3)CBCH): 3313 (BCH)(m), 2337 (CBC) (w), 1830
(F2C=CF) (w), 1796 (F2C=CF) (vs), 1306 (s), (1283 (vs), 1267 (s),
1081 (vs).
CF3CF=CFCH(CH3)C CH)]:
d
ꢀ68.6
(dd,
4JFF = 21.5 Hz,
3JFF = 11.1 Hz), ꢀ149.0 (ddq, 3JFF = 132.9 Hz, 3JFH = 27.5 Hz,
4JFF = 21.5 Hz), ꢀ172.6 (dqd, 3JFF = 132.9 Hz, 3JFF = 11.1 Hz,
4JFH = 4.0 Hz); 1H NMR:
d
1.47 (d, JHH = 7.2 Hz), 2.18 (d,
3
3
4JHH = 2.4 Hz), 3.69 (dm, JFH = 27.5 Hz); 13C NMR (Neat):
d 154.4
1
2
1
(dd, JCF = 266.2 Hz, JCF = 41.8 Hz), 136.5 (ddq, JCF = 247.6 Hz,
3.2.3. Preparation of 2-methyl-5,6,6-trifluoro-2,3,5-hexatriene
2JCF = 44.9 Hz,
2JCF = 40.7 Hz),
118.9
(qd,
1JCF = 270.3 Hz,
2
Similar to Section 3.2.1,
a
39-ml aliquot of
a
1.55-M
2JCF = 33.8 Hz), 79.1 (s), 70.1 (s), 24.5 (d, JCF = 23.1 Hz), 16.6 (s).
trifluorovinylzinc reagent (60 mmol), 7.9 g Cu(I)Br (55 mmol)
and 4.6 g (45 mmol) of 3-chloro-3-methyl-1-butyne gave 3.96 g
(59%) of 2-methyl-5,6,6-trifluoro-2,3,5-hexatriene after flash
GC–MS, m/z (relative intensity): 184 (4.8), 119 (74.4), 115 (100.0),
69 (90.7). 19F NMR: [(E)-CF3CF CFCH
C
CHCH3)]:
d
ꢀ67.9 (dd,
4JFF = 20.8 Hz, 3JFF = 12.2 Hz), ꢀ174.1 (dqdd, 3JFF = 127.5 Hz,
distillation (97% GLPC purity). 19F NMR:
d
ꢀ103.6 (ddd,
3JFF = 12.2 Hz,
4JFH = 3.3 Hz,
6JFH = 3.3 Hz),
ꢀ146.0
(ddq,
2JFF = 75.7 Hz, 3JFF = 29.3 Hz, 4JFH = 1.7 Hz), ꢀ122.2 (ddd,
3JFF = 112.3 Hz, 2JFF = 75.7 Hz, 4JFH = 3.9 Hz), ꢀ176.9 (ddd,
3JFF = 127.5 Hz, JFH = 22.8 Hz, JFF = 20.8 Hz); 1H NMR: 1.78 (dd,
3
4
3JHH = 7.2 Hz, JHH = 3.3 Hz) 5.76 (m), 6.09 (dddq, JFH = 22.8 Hz,
5
3
3JFF = 112.3 Hz, JFF = 29.3 Hz, JFH = 23.3 Hz); 1H NMR:
d
1.77 (d,
151.9 (ddd,
1JCF = 289.4 Hz, 1JCF = 280.4 Hz, 2JCF = 46.7 Hz), 124.0 (ddd,
1JCF = 229.6 Hz, 2JCF = 48.6 Hz, 2JCF = 18.4 Hz),
201.0 (d,
3JCF = 10.4 Hz), 101.6 (s), 79.1 (d, JCF = 23.0 Hz), 18.6 (s). GC–MS,
4JHH = 6.4 Hz, 4JFH = 3.3 Hz, 5JHH = 3.3 Hz); 13C NMR (Neat):
d
148.6
3
3
5JFH = 3.0 Hz), 5.56 (m); 13C NMR (Neat):
d
(dd, JCF = 253.0 Hz, JCF = 39.1 Hz), 136.5 (ddq, JCF = 247.6 Hz,
2JCF = 44.9 Hz, 2JCF = 40.7 Hz), 119.3 (qdd, 1JCF = 270.2 Hz,
1
2
1
3
3
2JCF = 34.7 Hz, JCF = 4.0 Hz), 207.3 (d, JCF = 5.1 Hz), 81.7 (d,
2JCF = 23.2 Hz), 92.2 (s), 12.0 (s). GC–MS, m/z (relative intensity):
184 (13.6), 115 (76.7), 69 (100.0). IR (mixture of isomers): 3313
2
m/z (relative intensity): 148 (100.0), 133 (38.8). IR: 1964 (C
C C)
(w), 1763 (F2C CF) (s), 1274 (vs), 1086 (vs).
(BCH) (m), 1957 (C C C) (m), 1734 (FC CF) (w), 1702 (FC CF)
(w), 1380 (vs), 1370 (vs), 1261 (vs), 1250 (s), 1202 (vs), 1147 (vs).
3.2.4. Preparation of 1-pentamethylene-4,5,5-trifluoro-1,2,4-
pentatriene
3.2.7. Preparation of (E)-2-methyl-5,6,7,7,7-pentafluoro-2,3,5-
heptatriene
Similar to Section 3.2.1,
a 46-ml aliquot of a 1.42-M
trifluorovinylzinc reagent, 0.6 g Cu(I)Cl (10 mol%) and 8.5 g
(60 mmols) of 1-chloro-1-ethynylcyclohexane gave 8.5 g (75%)
of 1-pentamethylene-4,5,5-trifluoro-1,2,4-pentatriene after dis-
Similar to Section 3.2.1, a 58-ml aliquot of 0.89 M (Z)-
pentafluoropropenylzinc reagent (52 mmol), 7.5 g Cu(I)Br
(52 mmol) and 5.12 g (50 mmol) of 3-chloro-3-methyl-1-butyne
gave after distillation 7.85 g (79%), bp 37–38 8C/21 mm Hg, of (E)-
2-methyl-5,6,7,7,7-pentafluoro-2,3,5-heptatriene (GLPC purity,
tillation, bp 34–35 8C/0.5 mm Hg (GLPC purity = 91%). 19F NMR:
d
ꢀ103.8 (dd, 2JFF = 75.7 Hz, 3JFF = 29.7 Hz), ꢀ122.4 (dd,
3JFF = 109.5 Hz, 2JFF = 75.7 Hz), ꢀ176.8 (ddd, 3JFF = 109.5 Hz,
100%). 19F NMR:
d
ꢀ67.8 (dd, JFF = 21.2 Hz, JFF = 11.7 Hz),
4
3
3
3JFF = 29.7 Hz, JFH = 22.5 Hz); 1H NMR:
d
1.59 (m), 2.15 (m), 5.45
ꢀ146.6 (ddq, 3JFF = 126.9 Hz, 3JFH = 23.7 Hz, 4JFF = 21.2 Hz),
(dm, 3JFH = 22.5 Hz); 13C NMR (Neat):
1JCF = 280.5 Hz, 2JCF = 47.0 Hz), 124.0 (ddd, 1JCF = 229.5 Hz,
d
151.8 (ddd, 1JCF = 290.0 Hz,
ꢀ175.0 (dqd, JFF = 126.9 Hz, JFF = 11.7 Hz, JFH = 3.7 Hz); 1H
3
3
4
5
3
NMR:
d 1.80 (d, JHH = 2.9 Hz), 5.86 (ddhept), JFH = 23.7 Hz,