E
A. M. Gates, W. L. Santos
Paper
Synthesis
1-(But-2-en-2-yl)-4-methylbenzene (7)
4-(But-2-en-2-yl)benzonitrile (13)
Reaction scale: 0.277 mmol; NMR yield: 63%; Z/E = 86:14.
Reaction scale: 0.161 mmol; NMR yield: 39%; Z/E = 81:19.
1H NMR (400 MHz, CDCl3): = 7.28 (d, J = 8.0 Hz, 2 H), 7.19–7.15 (m,
2 H), 7.12 (d, J = 8.2 Hz, 2 H, 2 H), 5.85 (qq, J = 6.8, 1.4 Hz, 1 H), 5.56
(qq, J = 6.9, 1.5 Hz, 1 H), 2.37 (s, 3 H), 2.34 (s, 3 H), 2.05–2.02 (m, 3 H,
3 H), 1.81 (dq, J = 7.0, 1.1 Hz, 3 H), 1.63 (dq, J = 6.9, 1.6 Hz, 3 H); data
consistent with literature values.17
1H NMR (400 MHz, CDCl3): = 7.63 (d, J = 8.1 Hz, 2 H), 7.57 (d, J = 6.8
Hz, 2 H), 7.44 (d, J = 8.4 Hz, 2 H), 7.29 (d, J = 8.4 Hz, 2 H), 5.99 (qq, J =
6.1, 1.2 Hz, 1 H), 5.66 (qq, J = 6.8, 1.3 Hz, 1 H), 2.04–2.01 (m, 3 H, 3 H),
1.83 (dq, J = 6.9, 1.1 Hz, 3 H), 1.58 (dq, J = 7.0, 1.5 Hz, 3 H).
13C NMR (101 MHz, CDCl3): = 147.0, 135.4, 132.1, 129.0, 123.9,
119.2, 110.2, 25.0, 15.0.
HRMS (ESI+): m/z [M + H]+ calcd for C11H12N: 158.0964; found:
158.0982.
1-(But-2-en-2-yl)-2-methylbenzene (8)
Reaction scale: 0.173 mmol; NMR yield: 58%; Z/E = 91:9.
1H NMR (400 MHz, CDCl3): = 7.22–7.08 (m, 4 H), 7.02–6.98 (m, 4 H),
5.54 (qq, J = 6.7, 1.5 Hz, 1 H), 5.36 (qq, J = 6.7, 1.5 Hz, 1 H), 2.26 (s,
3 H), 2.20 (s, 3 H), 1.94–1.91 (m, 3 H), 1.91–1.89 (m, 3 H), 1.76 (dq, J =
6.8, 1.1 Hz, 3 H), 1.35 (dq, J = 6.7, 1.6 Hz, 3 H); data consistent with
literature values.18
Prop-1-ene-1,1-diyldibenzene (14)
Reaction scale: 0.260 mmol; yield: 43 mg (85%); colorless solid; Rf =
0.39 (hexanes).
1H NMR (400 MHz, CDCl3): = 7.41–7.32 (m, 2 H), 7.33–7.14 (m, 8 H),
6.17 (q, J = 7.0 Hz, 1 H), 1.76 (d, J = 7.0 Hz, 3 H); data consistent with
literature values.20
1-(But-2-en-2-yl)-4-methoxybenzene (9)
Reaction scale: 0.312 mmol; NMR yield: 63%; Z/E = 85:15.
1H NMR (400 MHz, CDCl3): = 7.31 (d, J = 8.9 Hz, 2 H), 7.14 (d, J = 8.8
Hz, 2 H), 6.89 (d, J = 8.8 Hz, 2 H), 6.84 (d, J = 8.8 Hz, 2 H), 5.78 (qq, J =
6.9, 1.4 Hz, 1 H), 5.53 (qq, J = 6.9, 1.5 Hz, 1 H), 3.81 (s, 3 H), 3.80 (s,
3 H), 2.03–2.00 (m, 3 H, 3 H), 1.78 (dq, J = 6.8, 1.0 Hz, 3 H), 1.61 (dq, J =
6.9, 1.5 Hz, 3 H); data consistent with literature values.19
4,4′-(Prop-1-ene-1,1-diyl)bis(chlorobenzene) (15)
Reaction scale: 0.061 mmol; yield: 14 mg (87%); colorless oil; Rf = 0.52
(5% EtOAc in hexanes).
1H NMR (400 MHz, CDCl3): = 7.35 (d, J = 8.6 Hz, 2 H), 7.23 (d, J = 8.7
Hz, 2 H), 7.15–7.08 (m, 4 H), 6.16 (q, J = 7.1 Hz, 1 H), 1.75 (d, J = 7.1 Hz,
3 H); data consistent with literature values.21
1-(But-2-en-2-yl)-3-methoxybenzene (10)
Reaction scale: 0.312 mmol; NMR yield: 57%; Z/E = 86:14.
4,4′-(Prop-1-ene-1,1-diyl)bis(fluorobenzene) (16)
1H NMR (400 MHz, CDCl3): = 7.27–7.17 (m, 1 H, 1 H), 6.80–6.72 (m,
3 H, 3 H), 5.86 (qq, J = 6.9, 1.4 Hz, 1 H), 5.54 (qq, J = 6.9, 1.5 Hz, 1 H),
3.80 (s, 3 H), 3.79 (s, 3 H), 2.03–1.97 (m, 3 H, 3 H), 1.78 (dq, J = 6.9, 1.1
Hz, 3 H), 1.60 (dq, J = 6.9, 1.6 Hz, 3 H).
13C NMR (101 MHz, CDCl3): = 159.5, 143.6, 136.9, 129.2, 121.9,
120.7, 114.0, 111.8, 55.3, 25.5, 15.0.
Reaction scale: 0.22 mmol; yield: 43 mg (85%); colorless oil; Rf = 0.36
(hexanes).
1H NMR (400 MHz, CDCl3): = 7.21–7.11 (m, 4 H), 7.11–7.04 (m, 2 H),
7.00–6.91 (m, 2 H), 6.11 (q, J = 7.0 Hz, 1 H), 1.76 (d, J = 7.0 Hz, 3 H);
data consistent with literature values.22
HRMS (ESI+): m/z [M + H]+ calcd for C11H15O: 163.1123; found:
163.1130.
4,4′-(Prop-1-ene-1,1-diyl)bis(methylbenzene) (17)
Reaction scale: 0.23 mmol; yield: 45 mg (88%); colorless oil; Rf = 0.40
(hexanes).
1-(But-2-en-2-yl)-2-methoxybenzene (11)
1H NMR (400 MHz, CDCl3): = 7.22–7.16 (m, 2 H), 7.15–7.05 (m, 6 H),
6.12 (q, J = 7.0 Hz, 1 H), 2.40 (s, 3 H), 2.33 (s, 3 H), 1.77 (d, J = 7.0 Hz,
3 H).
13C NMR (101 MHz, CDCl3): = 142.3, 140.6, 137.3, 136.5, 136.5,
130.1, 128.9, 128.9, 127.3, 123.2, 21.4, 21.2, 15.8.
Reaction scale: 0.156 mmol; NMR yield: 72%; Z/E = 88:12.
1H NMR (400 MHz, CDCl3): = 7.26–7.21 (m, 1 H, 1 H), 7.10 (dd, J =
7.4, 1.8 Hz, 1 H), 7.04 (dd, J = 7.4, 1.8 Hz, 1 H), 6.96–6.82 (m, 2 H, 2 H),
5.60 (qq, J = 6.7, 1.5 Hz, 1 H), 5.54 (qq, J = 6.7, 1.4 Hz, 1 H), 3.82 (s,
3 H), 3.81 (s, 3 H), 2.00–1.95 (m, 3 H, 3 H), 1.76 (dq, J = 6.8, 1.1 Hz,
3 H), 1.45 (dq, J = 6.7, 1.5 Hz, 3 H).
HRMS (ESI+): m/z [M + H]+ calcd for C17H19
: 223.1487; found:
223.1478.
13C NMR (101 MHz, CDCl3): = 156.6, 134.9, 131.0, 130.1, 128.0,
122.6, 120.6, 111.0, 55.6, 24.6, 14.9.
HRMS (ESI+): m/z [M + H]+ calcd for C11H15O: 163.1123; found:
163.1128.
4,4′-(Prop-1-ene-1,1-diyl)bis(methoxybenzene) (18)
Reaction scale: 0.12 mmol; yield: 23 mg (74%); white solid; Rf = 0.52
(10% EtOAc in hexanes).
1H NMR (400 MHz, CDCl3): = 7.14 (d, J = 8.9 Hz, 2 H), 7.10 (d, J = 8.8
Hz, 2 H), 6.90 (d, J = 8.8 Hz, 2 H), 6.79 (d, J = 8.9 Hz, 2 H), 6.02 (q, J = 7.0
Hz, 1 H), 3.84 (s, 3 H), 3.79 (s, 3 H), 1.75 (d, J = 7.0 Hz, 3 H); data con-
sistent with literature values.23
5-(But-2-en-2-yl)benzo[d][1,3]dioxole (12)
Reaction scale: 0.287 mmol; NMR yield: 65%; Z/E = 86:14.
1H NMR (400 MHz, CDCl3): = 6.93–6.63 (m, 3 H, 3 H), 5.93 (s, 2 H),
5.91 (s, 2 H), 5.75 (qq, J = 6.9, 1.4 Hz, 1 H), 5.51 (qq, J = 6.9, 1.5 Hz,
1 H), 2.00–1.95 (m, 3 H, 3 H), 1.76 (dq, J = 6.9, 1.1 Hz, 3 H), 1.59 (dq, J =
6.9, 1.6 Hz, 3 H).
4,4′-(Prop-1-ene-1,1-diyl)bis(ethoxybenzene) (19)
Reaction scale: 0.18 mmol; yield: 41 mg (81%); white solid; mp 67–
72 °C; Rf = 0.64 (10% EtOAc in hexanes).
13C NMR (101 MHz, CDCl3): = 147.4, 146.0, 136.5, 135.9, 121.7,
121.4, 108.8, 108.1, 101.0, 25.7, 15.1.
HRMS (ESI+): m/z [M + H]+ calcd for C11H13O2: 177.0916; found:
177.0924.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2019, 51, A–F