G. He, X. Xiao, H.-Z. Jin et al.
Tetrahedron 83 (2021) 131963
132.7 (s), 132.0 (t, J ¼ 22.2 Hz), 128.9 (s), 128.5 (s), 127.9 (s), 127.5 (s),
126.9 (s), 126.0 (t, J ¼ 7.7 Hz), 122.0 (t, J ¼ 4.8 Hz), 115.4 (t,
J ¼ 236.1 Hz). GC-MS (EI) calcd. For C11H8F2 [M]þ: 178.1; Found:
178.1.
4.3.9. 6-(difluoromethyl)-2,3-dihydrobenzo[b][1,4]dioxine (3i) [19]
52 mg, 70%, yellow liquid. 1H NMR (300 MHz, CDCl3)
d 7.08e6.86
(m, 3H), 6.54 (t, J ¼ 56.7 Hz, 1H), 4.27 (s, 4H). 19F NMR (376 MHz,
CDCl3)
d
ꢁ108.37 (d, J ¼ 56.8 Hz, 2F). 13C NMR (101 MHz, CDCl3)
d
145.5 (t, J ¼ 1.8 Hz), 143.6 (s), 127.7 (t, J ¼ 22.8 Hz), 118.7 (t,
J ¼ 6.2 Hz), 117.5 (s), 114.8 (t, J ¼ 6.1 Hz), 114.5 (t, J ¼ 237.9 Hz), 64.4
(s), 64.2 (s). IR (neat) v ¼ 2933, 1687, 1602, 1582, 1462, 1391, 1315,
1290, 1166, 1064, 919, 888, 818, 792. HRMS (EI): calcd. for C9H8F2O2
[M]þ: 186.0492; Found: 186.0498.
4.3.3. 9-(difluoromethyl)phenanthrene (3c) [17]
68 mg, 75%, yellow solid. 1H NMR (400 MHz, CDCl3)
d 8.73 (d,
J ¼ 7.7 Hz,1H), 8.67 (d, J ¼ 8.1 Hz,1H), 8.20 (d, J ¼ 7.3 Hz,1H), 7.95 (s,
1H), 7.92 (d, J ¼ 8.1 Hz, 1H), 7.77e7.57 (m, 4H), 7.14 (t, J ¼ 55.0 Hz,
1H). 19F NMR (376 MHz, CDCl3)
NMR (101 MHz, CDCl3) d 131.4 (s), 130.8 (s), 130.1 (s), 129.5 (s), 128.3
d
ꢁ111.80 (d, J ¼ 55.0 Hz, 2F). 13
C
4.3.10. 4-Bromo-2-(difluoromethyl)-1-methoxybenzene (3j)
47 mg, 50%, yellow liquid. 1H NMR (400 MHz, CDCl3)
d 7.64 (d,
(s), 128.0 (t, J ¼ 20.8 Hz), 127.9 (t, J ¼ 1.9 Hz), 127.2 (s), 127.16 (s),
127.14 (s), 126.8 (t, J ¼ 9.3 Hz), 124.5 (t, J ¼ 1.7 Hz), 123.2 (s), 122.6
(s), 115.6 (t, J ¼ 238.6 Hz). GC-MS (EI) calcd. For C15H10F2 [M]þ:
228.1; Found: 228.1.
J ¼ 1.7 Hz, 1H), 7.50 (dd, J ¼ 8.8 Hz, 1.7 Hz, 1H), 6.86 (t, J ¼ 55.3 Hz,
1H), 6.80 (d, J ¼ 8.8 Hz, 1H), 3.83 (s, 3H). 19F NMR (376 MHz, CDCl3)
d
ꢁ116.06 (d, J ¼ 55.3 Hz, 2F). 13C NMR (101 MHz, CDCl3)
d 156.3 (t,
J ¼ 5.8 Hz), 134.6 (t, J ¼ 1.9 Hz),129.2 (t, J ¼ 6.2 Hz), 124.4 (t,
J ¼ 23.4 Hz), 112.80 (s), 112.79 (s), 110.6 (t, J ¼ 236.9 Hz), 55.9 (s). IR
(neat) v ¼ 2944, 1601, 1492, 1412, 1382, 1270, 1179, 1091, 812, 653,
549. HRMS (EI): calcd. for C8H7F2OBr [M]þ: 235.9648; Found:
235.9653.
4.3.4. 1-(difluoromethyl)naphthalene (3d) [17]
53 mg, 74%, yellow liquid. 1H NMR (400 MHz, CDCl3)
d 8.18 (d,
J ¼ 7.7 Hz,1H), 7.96 (d, J ¼ 7.6 Hz,1H), 7.91 (d, J ¼ 7.6 Hz, 1H), 7.69 (d,
J ¼ 5.7 Hz, 1H), 7.64e7.44 (m, 3H), 7.13 (t, J ¼ 55.2 Hz, 1H). 19F NMR
(376 MHz, CDCl3)
CDCl3)
d
ꢁ110.88 (d, J ¼ 55.2 Hz, 2F). 13C NMR (101 MHz,
d
133.8 (s), 131.5 (t, J ¼ 1.6 Hz), 129.7 (t, J ¼ 2.5 Hz), 129.5 (t,
4.3.11. 1-(difluoromethyl)-4-(3-methoxypropoxy)benzene (3k)
24 mg, 28%, colorless liquid. 1H NMR (400 MHz, CDCl3)
d 7.41 (d,
J ¼ 20.8 Hz), 128.8 (s), 127.1 (s), 126.3 (s), 124.8 (t, J ¼ 8.7 Hz), 124.6
(s), 123.5 (t, J ¼ 1.4 Hz), 115.4 (t, J ¼ 238.4 Hz). GC-MS (EI) calcd. For
J ¼ 8.6 Hz, 2H), 6.94 (d, J ¼ 8.6 Hz, 2H), 6.58 (t, J ¼ 56.8 Hz, 1H), 4.07
C
11H8F2 [M]þ: 178.1; Found: 178.1.
(t, J ¼ 6.3 Hz, 2H), 3.54 (t, J ¼ 6.1 Hz, 2H), 3.34 (s, 3H), 2.04 (p,
J ¼ 6.2 Hz, 2H). 19F NMR (376 MHz, CDCl3)
ꢁ108.23 (d, J ¼ 56.8 Hz,
d
4.3.5. 1-(benzyloxy)-4-(difluoromethyl)benzene (3e) [17]
2F). 13C NMR (101 MHz, CDCl3)
d
160.8 (t, J ¼ 1.5 Hz), 127.0 (t,
76 mg, 81%, yellow solid. 1H NMR (400 MHz, CDCl3)
d
7.48e7.31
J ¼ 6.0 Hz),126.6 (t, J ¼ 22.7 Hz),114.9 (t, J ¼ 237.3 Hz),114.5 (s), 69.0
(s), 64.8 (s), 58.4 (s), 29.5 (s). IR (neat) v ¼ 2930, 1616, 1518, 1383,
1253, 1176, 1119, 1070, 1019, 835, 642. HRMS (EI): calcd. for
(m, 7H), 7.02 (d, J ¼ 8.7 Hz, 2H), 6.59 (t, J ¼ 56.7 Hz, 1H), 5.09 (s, 2H).
19F NMR (376 MHz, CDCl3)
(101 MHz, CDCl3)
127.5 (s), 127.2 (t, J ¼ 6.0 Hz), 127.0 (t, J ¼ 22.0 Hz), 115.0 (s), 114.9 (t,
J ¼ 237.5 Hz), 70.1 (s). GC-MS (EI) calcd. For C14H12F2O [M]þ: 234.1;
Found: 234.0.
d
ꢁ108.17 (d, J ¼ 55.8 Hz, 2F). 13C NMR
d
160.6 (t, J ¼ 1.8 Hz), 136.5 (s), 128.7 (s), 128.2 (s),
C
11H14F2O2 [M]þ: 216.0962; Found: 216.0966.
4.3.12. 1-(difluoromethyl)-4-propoxybenzene (3l)
39 mg, 53%, colorless liquid. 1H NMR (300 MHz, CDCl3)
d 7.42 (d,
J ¼ 8.2 Hz, 2H), 6.94 (d, J ¼ 8.0 Hz, 2H), 6.60 (t, J ¼ 56.7 Hz, 1H), 3.94
(t, J ¼ 6.2 Hz, 2H), 1.87e1.76 (m, 2H), 1.04 (t, J ¼ 7.2 Hz, 3H). 19F NMR
4.3.6. 1-((allyloxy)-4-(difluoromethyl)benzene (3f)
40 mg, 54%, yellow liquid. 1H NMR (400 MHz, CDCl3)
d 7.41 (d,
(282 MHz, CDCl3)
CDCl3)
J ¼ 22.7 Hz), 114.9 (t, J ¼ 237.3 Hz), 114.5 (s), 69.6 (s), 22.4 (s), 10.4
(s). IR (neat) v ¼ 2913, 1719, 1617, 1482, 1457, 1246, 1048, 1005, 819,
548. HRMS (EI): calcd. for C10H12F2O [M]þ: 186.0856; Found:
186.0863.
d
ꢁ108.48 (d, J ¼ 56.7 Hz, 2F). 13C NMR (101 MHz,
J ¼ 8.6 Hz, 2H), 6.95 (d, J ¼ 8.7 Hz, 2H), 6.58 (t, J ¼ 56.8 Hz, 1H),
6.08e5.98 (m, 1H), 5.40 (dq, J ¼ 17.3, 1.5 Hz, 1H), 5.29 (dq, J ¼ 10.5,
1.3 Hz, 1H), 4.55 (dt, J ¼ 5.2, 1.3 Hz, 2H). 19F NMR (376 MHz, CDCl3)
d
160.9 (t, J ¼ 1.6 Hz), 127.0 (t, J ¼ 5.9 Hz), 126.5 (t,
d
ꢁ108.99 (d, J ¼ 56.6 Hz, 2F). 13C NMR (101 MHz, CDCl3)
d 160.3 (t,
J ¼ 1.8 Hz), 132.7 (s), 127.1 (t, J ¼ 5.9 Hz), 126.7 (t, J ¼ 22.7 Hz), 118.0
(s), 114.8 (t, J ¼ 237.4 Hz), 114.7 (s), 68.8 (s). IR (neat) v ¼ 2963, 1647,
1517, 1411, 1252, 1071, 1020, 929, 861, 833, 658. HRMS (EI): calcd. for
C
10H10F2O [M]þ: 184.0700; Found: 184.0703.
Declaration of competing interest
All authors declare that No conflict of interest exists.
4.3.7. 1-(difluoromethyl)-4-ethoxybenzene (3g) [17]
56 mg, 81%, colorless liquid. 1H NMR (400 MHz, CDCl3)
d 7.41 (d,
Acknowledgments
J ¼ 8.1 Hz, 2H), 6.92 (d, J ¼ 8.3 Hz, 2H), 6.58 (t, J ¼ 56.8 Hz, 1H), 4.04
(q, J ¼ 7.0 Hz, 2H), 1.41 (t, J ¼ 7.0 Hz, 3H). 19F NMR (376 MHz, CDCl3)
d
ꢁ108.18 (d, J ¼ 56.8 Hz, 2F). 13C NMR (101 MHz, CDCl3)
d 160.7 (t,
We thank the National Natural Science Foundation (21971252,
21991122), Key Research Program of Frontier Sciences, Chinese
Academy of Sciences (CAS) (QYZDJSSWSLH049), Youth Innovation
Promotion Association CAS (2019256), Science and Technology
Department of Gansu Province (19ZD2GC001), the Key Project
Foundation of Hunan Provincial Education Department (No.
19A085), and the Natural Science Foundation of Hunan Province
(No.2017JJ2018) for financial support.
J ¼ 1.6 Hz), 127.0 (t, J ¼ 5.9 Hz), 126.5 (t, J ¼ 22.8 Hz), 114.9 (t,
J ¼ 237.3 Hz), 114.5 (s), 63.6 (s), 14.7 (s). GC-MS (EI) calcd. For
C9H10F2O [M]þ: 172.1; Found 172.1.
4.3.8. 1-(difluoromethyl)-4-phenoxybenzene (3h) [18]
63 mg, 72%, yellow liquid. 1H NMR (400 MHz, CDCl3)
d 7.46 (d,
J ¼ 8.5 Hz, 2H), 7.42e7.33 (m, 2H), 7.16 (tt, J ¼ 7.7, 1.04 Hz, 1H),
7.08e7.01 (m, 4H), 6.62 (t, J ¼ 56.6 Hz, 1H). 19F NMR (376 MHz,
CDCl3)
d
ꢁ108.97 (d, J ¼ 56.6 Hz, 2F). 13C NMR (101 MHz, CDCl3)
Appendix A. Supplementary data
d
159.6 (t, J ¼ 1.9 Hz), 156.2 (s), 130.0 (s), 128.9 (t, J ¼ 22.8 Hz), 127.3
(t, J ¼ 5.9 Hz), 124.1 (s), 119.6 (s), 118.2 (s), 114.6 (t, J ¼ 238.0 Hz). GC-
Supplementary data to this article can be found online at
MS (EI) calcd. For C13H10F2O [M]þ: 220.1; Found 220.1.
4