6
J. Yang et al. / Tetrahedron xxx (xxxx) xxx
4.2.11. 2-Hydroxy-3-methylnaphthalene-1,4-dione (2k) (yellow
4.3.2. 2-Cyclooctyl-3-phenylnaphthalene-1,4-dione(3ac) (yellow
solid, 63.2 mg, 84%) [22]
liquid, 59.8 mg, 53%)12
m.p.122e124 ꢀC. 1H NMR (CDCl3, 400 MHz)
d
8.10 (d, J ¼ 8 Hz,
1H), 8.06 (d, J ¼ 8 Hz, 1H), 7.73 (t, J ¼ 8 Hz, 1H), 7.66 (d, J ¼ 8 Hz, 1H),
7.34 (s, 1H), 2.09 (s, 3H). 13C NMR (CDCl3, 100 MHz)
185.13, 181.14,
1H NMR (CDCl3, 400 MHz)
d 8.04-7.99 (m, 2H), 7.68-7.62 (m, 2H),
3.20 (bs, 1H), 2.19 (s, 3H), 2.07-1.98 (m, 2H), 1.85-1.78 (m, 2H), 1.74-
1.66 (m, 3H) 1.62-1.54 (m, 5H), 1.52-1.44 (m, 2H).
d
153.13, 134.80, 132.88, 129.37, 126.70, 126.10, 120.51, 109.99, 8.68.
4.3.3. 2-Bromo -3- cyclohexylnaphthalene-1,4-dione(3ja) (yellow
4.2.12. 2-Methoxy-3-methyl-1,4-naphthoquinone(2l) (yellow solid,
solid, 34.4 mg, 27%)
m.p.110e112 ꢀC. 1H NMR (CDCl3, 400 MHz)
d 8.14-8.11 (m, 1H),
35.5 mg, 44%) [23]
m.p.80e82 ꢀC. 1H NMR (CDCl3, 400 MHz)
d
8.06-8.01 (m, 2H),
7.68-7.66 (m, 2H), 4.10 (s, 3H), 2.08 (s, 3H). 13C NMR (CDCl3,
100 MHz) 185.75, 181.22, 157.77, 133.69, 133.21, 131.92, 131.75,
8.08-8.06-7 (m, 1H),7.76-7.69 (m, 2H), 3.25 (m, 1H), 2.18-2.08 (m,
2H),1.88-1.85 (m, 2H),1.77-1.75 (m,1H), 1.71-1.67 (m, 2H), 1,41-1.34
(m, 3H). 13C NMR (CDCl3, 100 MHz)
d 182.07, 178.02, 154.50, 138.85,
d
131.44, 126.13, 126.10, 61.02, 9.29.
134.04, 133.56, 132,23, 130.57, 127.21, 126.98, 46.01, 29.26, 26.68,
25.72. HRMS (ESI) m/z: C16H15BrNaOþ2 ([MNa]þ) calculated for:
341.0153, found: 341.0159.
4.2.13. 2,3,6,7-Tetramethylnaphthalene-1,4-dione (2m) (yellow
solid, 35.1 mg, 41%)
m.p.165e166 ꢀC. 1H NMR (CDCl3, 400 MHz)
d 7.77 (s, 2H), 2.35 (s,
4.3.4. Parvaquone(3ka) (yellow solid, 66.6 mg, 65%)12
6H), 2.12 (s, 6H). 13C NMR (CDCl3, 100 MHz)
d 185.12, 142.94, 130.09,
m.p.129e131 ꢀC. 1H NMR (CDCl3, 400 MHz)
d
8.09 (d, J ¼ 8 Hz,
127.22, 109.99, 20.11, 12.82. HRMS (ESI) m/z: C14H14NaOþ2 ([MNa]þ)
1H), 8.03 (d, J ¼ 8 Hz, 1H), 7.72 (t, J ¼ 8 Hz, 1H), 7.64 (t, J ¼ 8 Hz, 1H),
7.44 (s, 1H), 3.06 (tt, J ¼ 12 Hz, J ¼ 4 Hz, 1H), 2.01-1.91 (m, 2H), 1.82-
1.78 (m, 2H), 1.70-1.65 (m, 1H), 1.41-1.26 (m,3H). 13C NMR (CDCl3,
calculated for: 237.0891, found: 237.0893.
100 MHz)
d 184.54, 181.90, 152.81, 134.84, 133.12, 132.67, 129.17,
4.2.14. 6,7-Dibromo-2,3-dimethyl-1,4-naphthoquinone(2n) (yellow
127.86, 126.88, 125.87, 35.12, 29.19, 26.72, 25.93.
solid, 72.9 mg, 53%) [24]
m.p.201e203 ꢀC. 1H NMR (CDCl3, 400 MHz)
d
8.26 (s, 2H), 2.16 (s,
6H); 13C NMR (CDCl3, 100 MHz)
131.13, 13.00.
d 183.12, 143.76, 131.53, 131.33,
4.3.5. 2-Cyclohexyl-3,5,6-trimethylcyclohexa-2,5-diene-1,4-
dione(3pa) (yellow liquid, 47.3 mg, 51%)
1H NMR (CDCl3, 400 MHz)
d
2.71 (tt, J ¼ 12 Hz, 4 Hz, 1H), 2.04 (s,
3H), 1.97-1.96 (d, J ¼ 4 Hz, 6H), 1.91-1.86 (m, 2H), 1.80-1.77 (m, 2H),
4.2.15. 2,3,5,8-Tetramethylnaphthalene-1,4-dione (2o) (yellow
1.70-1.69 (m, 1H), 1.52-1.49 (m, 2H), 1.29-1.23 (m, 3H). 13C NMR
solid, 35.9 mg, 42%) [25]
m.p.120e121 ꢀC. 1H NMR (CDCl3, 400 MHz)
d
7.31 (s, 2H), 2.76 (s,
(CDCl3, 100 MHz)
d 188.05, 187.59, 147.52, 140.95, 139.91, 139.61,
40.05, 29.99, 26.96, 25.89, 12.27, 11.99. HRMS (ESI) m/z: C15H21O2þ
6H), 2.11 (s, 6H). 13C NMR (CDCl3, 100 MHz)
136.55, 131.35, 23.23, 12.82.
d 187.65, 142.83, 138.98,
([MH]þ) calculated for: 233.1542, found: 233.1546.
4.3.6. 2-Cyclohexyl-5,6-dimethoxy-3-methylcyclohexa-2,5-diene-
4.2.16. Tetramethyl-1,4-benzoquinone (2p) (yellow solid, 32.1 mg,
1,4-dione (3qa) (yellow liquid, 40.1 mg, 38%)7
49%) [26]
m.p.55e57 ꢀC. 1H NMR (CDCl3, 400 MHz)
d 3.96 (s, 3H), 3.94 (s,
m.p.90e91 ꢀC. 1H NMR (CDCl3, 400 MHz)
d
1.99 (s, 12H). 13C
3H), 2.70 (tt, J ¼ 12 Hz, 4 Hz, 1H), 2.03 (s, 3H), 1.93-1.86 (m, 2H),
NMR (CDCl3, 100 MHz)
d 187.42, 140.33, 12.33.
1.84-1.77 (m, 2H), 1.70-1.68 (m, 1H), 1.53-1.48 (m, 2H), 1.31-1.23 (m,
3H). 13C NMR (CDCl3, 100 MHz)
d 184.92, 184.31, 145.98, 144.37,
4.2.17. 2,3-Dimethoxy-5,6-dimethylcyclohexa-2,5-diene-1,4-
143.58, 138.59, 61.04, 60.99, 39.92, 29.91, 26.90, 25.80, 11.85.
dione(2q) (red solid, 41.4 mg, 53%) [27]
m.p.61e63 ꢀC. 1H NMR (CDCl3, 400 MHz)
d
3.97 (s, 6H), 1.98 (s,
6H). 13C NMR (CDCl3, 100 MHz)
d 184.30,144.32,138.90, 61.16, 12.14.
4.3.7. 2-(Hexan-2 or 3-yl)-3-methylnaphthalene-1,4-dione (yellow
liquid, 54.3 mg, 53%)
1H NMR (CDCl3, 400 MHz)
d 8.06-8.02 (m, 4H), 7.68-7.64 (m,
4.3. General procedure for the synthesis of alkylation of quinones
4H), 3.10-3.05 (m, 1H), 2.92 (bs, 1H), 2.20 (s, 6H), 1.90-1.83 (m, 3H),
1.79-1.65 (m, 3H), 1.32-1.30 (m, 4H), 1.29-1.24 (m, 5H), 10.89-0.81
To a sealed tube were added quinones derivative 1 (0.4 mmol),
Bi(OTf)3 (5 mol%), TBPB (1.2 mmol) and alkane (2 mL). Then, reac-
tion mixture was stirred at 100 ꢀC for 4 h or for the time indicated in
Table 3. After the completion of the reaction, the reaction was
quenched with saturated Na2SO3 (2 ml) and Saturated brine (2 ml).
The mixture was extracted with EtOAc (3 ꢁ 5 mL). The combined
organic layer was dried over anhydrous Mg2SO4 and concentrated
under reduced pressure. The crude products were purified on a
silica gel column using PE/EA to give 2d and 2s-u.
(m, 9H). 13C NMR (CDCl3, 100 MHz)
d 185.52, 185.29,184.91, 184.89,
150.78, 149.52, 143.40, 133.30, 133.07 133.05, 132.68, 132.59, 131.88,
131.82, 129.47, 128.23, 126.23, 126.18, 126.03, 126.01, 36.13, 34.76,
30.38, 26.97, 22.79, 21.60, 18.95, 14.28, 14.01, 12.88, 12.83, 12.57.
HRMS (ESI) m/z: C17H21Oþ2 ([MH]þ) calculated for: 257.1542, found:
257.1548.
Acknowledgments
We are grateful for the financial support from CAS “Light of West
China” Program, Technological Innovation Program of Chengdu,
Sichuan province, China (Nos. 2018-YF05-00244-SN).
4.3.1. 2-Cyclopentyl-3-methylnaphthalene-1,4-dione(3 ab) (yellow
solid, 54.8 mg, 57%)
m.p.93e95 ꢀC. 1H NMR (CDCl3, 400 MHz)
d 8.04-7.98 (m, 2H),
7.68-7.62 (m, 2H), 3.32-3.23 (m, 1H), 3.00 (s, 3H), 2.02-1.94 (m, 2H),
1.91-1.83 (m, 4H), 1.72-1.64 (m, 2H). 13C NMR (CDCl3, 100 MHz)
Appendix A. Supplementary data
d
185.26, 184.61, 150.21, 143.41, 133.24, 133.02, 132.85, 131.88,
126.10, 126.01, 39.84, 31.65, 27.30, 12.69. HRMS (ESI) m/z:
16H16NaOþ2 ([MNa]þ) calculated for: 263.1048, found: 263.1049.
Supplementary data to this article can be found online at
C
Please cite this article as: J. Yang et al., Bismuth-catalyzed methylation and alkylation of quinone derivatives with tert-butyl peroxybenzoate as