216
H.-H. Chen et al. / Tetrahedron 70 (2014) 212e217
under 80 ꢀC for 24 h. The product was isolated as a yellow oil
(74.6 mg, 66% yield). 1H NMR (600 MHz, CDCl3)
(m, 2H), 0.97 (t, J¼7.4 Hz, 3H); 13C NMR (151 MHz, CDCl3)
d 166.6,
d
7.90 (d, J¼8.3 Hz,
132.8, 130.5, 129.5, 128.3, 64.8, 30.8, 19.3, 13.8.
1H), 7.39 (t, J¼7.5 Hz, 1H), 7.25e7.23 (m, 2H), 4.33 (t, J¼6.0 Hz, 2H),
3.60 (t, J¼6.1 Hz, 2H), 2.59 (s, 3H), 1.94e1.92 (m, 4H); 13C NMR
4.2.22. Butyl benzoate (2v).12 According to the general procedure,
benzoic peroxyanhydride (0.25 mmol, 61 mg) was allowed to react
with 1-bromobutane (2.5 mmol) under 80 ꢀC for 24 h. The product
was isolated as a yellow oil (82.3 mg, 93% yield). 1H NMR (600 MHz,
(151 MHz, CDCl3)
d 167.5, 140.2, 132.0, 131.7, 130.51, 129.5, 125.7,
63.9, 44.6, 29.3, 26.2, 21.8; HRMS calcd for C12H15ClO2 (Mþ)
226.0761; found: 226.0767.
CDCl3)
d
8.04 (d, J¼7.8 Hz, 2H), 7.54 (t, J¼7.4 Hz, 1H), 7.43 (t,
4.2.16. 4-Chlorobutyl 3-chlorobenzoate (2p). According to the gen-
eral procedure, 2-methylbenzoic peroxyanhydride (0.25 mmol,
67.5 mg) was allowed to react with 1,5-dichloropentane (2.5 mmol)
under 80 ꢀC for 24 h. The product was isolated as a blue oil
J¼7.7 Hz, 2H), 4.32 (t, J¼6.6 Hz, 2H), 1.78e1.71 (m, 2H), 1.52e1.44
(m, 2H), 0.97 (t, J¼7.4 Hz, 3H); 13C NMR (151 MHz, CDCl3)
d 166.6,
132.8, 130.5, 129.5, 128.3, 64.8, 30.8, 19.3, 13.8.
(111.6 mg, 93% yield). 1H NMR (600 MHz, CDCl3)
d
7.90 (d, J¼9.3 Hz,
4.2.23. sec-Butyl benzoate (3a).17 According to the general pro-
cedure, benzoyl peroxide (0.25 mmol, 61 mg) was allowed to react
with 2-chlorobutane (2.5 mmol) under 80 ꢀC for 24 h. The product
was isolated as a yellow oil (83.7 mg, 94% yield). 1H NMR (600 MHz,
1H), 7.39 (t, J¼6.9 Hz, 1H), 7.24 (t, J¼7.2 Hz, 2H), 4.30 (t, J¼6.5 Hz,
2H), 3.56 (t, J¼6.6 Hz, 2H), 2.59 (s, 3H), 1.91e1.82 (m, 2H), 1.82e1.76
(m, 2H), 1.63e1.58 (m, 2H); 13C NMR (151 MHz, CDCl3)
d 167.7, 140.1,
131.9, 131.7, 130.5, 129.7, 125.7, 64.4, 44.8, 32.2, 28.0, 23.5, 21.1;
CDCl3)
d
8.04 (d, J¼7.0 Hz, 2H), 7.54 (t, J¼7.4 Hz, 1H), 7.43 (t,
HRMS calcd for C13H17ClO2 (Mþ) 240.0917; found: 240.0910.
J¼7.8 Hz, 2H), 5.12e5.06 (m, 1H), 1.33 (d, J¼6.3 Hz, 3H), 0.96 (t,
J¼7.5 Hz, 3H); 13C NMR (151 MHz, CDCl3)
d 166.2,132.7, 130.9, 129.5,
4.2.17. 2-Chloroethyl 3-chlorobenzoate (2q).10 According to the
general procedure, 3-chlorobenzoic peroxyanhydride (0.25
mmol, 77.5 mg) was allowed to react with 1,2-dichloro
ethane (2.5 mmol) under 80 ꢀC for 24 h. The product was iso-
lated as a yellow oil (103.8 mg, 95% yield). 1H NMR (600 MHz,
128.3, 72.8, 28.9, 19.6, 9.8.
4.2.24. sec-Butyl 4-methylbenzoate (3b).15 According to the general
procedure, 4-methylbenzoic peroxyanhydride (0.25 mmol,
67.5 mg) was allowed to react with 2-chlorobutane (2.5 mmol)
under 80 ꢀC for 24 h. The product was isolated as a yellow oil
CDCl3)
d
8.02 (s, 1H), 7.94 (d, J¼8.7 Hz, 1H), 7.53 (d, J¼8.0 Hz, 1H),
7.38 (t, J¼7.9 Hz, 1H), 4.56 (t, J¼6.4 Hz, 1H), 3.80 (t, J¼5.3 Hz, 1H);
(62.1 mg, 65% yield). 1H NMR (600 MHz, CDCl3)
d
7.93 (d, J¼8.2 Hz,
13C NMR (151 MHz, CDCl3)
127.9, 64.8, 41.6.
d
165.0, 134.6, 133.3, 131.3, 129.9, 129.8,
2H), 7.22 (d, J¼8.0 Hz, 2H), 5.10e5.04 (m, 1H), 2.39 (s, 3H), 1.31 (d,
J¼6.3 Hz, 3H), 0.96 (t, J¼7.5 Hz, 3H); 13C NMR (151 MHz, CDCl3)
d
166.3, 143.3, 129.5, 129.0, 128.1, 72.6, 29.0, 21.6, 19.6, 9.8.
4.2.18. 4-Chlorobutyl 3-chlorobenzoate (2r). According to the gen-
eral procedure, 3-chlorobenzoic peroxyanhydride (0.25 mmol,
77.5 mg) was allowed to react with 1,4-dichlorobutane (2.5 mmol)
under 80 ꢀC for 24 h. The product was isolated as a yellow oil
4.2.25. sec-Butyl 4-chlorobenzoate (3c).14 According to the general
procedure, 4-chlorobenzoic peroxyanhydride (0.25 mmol, 77.5 mg)
was allowed to react with 2-chlorobutane (2.5 mmol) under 80 ꢀC
for 24 h. The product was isolated as a yellow oil (80.6 mg, 76%
(89.8 mg, 73% yield). 1H NMR (600 MHz, CDCl3)
d 7.97 (s, 1H), 7.89
(d, J¼6.9 Hz, 1H), 7.50 (d, J¼9.0 Hz, 1H), 7.35 (t, J¼7.9 Hz, 1H), 4.33 (t,
yield). 1H NMR (600 MHz, CDCl3)
d
7.96 (d, J¼8.3 Hz, 2H), 7.39 (d,
J¼5.9 Hz, 2H), 3.59 (t, J¼6.0 Hz, 2H), 1.91 (m, 4H); 13C NMR
J¼8.5 Hz, 2H), 5.10e5.04 (m, 1H), 1.32 (d, J¼6.2 Hz, 3H), 0.95 (t,
(151 MHz, CDCl3)
d
165.3,134.5,133.0,131.9, 129.7, 129.6,127.7, 64.5,
J¼7.5 Hz, 3H); 13C NMR (151 MHz, CDCl3)
d 165.4,139.0,130.8,129.3,
44.5, 29.2, 26.1; HRMS calcd for C11H12Cl2O2 (Mþ) 246.0214; found:
246.0209.
128.6, 73.2, 28.9, 19.5, 9.7.
4.2.26. sec-Butyl 2-methylbenzoate (3d).16 According to the general
procedure, 3-chlorobenzoic peroxyanhydride (0.25 mmol, 67.5 mg)
was allowed to react with 2-chlorobutane (2.5 mmol) under 80 ꢀC
for 24 h. The product was isolated as a yellow oil (90.3 mg, 94%
4.2.19. 4-Chlorobutyl 3-chlorobenzoate (2s). According to the gen-
eral procedure, 3-chlorobenzoic peroxyanhydride (0.25 mmol,
77.5 mg) was allowed to react with 1,5-dichloropentane
(2.5 mmol) under 80 ꢀC for 24 h. The product was isolated as
yield). 1H NMR (600 MHz, CDCl3)
d
7.90 (d, J¼7.6 Hz, 1H), 7.37 (t,
a yellow oil (123.5 mg, 95% yield). 1H NMR (600 MHz, CDCl3)
d
8.00
J¼7.5 Hz, 1H), 7.23 (t, J¼7.6 Hz, 2H), 5.12e5.06 (m, 1H), 2.60 (s, 3H),
(s, 1H), 7.91 (d, J¼7.8 Hz, 1H), 7.52 (d, J¼8.0 Hz, 1H), 7.38 (t,
J¼7.9 Hz, 1H), 4.33 (t, J¼6.6 Hz, 2H), 3.56 (t, J¼6.6 Hz, 2H),
1.88e1.82 (m, 2H), 1.82e1.77 (m, 2H), 1.62e1.57 (m, 2H); 13C NMR
1.34 (d, J¼6.3 Hz, 3H), 0.98 (t, J¼7.5 Hz, 3H); 13C NMR (151 MHz,
CDCl3)
d 167.4, 139.8, 131.7, 131.6, 130.4, 130.3, 125.6, 72.6, 29.0, 21.8,
19.6, 9.8.
(151 MHz, CDCl3)
d 165.4, 134.5, 132.9, 132.0, 129.7, 129.6, 127.7,
65.1, 44.8, 32.1, 27.9, 23.4; HRMS calcd for C12H14Cl2O2 (Mþ)
260.0371; found: 260.0377.
4.2.27. sec-Butyl 3-chlorobenzoate (3e).14 According to the general
procedure, 4-chlorobenzoic peroxyanhydride (0.25 mmol, 77.5 mg)
was allowed to react with 2-chlorobutane (2.5 mmol) under 80 ꢀC
for 24 h. The product was isolated as a yellow oil (84.8 mg, 80%
4.2.20. Ethyl benzoate (2t).8 According to the general procedure,
benzoic peroxyanhydride (0.25 mmol, 61 mg) was allowed to react
with chloroethane (2.5 mmol) under 80 ꢀC for 24 h. The product
was isolated as a yellow oil (69.8 mg, 93% yield). 1H NMR (600 MHz,
yield). 1H NMR (600 MHz, CDCl3)
d
8.00 (s, 1H), 7.92 (d, J¼7.8 Hz,
1H), 7.50 (d, J¼8.0 Hz, 1H), 7.36 (t, J¼7.9 Hz, 1H), 5.11e5.05 (m, 1H),
1.75e1.64 (m, 2H), 1.32 (d, J¼6.3 Hz, 3H), 0.96 (t, J¼7.5 Hz, 3H); 13
C
CDCl3)
d
8.04 (d, J¼7.1 Hz, 2H), 7.54 (t, J¼7.4 Hz, 1H), 7.42 (t,
NMR (151 MHz, CDCl3)
73.5, 28.9, 19.5, 9.8.
d 16.0, 134.4, 132.7, 132.6, 129.6, 129.5, 127.6,
J¼7.8 Hz, 2H), 4.37 (q, J¼7.2 Hz, 2H), 1.39 (t, J¼7.1 Hz, 3H); 13C NMR
(151 MHz, CDCl3)
d 166.6, 132.8, 130.5, 129.5, 128.3, 60.9, 14.3.
4.3. Further synthetic transformations of benzoyl peroxide
4.2.21. Butyl benzoate (2u).12 According to the general procedure,
benzoic peroxyanhydride (0.25 mmol, 61 mg) was allowed to react
with 1-chlorobutane (2.5 mmol) under 80 ꢀC for 24 h. The product
was isolated as a yellow oil (84.6 mg, 95% yield). 1H NMR (600 MHz,
In air, Cu catalyst (0.025 mmol), benzoyl peroxide (0.25 mmol,
61 mg), ligand (0.025 mmol), base (3.0 equiv) were added to
a Schlenk tube equipped with a magneton. 1,2-Dichloroethane
CDCl3)
d
8.04 (d, J¼7.8 Hz, 2H), 7.54 (t, J¼7.4 Hz, 1H), 7.43 (t,
(0.25 mmol, 20.0
reaction mixture was stirred at the mentioned temperature for the
mL) and DMSO (1.0 mL) were added in turn. The
J¼7.7 Hz, 2H), 4.32 (t, J¼6.6 Hz, 2H), 1.78e1.71 (m, 2H), 1.52e1.44