J. An et al. / Tetrahedron 69 (2013) 8769e8776
8773
ArH), 6.68 (s, 1H, CHCl2); 13C NMR (68 MHz, CDCl3)
127.9, 124.1, 71.0.
d
139.4, 132.1,
2.1 Hz, 1H, ArH), 6.82 (d, J¼8.8 Hz, 1H, ArH), 6.69 (s, 1H, CHCl2), 3.93
(s, 3H, OCH3), 3.90 (s, 3H, OCH3); 13C NMR (68 MHz, CDCl3)
d 150.3,
149.3, 133.0, 118.5, 110.3, 109.1, 72.0, 56.0, 56.0.
4.3.3. 1-(Dichloromethyl)-4-methylbenzene 4c.43 The following re-
agents were combined in the amounts indicated below in accor-
dance with method a. 4-Methylbenzaldehyde (120 mg, 1.00 mmol),
4.3.8. 1-(Dichloromethyl)-3,5-dimethoxybenzene 4h.45 The follow-
ing reagents were combined in the amounts indicated below in
accordance with method b. 3,5-Dimethoxybenzaldehyde (166 mg,
oxalyl chloride (110
(21.0 mg, 75.5
mL, 1.30 mmol) and triphenylphosphine oxide
m
mol) gave 1-(dichloromethyl)-4-methylbenzene 4c
1.00 mmol), oxalyl chloride (110
mL, 1.30 mmol) and triphenyl-
(163 mg, 93%) by 1H NMR. Purification by flash column chroma-
tography (silica, 10% Et2O/pet. ether) afforded 1-(dichloromethyl)-
4-methylbenzene 4c as a colourless oil (159 mg, 91%). 1H NMR
phosphine oxide (21.0 mg, 75.5 mol). Purification by flash column
m
chromatography (silica, 10% Et2O/pet. ether) afforded 1-(dichlor-
omethyl)-3,5-dimethoxybenzene 4h as a colourless oil (195 mg,
(270 MHz, CDCl3)
6.71 (s, 1H, CHCl2), 2.39 (s, 3H, CH3); 13C NMR (68 MHz, CDCl3)
140.2, 137.7, 129.5, 126.1, 71.9, 21.4.
d
7.51e7.44 (m, 2H, ArH), 7.27e7.19 (m, 2H, ArH),
88%). 1H NMR (400 MHz, CDCl3)
d
6.74 (d, J¼2.3 Hz, 2H, ArH), 6.64
(s, 1H, CHCl2), 6.48 (t, J¼2.3 Hz, 1H, ArH), 3.83 (s, 6H, CH3 ꢃ2); 13C
d
NMR (68 MHz, CDCl3) d 160.9, 142.4, 104.3, 101.9, 71.7, 55.6.
4.3.4. 1-(Dichloromethyl)-4-methoxybenzene 4d.43 The following
reagents were combined in the amounts indicated below in ac-
cordance with method b. 4-Methoxybenzaldehyde (136 mg,
4.3.9. 1-(Allyloxy)-2-(dichloromethyl)benzene 4i. The following re-
agents were combined in the amounts indicated below in accor-
dance with method a. 2-(Allyloxy)benzaldehyde (150
0.998 mmol), oxalyl chloride (110 L, 1.30 mmol) and triphenyl-
phosphine oxide (21.0 mg, 75.5 mol). Purification by flash column
mL,
1.00 mmol), oxalyl chloride (110
phosphine oxide (21.0 mg, 75.5 mol) gave 1-(dichloromethyl)-4-
methoxybenzene 4d (187 mg, 98%) by 1H NMR. 1H NMR
(400 MHz, CDCl3) 7.54e7.49 (m, 2H, ArH), 7.94e7.89 (m, 2H, ArH),
6.71 (s, 1H, CHCl2), 3.84 (s, 3H, CH3); 13C NMR (100 MHz, CDCl3)
160.7, 132.8, 127.6, 114.0, 71.8, 55.5.
mL, 1.30 mmol) and triphenyl-
m
m
m
chromatography (silica, 10% Et2O/pet. ether) afforded 1-(allyloxy)-
d
2-(dichloromethyl)benzene 4i as a colourless oil (185 mg, 85%). 1H
NMR (400 MHz, CDCl3)
d
7.84 (dd, J¼7.8 and 1.8 Hz, 1H, ArH),
d
7.37e7.31 (m, 1H, ArH), 7.25 (s, 1H, CHCl2), 7.10e7.04 (m, 1H, ArH),
6.91e6.86 (m, 1H, ArH), 6.13e6.02 (m, 1H, OCH2CH), 5.49e5.42 (m,
1H, CH]CH2), 5.36e5.31 (m, 1H, CH]CH2), 4.66e4.61 (m, 2H,
4.3.5. 2-Bromo-4-(dichloromethyl)-1-methoxybenzene 4e. The fol-
lowing reagents were combined in the amounts indicated below in
accordance with method b. 3-Bromo-4-methoxybenzaldehyde
OCH2); 13C NMR (100 MHz, CDCl3)
d 153.6 (Cq), 132.7 (CH), 131.1
(CH), 129.0 (Cq), 128.2 (CH), 121.4 (CH), 117.9 (CH2), 112.1 (CH), 69.3
(CH2), 66.5 (CH); IR nmax (CHCl3) 3083, 2926, 1650, 1602, 1588, 1488,
1457, 1424, 1363, 1323, 1290, 1254, 1163, 1104, 1047, 1018, 996, 936,
850, 660, 594 cmꢂ1; HRMS (EIþ) [Mþ] C10H10OCl2 calcd 216.0109,
found 216.0111.
(215 mg, 1.00 mmol), oxalyl chloride (110
phenylphosphine oxide (21.0 mg, 75.5
m
L, 1.30 mmol) and tri-
mmol) gave 2-bromo-4-
(dichloromethyl)-1-methoxybenzene 4e (243 mg, 90%) by 1H NMR.
Purification by flash column chromatography (silica, 10% Et2O/pet.
ether) afforded 2-bromo-4-(dichloromethyl)-1-methoxybenzene
4e as a colourless oil (243 mg, 90%). 1H NMR (270 MHz, CDCl3)
4.3.10. 1-(Dichloromethyl)-4-(trifluoromethyl)benzene 4j.46 The fol-
lowing reagents were combined in the amounts indicated below in
accordance with method c. 4-(Trifluoromethyl)benzaldehyde
d
7.79 (d, J¼2.3 Hz, 1H, ArH), 7.49 (dd, J¼8.7 and 2.3 Hz, 1H, ArH),
6.90 (d, J¼8.7 Hz, 1H, ArH), 6.65 (s, 1H, CHCl2), 3.93 (s, 1H, CH3); 13
C
NMR (68 MHz, CDCl3)
d
157.0 (Cq),134.0 (Cq),131.4 (CH),126.6 (CH),
(174 mg, 1.00 mmol), oxalyl chloride (110
phenylphosphine oxide (21.0 mg, 75.5
m
L, 1.30 mmol) and tri-
111.8 (CH), 111.5 (CH), 70.6 (CH), 56.5 (CH3); IR nmax (CHCl3) 3011,
2971, 2946, 2910, 2841, 1602, 1572, 1498, 1462, 1441, 1407, 1309,
1289, 1281, 1263, 1190, 1151, 1055, 1020, 908, 893, 660 cmꢂ1; HRMS
(EIþ) [Mþ] C8H8OBrCl2 calcd 267.9057, found 267.9052.
mmol) gave 1-(dichlor-
omethyl)-4-(trifluoromethyl)benzene 4j (215 mg, 94%) by 1H NMR.
Purification by flash column chromatography (silica, 10% Et2O/pet.
ether) afforded 1-(dichloromethyl)-4-(trifluoromethyl)benzene 4j
as a colourless oil (204 mg, 89%). 1H NMR (400 MHz, CDCl3)
4.3.6. 4-Bromo-2-(dichloromethyl)-1-methoxybenzene 4f. The fol-
lowing reagents were combined in the amounts indicated below in
accordance with method b. 5-Bromo-2-methoxybenzaldehyde
d
7.75e7.67 (m, 4H, ArH), 6.75 (s, 1H, CHCl2); 13C NMR (100 MHz,
CDCl3)
(q, J¼270.1 Hz), 70.6.
d
143.9, 132.1 (q, J¼32.8 Hz), 126.8, 126.0 (q, J¼3.8 Hz), 123.7
(215 mg, 1.00 mmol), oxalyl chloride (110
phenylphosphine oxide (21.0 mg, 75.5
m
L, 1.30 mmol) and tri-
mmol) gave 4-bromo-2-
4.3.11. 1-(Dichloromethyl)-4-nitrobenzene 4k.42 The following re-
agents were combined in the amounts indicated below in accor-
dance with method c. 4-Nitrobenzaldehyde (151 mg, 1.00 mmol),
(dichloromethyl)-1-methoxybenzene 4f (202 mg, 94%) by 1H NMR.
Purification by flash column chromatography (silica, 10% Et2O/pet.
ether) afforded 4-bromo-2-(dichloromethyl)-1-methoxybenzene
4f as a white solid (185 mg, 86%). Mp 47.8e48.8 ꢀC; 1H NMR
oxalyl chloride (110
mL, 1.30 mmol) and triphenylphosphine oxide
(21.0 mg, 75.5 mol). Purification by flash column chromatography
m
(270 MHz, CDCl3)
2.5 Hz, 1H, ArH), 7.11 (s, 1H, CHCl2), 6.77 (d, J¼8.8 Hz, 1H, ArH), 3.88
(s, 3H, CH3); 13C NMR (68 MHz, CDCl3)
153.6 (Cq), 133.9 (Cq), 131.1
d
7.93 (d, 1H, J¼2.5 Hz, ArH), 7.45 (dd, J¼8.8 and
(silica, 10% Et2O/pet. ether) afforded 1-(dichloromethyl)-4-
nitrobenzene 4k as a colourless oil (190 mg, 92%). 1H NMR
d
(400 MHz, CDCl3) d 8.31e8.26 (m, 2H, ArH), 7.81e7.75 (m, 2H, ArH),
(CH),130.5 (CH),113.3 (CH),112.7 (CH), 65.3 (CH), 56.1 (CH3); IR nmax
6.78 (s, 1H, CHCl2); 13C NMR (100 MHz, CDCl3)
d 148.6, 146.3, 127.5,
(CHCl3) 3011, 2969, 2943, 2908, 2842, 1596, 1577, 1486, 1462, 1440,
124.2, 69.9.
1409, 1308, 1276, 1257, 1186, 1169, 1121, 1029, 885, 820, 624 cmꢂ1
;
HRMS (ESIþ) [MþHþ] C8H8OBrCl2 calcd 268.9130, found 268.9130.
4.3.12. (E)-(3,3-Dichloroprop-1-en-1-yl)benzene 4l.9a The following
reagents were combined in the amounts indicated below in ac-
cordance with method d. Cinnamaldehyde (132 mg, 1.00 mmol),
4.3.7. 4-(Dichloromethyl)-1,2-dimethoxybenzene 4g.44 The follow-
ing reagents were combined in the amounts indicated below in
accordance with method b. 3,4-Dimethoxybenzaldehyde (166 mg,
oxalyl chloride (110
(21.0 mg, 75.5
mL, 1.30 mmol) and triphenylphosphine oxide
mol) gave (E)-(3,3-dichloroprop-1-en-1-yl)benzene
m
1.00 mmol), oxalyl chloride (110
phosphine oxide (21.0 mg, 75.5 mol) gave 4-(dichloromethyl)-1,2-
dimethoxybenzene 4g (219 mg, 99%) by 1H NMR. 1H NMR
(270 MHz, CDCl3)
7.15 (d, J¼2.1 Hz, 1H, ArH), 7.06 (dd, J¼8.8 and
mL, 1.30 mmol) and triphenyl-
4l (178 mg, 95%) by 1H NMR. Purification by flash column chro-
matography (silica, 5% Et2O/pet. ether) afforded (E)-(3,3-
dichloroprop-1-en-1-yl)benzene 4l as a colourless oil (161 mg,
m
d
86%). 1H NMR (270 MHz, CDCl3)
d 7.50e7.31 (m, 5H, ArH), 6.74 (d,