Hu et al.
hydrocarbon (0.1 mol), paraformaldehyde (0.6 mol), conc.
5.96; Cl, 34.91.
HCl (70 ml), [C12minPEG800]Br (0.03 mol), methylcyclo-
hexane (70 ml). Hydrogen chloride gas was bubbled into the
flask at the flow rate of 80 ml min-1. The reaction mixture was
stirred at an appropriate temperature for an appropriate time
(Table 2). After the reaction, the reaction mixture was cooled
to room temperature, the organic phase was separated by
decantation, and rinsed with 5% NaHCO3 solution (3 × 10 ml)
and water (2 × 10 ml), then dried with sodium sulfate, filtered,
and evaporated to dryness in vacuo, and the organic residue
was resolved in methylene chloride and analyzed by HPLC.
The crude product was recrystallized from hexane and
methylene chloride and the desired product was identified by
NMR and Elemental analysis or compared with authentic
samples. The next run was performed under identical reaction
conditions.
4,4'-Bis(chloromethyl)biphenyl (9). White solid, m.p.:
133-135 °C (lit. [20] m.p.: 134-136 °C). 1H NMR (400 MHz,
CDCl3) δ = 4.63 (s, 4H, CH2), 7.48 (m, 4H, Ar-H), 7.57 (m,
4H, Ar-H) ppm. 13C NMR (400 MHz, CDCl3) δ = 46.1, 127.6,
129.4, 136.9, 140.7 ppm. Anal. Calcd. for C14H12Cl2: C, 66.93;
H, 4.83; Cl, 28.24. Found: C, 66.95; H, 4.82; Cl, 28.23.
6,7-Bis(chloromethyl)-1,2,3,4-tetrahydronaphthalene
(10). White solid, m.p.: 110-112 °C. IR (KBr, cm-1): 2946,
1
2832, 1643, 1510, 1447, 887, 812, 732, 667. H NMR (400
MHz, CDCl3) δ = 1.51 (s, 4H, CH2), 2.84 (s, 4H, CH2), 4.57
(s, 4H, CH2), 7.16 (s, 2H, Ar-H) ppm. 13C NMR (400 MHz,
CDCl3) δ = 22.4, 26.1, 44.7, 127.5, 136.1, 137.3 ppm. MS (EI,
70 eV) m/z (%): 228 (M+), 193, 179, 145, 131, 105, 91, 77.
Anal. Calcd. for C12H14Cl2: C, 62.87; H, 6.17; Cl, 30.95.
Found: C, 62.90; H, 6.16; Cl, 30.94.
1,4-Bis(chloromethyl)benzene (5). White solid, m.p.: 98-
101 °C (lit. [19] m.p.: 97-100 °C). 1H NMR (400 MHz,
CDCl3) δ = 4.61 (s, 4H, CH2), 7.27 (s, 4H, Ar-H) ppm. 13C
NMR (400 MHz, CDCl3) δ = 46.8, 128.4, 139.1 ppm. Anal.
Calcd. for C8H8Cl2: C, 54.86; H, 4.61; Cl, 40.52. Found: C,
54.89; H, 4.61; Cl, 40.50.
1,3-Bis(chloromethyl)-4,6-dimethylbenzene (6). White
solid, m.p.: 88-90 °C (lit. [24] m.p.: 87-89 °C). 1H NMR (400
MHz, CDCl3) δ = 2.37 (s, 6H, CH3), 4.69 (s, 4H, CH2), 7.04
(s, 1H, Ar-H), 7.25 (s, 1H, Ar-H) ppm. 13C NMR (400 MHz,
CDCl3) δ = 17.5, 40.5, 129.2, 131.2, 134.5, 136.8 ppm. Anal.
Calcd. for C10H12Cl2: C, 59.09; H, 5.97; Cl, 34.94. Found: C,
59.13; H, 5.96; Cl, 34.91.
1,4-Bis(chloromethyl)-2,5-dimethylbenzene (7). White
solid, m.p.: 102-104 °C. IR (KBr, cm-1): 2976, 2865, 1637,
1506, 1454, 1382, 895, 806, 656. 1H NMR (400 MHz, CDCl3)
δ = 2.34 (s, 6H, CH3), 4.67 (s, 4H, CH2), 7.16 (s, 2H, Ar-H)
ppm. 13C NMR (400 MHz, CDCl3) δ = 17.8, 40.6, 131.2,
133.7, 138.3 ppm. MS (EI, 70 eV) m/z (%): 202 (M+), 167,
153, 119, 105, 91, 77. Anal. Calcd. for C10H12Cl2: C, 59.03; H,
5.98; Cl, 34.97. Found: C, 59.13; H, 5.96; Cl, 34.91.
1,4-Bis(chloromethyl)-2,5-dimethoxybenzene
(11).
White solid, m.p.: 125-127 °C. IR (KBr, cm-1): 2981, 2859,
1
1635, 1504, 1462, 1386, 1157, 892, 812, 662. H NMR (400
MHz, CDCl3) δ = 3.89 (s, 6H, CH3), 4.64 (s, 4H, CH2), 7.21
(s, 2H, Ar-H) ppm. 13C NMR (400MHz, CDCl3) δ = 40.8,
54.7, 114.2, 126.7, 148.4 ppm. MS (EI, 70 eV) m/z (%): 234
(M+), 199, 185, 151, 137, 107, 77. Anal. Calcd. for
C10H12Cl2O2: C, 51.04; H, 5.14; Cl, 30.17; O, 13.63. Found: C,
51.09; H, 5.14; Cl, 30.16; O, 13.61.
1,2-Bis(chloromethyl)-4,5-dimethoxybenzene
(12).
White solid, m.p.: 118-121 °C. IR (KBr, cm-1): 2978, 2864,
1
1638, 1510, 1459, 1385, 1162, 894, 808, 665. H NMR (400
MHz, CDCl3) δ = 3.90 (s, 6H, CH3), 4.65 (s, 4H, CH2), 7.18
(s, 2H, Ar-H) ppm. 13C NMR (400 MHz, CDCl3) δ = 40.7,
54.8, 114.3, 126.8, 148.4 ppm. MS (EI, 70 eV) m/z (%): 234
(M+), 199, 185, 151, 137, 107, 77. Anal. Calcd. for
C10H12Cl2O2: C, 51.03; H, 5.16; Cl, 30.18; O, 13.61. Found: C,
51.09; H, 5.14; Cl, 30.16; O, 13.61.
1,3-Bis(chloromethyl)-4,6-dimethoxybenzene
(13).
White solid, m.p.: 112-114 °C. IR (KBr, cm-1): 2986, 2857,
1
1642, 1506, 1467, 1384, 1155, 887, 814, 668. H NMR (400
1,2-Bis(chloromethyl)-4,5-dimethylbenzene (8). White
solid, m.p.: 103-105 °C (lit. [22] m.p.: 102-104 °C). 1H NMR
(400 MHz, CDCl3) δ = 2.36 (s, 6H, CH3), 4.70 (s, 4H, CH2),
7.14 (s, 2H, Ar-H) ppm. 13C NMR (400 MHz, CDCl3) δ =
18.5, 40.7, 131.2, 134.1, 138.1 ppm. Anal. Calcd. for
C10H12Cl2: C, 59.07; H, 6.01; Cl, 34.92. Found: C, 59.13; H,
MHz, CDCl3) δ = 3.92 (s, 6H, CH3), 4.68 (s, 4H, CH2), 7.10
(s, 1H, Ar-H), 7.29 (s, 1H, Ar-H) ppm. 13C NMR (400 MHz,
CDCl3) δ = 40.6, 54.6, 97.3, 114.8, 133.2, 154.7 ppm. MS (EI,
70 eV) m/z (%): 234 (M+), 199, 185, 151, 137, 107, 77. Anal.
Calcd. for C10H12Cl2O2: C, 51.05; H, 5.15; Cl, 30.19; O, 13.61.
Found: C, 51.09; H, 5.14; Cl, 30.16; O, 13.61.
134