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18. 1,1,1,3-Tetrachloroundecane (20). Colorless oil; IR (neat)
mmax 2932, 1860, 1468,
1380, 1210, 1124, 1050, 962, 788, 701, 574 cmÀ1 1H NMR (CDCl3) d 0.89 (3H, t,
;
J = 6.6 Hz, CH3), 1.10–1.70 (12H, m, CH2), 1.70–2.18 (2H, m, CH2), 3.04 (1H, dd,
J = 15.0 and 4.8 Hz, CHCCl3), 3.33 (1H, dd, J = 15.8 and 5.1 Hz, CHCCl3), 4.08–
4.48 (1H, m, CHCl); 13C NMR (CDCl3) d 14.1 (q), 22.7 (t), 26.0 (t), 28.9 (t), 29.2
(t), 29.3 (t), 31.8 (t), 39.1 (t), 57.7 (d), 62.3 (t), 97.0 (s). Anal. Calcd for C11H20Cl4:
C, 44.92; H, 6.85. Found: C, 44.83; H, 7.00.
5. Traynham, J. G. J. Chem. Edu. 1983, 60, 937–941.
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7. Kagakubinran, 4th ed., The Chemical Society of Japan, Maruzen: Tokyo, 1993;
Vol. II, p 106.
19. 5-Chloro-6-trichloromethyldecane (22).21 Compound 22 was obtained as
a
mixture (1: 1) of anti/syn isomers. Colorless oil; IR (neat) mmax 2959, 2872,
1465, 1380, 987, 907, 984, 635 cmÀ1 1H NMR (CDCl3) d 0.93 (6H, t, J = 6.6 Hz,
;
CH3), 1.20–2.30 (12H, m, CH2), 2.55 (1Hsyn, td, J = 4.6 and 1.0 Hz, CHCCl3), 2.90–
3.15 (1Hanti, m, CHCCl3), 4.64 (1H, td, J = 6.3 and 1.6 Hz, CHCl); 13C NMR (CDCl3)
d 13.8 (q), 13.9 (q), 22.0 (t), 22.9 (t), 27.5 (Canti, t), 28.5 (Csyn, t), 29.0 (Csyn, t),
29.4 (Canti, t), 31.8 (Canti, t), 32.2 (Csyn, t), 32.7 (Canti, t), 39.0 (Csyn, t), 62.4 (Csyn, d),
62.7 (Canti, d), 63.3 (Csyn, d), 65.4 (Canti, d), 103.1 (Canti, s), 104.1 (Csyn, s). Anal.
Calcd for C11H20Cl4: C, 44.92; H, 6.85. Found: C, 44.64; H, 6.74.
8. A typical experimental procedure: A mixture of adamantane (1) (4.0 mmol) and
carbon tetrachloride (15 mL) in
a 28 mL Teflon-lined stainless autoclave
(purchased from OM Lab-Tech Co. Ltd., Japan)1f was heated at 250 °C under
nitrogen. The internal pressure reached ca. 7 MPa. The mixture was heated at
the same temperature for 4 h. After cooling, the solution was washed with
water, dried, and evaporated. The residue was chromatographed (hexane) on
silica gel to give 2, 3, and 4 in 52, 9, and 3% yields, respectively. Compound 1
was recovered in 15% yield (Table 1, entry 1). Caution: Attention should be
paid for the leak of the gas, since a large amount of harmful chlorine was
evolved during the reactions. It is important to firmly tighten the screw of
20. 1,3,3,3-Tetrachloro-2-methylpropylbenzene (24). Compound 24 was obtained as
a mixture (2:1) of anti/syn isomers. Colorless oil; IR (neat) mmax 3063, 3031,
2998, 2947, 1602, 1495, 1453, 1382, 1309, 1232, 1122, 1076, 1043, 950, 917,
856, 825, 768, 699, 639, 570 cmÀ1 1H NMR (CDCl3) d 1.47 (3Hsyn, t, J = 6.8 Hz,
;
CH3), 1.50 (3Hanti, t, J = 6.6 Hz, CH3), 2.99 (1Hanti, qd, J = 6.4 and 1.4 Hz, CHCCl3),
3.17–3.50 (1Hsyn, m, CHCCl3), 5.77 (1Hsyn, d, J = 3.6 Hz, CHCl), 5.81 (1Hanti, d,
the stainless autoclave. The operation should be carried out in
a well-
ventilated fume hood when the autoclave is opened. Many times use of the
stainless autoclave should be avoided because of the rust caused by chlorine
gas.
J = 1.6 Hz, CHCl), 7.17 (5H, m, ArH); 13C NMR (CDCl3) d 11.4 (Canti, q), 12.2 (Csyn
q), 60.8 (Canti, d), 61.2 (Csyn, d), 61.9 (Csyn, d), 62.1 (Canti, d), 103.2 (s), 126.8 (Canti
,
,
d) 127.9 (Csyn, d), 128.2 (Canti, d), 128.6 (Canti, d), 128.7 (Csyn, d), 129.3 (Csyn, d),
136.7 (Csyn, s), 140.6 (Canti, s). Anal. Calcd for C10H10Cl4: C, 44.16; H, 3.71.
Found: C, 44.40; H, 3.73.
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