PAPER
One-Pot Synthesis of a-Chloroketone Acetals
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1H NMR (300 MHz, CDCl3): d = 1.67–1.77 (m, 1 H), 1.80–2.00 (m,
3 H), 2.06–2.14 (m, 1 H), 2.21–2.28 (m, 1 H), 3.96–4.10 (m, 5 H).
2¢-Chloro-3¢,4¢-dihydro-2¢H-spiro([1,3]dioxolane-2,1¢-naphtha-
lene) (Table 1, entry 8)
Pale-yellow oil.
13C NMR (75 MHz, CDCl3): d = 18.73, 32.11, 33.02, 62.81, 64.98,
65.47, 116.18.
IR (KBr): 2968, 2895, 2674, 2295, 1958, 1932, 1832, 1700, 1605,
1484, 1442, 1342, 1311, 1232, 1158, 1026, 942, 868, 758, 663, 611,
568, 511, 458 cm–1.
1H NMR (300 MHz, CDCl3): d = 2.30–2.42 (m, 1 H), 2.45–2.55 (m,
1 H), 2.81–2.91 (m, 1 H), 3.06–3.17 (m, 1 H), 4.22–4.33 (m, 4 H),
4.37 (dd, J = 3.0, 7.8 Hz, 1 H), 7.11–7.14 (m, 1 H), 7.21–7.30 (m,
2 H), 7.49–7.52 (m, 1 H).
a-Chlorocyclooctanone Acetal (Table 1, Entry 3)
Colorless oil.
IR (KBr): 2926, 2684, 1726, 1642, 1447, 1332, 1158, 1084, 1032,
953, 853, 784, 716, 658, 505 cm–1.
1H NMR (300 MHz, CDCl3): d = 1.52–1.73 (m, 8 H), 1.78–1.86 (m,
1 H), 1.95–2.03 (m, 1 H), 2.08–2.23 (m, 2 H), 3.94–4.01 (m, 2 H),
4.10–4.14 (m, 2 H), 4.40 (dd, J = 3.0, 8.7 Hz, 1 H).
13C NMR (75 MHz, CDCl3): d = 25.86, 29.11, 61.39, 66.23, 66.38,
106.69, 126.11, 126.36, 128.42, 128.80, 135.53, 136.22.
13C NMR (75 MHz, CDCl3): d = 22.04, 25.10, 25.64, 27.41, 33.37,
HRMS (APCI): m/z [M + H]+ calcd for C12H13ClO2: 225.0677;
34.03, 65.30, 65.63, 66.12, 111.17.
found: 225.0682.
HRMS (APCI): m/z [M + H]+ calcd for C10H17ClO2: 205.0990;
found: 205.0997.
2-(1-Chloroethyl)-2-ethyl-1,3-dioxolane (Table 1, Entry 9)
Colorless oil.
2-Chloromethyl-2-phenyl[1,3]dioxolane (Table 1, Entry 4)3b
Colorless oil.
IR (KBr): 2981, 2939, 2885, 1454, 1377, 1196, 1157, 1066, 930,
783, 696 cm–1.
1H NMR (300 MHz, CDCl3): d = 3.76 (s, 2 H), 3.89–3.94 (m, 2 H),
4.17–4.21 (m, 2 H), 7.35–7.41 (m, 3 H), 7.50–7.54 (m, 2 H).
13C NMR (75 MHz, CDCl3): d = 49.36, 65.77, 107.86, 125.96,
128.23, 128.72, 139.70.
1H NMR (300 MHz, CDCl3): d = 0.93 (t, J = 7.5 Hz, 3 H), 1.50 (d,
J = 6.9 Hz, 3 H), 1.68–1.81 (m, 1 H), 1.88–2.00 (m, 1 H), 4.00–4.11
(m, 5 H).
13C NMR (75 MHz, CDCl3): d = 7.18, 19.68, 26.87, 60.18, 66.22,
66.38, 111.73.
2-Chloromethyl-2-p-tolyl-1,3-dioxolane (Table 1, Entry 5)18
Anal. Calcd for C7H13ClO2: C, 51.07; H, 7.96. Found: C, 50.88; H,
8.22.
Colorless oil.
1H NMR (300 MHz, CDCl3): d = 2.36 (s, 3 H), 3.75 (s, 2 H), 3.87–
3.95 (m, 2 H), 4.13–4.23 (m, 2 H), 7.18 (d, J = 5.7 Hz, 2 H), 7.40
(d, J = 5.7 Hz, 2 H).
Acknowledgment
13C NMR (75 MHz, CDCl3): d = 21.13, 49.38, 65.72, 107.89,
125.91, 128.95, 136.70, 138.60.
This work was financially supported by The National Natural Sci-
ence Foundation of China (No. 20572046 and No. 20872064) and
the Program for New Century Excellent Talents in University
(NCET-07-0461).
2-Chloromethyl-2-(4-chlorophenyl)-1,3-dioxolane (Table 1, En-
try 6)
White solid; mp 59–60 °C.
References
IR (KBr): 2958, 2895, 2853, 2284, 2053, 1916, 1874, 1800, 1642,
1600, 1479, 1437, 1389, 1295, 1221, 1174, 1079, 1026, 953, 826,
758, 689, 637, 511, 474 cm–1.
1H NMR (300 MHz, CDCl3): d = 3.72 (s, 2 H), 3.88–3.92 (m, 2 H),
4.16–4.20 (m, 2 H), 7.34 (d, J = 6.3 Hz, 2 H), 7.46 (d, J = 6.3 Hz,
2 H).
13C NMR (75 MHz, CDCl3): d = 49.16, 65.86, 107.59, 127.57,
128.48, 134.81, 138.27.
HRMS (APCI): m/z [M + H]+ calcd for C10H10Cl2O2: 233.0131;
(1) (a) Billings, S. B.; Woerpel, K. A. J. Org. Chem. 2006, 71,
5171. (b) Montgomery, J. A.; Thomas, H. J.; Brockman, R.
W.; Elliott, R. D. J. Med. Chem. 1984, 27, 680. (c) Treibs,
W.; Grossmann, P. Chem. Ber. 1959, 92, 267.
(d) Wanzliek, H. W.; Gollmer, G.; Milz, H. Chem. Ber.
1955, 88, 69. (e) Levin, R. H.; Magerlein, B. J.; Mcintosh,
A. V. Jr.; Hanze, A. R.; Fonken, G. S.; Thompson, J. L.;
Searcy, A. M.; Scheri, M. A.; Gutsell, E. S. J. Am. Chem.
Soc. 1954, 76, 546.
(2) (a) For sulfuryl chloride as a chlorinating reagent, see:
Wyman, D. P.; Kaufman, P. R. J. Org. Chem. 1964, 29,
1956. (b) For cupric chloride as a chlorinating reagent, see:
Kochi, J. K. J. Am. Chem. Soc. 1955, 77, 5274. (c) For p-
toluenesulfonyl chloride as a chlorinating, see: Brummond,
K. M.; Gesenberg, K. D. Tetrahedron Lett. 1999, 40, 2231.
(d) For N-chlorosuccinimide as a chlorinating reagent, see:
Buu-Hoï, N. P.; Demerseman, P. J. Org. Chem. 1953, 18,
649. (e) For tetraethylammonium trichloride as a
found: 233.0129.
2¢-Chloro-2¢,3¢-dihydrospiro([1,3]dioxolane-2,1¢-indene) (Table
1, Entry 7)
White solid; mp 44–46 °C.
IR (KBr): 2929, 1729, 1602, 1466, 1430, 1313, 1269, 1226, 1133,
1076, 1035, 1016, 942, 872, 815, 759, 685, 641, 581, 485 cm–1.
1H NMR (300 MHz, CDCl3): d = 3.15 (dd, J = 7.2, 15.6 Hz, 1 H),
3.40 (dd, J = 7.2, 15.6 Hz, 1 H), 4.21–4.34 (m, 4 H), 4.47 (t, J = 7.2
Hz, 1 H), 7.22–7.39 (m, 4 H).
chlorinating reagent, see: Schlama, T.; Gabriel, K.;
Gouverneur, V.; Mioskowski, C. Angew. Chem., Int. Ed.
Engl. 1997, 36, 2342.
13C NMR (75 MHz, CDCl3): d = 38.83, 63.23, 66.08, 66.36, 114.24,
(3) (a) Greene, T. W.; Wuts, P. G. M. Protective Groups in
Organic Synthesis, 4th ed.; Wiley-Interscience: New York,
1999, Chap. 4. (b) Carlson, R.; Gautun, H.; Westerlund, A.
Adv. Synth. Catal. 2002, 344, 57. (c) Chan, T. H.; Brook, M.
A.; Chaly, T. Synthesis 1983, 203.
123.36, 124.81, 127.64, 130.18, 139.29, 139.42.
HRMS (APCI): m/z [M + H]+ calcd for C11H11ClO2: 211.0520;
found: 211.0517.
(4) Gallucci, R. R.; Going, R. J. Org. Chem. 1981, 46, 2532.
Synthesis 2009, No. 14, 2324–2328 © Thieme Stuttgart · New York