Catalytic oxidation of alcohols by CCl4
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 11, November, 2002 2079
0.89 (t, 3 H, Me, J = 6.6 Hz); 0.91 (t, 3 H, Me, J = 6.6 Hz); 1.24
(m, 26 H, Me); 1.62 (m, 4 H, CH2); 2.34 (t, 2 H, CH2OCO, J =
7.2 Hz); 4.40 (t, 2 H, CH2OCO, J = 6.6 Hz). 13C NMR, δ: 14.00
(C(20)); 14.02 (C(1)); 22.60 (C(2)); 22.67 (C(19)); 26.25 (C(8));
26.33 (C(13)); 28.65 (C(12)); 29.15 (C(6)); 29.20 (C(4)); 29.25
(C(5)); 29.30 (C(7)); 29.56 (C(14)); 29.60 (C(17)); 29.80
(C(15)); 30.10 (C(16)); 31.80 (C(3)); 31.90 (C(18)); 34.31
(C(9)); 64.22 (C(11)); 173.80 (C(10)). MS, m/z (Irel (%)): 85
(20), 84 (21), 83 (24), 82 (12), 81 (6), 73 (19), 71 (32), 70 (32),
69 (35), 68 (12), 67 (9), 61 (18), 60 (10), 53 (53), 51 (32), 50
(53), 43 (100), 42 (23), 41 (58).
4ꢀChlorobutanal (14). B.p. 85 °C (95 Torr). Found (%):
C, 45.31; H, 6.54; Cl, 32.98. C4H7ClO. Calculated (%): C, 45.09;
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H, 6.62; Cl, 33.28. IR, ν/cm–1: 790, 1730. H NMR, δ: 3.47 (t,
2 H, CH2Cl, J = 6.5 Hz); 1.81 (m, 2 H, CH2, H(3)); 2.42 (m,
2 H, CH2, H(2)); 9.75 (s, 1 H, CHO). 13C NMR, δ: 26.32
(C(3)); 45.75 (C(2)); 46.82 (C(4)); 207.64 (C(4)).
Hexanꢀ6ꢀolide (15a). B.p. 109 °C (20 Torr). Found (%):
C, 63.21; H, 8.90. C6H10O2. Calculated (%): C, 63.13; H, 8.83.
13C NMR, δ: 23.15 (C(3)); 28.92 (C(5)); 29.44 (C(4)); 34.55
(C(2)); 68.86 (C(6)); 176.08 (C(1)).
Dodecanꢀ12ꢀolide (15b). B.p. 118 °C (10 Torr). Found (%):
C, 72.68; H, 11.09. C12H22O2. Calculated (%): C, 72.68;
H, 11.18. IR, ν/cm–1: 1050, 1160, 1245, 1365, 1470, 1730, 2920.
1H NMR, δ: 1.28 (s, 14 H, CH2); 1.62 (m, 2 H, CH2); 2.05 (s,
2 H, CH2); 3.68 (m, 2 H, CH2); 4.05 (m, 2 H, CH2). 13C NMR,
δ: 25.66 (C(2)); 28.39 (C(3)); 29.24 (C(4)—C(9)); 29.69 (C(10));
34.12 (C(11)); 65.13 (C(1)); 173.87 (C(12)).
2ꢀ(2ꢀHydroxypropyl)ꢀ4ꢀmethylꢀ1,3ꢀdioxane (17) (see Ref. 2).
B.p. 75—76 °C (2 Torr). Found (%): C, 60.08; H, 10.05.
C8H16O3. Calculated (%): C, 59.98; H, 10.07. IR, ν/cm–1: 780,
850, 900, 1050, 1090, 1126, 1380, 2860, 2930, 2965, 3460.
1H NMR, δ: 1.15 (d, 3 H, Me, J = 6.2 Hz); 1.20 and 1.27
(both d, 3 H each, Me, J = 6.0 Hz); 1.44—1.51 (m, 1 H,
H(5)ax); 1.66—1.72 (m, 1 H, H(5)eq); 1.78 (t, 2 H, CH2, H(8),
J = 3.7 Hz); 2.98 (s, 1 H, OH); 3.74—3.85 (m, 2 H, H(4)
and H(6)ax); 4.02—4.13 (m, 2 H, H(9) and H(6)eq); 4.78 (t,
1 H, H(2)). 13C NMR, δ: 21.69 (C(7)); 23.26 (C(10)); 32.88
(C(5)); 43.55 (C(8)); 64.42 (C(9)); 66.37 (C(6)); 72.87 (C(4));
100.84 (C(2)).
2,2,3,3ꢀTetrafluoropropyl 2´,2´,3´,3´ꢀtetrafluoropropionate
(3j). B.p. 75 °C (100 Torr). Found (%): C, 27.67; H, 1.52;
F, 58.42. C6H4F8O2. Calculated (%): C, 27.71; H, 1.55; F, 58.44.
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IR, ν/cm–1: 910, 925, 1110, 1190, 1210, 1725, 2940. H NMR,
δ: 5.30—6.54 (m, 2 H, CF2H); 3.41—3.95 (m, 2 H, CH2).
13C NMR, δ: 59.80 (C(4)); 98.37 (C(1)); 109.42 (C(6)); 115.40
(C(2)); 120.47 (C(5)); 168.60 (C(3)).
nꢀOctyl acetate (7d). B.p. 105 °C (10 Torr). Found (%):
C, 69.74; H, 11.60. C10H20O2. Calculated (%): C, 69.72;
H, 11.70. IR, ν/cm–1: 1745 (O—C=O). 13C NMR, δ: 13.85
(C(10)); 20.84 (C(1)); 22.63 (C(9)); 26.33 (C(5)); 28.66
(C(4)); 29.33 (C(8)); 29.50 (C(6)); 29.90 (C(7)); 64.48 (C(3));
174.01 (C(2)).
nꢀDecyl acetate (7e). B.p. 121—122 °C (10 Torr). Found (%):
C, 71.96; H, 11.97. C12H24O2. Calculated (%): C, 71.95;
H, 12.08. IR, ν/cm–1: 1740 (O—C=O). 13C NMR, δ: 13.87
(C(12)); 20.82 (C(1)); 22.80 (C(11)); 26.33 (C(5)); 28.66 (C(4));
29.52 (C(6)); 29.65 (C(9)); 29.78 (C(7)); 29.92 (C(8)); 32.00
(C(10)); 64.48 (C(3)); 173.29 (C(2)).
1ꢀAdamantylmethanol acetate (7f). B.p. 78—79 °C (0.5 Torr).
Found (%): C, 74.93; H, 9.63. C13H20O2. Calculated (%):
C, 74.96; H, 9.68. IR, ν/cm–1: 1720 (O—C=O). 13C NMR, δ:
20.94 (C(13)); 28.30 (C(3), C(5), C(7)); 33.43 (C(1)); 37.35
(C(4), C(6), C(10)); 39.38 (C(2), C(8), C(9)); 67.62 (C(11));
170.90 (C(12)).
3ꢀHydroxybutanꢀ2ꢀone (18) (see Ref. 8). M.p. 89—90 °C
(MeOH). Found (%): C, 54.51; H, 9.02. C4H8O2. Calculated (%):
C, 54.53; H, 9.15. IR, ν/cm–1: 1100, 1710, 3450. 13C NMR, δ:
18.90 (C(4)); 28.26 (C(1)); 64.08 (C(3)); 200.62 (C(2)).
Hexaneꢀ2,5ꢀdione (19) (see Ref. 8). B.p. 85 °C (20 Torr).
IR, ν/cm–1: 1715 (C=O).
1ꢀAdamantane carbaldehyde (see Ref. 7). M.p. 125—126 °C
(MeOH). Found (%): C, 80.42; H, 9.74. C11H16O. Calcuꢀ
lated (%): C, 80.44; H, 9.83. IR, ν/cm–1: 1725 (CHO). 1H NMR,
δ: 1.59 (m, 12 H, CH2); 1.75 (m, 3 H, CH); 9.46 (s, 1 H, CHO).
13C NMR, δ: 28.14 (C(3), C(5), C(7)); 36.17 (C(4), C(6),
C(10)); 36.80 (C(2), C(8), C(9)); 48.80 (C(1)); 204.89 (C(11)).
MS, m/z (Irel (%)): 164 [M]+ (25), 137 (100), 107 (24), 91 (33),
79 (45), 67 (39), 65 (21).
Ethyl 1ꢀadamantanecarboxylate (8). B.p. 121—122 °C
(4 Torr). Found (%): C, 74.95; H, 9.58. C13H20O2. Calcuꢀ
lated (%): C, 74.96; H, 9.68. 13C NMR, δ: 14.57 (C(13)); 28.24
(C(3), C(5); C(7)); 36.80 (C(4), C(6), C(10)); 39.01 (C(2),
C(8), C(9)); 40.72 (C(1)); 59.21 (C(12)); 177.33 (C(11)). MS,
m/z (Irel (%)): 208 [M]+ (26), 180 (13), 163 (3), 136 (44), 135
(100), 107 (18), 93 (45), 91 (17), 79 (54), 67 (24).
Benzyl benzoate. B.p. 142 °C (3 Torr). Found (%): C, 79.23;
H, 5.63. C14H12O2. Calculated (%): C, 79.22; H, 5.70. IR,
ν/cm–1: 1720 (O—C=O). 13C NMR, δ: 64.30 (C(8)); 128.75
(C(12)); 128.82 (C(9), C(14)); 128.96 (C(2), C(6)); 129.15
(C(11), C(13)); 129.64 (C(1)); 133.95 (C(4)); 140.90 (C(9));
166.98 (C(7)); 309.15 (C(3), C(5)).
Chloroacetaldehyde (10) (see Ref. 5). B.p. 51—52 °C. IR,
ν/cm–1: 1720, 800. 13C NMR, δ: 40.74 (C(1)); 176.85 (C(2)).
1,4ꢀDioxane (11) (see Ref. 5). B.p. 102—103 °C. 13C NMR,
δ: 66.82.
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Received October 5, 2001;
in revised form April 3, 2002