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D´yakonov et al.
0.37—0.61 (m, 3 H). 13С NMR, δ: 14.0 (С(12)), 18.4 (С(3)),
20.2 (С(13)), 22.8 (С(11)), 26.1 (С(1)), 28.6 (С(2)), 32.9 (С(10)),
125.8 (С(7)), 126.2 (С(6), С(8)), 128.0 (С(5), С(9)), 144.5 (С(4)).
MS (EI, 70 eV), m/z: 174.
9.6 (С(3)), 13.7 (t, С(12), JC,D = 19.0 Hz), 18.5 (t, С(2),
JC,D = 19.0 Hz), 20.8 (С(1)), 22.4 (С(11)), 30.5 (С(10)), 125.8
(С(7)), 127.8 (С(6), С(8)), 129.0 (С(5), С(9)), 139.8 (С(4)). MS
(EI, 70 eV), m/z: 162.
endoꢀ7ꢀPropylbicyclo[4.1.0]heptane (5e). B.p. 66—68 °C
(20 Torr). Found (%): С, 86.83; H, 13.14. С10H18. Calculated (%):
С, 86.88; H, 13.12. IR, ν/cm–1: 785, 1385, 1450, 1465, 3000.
1H NMR, δ: 1.76 (d, 1 H, J = 10.0 Hz); 1.61—1.84 (m, 8 H);
1.05—1.29 (m, 3 H); 0.89 (t, 3 H, J = 7.0 Hz); 0.79 (m, 2 H);
0.58 (m, 1 H). 13С NMR, δ: 10.1 (С(1), С(6)), 14.2 (С(10)), 18.5
(С(7)), 19.0 (С(2), С(5)), 22.6 (С(3), С(4)), 23.0 (С(9)), 32.5
(С(8)). MS (EI, 70 eV), m/z: 138.
endoꢀ9ꢀPropylbicyclo[6.1.0]nonane (5f). B.p. 74—76 °C
(5 Torr). Found (%): С, 86.53; H, 13.34. С12H22. Calculated (%):
С, 86.67; H, 13.33. IR, ν/cm–1: 780, 1380, 1450, 1465, 2985,
3000. 1H NMR, δ: 1.23—1.69 (m, 16 H); 0.93 (t, 3 H, J = 7.2 Hz);
0.59—0.66 (m, 2 H); 0.29—0.37 (m, 1 H). 13С NMR, δ: 14.2
(С(12)), 17.7 (С(9)), 17.9 (С(1), С(8)), 21.7 (С(3), С(6)), 23.6
(С(11)), 26.5 (С(4), С(5)), 29.7 (С(10)), 29.8 (С(2), С(7)). MS
(EI, 70 eV), m/z: 166.
2ꢀDeuteroꢀ2ꢀ(3ꢀdeuteropropyl)ꢀ1ꢀmethylꢀ1ꢀphenylcycloꢀ
propane (7d). B.p. 79—82 °C (3 Torr). Found (%): С, 88.48;
H + D, 11.49. С12H14D2. Calculated (%): С, 88.57; H, 9.15;
D, 2.28. IR, ν/cm–1: 2160 (C—D). 1H NMR, δ: 7.25—7.33 (m, 5 H,
Ph); 1.48 (s, 3 H); 1.09—1.30 (m, 4 H); 0.81 (t, 2 H, J = 7.0 Hz);
0.36—0.59 (m, 2 H). 13С NMR, δ: 13.7 (t, С(12), JC,D
=
= 19.0 Hz), 18.3 (С(3)), 20.3 (С(13)), 22.8 (С(11)), 26.2 (С(1)),
28.3 (t, С(2), JC,D = 19.0 Hz), 32.8 (С(10)), 125.8 (С(7)), 126.2
(С(6), С(8)), 128.0 (С(5), С(9)), 144.4 (С(4)). MS (EI, 70 eV),
m/z: 176.
endoꢀ7ꢀDeuteroꢀ7ꢀ(3ꢀdeuteropropyl)bicyclo[4.1.0]heptane
(7e). B.p. 66—68 °C (20 Torr). Found (%): С, 85.58; H + D,
14.34. С10H16D2. Calculated (%): С, 85.64; H, 11.50; D, 2.87.
IR, ν/cm–1: 2160 (C—D). 1H NMR, δ: 1.81 (s, 1 H); 1.60—1.84
(m, 8 H); 1.06—1.28 (m, 3 H); 0.88 (t, 2 H, J = 7.0 Hz); 0.78
(m, 2 H). 13С NMR, δ: 10.0 (С(1), С(6)), 13.9 (t, С(10), JC,D
=
1ꢀ(2ꢀDeuteroethyl)ꢀ1ꢀdeuteromethylꢀ2ꢀpentylcyclopropane
(6a) (cis : trans, 1 : 1). Found (%): C, 84.44; H + D, 14.98.
C11H20D2. Calculated (%): C, 84.53; H, 12.9; D, 2.57. IR,
= 19.0 Hz), 18.2 (t, С(7), JC,D = 22.5 Hz), 19.0 (С(2), С(5)),
22.5 (С(3), С(4)), 23.0 (С(9)), 32.4 (С(8)). MS (EI, 70 eV),
m/z: 140.
1
ν/cm–1: 2160 (C—D). H NMR, δ: 1.18—1.44 (m, 10 H); 1.03
endoꢀ9ꢀDeuteroꢀ9ꢀ(3ꢀdeuteropropyl)bicyclo[6.1.0]nonane
(7f). B.p. 74—76 °C (5 Torr). Found (%): С, 85.55; H + D,
14.41. С12H20D2. Calculated (%): С, 85.63; H, 11.98; D, 2.39.
IR, ν/cm–1: 2165 (C—D). 1H NMR, δ: 1.22—1.67 (m, 16 H);
0.92 (t, 2 H, J = 7.2 Hz); 0.59—0.68 (m, 2 H). 13С NMR, δ: 13.9
(t, С(12), JC,D = 19.0 Hz), 17.3 (t, С(9), JC,D = 24.0 Hz), 17.8
(С(1), С(8)), 21.7 (С(3), С(6)), 23.4 (С(11)), 26.5 (С(4), С(5)),
29.7 (С(10)), 29.8 (С(2), С(7)). MS (EI, 70 eV), m/z: 168.
Synthesis of spiro[2.3]hexanes (general procedure). Hexane
(15 mL), methylidenecyclopropane 1a,с,f (2.0 mmol), Cp2ZrCl2
(0.1 mmol), and Et3Al (4 mmol) were placed in a glass reactor
under a dry argon atmosphere at –10—15 °С with stirring. The
temperature was brought to room temperature (20—21 °С), and
the mixture was stirred for 4 h. Then at 0 °С Et2O (10 mL), Ph3P
(0.2 mmol), Pd(acac)2 (0.1 mmol), and allyl chloride (6 mmol)
were added, the temperature was increased to room temperature,
and the reaction mixture was stirred for 8 h. The reaction mixture
was treated with a 7—10% aqueous solution, and the reaction
products were extracted with ether, dried over MgSO4, and
isolated by distillation in vacuo.
(s, 2 H); 0.97 (t, 3 H, J = 7.0 Hz); 0.91 (t, 2 H, J = 7.0 Hz);
0.15—0.44 (m, 3 H). 13С NMR, δ: 34.4 (34.2), 32.6, 30.5, 28.6,
26.6, 22.6, 20.3 (20.1) (t, JC,D = 19.0 Hz), 18.6 (19.0), 14.2, 10.8
(10.7) (t, JC,D = 19.0 Hz). MS (EI, 70 eV), m/z: 156.
1ꢀ(2ꢀDeuteroethyl)ꢀ1ꢀdeuteromethylꢀ2ꢀheptylcyclopropane
(6b) (cis : trans, 1 : 1). Found (%): С, 84.65; H + D, 15.03.
С13H24D2. Calculated (%): С, 84.70; H, 13.12; D, 2.18. IR,
1
ν/cm–1: 2160 (C—D). H NMR, δ: 1.10—1.45 (m, 14 H); 1.03
(s, 2 H); 0.94 (t, 3 H, J = 7.0 Hz); 0.91 (t, 2 H, J = 6.5 Hz);
0.18—0.44 (m, 3 H). 13С NMR, δ: 34.6 (34.5), 32.8, 30.6, 29.7,
29.5, 28.6, 26.8, 22.6, 20.4 (20.2) (t, JC,D = 19.5 Hz), 18.6 (19.0),
14.1, 10.9 (11.1) (t, JC,D = 19.0 Hz). MS (EI, 70 eV), m/z: 184.
cisꢀ2ꢀDeuteroꢀ2ꢀ(3ꢀdeuteropropyl)ꢀ1ꢀpentylcyclopropane
(7a). nD20 1.4371. Found (%): С, 84.34; H + D, 14.95. С11H20D2.
Calculated (%): С, 84.53; H, 12.90; D, 2.57. IR, ν/cm–1: 2160
(C—D). 1H NMR, δ: 1.25—1.44 (m, 10 H); 1.09—1.15 (m, 2 H);
0.93 (t, 2 H, J = 7.0 Hz); 0.90 (t, 3 H, J = 7.0 Hz); 0.64 (m, 1 H);
0.58 (m, 2 H). 13С NMR, δ: 10.8 (С(3)), 13.8 (t, С(11), JC,D
=
= 19.0 Hz), 14.0 (С(8)), 15.3 (t, С(2), JC,D = 19.0 Hz), 15.8
(С(1)), 22.6 (С(7)), 23.4 (С(10)), 28.9 (С(5)), 30.1 (С(4)), 30.9
(С(9)), 32.1 (С(6)). MS (EI, 70 eV), m/z: 156.
1ꢀPentylspiro[2.3]hexane (8). B.p. 78—85 °C (12 Torr). The
yield was 59%. Found (%): С, 87.73; H, 12.27. C11H20. Calcuꢀ
lated (%): C, 88.76; H, 13.24. IR, ν/cm–1: 3069, 2995, 1705,
cisꢀ2ꢀDeuteroꢀ2ꢀ(3ꢀdeuteropropyl)ꢀ1ꢀheptylcyclopropane
(7b). nD20 1.4413. Found (%): С, 84.62; H + D, 15.04. С13H24D2.
Calculated (%): С, 84.70; H, 13.12; D, 2.18. IR, ν/cm–1: 2165
(C—D). 1H NMR, δ: 1.23—1.45 (m, 14 H); 1.10—1.18 (m, 2 H);
0.93 (t, 2 H, J = 7.0 Hz); 0.90 (t, 3 H, J = 7.0 Hz); 0.67 (m, 1 H);
1
1460, 1160, 760. H NMR, δ: 2.05—2.10 (m, 4 H); 1.92—1.96
(m, 2 H); 1.12—1.36 (m, 8 H); 0.91 (t, 3 H, J = 6.5 Hz);
0.49—0.56 (m, 3 H). 13С NMR, δ: 31.2 (С(9)), 30.9 (С(6)), 30.4
(С(7)), 29.3 (С(8)), 28.1 (С(3)), 26.4 (С(4)), 22.4 (С(10)), 22.1
(С(1)), 18.1 (С(2)), 17.4 (С(5)), 14.0 (С(11)). MS (EI, 70 eV),
m/z: 152.
Spiro[bicyclo[6.1.0]nonaneꢀ9ꢀcyclobutane] (10). B.p.
86—91 °C (5 Torr). The yield was 83%. Found (%): С, 87.68; H,
0.57 (m, 2 H). 13С NMR, δ: 10.8 (С(3)), 13.7 (t, С(11), JC,D
=
= 19.0 Hz), 14.0 (С(10)), 15.2 (t, С(2), JC,D = 19.5 Hz), 15.8
(С(1)), 22.7 (С(9)), 23.2 (С(12)), 28.7 (С(5)), 29.4 (С(7)), 29.6
(С(6)), 30.2 (С(4)), 30.9 (С(11)), 31.9 (С(8)). MS (EI, 70 eV),
m/z: 184.
cisꢀ2ꢀDeuteroꢀ2ꢀ(3ꢀdeuteropropyl)ꢀ1ꢀphenylcyclopropane
(7c). B.p. 71—73 °C (3 Torr). Found (%): С, 88.75; Н + D,
11.23. С12Н14D2. Calculated (%): С, 88.83; Н, 8.70; D, 2.48.
IR, ν/cm–1: 2160 (C—D). 1Н NMR, δ: 7.17—7.31 (m, 5 Н, Ph);
2.12 (m, 1 Н); 1.32 (m, 2 Н); 1.19 (m, 1 Н); 0.99 (m, 1 Н); 0.92
(m, 1 Н); 0.82 (t, 2 Н, J = 7.0 Hz); 0.65 (m, 1 Н). 13С NMR, δ:
12.28. С12H20. Calculated (%): С, 87.73; H, 12.27. IR, ν/cm–1
:
1
3071, 2999, 1700, 1462, 1160, 760. Н NMR, δ: 2.02 (m, 4 H);
1.91 (m, 2 H); 1.73—1.85 (m, 2 H); 1.26—1.69 (m, 8 H);
0.72—0.91 (m, 2 H); 0.45 (m, 2 H). 13С NMR, δ: 17.8 (С(11)),
22.4 (С(10)), 23.1 (С(3), С(6)), 24.8 (С(1), С(8)), 25.6 (С(9)),
26.6 (С(4), С(5)), 29.4 (С(2), С(7)), 31.4 (С(12)). MS (EI,
70 eV), m/z: 164.