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Russ.Chem.Bull., Int.Ed., Vol. 57, No. 7, July, 2008
Koldobskii et al.
Found (%): C, 51.89; H, 4.68; Cl, 15.90. C10H11ClO4. Calculated
(%): C, 52.08; H, 4.81; Cl, 15.37. IR, ν/cm–1: 1600 (C=C); 1674,
1737 (C=O). 1H NMR, δ: 1.25 (t, 3 H, CH3, J = 7.1 Hz);
1.27—1.69 (m, 1 H, CH2CH); 1.86 (dd, 1 H, CH2CH, J = 13.2 Hz,
J = 5.2 Hz); 3.54 (dd, 1 H, CH, J = 8.4 Hz, J = 3.3 Hz);
3.72—3.75 (m), 4.05 (t) (a total of 2 H, OCH2); 4.25 (q, 2 H,
OCH2CH3, J = 7.1 Hz); 5.26 (d, 1 H, OCH, J = 3.3 Hz).
13C NMR, δ: 13.87 (CH3); 25.23 (CH2); 53.99 (CH2O); 62.58
(OCH2CH3); 66.37, 77.45 (CH—CH); 135.51, 149.09 (C=C);
160.95 (COOEt); 177.05 (C=O).
Ethyl (7ꢀchloroꢀ2ꢀoxabicyclo[4.2.0]octꢀ7ꢀenꢀ8ꢀyl)(oxo)acetꢀ
ate (4). The product was obtained according to the general proceꢀ
dure from ethyl 4ꢀchloroꢀ2ꢀoxobutꢀ3ꢀynoate (2) and 3,4ꢀdihydroꢀ
2Hꢀpyran. The reaction time was 18 h, ethyl acetate—hexane (1 : 5)
was the eluent. The yield was 0.46 g (62%). Found (%): C, 54.33;
H, 5.23; Cl, 15.00. C11H13ClO4. Calculated (%): C, 54.00; H, 5.36;
Cl, 14.49. IR, ν/cm–1: 1594 (C=C); 1672, 1740 (C=O). 1H NMR,
δ: 1.26 (t, 3 H, CH3, J = 7.1 Hz); 1.48—1.60, 1.78—1.85, 1.88—1.95
(all m, a total of 4 H, (CH2)2); 3.08—3.12 (m, 1 H, CH); 3.56—3.63,
3.68—3.74 (both m, 1 H each, CH2O); 4.25 (q, 2 H, OCH2CH3,
J = 7.1 Hz); 4.80 (d, 1 H, CH, J = 4.1 Hz). 13C NMR, δ: 13.85
(CH3); 19.42, 20.81 (CH2—CH2); 47.36 (OCH2); 62.02, 69.34
(CH—CH); 62.53 (OCH2CH3); 138.68; 151.61 (C=C); 161.29
(COOEt); 177.23 (C=O).
(m, 2 H, CH2—C—OMe); 3.25—3.27 (m, 3 H, OCH3); 4.28
(q, 2 H, OCH2CH3, J = 7.1 Hz). 13C NMR, δ: 13.87 (CH3); 23.01,
30.59, 53.91 (CH2); 62.55 (OCH2CH3); 57.13, 63.03 (C≡C);
90.63 (OCH3); 136.42, 148.62 (C=C); 162.02 (COOEt);
178.33 (C=O).
Ethyl 4ꢀ(2ꢀmethoxycyclohexꢀ1ꢀenyl)ꢀ2ꢀoxobutꢀ3ꢀynoate (7).
The product was obtained according to the general procedure from
ethyl 4ꢀchloroꢀ2ꢀoxobutꢀ3ꢀynoate (2) and 1ꢀmethoxycyclohexene.
The reaction time was 18 h, ethyl acetate—hexane (1 : 10) was the
eluent. The yield was 0.57 g (68%). Found (%): C, 65.89; H, 6.46.
C13H16O4. Calculated (%): C, 66.09; H, 6.83. IR, ν/cm–1: 602
(C=C); 1672, 1742 (C=O); 2207 (C≡C). 1H NMR, δ: 1.31 (t, 3 H,
COOCH2CH3, J = 7.1 Hz); 1.28—1.34, 1.37—1.43 (both m,
2 H each, CH2—CH2—CH2—CH2); 1.48—1.59, 1.67—1.87 (both m,
1 H each, CH2—C=); 1.97—2.23 (m, 2 H, CH2—C—OMe);
3.32—3.37 (m, 3 H, OCH3); 4.29 (q, 2 H, OCH2CH3, J = 7.1 Hz).
13C NMR, δ: 13.90 (CH3); 23.15, 28.45, 36.17, 55.29 (CH2);
62.55 (OCH2CH3); 57.13, 63.03 (C≡C); 90.63 (OCH3); 136.42,
148.62 (C=C); 162.02 (COOEt); 178.33 (C=O).
References
1. C. Zhang, C. J. Ballay, II, M. L. Trudell, J. Chem. Soc., Perkin
Trans. 1, 1999, 675.
Ethyl (Z)ꢀ4ꢀchloroꢀ3ꢀethoxymethylideneꢀ2ꢀoxopentꢀ4ꢀenoate
(5). The product was obtained according to the general procedure
from ethyl 4ꢀchloroꢀ2ꢀoxobutꢀ3ꢀynoate (2) and ethyl vinyl ether.
The reaction time was 18 h, ethyl acetate—hexane (1 : 10) was the
eluent. The yield was 0.40 g (56%). Found (%): C, 51.23; H, 5.44;
Cl, 15.48. C10H13ClO4. Calculated (%): C, 51.62; H, 5.63;
Cl, 15.24. IR, ν/cm–1: 1593, 1640 (C=C), 1673, 1740 (C=O).
1H NMR, δ: 1.27 (t, 3 H, OCH2CH3, J = 7.1 Hz); 1.32 (t, 3 H,
CH3, J = 7.1 Hz); 4.18—4.26 (m, 2 H, CH2); 4.28 (q, 2 H,
OCH2CH3, J = 7.1 Hz); 5.28, 5.57 (both d, 1 H each, C=CH2,
J = 1.5 Hz); 7.63 (s, 1 H, CH). 13C NMR, δ: 13.91 (OCH2CH3);
15.25 (CH3); 62.19 (OCH2CH3); 73.00 (OCH2); 117.24, 119.97,
129.32, 163.41 (all C=C); 165.75 (COOEt); 182.72 (C=O).
Ethyl 4ꢀ(2ꢀmethoxycyclopentꢀ1ꢀenyl)ꢀ2ꢀoxobutꢀ3ꢀynoate (6).
The product was obtained according to the general procedure from
ethyl 4ꢀchloroꢀ2ꢀoxobutꢀ3ꢀynoate (2) and 1ꢀmethoxycyclopenteꢀ
ne. The reaction time was 1 h, ethyl acetate—hexane (1 : 20) was the
eluent. The yield was 0.41 g (60%). Found (%): C, 64.33; H, 6.54.
C12H14O4. Calculated (%): C, 64.85; H, 6.35. IR, ν/cm–1: 1600
(C=C); 1674, 1737 (C=O); 2200 (C≡C). 1H NMR, δ: 1.30 (t, 3 H,
COOCH2CH3, J= 7.1 Hz); 1.36—1.39 (m, 2 H, CH2—CH2—CH2);
1.43—1.53, 1.62—1.81 (both m, 1 H each, CH2—C=); 1.93—2.15
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Received April 28, 2008