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CAS No. : | 1224157-88-3 | MDL No. : | MFCD22370351 |
Formula : | C12H14O4 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | LBSSNJFKFJEHIA-UHFFFAOYSA-N |
M.W : | 222.24 | Pubchem ID : | 73553873 |
Synonyms : |
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Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302-H315-H319-H335 | Packing Group: | N/A |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | With sodium periodate In water; acetonitrile at 20℃; for 48 h; | To a stirred solution of the compound 5a (2.00 g, 8.93 mmol) and ethyl acrylate (7 mL, excess) in acetonitrile (10 mL) was added a solution of NaIO4 (6.00 g, 28.00 mmol) in water (20 mL) drop wise at 0 °C and the reaction mixture was stirred at ambient temperature for 48 h. Acetonitrile was evaporated under reduced pressure, residue was diluted with water (30 mL) and extracted with ethyl acetate (3 × 50 mL). The organic extract was combined, washed with brine (50 mL) and dried over anhydrous Na2SO4. Solvent was removed under reduced pressure and product was chromatographed on silica gel.Elution with petroleum ether / ethyl acetate (85:15) first gave the minor aldehyde 8a as a colorless solid (0.183 g, 18percent); mp 85 - 87 oC. [Rf = 0.5 petroleum ether/EtOAc (90:10)]. IR νmax: 3390, 1663 cm-1. 1H NMR (400 MHz, CD3COCD3): δ 11.35 (s, 1H), 10.13 (s, 1H), 8.40 (d, J = 2.0 Hz, 1H), 8.14 (dd, J1 = 8.7 Hz, J2 = 2.0 Hz, 1H), 7.06 (d, J = 8.7 Hz, 1H), 1.59 (s, 9H). 13C NMR (100 MHz, CD3COCD3): δ 197.9, 165.3, 164.8, 138.2, 136.3, 125.0, 121.4, 118.2, 81.7, 28.3. HRMS (ESI): m/z [M + K]+ calcd for C12H14KO4: 261.0524; found: 261.0525. The above data is in agreement with those reported in literature[13]. Continued elution with petroleum ether/ethyl acetate (70:30) gave the desired adduct 9a as a colorless solid (1.77 g, 62percent); mp 104 - 106 °C. [Rf = 0.5 petroleum ether/EtOAc (70:30)]. IR max: 1732, 1712 cm-1. 1H NMR (400 MHz, CDCl3): δ 7.06 (dd, J1 = 6.4 Hz, J2 = 1.8 Hz, 1H), 4.15 (q, J = 7.1 Hz, 2H), 3.86 (dd, J1 = 6.4 Hz, J2 = 2.2 Hz, 1H), 3.21-3.15 (m, 2H), 3.11 (part of an AB system, JAB = 6.2 Hz, 1H), 2.93 (part of an AB system, JAB = 6.2 Hz, 1H), 2.44 (partly merged ddd, J1 = 13.3 Hz, J2 = 10.5 Hz, J3 = 2.6 Hz, 1H ), 2.02 (ddd, J1 = 13.3 Hz, J2 = 5.2 Hz, J3 = 2.9 Hz, 1H), 1.50 (s, 9H), 1.26 (t, J = 7.1 Hz, 3H). 13C NMR (100 MHz, CDCl3): δ 203.2, 172.1, 162.5, 140.4, 135.4, 81.9, 61.7, 57.3, 53.2, 51.2, 40.6, 37.8, 28.2, 25.8, 14.2. HRMS (ESI): m/z [M + Na]+ calcd for C17H22NaO6: 345.1309; found: 345.1306.Crystal data of 9a: Crystal data of compound 9a: C17H22O6, M = 322.36, triclinic, space group P-1 ( 2), a = 6.636 (4) Å, b = 9.419 (6) Å, c = 13.627 (8) Å, = 92.616 (10), = 99.969(12), = 93.654(9), V = 835.8 (9) Å3, Dc = 1.281 g/ cm3, Z = 2, F(000) = 344.00, Size: 0.45 x 0.20 x 0.09 mm3, Wavelength = 0.71070 Å, GoF = 0.885, Absorption coefficient = 0.965 cm-1, Total/unique reflections = 8828 / 2929 [R(int) = 0.0950], T = 100 K, 2 range = 5.0 to 50.0, Final R [I > 2s(I)]: R1 = 0.0567, wR2 = 0.1604, R (all data): R1 = 0.0854, wR2 = 0.1604. Crystallographic data has been deposited with Cambridge Crystallographic data Centre, CCDC no. 1004667. Copy of the data can be obtained, free of charge, on application to CCDC. E-mail. Depositccdc.cam.ac.UK |
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