摘要: (1; R = Me) [37734-05-7] C6H8O3 (MW 128.14) InChI = 1S/C6H8O3/c1-3-5(7)4-6(8)9-2/h3H,1,4H2,2H3 InChIKey = ZQUPQDCVMAQIKI-UHFFFAOYSA-N (2; R = Et) [22418-80-0] C7H10O3 (MW 142.17) InChI = 1S/C7H10O3/c1-3-6(8)5-7(9)10-4-2/h3H,1,4-5H2,2H3 InChIKey = IEZWUJDDYLWKEP-UHFFFAOYSA-N (Michael acceptor in the Robinson annulation2) Alternate Names: Nazarov's reagent; methyl acryloylacetate; vinyl β-methoxycarbonylmethyl ketone. Physical Data: (1) bp 65 °C/19 mmHg. (2) 76–78 °C/18 mmHg. Solubility: sol common organic solvents. Form Supplied in: colorless liquid; not commercially available. Analysis of Reagent Purity: exists as a mixture keto and enol forms; IR (film) cm−1 2984, 1741, 1659, 1588, 1423, 1242, 1150, 1038, 812; 1H NMR (CDCl3) δ 1.2–1.3 (overlapping t, 3 H), 3.6 (s, ketonic H at C-2), 4.1–4.3 (m, 2 5.05 enolic 5.50 (appt, 1 5.91–6.43 11.8 OH); 13C 14.0, 14.2, 46.4, 60.2, 61.4, 91.8, 122.5, 130.2, 131.2, 135.7, 167.1, 168.6, 172.7, 192.6. Preparative Methods: first prepared by Nazarov3 1953 reaction shown eq 1. is known Nazarov's reagent, although (1) often referred to reagent also. (1) The original preparation suffers several problems. It has been termed ‘tedious’4 low overall yield. Several new syntheses esters 3-oxo-4-pentenoic acid have reported since 1953.2, 4-10 The most facile ester analogs was Zibuck Streiber 1989. A variety enolates react with Acrolein provide good yields β-hydroxy that can be oxidized β-keto such (eqs 3).1 The sequence safely successfully carried out on mol scale. Also, may without purification. Interestingly, (−)-bornyl acetate leads an annulating agent contains chiral auxiliary. Methacrolein Crotonaldehyde give 4- 5-methyl substituted reagents. C-4 C-5 many other research groups, using reactions similar those presented above.11-16 (2) (3) Purification: by Kugelrohr distillation 0.6 mmHg (oven temperature 45 °C) receiving bulb cooled −78 °C. Handling, Storage, Precautions: polymerizes rapidly rt; stable storage −20 °C under nitrogen for up 6 months; toxic; handle fume hood.
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