Acyllacton‐Umlagerung, XXXIV. Synthesen und Reaktionen von phosphorylierten α‐Acyl‐lactonen

Abstract

Bd. 685 b) Hydrolysiert man 2.3 g (5 mMol) ( t ) -I X in der gleichen Weise und arbeitet wie bei a) auf, so erhalt man 0.6 g (49 %) Methyl-n-propyl-phenyl-phosphinoxyd rnit [=ID = -15.1"

Synthesis and Biological Evaluation of a Phosphonate Analog of the Natural Acetyl Cholinesterase Inhibitor Cyclophostin

“…Phosphorylation of 2-acetyl butyrolactone 18 was accomplished by reaction with dimethyl chlorophosphate using a reported procedure 14. Alternatively, the enol phosphate 19 was formed as a mixture of geometrical isomer by reaction of 2-acetyl butyrolactone 18 with dimethyl phosphoric acid and DCC.…”

Reactions of an .alpha.-phosphono-.gamma.-butyrolactone carbanion with acid anhydrides, epoxides, carbonates, and a lactone

“…a-(0,0-Diethylphosphone)-7-butyrolactone,2•6 thio-phthalic7 (3). homophthaiic8 (6), and TV-methylisatoic anhydrides9 (11), isobutylene10 (14c) and methylenecyclohexane oxides10 (14d), 3,4-epoxy-4-methyl-2-pentanonen (18a), chalconepoxide11 (18b), and 1,2-carbonyldioxybenzene12 (20) were prepared according to the established procedures.…”

“…3-(2-Oxotetrahydrofuran-3-yl)isocoumarin (7). The reaction of 1 with homophthaiic anhydride (6) was carried out in a sealed tube at 140 °C for 4 h. After removal of sodium diethyl phosphate by filtration, the filtrate was concentrated under reduced pressure. The residue was chromatographed on silica gel to give 3.40 g (74%) of 7: mp 174-175 °C (from acetonitrile); IR (Nujol) 1760 and 1715 (C=0) and 1650 cm-1 (C=C); NMR (CD3CN) 2.64 (m, 2 H, methylene protons), 3.84 (t, J = 9 Hz, 1 H, methine proton), 4.42 (m, 2 H, OCH2), 6.65 (s, 1 H, vinylic proton), 7.30-7.90 (m, 3 H, aromatic protons), and 8.24 (d, J = 8 Hz, 1 H, aromatic proton); mass spectrum (70 eV) m/e 230 (M+).…”

“…The phosphonate carbanion 1 easily reacted with phthalic (2) and thiophthalic anhydrides (3) in refluxing benzene for 3 h to give a mixture of (Z)-3-(4a, 58%) and (E) -3 -(2-oxotetrahydrofuran-3-ylidene)phthalide (4b, 42%) and (Z)-3-(2-oxotetrahydrofuran-3-ylidene)thiophthalide (5), respectively, in quantitative yields. 0 0 2, X = O 3, X = S 4a, X = O 5, X = S 0 Although the reaction with homophthalic anhydride (6) required relatively vigorous conditions (at 140 °C for 4 h in a sealed tube), 3-(2-0xotetrahydrofuran-3-yl)isocoumarin (7) was obtained in good yield. However, treatment of maleic and succinic anhydrides with 1 under similar conditions gave no corresponding product.…”

“…The structural assignment of product 9 was made by spectral data and elemental analysis and by alkaline hydrolysis of the product 9 yielding 2-.ZV-(2-oxotetrahydrofuran-3-carboxyamido)benzoic acid (10) (Scheme I). Whereas the reaction of 11 in benzene solvent at 140 °C for 7 h in a sealed tube gave 2/i,4H-l-methyl-(E)-4-(2-oxotetrahydrofuran-3-ylidene)benz [d][l,3]oxazin-2-one (12a, 43%) along with 2íf,3/í,4íf-9-methylfuro [2,[3][4][5][6]quinolin-4-one (13, 5%), the reaction in DMF at 110 °C for 4 h produced only 13 in high yield with the accompanying evolution of carbon dioxide gas. Heat of the separated (E) isomer 12a in refluxing ethanol containing NaOH for confirmation of its stereochemistry led to the corresponding (Z) isomer 12b.…”