7-氮杂双环[4.2.0]辛-3-烯-8-酮

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Benzyl glyoxylate (2.73 g) was refluxed in benzene (25 ml) with provision for the removal of water. After 45 minutes 8-oxo-7-azabicyclo[4,2,0]oct-3-ene (28) (ref: I. A. Paquette and T. Kakihana, J. Amer. Chem. Soc., 1968, 90, 2897) (1.23 g) was added and refluxing continued for 3 hours. Removal of solvent under reduced pressure followed by chromatography gave two separate isomers of the alcohol (32) (90%) Isomer I, m.p. 92°-93°, νmax (CHCl3) 3450, 1750 (b) cm-1. δ ppm (CDCl3) 1.76-2.73 (4H, m, 2-CH2), 3.12-3.33 (1H, m, β-lactam proton), 3.76-3.93 (1H, m, β-lactam proton), 4.40 (1H, d, J 6 Hz, exch. D2O), 5.16 (2H, s, CH2), 5.47 (1H, d, J 6 Hz collapsing to s on D2O exch. CH-OH), 5.67-5.83 (2H, m, CH=CH), 7.34 (5H, Ar). M+ at m/e 287 (Found; C, 66.2; H, 5.9; N, 4.9.C16H17NO4 requires C, 66.9; H, 6.0; N, 4.9%). Isomer II, m.p. 100°-101°, νmax (CHCl3) 3450, 1750 (b), δ ppm (CDCl3) 1.80-2.63 (4H, m, 2-CH2), 3.13-3.36 (1H, m, β-lactam proton), 3.93-4.13 (1H, m, β-lactam proton), 4.20 (1H, bs, exch, D2O), 5.16 (2H, s, CH2), 5.50 (1H, b, sharpening to s on D6O exchange), 5.50-6.00 (2H, m, CH=CH), 7.34 (5H, Ar). (Found; C, 67.2; H, 6.0; N, 4.8. C16H17NO4 requires C, 66.9; H, 6.0; N, 4.9%). , 1968, 90, 2897) (1.23 g) was added refluxing Removal of solvent under reduced pressure gave two separate isomers of the alcohol (32) (90%) Isomer I, m.p. 92°-93°, νmax (CHCl3) 3450, 1750 (b) cm-1

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Benzyl glyoxylate (2.73 g) was refluxed in benzene (25 ml) with provision for the removal of water. After 45 minutes 8-oxo-7-azabicyclo[4,2,0]oct-3-ene (28) (ref: I. A. Paquette and T. Kakihana, J. Amer. Chem. Soc., 1968, 90, 2897) (1.23 g) was added and refluxing continued for 3 hours. Removal of solvent under reduced pressure followed by chromatography gave two separate isomers of the alcohol (32) (90%) Isomer I, m.p. 92°-93°, νmax (CHCl3) 3450, 1750 (b) cm-1. δppm (CDCl3) 1.76-2.73 (4H, m, 2-CH2), 3.12-3.33 (1H, m, β-lactam proton), 3.76-3.93 (1H, m, β-lactam proton), 4.40 (1H, d, J 6 Hz, exch. D2O), 5.16 (2H, s, CH2), 5.47 (1H, d, J 6 Hz collapsing to s on D2O exch. CH--OH), 5.67-5.83 (2H, m, CH=CH), 7.34 (5H, Ar). M+ at m/e 287 (Found; C, 66.2; H, 5.9; N, 4.9.C16H17NO4 requires C, 66.9; H, 6.0; N, 4.9%). Isomer II, m.p. 100°-101°, νmax (CHCl3) 3450, 1750 (b), δppm (CDCl3) 1.80-2.63 (4H, m, 2-CH2), 3.13-3.36 (1H, m, β-lactam proton), 3.93-4.13 (1H, m, β-lactam proton), 4.20 (1H, bs, exch, D2O), 5.16 (2H, s, CH2), 5.50 (1H, b, sharpening to s on D2O exchange), 5.50-6.00 (2H, m, CH=CH), 7.34 (5H, Ar). (Found; C, 67.2; H, 6.0; N, 4.8. C16H17NO4 requires C, 66.9; H, 6.0; N, 4.9%). , 1968, 90, 2897) (1.23 g) was added refluxing Removal of solvent under reduced pressure gave two separate isomers of the alcohol (32) (90%) Isomer I, m.p. 92°-93°, νmax (CHCl3) 3450, 1750 (b) cm-1

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Benzyl glyoxylate (2.73 g) was refluxed in benzene (25 ml) with provision for the removal of water. After 45 minutes 8-oxo-7-azabicyclo[4,2,0]oct-3-ene (28) (ref: I. A. Paquette and T. Kakihana, J. Amer. Chem. Soc., 1968, 90, 2897) (1.23 g) was added and refluxing continued for 3 hours. Removal of solvent under reduced pressure followed by chromatography gave two separate isomers of the alcohol (32) (90%) Isomer I, m.p. 92°-93°, νmax (CHCl3) 3450, 1750 (b) cm-1. δ ppm (CDCl3) 1.76-2.73 (4H, m, 2-CH2), 3.12-3.33 (1H, m, β-lactam proton), 3.76-3.93 (1H, m, β-lactam proton), 4.40 (1H, d, J 6 Hz, exch. D2O), 5.16 (2H, s, CH2), 5.47 (1H, d, J 6 Hz collapsing to s on D2O exch. CH-OH), 5.67-5.83 (2H, m, CH=CH), 7.34 (5H, Ar). M+ at m/e 287 (Found; C, 66.2; H, 5.9; N, 4.9.C16H17NO4 requires C, 66.9; H, 6.0; N, 4.9%). Isomer II, m.p. 100°-101°, νmax (CHCl3) 3450, 1750 (b), δ ppm (CDCl3) 1.80-2.63 (4H, m, 2-CH2), 3.13-3.36 (1H, m, β-lactam proton), 3.93-4.13 (1H, m, β-lactam proton), 4.20 (1H, bs, exch, D2O), 5.16 (2H, s, CH2), 5.50 (1H, b, sharpening to s on D6O exchange), 5.50-6.00 (2H, m, CH=CH), 7.34 (5H, Ar). (Found; C, 67.2; H, 6.0; N, 4.8. C16H17NO4 requires C, 66.9; H, 6.0; N, 4.9%). , 1968, 90, 2897) (1.23 g) was added refluxing Removal of solvent under reduced pressure gave two separate isomers of the alcohol (32) (90%) Isomer I, m.p. 92°-93°, νmax (CHCl3) 3450, 1750 (b) cm-1

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Benzyl glyoxylate (2.73 g) was refluxed in benzene (25 ml) with provision for the removal of water. After 45 minutes 8-oxo-7-azabicyclo[4,2,0]oct-3-ene (28) (ref: I. A. Paquette and T. Kakihana, J. Amer. Chem. Soc., 1968, 90, 2897) (1.23 g) was added and refluxing continued for 3 hours. Removal of solvent under reduced pressure followed by chromatography gave two separate isomers of the alcohol (32) (90%) Isomer I, m.p. 92°-93°, νmax (CHCl3) 3450, 1750 (b) cm-1. δppm (CDCl3) 1.76-2.73 (4H, m, 2-CH2), 3.12-3.33 (1H, m, β-lactam proton), 3.76-3.93 (1H, m, β-lactam proton), 4.40 (1H, d, J 6 Hz, exch. D2O), 5.16 (2H, s, CH2), 5.47 (1H, d, J 6 Hz collapsing to s on D2O exch. CH--OH), 5.67-5.83 (2H, m, CH=CH), 7.34 (5H, Ar). M+ at m/e 287 (Found; C, 66.2; H, 5.9; N, 4.9.C16H17NO4 requires C, 66.9; H, 6.0; N, 4.9%). Isomer II, m.p. 100°-101°, νmax (CHCl3) 3450, 1750 (b), δppm (CDCl3) 1.80-2.63 (4H, m, 2-CH2), 3.13-3.36 (1H, m, β-lactam proton), 3.93-4.13 (1H, m, β-lactam proton), 4.20 (1H, bs, exch, D2O), 5.16 (2H, s, CH2), 5.50 (1H, b, sharpening to s on D2O exchange), 5.50-6.00 (2H, m, CH=CH), 7.34 (5H, Ar). (Found; C, 67.2; H, 6.0; N, 4.8. C16H17NO4 requires C, 66.9; H, 6.0; N, 4.9%). , 1968, 90, 2897) (1.23 g) was added refluxing Removal of solvent under reduced pressure gave two separate isomers of the alcohol (32) (90%) Isomer I, m.p. 92°-93°, νmax (CHCl3) 3450, 1750 (b) cm-1

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: The azetidinone (1) (0.4 g) in anhydrous dimethylformamide (2 ml) was stirred with glyoxylic acid hydrate (0.32 g) in the presence of hexamethylphosphorictriamide (0.1 ml) and molecular sieves (3A; 4 pieces) for 5 h. Potassium carbonate (0.226 g) was added, and the solution stirred until effervescence had ceased (5 min.). p-Bromophenylbromide (1.00 g; 1.05 equiv.) in dimethylformamide (1.0 ml) and hexamethylphosphorictriamide (0.25 ml) was added, and the solution stirred overnight. The solution was diluted with ethyl acetate, washed with saturated aqueous sodium chloride solution (×3), dried (Na2SO4) and evaporated to give a gum (1.9 g) which was chromatographed on Kieselgel. Elution of the column with ethyl acetate-petroleum ether (1:1) gave the glyoxylate ester (58). Isomer I as a foam, which slowly crystallised (ethyl acetate-petroleum ether) as needles (0.60 g), (47%) m.p. 135°-136°, νmax (CHCl3) 3250br, 1760sh, 1750, 1710, 1590, 970 cm-1 ; δ (d6DMSO) 1.9-2.8 (4H, m), 3.35 (1H, m), 4.17 (1H, m) 5.51 (1H, d, J 6.5 Hz; sharpens to a singlet on D2O exchange) 5.55 (2H, s, phenacyl CH2), 5.72br (2H, s), 6.81 (1H, d, J 6.5H, D2O exchangeable), 7.75 (2H, d, J 9 Hz) and 7.90 (2H, d, J 9 Hz) (Found: C, 51.9; H, 4.2; N, 3.6; Br, 20.00. C17H16BrNO5 requires C, 51.8; H, 4.1; N, 3.6; Br, 20.3%). (5 min.) the solution stirred overnight washed with saturated aqueous sodium chloride solution (×3) dried (Na2SO4) evaporated

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: p-Nitrobenzyl glyoxylate hydrate (9.08 g) was refluxed in benzene (150 ml) with provision for the removal of water. After 1 hour 8-oxo-7-azabicyclo [4.2.0]oct-3-ene (1) (2.46 g) was added and refluxing continued for 3.5 hours. The cooled solution was washed with water (x2), then brine. After back extraction of the first aqueous extract with ethyl acetate, the organic solutions were dried over magnesium sulphate, filtered combined, and evaporated. Chromatography on silica, eluting with ethyl acetate-petroleum ether mixtures gave two separate isomers of the alcohol (54) (43%). Less polar isomer I m.p. 153°-5° (crystalline plates ex ethyl acetate/ether). νmax (CHCl3) 3400 (broad), 1760, 1745, 1520, 1350 cm-1. δppm (CDCl3) 1.90-2.83 (4H, m, 2-CH2), 3.23-3.55 (1H, m, β-lactam proton), 4.00-4.20 (1H, m, β-lactam) proton), 4.27 (1H, d, J 8 Hz, exchangeable with D2O, OH), 5.33 (2H, s, CH2Ar)obscuring 1H, CHOH; 5.67-5.88 (2H, m, CH=CH), 7.55 (2H, d, J 8.5 Hz, Ar), 8.23 (2H, d, J 8.5 Hz, Ar) (Found: C, 58.07; H, 5.15; N, 8.51%, C16H16N2O6 requires C, 57.83; H, 4.85; N, 8.43%). More polar isomer II m.p. 118°-120° (fine crystalline needles ex ethyl acetate/ether). νmax (CHCl3) 3400 (broad), 1760-1745, 1520, 1350 cm-1. δ ppm (CDCl3) 1.83-2.77 (4H, m, 2-CH2), 3.25-3.55 (1H, m, β-lactam proton), 4.02-4.37 (2H, m, β-lactam proton and CHOH, --OH exchangeable with D2O), 5.31-5.98 [5H, 5.35 (2H, s, CH2Ar), obscuring, 1H, which sharpens to s, at δ 5.40 on D2O exchange, CHOH, and 2H, m, CH=CH], 7.56 (2H, d, J 8 Hz, Ar), 8.23 (2H, d, J 8 Hz, Ar) (Found: C, 57.95; H, 4.95; N, 8.50%. C16H16N2O6 requires C, 57.83; H, 4.85; N, 8.43%). refluxing The cooled solution was washed with water (x2) After back extraction of the first aqueous extract with ethyl acetate the organic solutions were dried over magnesium sulphate filtered evaporated Chromatography on silica, eluting with ethyl acetate-petroleum ether mixtures gave two separate isomers of the alcohol (54) (43%)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Benzyl glyoxylate (2.73 g) was refluxed in benzene (25 ml) with provision for the removal of water. After 45 minutes 8-oxo-7-azabicyclo[4,2,0]oct-3-ene (1) (ref: I. A. Paquette and T. Kakihana, J. Amer. Chem. Soc., 1968, 90, 2897) (1.23 g) was added and refluxing continued for 3 hours. Removal of solvent under reduced pressure followed by chromatography gave two separate isomers of the alcohol (2)(90%) Isomer I, m.p. 92°-93°, λmax (CHCl3) 3450, 1750 (b) cm-1. δppm (CDCl3) 1.76-2.73 (4H, m, 2-CH2), 3.12-3.33 (1H, m, β-lactam proton), 3.76-3.93 (1H, m, β-lactam proton), 4.40 (1H, d, J 6 Hz, exch., D2O), 5.16 (2H, s, CH2), 5.47 (1H, d, J 6 Hz collapsing to s on D2O exch., CH-OH), 5.67-5.83 (2H, m, CH=CH), 7.34 (5H, Ar). M+ at m/e 287 (Found: C, 66.2; H, 5.9; N, 4.9. C16H17NO4 requires C, 66.9; H, 6.0; N, 4.9%). Isomer II, m.p. 100°-101°, νmax (CHCl3) 3450, 1750 (b), δppm (CDCl3) 1.80-2.63 (4H, m,2-CH2), 3.13-3.36 (1H, m, β-lactam proton), 3.93-4.13 (1H, m, β-lactam proton), 4.20 (1H, bs, exch., D2O), 5.16 (2H, s, CH2), 5.50 (1H, b, sharpening to s on D2O exchange), 5.50-6.00 (2H, m, CH=CH), 7.34 (5H, Ar). H+ at m/e (Found: C, 67.2; H, 6.0; N, 4.8. C16H17NO4 requires C, 66.9; H, 6.0; N, 4.9%). , 1968, 90, 2897) (1.23 g) was added refluxing Removal of solvent under reduced pressure gave two separate isomers of the alcohol (2)(90%) Isomer I, m.p. 92°-93°, λmax (CHCl3) 3450, 1750 (b) cm-1

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: The azetidinone (1) (0.4 g) in anhydrous dimethylformamide (2 ml) was stirred with glyoxylic acid hydrate (0.32 g) in the presence of hexamethylphosphorictriamide (0.1 ml) and molecular sieves (3 A; 4 pieces) for 5 h. Potassium carbonate (0.226 g) was added, and the solution stirred until effervescence had ceased (5 min.). p-Bromophenacylbromide (1.00 g; 1.05 equiv.) in dimethylformamide (1.0 ml) and hexamethylphosphorictriamide (0.25 ml) was added, and the solution stirred overnight. The solution was diluted with ethyl acetate, washed with saturated aqueous sodium chloride solution (x 3), dried (Na2SO4) and evaporated to give a gum (1.9 g) which was chromatographed on Kieselgel. Elution of the column with ethyl acetate-petroleum ether (1:1) gave the glyoxylate ester (58). Isomer I as a foam, which slowly crystallised (ethyl acetate-petroleum ether) as needles (0.60 g.) (47%) m.p. 135°-136°, νmax (CHCl3) 3250br, 1760sh, 1750, 1710, 1590, 970 cm-1 ; δ(d6DMSO) 1.9-2.8 (4H, m), 3.35 (1H, m), 4.17 (1H, m) 5.51 (1H, d, J 6.5 Hz; sharpens to a signlet on D2O exchange) 5.55 (2H, s, phenacyl CH2), 5.72br (2H, s), 6.81 (1H, d, J 6.5H, D2O enchangeable), 7.75 (2H, d, J 9 Hz) and 7.90 (2H, d, J 9 Hz) (Found: C, 51.9; H, 4.2; N, 3.6; Br, 20.00. C17H16BrNO5 requires C, 51.8; H, 4.1; N, 3.6; Br, 20.3%). (5 min.) the solution stirred overnight washed with saturated aqueous sodium chloride solution (x 3) dried (Na2SO4) evaporated

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: p-Nitrobenzyl glyoxylate hydrate (9.08 g) was refluxed in benzene (150 ml) with provision for the removal of water. After 1 hour 8-oxo-7-azabicyclo[4.2.0]oct-3-ene (1) (2.46 g) was added and refluxing continued for 3.5 hours. The cooled solution was washed with water (x2), then brine. After back extraction of the first aqueous extract with ethyl acetate, the organic solutions were dried over magnesium sulphate, filtered combined, and evaporated. Chromatography on silica, eluting with ethyl acetate-petroleum ether mixtures gave two separate isomers of the alcohol (54) (43%). Less polar isomer I m.p. 153°-5° (crystalline plates ex ethyl acetate/ether). νmax (CHCl3) 3400 (broad), 1760, 1745, 1520, 1350 cm-1. δ ppm (CDCl3) 1.90-2.83 (4H, m, 2-CH2), 3.23-3.55 (1H, m, β-lactam proton), 4.00-4.20 (1H,m, β-lactam proton), 4.27 (1H, d, J 8 Hz, exchangeable with D2O, OH), 5.33 (2H, s, CH2Ar)obscuring 1H, CHOH; 5.67-5.88 (2H, m, CH=CH), 7.55 (2H, d, J 8.5 Hz, Ar), 8.23 (2H, d, J 8.5 Hz, Ar) (Found: C, 58.07; H, 5.15; N, 8.51%. C16H16N2O6 requires C, 57.83; H, 4.85; N, 8.43%). More polar isomer II m.p. 118°-120° (fine crystalline needles ex ethyl acetate/ether). νmax (CHCl3) 3400 (broad), 1760-1745, 1520, 1350 cm-1. δ ppm (CDCl3) 1.83-2.77 (4H, m, 2-CH2), 3.25-3.55 (1H, m, β-lactam proton), 4.02-4.37 (2H, m, β-lactam proton and CHOH, --OH exchangeable with D2O), 5.31-5.98 [5H, 5.35 (2H, s, CH2Ar), obscuring, 1H, which sharpens to s, at δ 5.40 and D2O exchange, CHOH, and 2H, m, CH=CH], 7.56 (2H, d, J 8 Hz, Ar), 8.23 (2H, d, J 8 Hz, Ar) (Found: C, 57.95; H, 4.95; N, 8.50%. C16H16N2O6 requires C, 57.83; H, 4.85; N, 8.43%). refluxing The cooled solution was washed with water (x2) After back extraction of the first aqueous extract with ethyl acetate the organic solutions were dried over magnesium sulphate filtered evaporated Chromatography on silica, eluting with ethyl acetate-petroleum ether mixtures gave two separate isomers of the alcohol (54) (43%)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Benzyl glyoxylate (2.73 g) was refluxed in benzene (25 ml) with provision for the removal of water. After 45 minutes 8-oxo-7-azabicyclo[4,2,0]oct-3-ene (1) (ref: I. A. Paquette and T. Kakihana, J. Amer. Chem. Soc., 1968, 90, 2897) (1.23 g) was added and refluxing continued for 3 hours. Removal of solvent under reduced pressure followed by chromatography gave two separate isomers of the alcohol (2)(90%) Isomer I, m.p. 92°-93°, νmax (CHCl3)3450, 1750 (b) cm-1. δppm (CDCl3) 1.76-2.73 (4H, m, 2-CH2), 3.12-3.33 (1H, m, β-lactam proton), 3.76-3.93 (1H, m, β-lactam proton), 4.40 (1H, d, J 6 Hz, exch., D2O), 5.16 (2H, s CH2), 5.47 (1H, d, J 6 Hz collapsing to s on D 2 O exch., CH-OH), 5.67-5.83 (2H, m, CH=CH), 7.34 (5H, Ar). M+ at m/e 287 (Found: C, 66.2; H, 5.9; N, 4.9. C16H17NO4 requires C, 66.9; H, 6.0; N, 4.9%). Isomer II, m.p. 100°-101°, νmax (CHCl3) 3450, 1750 (b), δppm (CDCl3) 1.80-2.63 (4H, m,2-CH2), 3.13-3.36 (1H, m, β-lactam proton), 3.93-4.13 (1H, m, β-lactam proton), 4.20 (1H, bs, exch., D2O), 5.16 (2H, s, CH2), 5.50 (1H, b, sharpening to s on D2O exchange), 5.50-6.00 (2H, m, CH=CH), 7.34 (5H, Ar). H+ at m/e (Found: C, 67.2; H, 6.0; N, 4.8. C16H17NO4 requires C, 66.9; H, 6.0; N, 4.9%). , 1968, 90, 2897) (1.23 g) was added refluxing Removal of solvent under reduced pressure gave two separate isomers of the alcohol (2)(90%) Isomer I, m.p. 92°-93°, νmax (CHCl3)3450, 1750 (b) cm-1

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Benzyl glyoxylate (2.73 g) was refluxed in benzene (25 ml) with provision for the removal of water. After 45 minutes 8-oxo-7-azabicyclo[4,2,0]oct-3-ene (28) (ref: I. A. Paquette and T. Kakihana, J. Amer. Chem. Soc., 1968, 20, 2897) (1.23 g) was added and refluxing continued for 3 hours. Removal of solvent under reduced pressure followed by chromatography gave two separate isomers of the alcohol (32) (90%) Isomer I, m.p. 92°-93°, νmax (CHCl3) 3450, 1750 (b) cm-1. δ ppm (CDCl3) 1.76-2.73 (4H, m, 2-CH2), 3.12-3.33 (1H, m, β-lactam proton), 3.76-3.93 (1H, m, β-lactam proton), 4.40 (1H, d, J6 Hz, exch. D2O), 5.16 (2H, s, CH2), 5.47 (1H, d, J 6 Hz collapsing to s on D2O exch. CH-OH), 5.67-5.83 (2H, m, CH=CH), 7.34 (5H, Ar). M+ at m/e 287 (Found: C, 66.2; H, 5.9; N, 4.9. C16H17NO4 requires C, 66.9; H, 6.0; N, 4.9%). Isomer II, m.p. 100°-101°, νmax (CHCl3) 3450, 1750 (b), δ ppm (CDCl3) 1.80-2.63 (4H, m, 2-CH2), 3.13-3.36 (1H, m, β-lactam proton), 3.93-4.13 (1H, m, β-lactam proton), 4.20 (1H, bs, exch, D2O), 5.16 (2H, s, CH2), 5.50 (1H, b, sharpening to s on D2O exchange), 5.50-6.00 (2H, m, CH=CH), 7.34 (5H, Ar). (Found; C, 67.2; H, 6.0; N, 4.8. C16H17NO4 requires C, 66.9; H, 6.0; N, 4.9%). , 1968, 20, 2897) (1.23 g) was added refluxing Removal of solvent under reduced pressure gave two separate isomers of the alcohol (32) (90%) Isomer I, m.p. 92°-93°, νmax (CHCl3) 3450, 1750 (b) cm-1

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: The azetidinone (1) (0.4 g) in ahydrous dimethylformamide (2 ml) was stirred with glyoxylic acid hydrate (0.32 g) in the presence of hexamethylphosphorictriamide (0.1 ml) and molecular sieves (3A; 4 pieces) for 5 h. Potassium carbonate (0.226 g) was added, and the solution stirred until effervescence had ceased (5 min.). p-Bromophenacylbromide (1.00 g; 1.05 equiv.) in dimethylformamide (1.0 ml) and hexamethylphosphorictriamide (0.25 ml) was added, and the solution stirred overnight. The solution was diluted with ethyl acetate, washed with saturated aqueous sodium chloride solution (x 3), dried (Na2SO4) and evaporated to give a gum (1.9 g) which was chromatographed on Kieselgel. Elution of the column with ethyl acetate-petroleum ether (1:1) gave the glyoxylate ester (58). Isomer I as a foam, which slowly crystallised (ethyl acetate-petroleum ether) as needles (0.60 g.) (47%) m.p. 135°-136°, νmax (CHCl3) 3250br, 1760sh, 1750, 1710, 1590, 970 cm-1 ; δ (d6DMSO) 1.9-2.8 (4H, m), 3.35 (1H, m), 4.17 (1H, m) 5.51 (1H, d, J 6.5 Hz; sharpens to a singlet on D2O exchange) 5.55 (2H, s, phenacyl CH2), 5.72br (2H, s), 6.81 (1H, d, J 6.5H, D2O exchangeable), 7.75 (2H, d, J 9 Hz) and 7.90 (2H, d, J 9 Hz) (Found: C, 51.9; H, 4.2; N, 3.6; Br, 20.00. C17H16BrNO5 requires C, 51.8; H, 4.1; N, 3.6; Br, 20.3%). (5 min.) the solution stirred overnight washed with saturated aqueous sodium chloride solution (x 3) dried (Na2SO4) evaporated