1,1-diiodoethane

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To 25 ml of N,N-dimethylformamide were added 12 g of diiodoethane and 8.3 g of potassium carbonate, a solution of 6.07 g of the compound obtained in Example 4 dissolved in 60 ml of N,N-dimethylformamide was gradually dropped thereinto, and the mixture was stirred for 30 minutes at the same temperature. N,N-Dimethylformamide was evaporated therefrom in vacuo, the residue was dissolved in a mixture of chloroform and methanol (2:1), washed with water, dried over magnesium sulfate, the solvent was evaporated therefrom, and the crystals separated out therefrom were washed with ether to give 3.35 g of ethyl 6,7,8-trifluoro-1-methyl-4-oxo-4H-[1,3]thiazeto[3,2-a]quinoline-3-carboxylate. was gradually dropped N,N-Dimethylformamide was evaporated in vacuo, the residue was dissolved in a mixture of chloroform and methanol (2:1) washed with water dried over magnesium sulfate the solvent was evaporated the crystals separated out therefrom were washed with ether

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 8-methylene-1,4-dioxa-spiro[4.5]decane (6.0 g, 39 mmol, prepared according to a literature procedure (K. C. Nicolaou, R. L. Magolda, D. A. Claremon, J. Am. Chem. Soc. 102 (1980) 1404-1409)) in toluene (10 mL), a solution of diethyl zinc (100 mL, 1 M in hexane) is added at −40 to −20° C. The mixture is stirred for 10 min before diiodoethane (53.6 g, 200 mmol) is added dropwise over a period of 20 min. The reaction is warmed to rt and stirring is continued for 18 h. The reaction mixture is poured onto ice-cooled sat. aq. NH4Cl solution and extracted twice with diethyl ether. The combined organic extracts are washed with sat. aq. Na2S2O3 and water, dried over Na2SO4, filtered and the solvent of the filtrate is evaporated to give 7,10-dioxa-dispiro[2.2.4.2]dodecane (12.35 g) as a colourless liquid containing approx. 20% of toluene (product volatile). is added dropwise over a period of 20 min The reaction mixture is poured onto ice- extracted twice with diethyl ether The combined organic extracts are washed with sat. aq. Na2S2O3 and water dried over Na2SO4 filtered the solvent of the filtrate is evaporated

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 8-methylene-1,4-dioxa-spiro[4.5]decane (6.0 g, 39 mmol, prepared according to a literature procedure (K. C. Nicolaou, R. L. Magolda, D. A. Claremon, J. Am. Chem. Soc. 102 (1980) 1404-1409)) in toluene (10 mL), a solution of diethyl zinc (100 mL, 1 M in hexane) is added at −40 to −20° C. The mixture is stirred for 10 min before diiodoethane (53.6 g, 200 mmol) is added dropwise over a period of 20 min. The reaction is warmed to rt and stirring is continued for 18 h. The reaction mixture is poured onto ice-cooled sat. aq. NH4Cl solution and extracted twice with diethyl ether. The combined organic extracts are washed with sat. aq. Na2S2O3 and water, dried over Na2SO4, filtered and the solvent of the filtrate is evaporated to give 7,10-dioxa-dispiro[2.2.4.2]dodecane (12.35 g) as a colourless liquid containing approx. 20% of toluene (product volatile). is added dropwise over a period of 20 min The reaction mixture is poured onto ice- extracted twice with diethyl ether The combined organic extracts are washed with sat. aq. Na2S2O3 and water dried over Na2SO4 filtered the solvent of the filtrate is evaporated

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 8-methylene-1,4-dioxa-spiro[4.5]decane (6.0 g, 39 mmol, prepared according to a literature procedure (K. C. Nicolaou, R. L. Magolda, D. A. Claremon, J. Am. Chem. Soc. 102 (1980) 1404-1409)) in toluene (10 mL), a solution of diethyl zinc (100 mL, 1 M in hexane) is added at −40 to −20° C. The mixture is stirred for 10 min before diiodoethane (53.6 g, 200 mmol) is added dropwise over a period of 20 min. The reaction is warmed to rt and stirring is continued for 18 h. The reaction mixture is poured onto ice-cooled sat. aq. NH4Cl solution and extracted twice with diethyl ether. The combined organic extracts are washed with sat. aq. Na2S2O3 and water, dried over Na2SO4, filtered and the solvent of the filtrate is evaporated to give 7,10-dioxa-dispiro[2.2.4.2]dodecane (12.35 g) as a colourless liquid containing approx. 20% of toluene (product volatile). is added dropwise over a period of 20 min The reaction mixture is poured onto ice- extracted twice with diethyl ether The combined organic extracts are washed with sat. aq. Na2S2O3 and water dried over Na2SO4 filtered the solvent of the filtrate is evaporated

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: The 2-iodooxazole derivative was prepared as for [6-(2-chloro-oxazol-5-yl)-pyridin-2-yl]-(4-methyl-pyridin-2-yl)-amine above from (4-methyl-pyridin-2-yl)-(6-oxazol-5-yl-pyridin-2-yl)-amine with LiHMDS (1M solution in THF) and diiodoethane in anhydrous THF to give the title compound as a yellow solid (41%) after purification by column chromatography on SiO2 eluting with 40% EtOAc in cyclohexane. 1H NMR (300 MHz, DMSO-d6) δ=9.81 (s, 1H), 8.10 (d, J=5.0 Hz, 1H), 7.84-7.51 (m, 4H), 7.23 (d, J=7.2 Hz, 1H), 6.77 (d, J=4.6 Hz, 1H), 2.33 (s, 3H).

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To the solution of 1-bromo-4-(4-methoxybutoxy)benzene (4.94 g) and magnesium (463 mg) in tetrahydrofuran (50 ml) was added iodine at room temperature. The solution was refluxed for 7.5 hours, during which period diiodoethane was added to the mixture. After cooling to 0° C., 4-[4-(4-oxopiperidin-1-yl)phenyl]piperazine-1-carboxylic acid benzyl ester (4.94 g) in tetrahydrofuran (20 ml) was added dropwise with stirring to the solution. The mixture was stirred at room temperature for 2 hours. The reaction mixture was added to a mixture of ammonium chloride solution and ethyl acetate. The organic layer was taken, washed with brine, sodium hydrogen carbonate solution and brine and dried over magnesium sulfate. The magnesium sulfate was filtered off, and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel chromatography (50:1 dichloromethane-methanol elution) to give 4-[4-[4-hydroxy-4-[4-(4-methoxybutoxy)phenyl]piperidin-1-yl]phenyl]piperazine-1-carboxylic acid benzyl ester (3.42 g). was added to the mixture The mixture was stirred at room temperature for 2 hours washed with brine, sodium hydrogen carbonate solution and brine dried over magnesium sulfate The magnesium sulfate was filtered off the filtrate was concentrated under reduced pressure The residue was purified by silica gel chromatography (50:1 dichloromethane-methanol elution)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 8-methylene-1,4-dioxa-spiro[4.5]decane (6.0 g, 39 mmol, prepared according to a literature procedure (K. C. Nicolaou, R. L. Magolda, D. A. Claremon, J. Am. Chem. Soc. 102 (1980) 1404-1409)) in toluene (10 mL), a solution of diethyl zinc (100 mL, 1 M in hexane) is added at −40 to −20° C. The mixture is stirred for 10 min before diiodoethane (53.6 g, 200 mmol) is added dropwise over a period of 20 min. The reaction is warmed to rt and stirring is continued for 18 h. The reaction mixture is poured onto ice-cooled sat. aq. NH4Cl solution and extracted twice with diethyl ether. The combined organic extracts are washed with sat. aq. Na2S2O3 and water, dried over Na2SO4, filtered and the solvent of the filtrate is evaporated to give 7,10-dioxa-dispiro[2.2.4.2]dodecane (12.35 g) as a colourless liquid containing approx. 20% of toluene (product volatile). is added dropwise over a period of 20 min The reaction mixture is poured onto ice- extracted twice with diethyl ether The combined organic extracts are washed with sat. aq. Na2S2O3 and water dried over Na2SO4 filtered the solvent of the filtrate is evaporated

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A series of ionene polymers were prepared according to the procedure of Example 1 except that equivalent amounts of iodo-propane, iodo-hexane, iodo-dodecane, iodo-butane or a mixture of dibromobutene and diiodopropane or diiodoethane were substituted for dibromo-p-xylene.

反応条件: temp:45.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of diethyl zinc in n-hexane(1M, 12 ml) was added to a solution of 2-(2,3-dihydro-6-methyl-4-oxo-5-phenyl-4H-1,3-oxazin-3-yl)-2-methyl-hex-5-en-3-ol (1.6 g) in dichloromethane at 20° C. 1,1-Diiodoethane (3.5 g) was added and the solution warmed to 45° C. for 3 hours. Hydrochloric acid (1N) was added and the organic layer washed (brine), dried (magnesium sulphate) and evaporated. Purification by silica gel column chromatography eluting with n-hexane/ethyl acetate (3:1) gave 2-(2,3-dihydro-6-methyl-4-oxo-5-phenyl-4H-1,3-oxazin-3-yl)-2-methyl-4-(2-methylcyclopropyl)butan-3-ol (0.55 g), NMR:1.05-1.75(4H), 1.01(d,3H), 1.36(s,3H), 1.52(s,3H), 1.4-1.5(2H), 1.89(s,3H), 3.70(1H), 4.59(1H), 5.10(d,1H), 5.24(d,1H),7.23-7.40(5H). Powdered molecular sieve (4 A, 3.2 g) and pyridinium chlorochromate (0.8 g) were added to a stirred solution of the above compound in dichloromethane at 20° C. After 3 hours, ether was added and the mixture filtered. The filtrate was evaporated and the residue purified by silica gel column chromatography eluting with n-hexane/ethyl acetate (3:1) to give 2-(2,3-dihydro-6-methyl-4-oxo-5-phenyl-4H-1,3-oxazin-3-yl)-2-methyl-4-(2-methylcyclopropyl)butan-3-one (Compound 1074, 0.47 g), NMR: 0.20-0.30(2H), 0.42-0.52(1H), 0.68-0.78(1H), 1.03(d,3H), 1.42(s,6H), 1.93(s,3H), 2.43(d,2H), 5.26(s,2H), 7.20-7.40(5H). the organic layer washed (brine) dried (magnesium sulphate) evaporated Purification by silica gel column chromatography eluting with n-hexane/ethyl acetate (3:1)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To 25 ml of N,N-dimethylformamide were added 12 g of diiodoethane and 8.3 g of potassium carbonate, a solution of 6.07 g of the compound obtained in Example 4 dissolved in 60 ml of N,N-dimethylformamide was gradually dropped thereinto, and the mixture was stirred for 30 minutes at the same temperature. N,N-Dimethylformamide was evaporated therefrom in vacuo, the residue was dissolved in a mixture of chloroform and methanol (2:1), washed with water, dried over magnesium sulfate, the solvent was evaporated therefrom, and the crystals separated out therefrom were washed with ether to give 3.35 g of ethyl 6,7,8-trifluoro-1-methyl-4-oxo-4H-[1,3]thiazeto[3,2-a]quinoline-3-carboxylate. was gradually dropped N,N-Dimethylformamide was evaporated in vacuo, the residue was dissolved in a mixture of chloroform and methanol (2:1) washed with water dried over magnesium sulfate the solvent was evaporated the crystals separated out therefrom were washed with ether