bromoethene

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of Grignard reagent prepared from vinyl bromide (10.7 g), and magnesium (2.43 g) in dry tetrahydrofuran (40 ml) is added gradually a solution of 1-(dimethylamino)-1-octen-3-one (16.9 g), described in Example 37, in dry tetrahydrofuran (20 ml). The mixture is stirred and heated to reflux for 1 hr. The reaction mixture is cooled to room temperature, diluted with ether, washed with hydrochloric acid (10 ml), followed by saturated ammonium chloride solution. The ether extract is dried, and the solvent is removed. The residue is chromatographed to yield the title compound, λmaxEtOH 260nm (ε = 17,050), γmaxfilm 1686, 1668 cm-1. heated to reflux for 1 hr washed with hydrochloric acid (10 ml) The ether extract is dried the solvent is removed The residue is chromatographed

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Magnesium metal (5 g., 0.206 mole) is suspended in tetrahydrofuran (100 ml.) in a three-necked, round-bottomed flask protected by a dry ice condenser and equipped with a mechanical stirrer. The stirrer is started and vinyl bromide (22 g., 0.206 mole) in tetrahydrofuran is added at such a rate as to keep the solvent refluxing. The reaction mixture is refluxed for 0.5 hours after the addition is complete. The reaction mixture is then cooled to 0°-5° C. and benzyloxyacetaldehyde (24 g., 0.16 mole) in tetrahydrofuran (15 ml.) is added dropwise. After 1.5 hours at 0°-5° C., there is added acetic anhydride (26 g., 0.255 mole) and the reaction mixture is allowed to come to room temperature. After 20 hours at room temperature, ice water (500 ml.) is added and the product is extracted into ethyl acetate (3 × 100 ml.). The ethyl acetate extract is washed with brine, dried (Na2SO4), and distilled. There is obtained 17 g. (49%) of the title compound, b.p. 85°-95° C./0.05 mm. protected by a dry ice condenser equipped with a mechanical stirrer refluxing The reaction mixture is refluxed for 0.5 hours after the addition The reaction mixture is then cooled to 0°-5° C. to come to room temperature After 20 hours at room temperature the product is extracted into ethyl acetate (3 × 100 ml.) The ethyl acetate extract is washed with brine dried (Na2SO4) distilled There is obtained 17 g

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To crude N-hydroxy-6-methylnicotinimidoyl chloride in 10 mL toluene was added vinyl bromide (1 M in THF, 11 mL, 11.0 mmol), followed by bis(tributyltin)oxide (2.12 g, 1.87 mL, 3.67 mmol). The reaction mixture was stirred at room temperature for 5 h and then concentrated. The crude product was purified by automated silica gel chromatography (eluted with ethyl acetate-hexanes) to isolate 155 mg (26%, for two steps) of the title compound as a white solid. HPLC/MS: retention time=0.39 min, [M+H]+=161. concentrated The crude product was purified by automated silica gel chromatography (eluted with ethyl acetate-hexanes)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To crude N-hydroxy-6-methylnicotinimidoyl chloride in 10 mL toluene was added vinyl bromide (1 M in THF, 11 mL, 11.0 mmol), followed by bis(tributyltin)oxide (2.12 g, 1.87 mL, 3.67 mmol). The reaction mixture was stirred at room temperature for 5 h and then concentrated. The crude product was purified by automated silica gel chromatography (eluted with ethyl acetate-hexanes) to isolate 155 mg (26%, for two steps) of the title compound as a white solid. HPLC/MS: retention time=0.39 min, [M+H]+=161. concentrated The crude product was purified by automated silica gel chromatography (eluted with ethyl acetate-hexanes)