(E)-1,2-dichloroethene

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:

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

Procedure: 1,2-Dichloroethylene was reacted with cyclopentadiene at 175° C. in the same manner as Examples 1-7 to produce 5,6-dichloronorbornene (called "DCN" hereinafter).

Conditions: temp:-10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: An attempt was also made to prepare the organometallic reagent with 1,2-dichloroethylene. A 100 mL three-neck flask equipped with a N2 gas bubbler, a thermometer, and a dropping funnel was charged with 1,2-dichloroethylene (cis, Aldrich, 0.16 mL, 2 mmol, mw=97, d=1.28). Dry THF (7 mL) was added, and the solution was cooled to -10° C., n-BuLi (2.5M in THF, 1.6 mL, 4 mmol) was added dropwise over a period of 10 min. The mixture was stirred at -30° C. for 20 min and then at 0°-5° C. for 10 more min. The resulting reagent was then recooled to -30° C. and was treated dropwise with a solution of 5β-pregnan-3,20-dione, 20-ketal (360 mg, 1 mmol) in THF (15 mL). The cooling bath was removed and the mixture was stirred at room temp. for 30 min. (100% conversion as detected by TLC). The cooling bath was removed and the resulting solution was quenched with sat. NH4Cl solution (1 mL). The solvent was removed and the residue was dissolved in acetone (30 mL). After adding 2N HCl (5 mL) the solution was stirred at ambient temperature for 1.5 h. The mixture was neutralized with dil. NaOH solution (pH 5-6). The precipitated solid (429 mg) was collected by filtration, washed with water, and dried. The crude product was then purified by column chromatography over silica gel (toluene acetone 95:5) to yield 3β-chloroethynyl-3α-hydroxy-5β-pregnan-20-one (130 mg); TLC-Rf 0.33 (toluene:acetone 95:5), NMR (CDCl3) δ 0.59 (s, 3H, Me), 0.97 (s, 3H, Me), 2.11 (s, 3H, Me), 2.55 (m, 1H). at 0°-5° C. was then recooled to -30° C. The cooling bath was removed the mixture was stirred at room temp. for 30 min. (100% conversion as detected by TLC) The cooling bath was removed the resulting solution was quenched with sat. NH4Cl solution (1 mL) The solvent was removed the residue was dissolved in acetone (30 mL) After adding 2N HCl (5 mL) the solution was stirred at ambient temperature for 1.5 h The precipitated solid (429 mg) was collected by filtration washed with water dried The crude product was then purified by column chromatography over silica gel (toluene acetone 95:5)

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

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

Conditions: temp:40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a 250 ml, three-necked flask fitted with a magnetic stirrer, 1-(hydroxymethyl)pyrrolidin-2-one x82 (15 g, 0.13 mol) is cooled to −10° C. Cold concentrated sulfuric acid (150 ml) is added dropwise. At this temperature, 1,2-dichloroethene (46.73 g, 0.482 mol) is added while the temperature is kept below 0° C. At the end of the addition the mixture is stirred at 40° C. for 2 h. Water is added and the pH is adjusted with K2CO3. The aqueous phase is extracted with CH2Cl2, the combined organic phases are dried over MgSO4, filtered and concentrated. The crude 2-chloro-3-(2-oxopyrrolidin-1-yl)propanal x83 is used in the next step without any further purification. In a 250 ml, three-necked flask fitted with a magnetic stirrer is kept below 0° C At the end of the addition the mixture The aqueous phase is extracted with CH2Cl2 the combined organic phases are dried over MgSO4 filtered concentrated The crude 2-chloro-3-(2-oxopyrrolidin-1-yl)propanal x83 is used in the next step without any further purification

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

Procedure: The reaction of chloroacetyl chloride and aluminum chloride with a molar excess of 1,2-dichloroethylene has been reported by Catch et al., J. Chem. Soc. (London) 278 (1948) to afford chloromethyl 1,2,2-trichloroethyl ketone. McLamore et al., J. Org. Chem., 20, 109 (1955) have reported propionyl chloride to react with 1,2-dichloroethylene to provide ethyl 1,2,2-trichloroethyl ketone.