5-fluoro-2-methyl-2,3-dihydroinden-1-one

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:

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:

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: 13.44 Grams (0.56 mole) of magnesium turnings are placed in a dried flask under N2 with 125 ml. of ether and a crystal of iodine. Six ml. of 65 ml. solution of 24.2 g. (0.14 mole) of p-methylthiobenzyl chloride in ether is added. After 3 to 5 minutes of stirring the iodine color disappears and the reaction begins. After aging for 5 minutes, the rest of the benzyl chloride is added dropwise over 45 minutes. It is rinsed in with 10 ml. of ether and the reaction aged for 2 hours with stirring. 21 Grams (0.128 mole) of 5-fluoro-2-methyl-1-indanone dissolved in 50 ml. of ether is added dropwise over 30 minutes. After aging for 1 hour, the milky supernatent mixture is decanted from the magnesium into 100 ml. of acetic acid. The flask and residual magnesium are rinsed into the acid solution with 4 × 50 ml. of benzene. Two hundred ml. of water are added, the layers are separated and the organic layer is washed with 5 × 200 ml. water. It is stripped to dryness after drying over Na2SO4. The crude reaction product is crystallized from hexane to give pure 5-fluoro-2-methyl-1-(p-methylthiobenzyl)-indene, melting point 58°-59°C. It is rinsed in with 10 ml of ether and the reaction aged for 2 hours After aging for 1 hour the milky supernatent mixture is decanted from the magnesium into 100 ml The flask and residual magnesium are rinsed into the acid solution with 4 × 50 ml of water are added the layers are separated the organic layer is washed with 5 × 200 ml after drying over Na2SO4 The crude reaction product is crystallized from hexane

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

実験手順: 13.44 Grams (0.56 mole) of magnesium turnings are placed in a dried flask under N2 with 125 ml. of ether and a crystal of iodine. Six ml. of 65 ml. solution of 24.2 g. (0.14 mole) of p-methylthiobenzyl chloride in ether is added. After 3 to 5 minutes of stirring the iodine color disappears and the reaction begins. After aging for 5 minutes, the rest of the benzyl chloride is added dropwise over 45 minutes. It is rinsed in with 10 ml. of ether and the reaction aged for 2 hours with stirring. 21 Grams (0.128 mole) of 5-fluoro-2-methyl-1-indanone dissolved in 50 ml. of ether is added dropwise over 30 minutes. After aging for 1 hour, the milky supernatent mixture is decanted from the magnesium into 100 ml. of acetic acid. The flask and residual magnesium are rinsed into the acid solution with 4 × 50 ml. of benzene. Two hundred ml. of water are added, the layers are separated and the organic layer is washed with 5 × 200 ml. water. It is stripped to dryness after drying over Na2SO4. The crude reaction product is crystallized from hexane to give pure 5-fluoro-2-methyl-1-(p-methylthiobenzyl)-indene, melting point 58°-59°C. It is rinsed in with 10 ml of ether and the reaction aged for 2 hours After aging for 1 hour the milky supernatent mixture is decanted from the magnesium into 100 ml The flask and residual magnesium are rinsed into the acid solution with 4 × 50 ml of water are added the layers are separated the organic layer is washed with 5 × 200 ml after drying over Na2SO4 The crude reaction product is crystallized from hexane

反応条件: temp:75.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 169 Mg. (1.5 mm) of potassium t-butoxide is dissolved in 2 ml. of DMSO and treated with 651 mg. (1.5 mm) of p-methylthiobenzyltriphenylphosphonium chloride dissolved in 1 ml. of DMSO. To this solution is added 270 mg. (1.65 mm) of 5-fluoro-2-methyl-1-indanone in 2 ml. of DMSO. The solution is heated at 75°C for 15.5 hours. Benzene and water are added and the benzene layer is washed five times with water. The benzene layer is dried over Na2SO4 and evaporated to dryness under vacuum. The weight is 915.6 mg. This material is eluted through 8 g. of silica gel with benzene to remove triphenylphosphine oxide. The eluate weights 372 mg. after removal of solvent. This is rechromatographed through 15 g. of silica gel using hexane and 95.9 mg. of 5-fluoro-2-methyl-1-(p-methylthiobenzylidene)-indane is isolated, melting point 67°-70°C. To this solution is added 270 mg the benzene layer is washed five times with water The benzene layer is dried over Na2SO4 evaporated to dryness under vacuum This material is eluted through 8 g of silica gel with benzene to remove triphenylphosphine oxide after removal of solvent This is rechromatographed through 15 g

反応条件: temp:75.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 169 Mg. (1.5 mm) of potassium t-butoxide is dissolved in 2 ml. of DMSO and treated with 651 mg. (1.5 mm) of p-methylthiobenzyltriphenylphosphonium chloride dissolved in 1 ml. of DMSO. To this solution is added 270 mg. (1.65 mm) of 5-fluoro-2-methyl-1-indanone in 2 ml. of DMSO. The solution is heated at 75°C for 15.5 hours. Benzene and water are added and the benzene layer is washed five times with water. The benzene layer is dried over Na2SO4 and evaporated to dryness under vacuum. The weight is 915.6 mg. This material is eluted through 8 g. of silica gel with benzene to remove triphenylphosphine oxide. The eluate weights 372 mg. after removal of solvent. This is rechromatographed through 15 g. of silica gel using hexane and 95.9 mg. of 5-fluoro-2-methyl-1-(p-methylthiobenzylidene)-indane is isolated, melting point 67°-70°C. To this solution is added 270 mg the benzene layer is washed five times with water The benzene layer is dried over Na2SO4 evaporated to dryness under vacuum This material is eluted through 8 g of silica gel with benzene to remove triphenylphosphine oxide after removal of solvent This is rechromatographed through 15 g

反応条件: temp:30.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Twenty-five grams (1.04 moles) of magnesium turnings were placed in a dried flask under N2 with 400 ml. of ether. Ten ml. of 0.05 molar p-methylthiobenzyl magnesium chloride in ether is added and the mixture is warmed to 30°C. About 2-3% of 39.7 g. (0.23 moles) of p-methylthiobenzyl chloride in 75 ml. of toluene is added. After 3-5 minutes of stirring an exotherm to 32°-33°C occurs signifying initiation of the reaction. After aging for 5 minutes, the rest of the benzyl chloride is added dropwise over 90 minutes. The reaction is aged for 30 minutes with stirring. 5-Fluoro-2-methyl-1-indanone (32.6 g., 0.199 mole) is added dropwise over 45 minutes. After aging for 30 minutes, the milky supernatant mixture is decanted from the magnesium. The flask and residual magnesium are rinsed with toluene. The reaction is then quenched by the addition of 120 ml. of 3N sulfuric acid. The lower layer is discarded. To the organic layer is added 80 ml. of 1:10 concentrated sulfuric acid, acetic acid and the two-phase mixture, stirred vigorously for one hour and water (100 ml.) is added. The bottom layer is discarded and the organic layer is washed with 100 ml. of water and 200 ml. of 2N sodium hydroxide. After a final water wash the organic layer is concentrated to give 5-fluoro-2-methyl-1-(p-methylthiobenzyl)-indene. Similarly, when p-methylsulfinylbenzyl chloride is used in place of p-methylthiobenzyl chloride in the above example, the corresponding p-methylsulfinylbenzyl indene is obtained. initiation of the reaction After aging for 5 minutes The reaction is aged for 30 minutes with stirring After aging for 30 minutes the milky supernatant mixture is decanted from the magnesium The flask and residual magnesium are rinsed with toluene The reaction is then quenched by the addition of 120 ml To the organic layer is added 80 ml of 1:10 concentrated sulfuric acid, acetic acid and the two-phase mixture, stirred vigorously for one hour water (100 ml.) is added the organic layer is washed with 100 ml After a final water wash the organic layer is concentrated