2-bromo-2-methylpropanal

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

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

Procedure: Triphenylmethylmercaptan (362.94 g, 1.31 mol, 100 mol %) dissolved in anhydrous THF (2 L) was cooled in an ice bath under argon. Sodium hydride (60% in oil; 54.39 g, 1.35 mol, 104 mol %) was added in portions over 20 min. 2-bromo-2-methylpropanal (206.06 g, 1.36 mol, 104 mol %; see Stevens & Gillis, 1957, J. Amer. Chem. Soc. 79: 3448-51) was then added slowly over 20 min. The reaction mixture was allowed to warm to room temperature and stirred for 12 hours. The reaction was quenched with water (1 L) and extracted with diethyl ether (3×1 L). The ether extracts were combined, washed with saturated NaCl solution (500 mL), dried over Na2SO4 and filtered. The solvent was removed under reduced pressure to afford a thick orange oil. The crude oil was dissolved in toluene (200 mL) and diluted to 2 L with hot hexanes. The mixture was filtered through a sintered glass funnel and cooled at −5° C. for 12 hours. The white crystalline solid which formed was removed by filtration to afford 266.36 g (59% yield) of the title compound. The melting point of the resulting compound was determined to be 83-85° C. Nuclear magnetic resonance characterization experiments yielded the following molecular signature: was cooled in an ice bath under argon The reaction was quenched with water (1 L) extracted with diethyl ether (3×1 L) washed with saturated NaCl solution (500 mL) dried over Na2SO4 filtered The solvent was removed under reduced pressure to afford a thick orange oil The mixture was filtered through a sintered glass funnel cooled at −5° C. for 12 hours The white crystalline solid which formed was removed by filtration

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

Procedure: Triphenylmethylmercaptan (362.94 g, 1.31 mol, 100 mol %) dissolved in anhydrous THF (2 L) was cooled in an ice bath under argon. Sodium hydride (60% in oil; 54.39 g, 1.35 mol, 104 mol %) was added in portions over 20 min. 2-bromo-2-methylpropanal (206.06 g, 1.36 mol, 104 mol %; see Stevens & Gillis, 1957, J. Amer. Chem. Soc. 79: 3448-51) was then added slowly over 20 min. The reaction mixture was allowed to warm to room temperature and stirred for 12 hours. The reaction was quenched with water (1 L) and extracted with diethyl ether (3x 1 L). The ether extracts were combined, washed with saturated NaCl solution (500 mL), dried over Na2SO4 and filtered. The solvent was removed under reduced pressure to afford a thick orange oil. The crude oil was dissolved in toluene (200 mL) and diluted to 2 L with hot hexanes. The mixture was filtered through a sintered glass funnel and cooled at -5° C. for 12 hours. The white crystalline solid which formed was removed by filtration to afford 266.36 g (59% yield) of the title compound. The melting point of the resulting compound was determined to be 83°-85° C. Nuclear magnetic resonance characterization experiments yielded the following molecular signature: was cooled in an ice bath under argon The reaction was quenched with water (1 L) extracted with diethyl ether (3x 1 L) washed with saturated NaCl solution (500 mL) dried over Na2SO4 filtered The solvent was removed under reduced pressure to afford a thick orange oil The mixture was filtered through a sintered glass funnel cooled at -5° C. for 12 hours The white crystalline solid which formed was removed by filtration

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

Procedure: Triphenylmethylmercaptan (362.94 g, 1.31 mol, 100 mol %) dissolved in anhydrous THF (2 L) was cooled in an ice bath under argon. Sodium hydride (60% in oil; 54.39 g, 1.35 mol, 104 mol %) was added in portions over 20 min. 2-bromo-2-methylpropanal (206.06 g, 1.36 mol, 104 mol %; see Stevens & Gillis, 1957, J. Amer. Chem. Soc. 79: 3448-51) was then added slowly over 20 min. The reaction mixture was allowed to warm to room temperature and stirred for 12 hours. The reaction was quenched with water (1 L) and extracted with diethyl ether (3x 1 L). The ether extracts were combined, washed with saturated NaCl solution (500 mL), dried over Na2SO4 and filtered. The solvent was removed under reduced pressure to afford a thick orange oil. The crude oil was dissolved in toluene (200 mL) and diluted to 2 L with hot hexanes. The mixture was filtered through a sintered glass funnel and cooled at -5° C. for 12 hours. The white crystalline solid which formed was removed by filtration to afford 266.36 g (59% yield) of the title compound. The melting point of the resulting compound was determined to be 83°-85° C. Nuclear magnetic resonance characterization experiments yielded the following molecular signature: was cooled in an ice bath under argon The reaction was quenched with water (1 L) extracted with diethyl ether (3x 1 L) washed with saturated NaCl solution (500 mL) dried over Na2SO4 filtered The solvent was removed under reduced pressure to afford a thick orange oil The mixture was filtered through a sintered glass funnel cooled at -5° C. for 12 hours The white crystalline solid which formed was removed by filtration

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

Procedure: Triphenylmethylmercaptan (362.94 g, 1.31 mol, 100 mol %) dissolved in anhydrous THF (2 L) was cooled in an ice bath under argon. Sodium hydride (60% in oil; 54.39 g, 1.35 mol, 104 mol %) was added in portions over 20 min. 2-bromo-2-methylpropanal (206.06 g, 1.36 mol, 104 mol %; see Stevens & Gillis, 1957, J. Amer. Chem. Soc. 79: 3448-51) was then added slowly over 20 min. The reaction mixture was allowed to warm to room temperature and stirred for 12 hours. The reaction was quenched with water (1 L) and extracted with diethyl ether (3×1 L). The ether extracts were combined, washed with saturated NaCl solution (500 mL), dried over Na2SO4 and filtered. The solvent was removed under reduced pressure to afford a thick orange oil. The crude oil was dissolved in toluene (200 mL) and diluted to 2 L with hot hexanes. The mixture was filtered through a sintered glass funnel and cooled at -5° C. for 12 hours. The white crystalline solid which formed was removed by filtration to afford 266.36 g (59% yield) of the title compound. The melting point of the resulting compound was determined to be 83-85° C. Nuclear magnetic resonance characterization experiments yielded the following molecular signature: was cooled in an ice bath under argon The reaction was quenched with water (1 L) extracted with diethyl ether (3×1 L) washed with saturated NaCl solution (500 mL) dried over Na2SO4 filtered The solvent was removed under reduced pressure to afford a thick orange oil The mixture was filtered through a sintered glass funnel cooled at -5° C. for 12 hours The white crystalline solid which formed was removed by filtration

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

Procedure: Triphenylmethylmercaptan (362.94 g, 1.31 mol, 100 mol %) dissolved in anhydrous THF (2 L) was cooled in an ice bath under argon. Sodium hydride (60% in oil; 54.39 g, 1.35 mol, 104 mol %) was added in portions over 20 min. 2-bromo-2-methylpropanal (206.06 g, 1.36 mol, 104 mol %; see Stevens & Gillis, 1957, J. Amer. Chem. Soc. 79: 3448-51) was then added slowly over 20 min. The reaction mixture was allowed to warm to room temperature and stirred for 12 hours. The reaction was quenched with water (1 L) and extracted with diethyl ether (3×1 L). The ether extracts were combined, washed with saturated NaCl solution (500 mL), dried over Na2SO4 and filtered. The solvent was removed under reduced pressure to afford a thick orange oil. The crude oil was dissolved in toluene (200 mL) and diluted to 2 L with hot hexanes. The mixture was filtered through a sintered glass funnel and cooled at -5° C. for 12 hours. The white crystalline solid which formed was removed by filtration to afford 266.36 g (59% yield) of the title compound. The melting point of the resulting compound was determined to be 83-85° C. Nuclear magnetic resonance characterization experiments yielded the following molecular signature: was cooled in an ice bath under argon The reaction was quenched with water (1 L) extracted with diethyl ether (3×1 L) washed with saturated NaCl solution (500 mL) dried over Na2SO4 filtered The solvent was removed under reduced pressure to afford a thick orange oil The mixture was filtered through a sintered glass funnel cooled at -5° C. for 12 hours The white crystalline solid which formed was removed by filtration

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

Procedure: Triphenylmethylmercaptan (362.94 g, 1.31 mol, 100 mol %) dissolved in anhydrous THF (tetrahydrafuran; 2 L) was cooled in an ice bath under argon. Sodium hydride (60% in oil: 54.39 g, 1.35 mol, 104 mol %) was added in portions over 20 min. 2-bromo-2-methylpropanal (206.06 g, 1.36 mol, 104 mol %: see Stevens & Gillis. 1957. J. Amer. Chem. Soc. 79: 3448-51) was then added slowly over 20 min. The reaction mixture was allowed to warm to room temperature and stirred for 12 hours. The reaction was quenched with water (1 L) and extracted with diethyl ether (3×1 L). The ether extracts were combined, washed with saturated NaCl solution (500 mL), dried over Na2SO4 and filtered. The solvent was removed under reduced pressure to afford a thick orange oil. The crude oil was dissolved in toluene (200 mL) and diluted to 2 L with hot hexanes. The mixture was filtered through a sintered glass funnel and cooled at -5° C. for 12 hours. The white crystalline solid which formed was removed by filtration to afford 266.36 g (59% yield) of the title compound. The melting point of the resulting compound was determined to be 83-85° C. Nuclear magnetic resonance characterization experiments yielded the following molecular signature: was cooled in an ice bath under argon The reaction was quenched with water (1 L) extracted with diethyl ether (3×1 L) washed with saturated NaCl solution (500 mL) dried over Na2SO4 filtered The solvent was removed under reduced pressure to afford a thick orange oil The mixture was filtered through a sintered glass funnel cooled at -5° C. for 12 hours The white crystalline solid which formed was removed by filtration

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

Procedure: Triphenylmethylmercaptan (362.94 g, 1.31 mol, 100 mol %) dissolved in anhydrous THF (2 L) was cooled in an ice bath under argon. Sodium hydride (60% in oil; 54.39 g, 1.35 mol, 104 mol %) was added in portions over 20 min. 2-bromo-2-methylpropanal (206.06 g, 1.36 mol, 104 mol %; see Stevens & Gillis, 1957, J. Amer. Chem. Soc. 79: 3448-51) was then added slowly over 20 min. The reaction mixture was allowed to warm to room temperature and stirred for 12 hours. The reaction was quenched with water (1 L) and extracted with diethyl ether (3×1 L). The ether extracts were combined, washed with saturated NaCl solution (500 mL), dried over Na2SO4 and filtered. The solvent was removed under reduced pressure to afford a thick orange oil. The crude oil was dissolved in toluene (200 mL) and diluted to 2 L with hot hexanes. The mixture was filtered through a sintered glass funnel and cooled at -5° C. for 12 hours. The white crystalline solid which formed was removed by filtration to afford 266.36 g (59% yield) of the title compound. The melting point of the resulting compound was determined to be 83-85° C. Nuclear magnetic resonance characterization experiments yielded the following molecular signature: was cooled in an ice bath under argon The reaction was quenched with water (1 L) extracted with diethyl ether (3×1 L) washed with saturated NaCl solution (500 mL) dried over Na2SO4 filtered The solvent was removed under reduced pressure to afford a thick orange oil The mixture was filtered through a sintered glass funnel cooled at -5° C. for 12 hours The white crystalline solid which formed was removed by filtration

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

Procedure: A solution of 100 g 2-bromo-2-methyl-propionaldehyde in 20 ml of ethanol is added dropwise to a mixture of 25.0 g N-[(ethoxycarbonyl)methyl]-piperazine in 80 ml of ethanol at room temperature. The resulting mixture is stirred for 72 hours, concentrated in vacuo, and submitted directly to column chromatography on silica gel with methylene chloride/methanol (95:5 to 80:20) to give the title compound as a yellow oil. Yield: 10.0 g (62% of theory), Rf value: 0.60 (silica gel, methylene chloride/methanol=9:1) Mass spectrum (ESI*): m/z=241 [M−H]* concentrated in vacuo

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

Procedure: A solution of 100 g 2-bromo-2-methyl-propionaldehyde in 20 ml of ethanol is added dropwise to a mixture of 25.0 g N-[(ethoxycarbonyl)methyl]-piperazine in 80 ml of ethanol at room temperature. The resulting mixture is stirred for 72 hours, concentrated in vacuo, and submitted directly to column chromatography on silica gel with methylene chloride/methanol (95:5 to 80:20) to give the title compound as a yellow oil. Yield: 10.0 g (62% of theory), Rf value: 0.60 (silica gel, methylene chloride/methanol=9:1) Mass spectrum (ESI*): m/z=241 [M−H]* concentrated in vacuo

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

Procedure: To a mixture of 10 g of 2-nitro-4-trifluoromethylphenol, 8.0 g of anhydrous calcium carbonate and 30 ml of N,N-dimethylformamide was added dropwise a solution of 8.8 g of 2-bromoisobutyraldehyde in 23 ml of N,N-dimethylformamide and the mixture was stirred at room temperature for 4 days. The reaction mixture was then poured in ice-water and extracted with toluene. The organic layer was washed with 0.5 N aqueous sodium hydroxide solution and water in that order and dried over anhydrous magnesium sulfate and the solvent was distilled off. The residue was chromatographed on a silica gel column and elution was carried out with hexane-ethyl acetate (3:1). The Crystals from the eluate were recrystallized from 15 ml of hexane twice to give 4.428 g of 2-(2-nitro-4-trifluoromethylphenoxy)isobutyraldehyde. extracted with toluene The organic layer was washed with 0.5 N aqueous sodium hydroxide solution and water in that order dried over anhydrous magnesium sulfate the solvent was distilled off The residue was chromatographed on a silica gel column and elution The Crystals from the eluate were recrystallized from 15 ml of hexane twice

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