2-methyl-1-nitropropane

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

Procedure: To a solution of 2-methyl-1-nitropropane (38.7 g, 0.375 mol, prepared by the procedure of N. Kornblum, B. Tunbe, and H. Ungnade, J. Amer. Chem. Soc., 76, 3209 (1954)) and NEt3 (Eastman, 3.79 g, 0.0375 mol) in CH3OH (50 mL) was added dropwise 37% aqueous formaldehyde solution (Mallinckrodt, 76.2 g, 0.938 mol) at a rate such that the reaction mixture temperature did not exceed 30°. After 72 h, the solution was concentrated under vacuum and the residue was dissolved in H2O (250 mL). The solution was continuously extracted for 1 h with CH2Cl2 (1 L). The CH2Cl2 solution was dried (MgSO4), filtered, and concentrated to give 53.3 g (87%) of 2-isopropyl-2-nitro-1,3-propanediol, as a waxy, white solid, mp 67°-72° C. (lit. mp 87°-88°, B. M. Vanderbilt and H. B. Hass, Ind. Eng. Chem. 32, 34 (1940). In our hands this literature procedure failed to give the desired compound). did not exceed 30° the solution was concentrated under vacuum the residue was dissolved in H2O (250 mL) The solution was continuously extracted for 1 h with CH2Cl2 (1 L) The CH2Cl2 solution was dried (MgSO4) filtered concentrated

Conditions: temp:15.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 3A Molecular sieves (27.04 g) were heated at 120° C. under vacuum for 20 hours and added to a solution of 2-methyl-1-nitropropane (13.0 g) in methyl tert-butyl ether (420 ml). The mixture was stirred for 5 minutes, potassium carbonate (64.5 g) added and the mixture stirred a further 30 minutes. The mixture was cooled to 15° C. and fluoral hydrate (22.0 g) was added over 30 minutes. The reaction mixture was stirred at ambient temperature for 16 hours, then cooled to 15° C. and water (270 ml) added. After stirring for 5 minutes at ambient temperature, the organic phase was separated and washed with 10% aqueous potassium carbonate, 2M hydrochloric acid solution and water. Solvent was then removed by evaporation under reduced pressure at a temperature below 40° C. and the oil azeotroped dry with isopropyl alcohol at a temperature below 50° C. to give 4-methyl-3-nitro-1,1,1-trifluoro-2-pentanol (21.3 g) as an oil which was used without further purification. the mixture stirred a further 30 minutes The reaction mixture was stirred at ambient temperature for 16 hours cooled to 15° C. After stirring for 5 minutes at ambient temperature the organic phase was separated washed with 10% aqueous potassium carbonate, 2M hydrochloric acid solution and water Solvent was then removed by evaporation under reduced pressure at a temperature below 40° C. the oil azeotroped dry with isopropyl alcohol at a temperature below 50° C.

Conditions: temp:15.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 3A Molecular sieves (27.04 g) were heated at 120° C. under vacuum for 20 hours and added to a solution of 2-methyl-1-nitropropane (13.0 g) in methyl tert-butyl ether (420 ml). The mixture was stirred for 5 minutes, potassium carbonate (64.5 g) added and the mixture stirred a further 30 minutes. The mixture was cooled to 15° C. and fluoral hydrate (22.0 g) was added over 30 minutes. The reaction mixture was stirred at ambient temperature for 16 hours, then cooled to 15° C. and water (270 ml) added. After stirring for 5 minutes at ambient temperature, the organic phase was separated and washed with 10% aqueous potassium carbonate, 2M hydrochloric acid solution and water. Solvent was then removed by evaporation under reduced pressure at a temperature below 40° C. and the oil azeotroped dry with isopropyl alcohol at a temperature below 50° C. to give 4-methyl-3-nitro-1,1,1-trifluoro-2-pentanol (21.3 g) as an oil, which was used without further purification. the mixture stirred a further 30 minutes The reaction mixture was stirred at ambient temperature for 16 hours cooled to 15° C. After stirring for 5 minutes at ambient temperature the organic phase was separated washed with 10% aqueous potassium carbonate, 2M hydrochloric acid solution and water Solvent was then removed by evaporation under reduced pressure at a temperature below 40° C. the oil azeotroped dry with isopropyl alcohol at a temperature below 50° C.

Conditions: temp:15.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 3A Molecular sieves (27.04 g) were heated at 120° C. under vacuum for 20 hours and added to a solution of 2-methyl-1-nitropropane (13.0 g) in methyl tert-butyl ether (420 ml). The mixture was stirred for 5 minutes, potassium carbonate (64.5 g) added and the mixture stirred a further 30 minutes. The mixture was cooled to 15° C. and fluoral hydrate (22.0 g) was added over 30 minutes. The reaction mixture was stirred at ambient temperature for 16 hours, then cooled to 15° C. and water (270 ml) added. After stirring for 5 minutes at ambient temperature, the organic phase was separated and washed with 10% aqueous potassium carbonate, 2M hydrochloric acid solution and water. Solvent was then removed by evaporation under reduced pressure at a temperature below 40° C. and the oil azeotroped dry with isopropyl alcohol at a temperature below 50° C. to give 4-methyl-3-nitro-1,1,1-trifluoro-2-pentanol (21.3 g) as an oil, which was used without further purification. the mixture stirred a further 30 minutes The reaction mixture was stirred at ambient temperature for 16 hours cooled to 15° C. After stirring for 5 minutes at ambient temperature the organic phase was separated washed with 10% aqueous potassium carbonate, 2M hydrochloric acid solution and water Solvent was then removed by evaporation under reduced pressure at a temperature below 40° C. the oil azeotroped dry with isopropyl alcohol at a temperature below 50° C.

Conditions: temp:15.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 3A Molecular sieves (27.04 g) were heated at 120° C. under vacuum for 20 hours and added to a solution of 2-methyl-1-nitropropane (13.0 g) in methyl tert-butyl ether (420 ml). The mixture was stirred for 5 minutes, potassium carbonate (64.5 g) added and the mixture stirred a further 30 minutes. The mixture was cooled to 15° C. and fluoral hydrate (22.0 g) was added over 30 minutes. The reaction mixture was stirred at ambient temperature for 16 hours, then cooled to 15° C. and water (270 ml) added. After stirring for 5 minutes at ambient temperature, the organic phase was separated and washed with 10% aqueous potassium carbonate, 2M hydrochloric acid solution and water. Solvent was then removed by evaporation under reduced pressure at a temperature below 40° C. and the oil azeotroped dry with isopropyl alcohol at a temperature below 50° C. to give 4-methyl-3-nitro-1,1,1-trifluoro-2-pentanol (21.3 g) as an oil, which was used without further purification. the mixture stirred a further 30 minutes The reaction mixture was stirred at ambient temperature for 16 hours cooled to 15° C. After stirring for 5 minutes at ambient temperature the organic phase was separated washed with 10% aqueous potassium carbonate, 2M hydrochloric acid solution and water Solvent was then removed by evaporation under reduced pressure at a temperature below 40° C. the oil azeotroped dry with isopropyl alcohol at a temperature below 50° C.

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

Procedure: A solution of 2-methyl-1-nitropropane (38.7 g, 0.375 mol prepared by the procedure of N. Kornblum, B. Taube, and H. Ungnade, J. Am. Chem. Soc. 76, 3209 (1954) and NEt3 (Eastman 3.79 g, 0.0375 mol) in CH3OH (50 mL) was added dropwise 37% aqueous formaldehyde solution (Mallinckrodt, 76.2 g, 0.938 mol), at a rate such that the reaction mixture temperature did not exceed 30°. After 72 h, the solution was concentrated under vacuum and the residue was dissolved in H2O (250 mL). The solution was continuously extracted for 1 h with CH2Cl2 (1 L). The CH2Cl2 solution was dried (MgSO4), filtered, and concentrated to give 53.3 g (87%)of 2-isopropyl-2-nitro-1,3-propanediol a waxy, white solid mp 67°-72° (lit. mp 87°-88°, B. M. Vanderbilt and H. B. Hass, Ind. Eng. Chem. 32, 34 (1940). In our hands this procedure failed to give the desired compound). did not exceed 30° the solution was concentrated under vacuum the residue was dissolved in H2O (250 mL) The solution was continuously extracted for 1 h with CH2Cl2 (1 L) The CH2Cl2 solution was dried (MgSO4) filtered concentrated

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

Procedure: A solution of 2-methyl-1-nitropropane (38.7 g, 0.375 mol prepared by the procedure of N. Kornblum, B. Taube, and H. Ungnade, J. Am. Chem. Soc. 76, 3209 (1954) and NEt3 (Eastman 3.79 g, 0.0375 mol) in CH3OH (50 mL) was added dropwise 37% aqueous formaldehyde solution (Mallinckrodt, 76.2 g, 0.938 mol), at a rate such that the reaction mixture temperature did not exceed 30°. After 72 h, the solution was concentrated under vacuum and the residue was dissolved in H2O (250 mL). The solution was continuously extracted for 1 h with CH2Cl2 (1 L). The CH2Cl2 solution was dried (MgSO4), filtered, and concentrated to give 53.3 g (87%)of 2-isopropyl-2-nitro-1,3-propanediol a waxy, white solid mp 67°-72° (lit. mp 87°-88°, B. M. Vanderbilt and H. B. Hass, Ind. Eng. Chem. 32, 34 (1940). In our hands this procedure failed to give the desired compound). did not exceed 30° the solution was concentrated under vacuum the residue was dissolved in H2O (250 mL) The solution was continuously extracted for 1 h with CH2Cl2 (1 L) The CH2Cl2 solution was dried (MgSO4) filtered concentrated

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

Procedure: To a solution of 2-methyl-1-nitropropane (38.7 g, 0.375 mol, prepared by the procedure of N. Kornblum, B. Tunbe, and H. Ungnade, J. Amer. Chem. Soc., 76, 3209 (1954)) and NEt3 (Eastman, 3.79 g, 0.0375 mol) in CH3OH (50 mL) was added dropwise 37% aqueous formaldehyde solution (Mallinckrodt, 76.2 g, 0.938 mol) at a rate such that the reaction mixture temperature did not exceed 30°. After 72 h, the solution was concentrated under vacuum and the residue was dissolved in H2O (250 mL). The solution was continuously extracted for 1 h with CH2Cl2 (1 L). The CH2Cl2 solution was dried (MgSO4), filtered, and concentrated to give 53.3 g (87%) of 2-isopropyl-2-nitro-1,3-propanediol, as a waxy, white solid, mp 67°-72° C. (lit. mp 87°-88°, B. M. Vanderbilt and H. B. Hass, Ind. Eng. Chem. 32, 34 (1940). In our hands this literature procedure failed to give the desired compound). did not exceed 30° the solution was concentrated under vacuum the residue was dissolved in H2O (250 mL) The solution was continuously extracted for 1 h with CH2Cl2 (1 L) The CH2Cl2 solution was dried (MgSO4) filtered concentrated

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

Procedure: To a solution of 2-methyl-1-nitropropane (38.7 g, 0.375 mol, prepared by the procedure of N. Kornblum, B. Tunbe, and H. Ungnade, J. Amer. Chem. Soc., 76, 3209 (1954)) and NEt3 (Eastman, 3.79 g, 0.0375 mol) in CH3OH (50 mL) was added dropwise 37% aqueous formaldehyde solution (Mallinckrodt, 76.2 g, 0.938 mol) at a rate such that the reaction mixture temperature did not exceed 30°. After 72 h, the solution was concentrated under vacuum and the residue was dissolved in H2O (250 mL). The solution was continuously extracted for 1 h with CH2Cl2 (1 L). The CH2Cl2 solution was dried (MgSO4), filtered, and concentrated to give 53.3 g (87%) of 2-isopropyl-2-nitro-1,3-propanediol, as a waxy, white solid, mp 67°-72° C. (lit. mp 87°-88°, B. M. Vanderbilt and H. B. Hass, Ind. Eng. Chem. 32, 34 (1940). In our hands this literature procedure failed to give the desired compound). did not exceed 30° the solution was concentrated under vacuum the residue was dissolved in H2O (250 mL) The solution was continuously extracted for 1 h with CH2Cl2 (1 L) The CH2Cl2 solution was dried (MgSO4) filtered concentrated

Conditions: temp:15.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 3A Molecular sieves (27.04 g) were heated at 120° C. under vacuum for 20 hours and added to a solution of 2-methyl-1-nitropropane (13.0 g) in methyl tert-butyl ether (420 ml). The mixture was stirred for 5 minutes, potassium carbonate (64.5 g) added and the mixture stirred a further 30 minutes. The mixture was cooled to 15° C. and fluoral hydrate (22.0 g) was added over 30 minutes. The reaction mixture was stirred at ambient temperature for 16 hours, then cooled to 15° C. and water (270 ml) added. After stirring for 5 minutes at ambient temperature, the organic phase was separated and washed with 10% aqueous potassium carbonate, 2M hydrochloric acid solution and water. Solvent was then removed by evaporation under reduced pressure at a temperature below 40° C. and the oil azeotroped dry with isopropyl alcohol at a temperature below 50° C. to give 4-methyl-3-nitro-1,1,1-trifluoro-2-pentanol (21.3 g) as an oil which was used without further purification. the mixture stirred a further 30 minutes The reaction mixture was stirred at ambient temperature for 16 hours cooled to 15° C. After stirring for 5 minutes at ambient temperature the organic phase was separated washed with 10% aqueous potassium carbonate, 2M hydrochloric acid solution and water Solvent was then removed by evaporation under reduced pressure at a temperature below 40° C. the oil azeotroped dry with isopropyl alcohol at a temperature below 50° C.

Conditions: temp:15.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 3A Molecular sieves (27.04 g) were heated at 120° C. under vacuum for 20 hours and added to a solution of 2-methyl-1-nitropropane (13.0 g) in methyl tert-butyl ether (420 ml). The mixture was stirred for 5 minutes, potassium carbonate (64.5 g) added and the mixture stirred a further 30 minutes. The mixture was cooled to 15° C. and fluoral hydrate (22.0 g) was added over 30 minutes. The reaction mixture was stirred at ambient temperature for 16 hours, then cooled to 15° C. and water (270 ml) added. After stirring for 5 minutes at ambient temperature, the organic phase was separated and washed with 10% aqueous potassium carbonate, 2M hydrochloric acid solution and water. Solvent was then removed by evaporation under reduced pressure at a temperature below 40° C. and the oil azeotroped dry with isopropyl alcohol at a temperature below 50° C. to give 4-methyl-3-nitro-1,1,1-trifluoro-2-pentanol (21.3 g) as an oil which was used without further purification. the mixture stirred a further 30 minutes The reaction mixture was stirred at ambient temperature for 16 hours cooled to 15° C. After stirring for 5 minutes at ambient temperature the organic phase was separated washed with 10% aqueous potassium carbonate, 2M hydrochloric acid solution and water Solvent was then removed by evaporation under reduced pressure at a temperature below 40° C. the oil azeotroped dry with isopropyl alcohol at a temperature below 50° C.

Conditions: temp:15.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 3A Molecular sieves (27.04 g) were heated at 120° C. under vacuum for 20 hours and added to a solution of 2-methyl-1-nitropropane (13.0 g) in methyl tert-butyl ether (420 ml). The mixture was stirred for 5 minutes, potassium carbonate (64.5 g) added and the mixture stirred a further 30 minutes. The mixture was cooled to 15° C. and fluoral hydrate (22.0 g) was added over 30 minutes. The reaction mixture was stirred at ambient temperature for 16 hours, then cooled to 15° C. and water (270 ml) added. After stirring for 5 minutes at ambient temperature, the organic phase was separated and washed with 10% aqueous potassium carbonate, 2M hydrochloric acid solution and water. Solvent was then removed by evaporation under reduced pressure at a temperature below 40° C. and the oil azeotroped dry with isopropyl alcohol at a temperature below 50° C. to give 4-methyl-3-nitro-1,1,1-trifluoro-2-pentanol (21.3 g) as an oil, which was used without further purification. the mixture stirred a further 30 minutes The reaction mixture was stirred at ambient temperature for 16 hours cooled to 15° C. After stirring for 5 minutes at ambient temperature the organic phase was separated washed with 10% aqueous potassium carbonate, 2M hydrochloric acid solution and water Solvent was then removed by evaporation under reduced pressure at a temperature below 40° C. the oil azeotroped dry with isopropyl alcohol at a temperature below 50° C.