2H-furan-5-one

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:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 3.86 g (19 mmol) of 4-bromothioanisole in 90 mL of Et2O cooled at -78° C., is added 22 mL of 1.7M solution of t-BuLi in pentane (38 mmol) dropwise. The reaction mixture is stirred for 15 min at -78° C. and 3.8 g of CuI is added and the reaction mixture is allowed to warm to -40° C. over a period of 30 min. A solution of 1.7 g of 2(5H)-furanone in 10 ml of THF is added. After stirring for 1 h, 2 ml of freshly distilled TMSCl is added dropwise. The reaction mixture is then treated with 2 ml of Et3N and 50 ml of sat. NaHCO3, and extracted with 100 ml of ether. The ether layer is dried over Na2SO4 and concentrated to the crude title compound which is used for the next step without further purification. to warm to -40° C. over a period of 30 min After stirring for 1 h extracted with 100 ml of ether The ether layer is dried over Na2SO4 concentrated to the crude title compound which is used for the next step without further purification

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 3.86 g (19 mmol) of 4-bromothioanisole in 90 mL of Et2O cooled at -78° C., is added 22 mL of a 1.7 M solution of t-BuLi in pentane (38 mmol) dropwise. The reaction mixture is stirred for 15 min at -78° C. and 3.8 g of CuI is added and the reaction mixture is allowed to warm to -40° C. over a period of 30 min. A solution of 1.7 g of 2(5H)-furanone in 10 mL of THF is added. After stirring for 1 h, 2 mL of freshly distilled TMSCl is added dropwise. The reaction mixture is then treated with 2 mL of Et3N and 50 mL of sat. NaHCO3, and extracted with 100 mL of Et2O. The Et2O layer is dried over Na2SO4 and concentrated to give the crude title compound which is used for the next step without further purification. to warm to -40° C. over a period of 30 min After stirring for 1 h extracted with 100 mL of Et2O The Et2O layer is dried over Na2SO4 concentrated

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 3.86 g (19 mmol) of 4-bromothioanisole in 90 mL of Et2O cooled at -78° C., is added 22 mL of a 1.7 M solution of t-BuLi in pentane (38 mmol) dropwise. The reaction mixture is stirred for 15 min at -78° C. and 3.8 g of CuI is added and the reaction mixture is allowed to warm to -40° C. over a period of 30 min. A solution of 1.7 g of 2(5H)-furanone in 10 mL of THF is added. After stirring for 1 h, 2 mL of freshly distilled TMSCl is added dropwise. The reaction mixture is then treated with 2 mL of Et3N and 50 mL of sat. NaHCO3, and extracted with 100 mL of Et2O. The Et2O layer is dried over Na2SO4 and concentrated to give the crude title compound which is used for the next step without further purification. to warm to -40° C. over a period of 30 min After stirring for 1 h extracted with 100 mL of Et2O The Et2O layer is dried over Na2SO4 concentrated

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

Procedure: To a solution of 3.86 g (19 mmol) of 4-bromothioanisole in 90 mL of Et2O cooled at −78iC, is added 22 mL of 1.7 M solution of t-BuLi in pentane (38 mmol) dropwise. The reaction mixture is stirred for 15 min at −78 iC and 3.8 g of CuI is added and the reaction mixture is allowed to warm to −40 iC over a period of 30 min. A solution of 1.7 g of 2(5H)-furanone in 10 ml of THF is added. After stirring for 1 h, 2 ml of freshly distilled TMSCl is added dropwise. The reaction mixture is then treated with 2 ml of Et3N and 50 ml of sat. NaHCO3, and extracted with 100 ml of ether. The ether layer is dried over Na2SO4 and concentrated to the crude title compound which is used for the next step without further purification. is added to warm to −40 iC over a period of 30 min extracted with 100 ml of ether The ether layer is dried over Na2SO4 concentrated to the crude title compound which is used for the next step without further purification

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Tetrahydrofuran (50 mL) and Lithium diisopropylamide mono tetrahydrofuran complex (20 mL of 1.5 M in cyclohexane) was cooled in a dry ice/Isopropanol bath for 10 min. Tert-butyl acetate (3.5 mL 26 mmoles) was added via syringe and stirred at −78° C. for 30 min. 2(5H)-Furanone (1.59 g, 19 mmoles) was added dropwise and the reaction was stirred for 1 h at −78° C. The reaction was poured into water and extracted with ether 2×150 mL The ether extracts were combined and washed with water 100 mL then brine 3×100 mL, dried and the ether removed under reduced pressure to give 2.74 g of product (72%). MS (ESI+) for C10H16O4 m/z 223 (M+Na)+. the reaction was stirred for 1 h at −78° C extracted with ether 2×150 mL The ether extracts washed with water 100 mL brine 3×100 mL, dried the ether removed under reduced pressure

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Tetrahydrofuran (50 mL) and Lithium diisopropylamide mono tetrahydrofuran complex (20 mL of 1.5 M in cyclohexane) was cooled in a dry ice/Isopropanol bath for 10 min. Tert-butyl acetate (3.5 mL 26 mmoles) was added via syringe and stirred at −78° C. for 30 min. 2(5H)-Furanone (1.59 g, 19 mmoles) was added dropwise and the reaction was stirred for 1 h at −78° C. The reaction was poured into water and extracted with ether 2×150 mL The ether extracts were combined and washed with water 100 mL then brine 3×100 mL, dried and the ether removed under reduced pressure to give 2.74 g of product (72%). MS (ESI+) for C10H16O4 m/z 223 (M+Na)+. the reaction was stirred for 1 h at −78° C extracted with ether 2×150 mL The ether extracts washed with water 100 mL brine 3×100 mL, dried the ether removed under reduced pressure

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

Procedure: The reaction sequences for preparing these branched polynitroalkyl diols can be summarized as follows: ##STR6## where Z is --C(NO2)3, --CF(NO2)2, --C(NO2)2CH3, or --N(NO2)CH3. The reaction of one mole of trinitromethane with one mole of gamma-crotonolactone under the reaction conditions of example 1 produces 4-hydroxy-3-(trinitromethyl)butyric acid, gamma-lactone which is reduced by borane-tetrahydrofuran to produce 2-(trinitromethyl)-1,4-butanediol as shown in example 3. Similarly, the reaction of one mole of fluorodinitromethane with gamma-crotonolactone under the reaction conditions of example 2 produces 4-hydroxy-3-(fluorodinitromethyl)butric acid, gamma-lactone which is reduced by borane-tetrahydrofuran to produce 2-(fluorodinitromethyl)-1,4-butanediol as shown in example 4. Using the same procedure, 1,1-dinitroethane and gamma-crotonolactone can be used to produce 2-(1,1-dinitroethyl)-1,4-butanediol and methyl nitramine and gamma-crotonolactone can be used to produce 2-(methylnitraza)-1,4-butanediol.

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

Procedure: To a freshly distilled solution of 2(5H)-furanone (2.86 g, 34 mmol) in dichloromethane (20 ml), distilled triethylamine (6.6 ml. 47.4 mmol) is added under argon at 0° C. and then rapidly followed by tert-butyldimehylsilyltrifluoromethane sulfonate (8.6 ml, 37.3 mmol) The reaction mixture is allowed to return to room temperature and the stirring is maintained for two hours. The solvent is then removed under reduced pressure and the oily residue is purified by flash chromatography on silica gel (ethyl acetate-heptane, 1:9) in order to thus obtain compound 10 (Z=O) in the form of a slightly colored oil (5.3 g, 79%). The spectroscopic data for this compound (1H and 13C NMR) are identical to those described in the literature (G. Rassu, Z. Zanardi, L. Battistini, E. Gaetani, G. Casiraghi, J. Med. Chem ., 1997, 40, 168). is added under argon at 0° C. to return to room temperature the stirring is maintained for two hours The solvent is then removed under reduced pressure the oily residue is purified by flash chromatography on silica gel (ethyl acetate-heptane, 1:9) in order to thus obtain compound 10 (Z=O) in the form of a slightly colored oil (5.3 g, 79%)

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

Procedure: To a freshly distilled solution of 2(5H)-furanone (2.86 g, 34 mmol) in dichloromethane (20 ml), distilled triethylamine (6.6 ml. 47.4 mmol) is added under argon at 0° C. and then rapidly followed by tert-butyldimehylsilyltrifluoromethane sulfonate (8.6 ml, 37.3 mmol) The reaction mixture is allowed to return to room temperature and the stirring is maintained for two hours. The solvent is then removed under reduced pressure and the oily residue is purified by flash chromatography on silica gel (ethyl acetate-heptane, 1:9) in order to thus obtain compound 10 (Z=O) in the form of a slightly colored oil (5.3 g, 79%). The spectroscopic data for this compound (1H and 13C NMR) are identical to those described in the literature (G. Rassu, Z. Zanardi, L. Battistini, E. Gaetani, G. Casiraghi, J. Med. Chem ., 1997, 40, 168). is added under argon at 0° C. to return to room temperature the stirring is maintained for two hours The solvent is then removed under reduced pressure the oily residue is purified by flash chromatography on silica gel (ethyl acetate-heptane, 1:9) in order to thus obtain compound 10 (Z=O) in the form of a slightly colored oil (5.3 g, 79%)