methyl 2-chloro-3-oxopentanoate

Conditions: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: NH3 gas is passed with cooling (max. 50° C.) through a solution of 99.7 g (0.6 mol) of methyl 2-chloro-3-oxo-valerate in 130 ml of formamide until the mixture takes up no more NH3 (about 1 h). The ammonia residues are removed by blowing out with nitrogen and applying a vacuum. The reaction solution is subsequently added dropwise to 450 ml of a 30% NaOMe solution in methanol at 50° C. Addition of a further 50 ml of formamide is followed by heating at 50° C. for 3 h. The volatile constituents are evaporated in vacuo, and subsequently the mixture is added to water and the pH is adjusted to 6 with HCl. Extraction with ethyl acetate and evaporation provide 91.2 g of crude product, which is recrystallized from cold acetone. Yield: 66.3 g (70%) The ammonia residues are removed The reaction solution is subsequently added dropwise to 450 ml of a 30% NaOMe solution in methanol at 50° C Addition of a further 50 ml of formamide The volatile constituents are evaporated in vacuo subsequently the mixture is added to water Extraction with ethyl acetate and evaporation

Conditions: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: NH3 gas is passed with cooling (max. 50° C.) through a solution of 99.7 g (0.6 mol) of methyl 2-chloro-3-oxo-valerate in 130 ml of formamide until the mixture takes up no more NH3 (about 1 h). The ammonia residues are removed by blowing out with nitrogen and applying a vacuum. The reaction solution is subsequently added dropwise to 450 ml of a 30% NaOMe solution in methanol at 50° C. Addition of a further 50 ml of formamide is followed by heating at 50° C. for 3 h. The volatile constituents are evaporated in vacuo, and subsequently the mixture is added to water and the pH is adjusted to 6 with HCl. Extraction with ethyl acetate and evaporation provide 91.2 g of crude product, which is recrystallized from cold acetone. Yield: 66.3 g (70%) The ammonia residues are removed The reaction solution is subsequently added dropwise to 450 ml of a 30% NaOMe solution in methanol at 50° C Addition of a further 50 ml of formamide The volatile constituents are evaporated in vacuo subsequently the mixture is added to water Extraction with ethyl acetate and evaporation

Conditions: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Dry NH3 gas is passed through a solution of 376.3 g (2.064 mol) of methyl 2-chloro-3-oxovalerate in 100 ml of methanol while stirring at 65° C. for 3 h. The solvent is removed in vacuo, the residue is taken up in diisopropyl ether, the solution is filtered through sea sand, and the solvent is evaporated. Yield: 87.6% [GC] The solvent is removed in vacuo the solution is filtered through sea sand the solvent is evaporated

Conditions: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Dry NH3 gas is passed through a solution of 376.3 g (2.064 mol) of methyl 2-chloro-3-oxovalerate in 100 ml of methanol while stirring at 65° C. for 3 h. The solvent is removed in vacuo, the residue is taken up in diisopropyl ether, the solution is filtered through sea sand, and the solvent is evaporated. Yield: 87.6% [GC] The solvent is removed in vacuo the solution is filtered through sea sand the solvent is evaporated

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

Procedure: A solution of 47.5 g (0.75 mol) of ammonium formate and 49.0 g (0.3 mol) of methyl 2-chloro-3-oxovalerate in 800 ml of ethanol is reacted and worked up in analogy to Example 2. Yield: 72.0% [GC]

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

Procedure: A solution of 47.5 g (0.75 mol) of ammonium formate and 49.0 g (0.3 mol) of methyl 2-chloro-3-oxovalerate in 800 ml of ethanol is reacted and worked up in analogy to Example 2. Yield: 72.0% [GC]

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

Procedure: A solution of 576.1 g (3.5 mol) of methyl 2-chloro-3-oxovalerate and 674.5 g (8.75 mol) of ammonium acetate in 1.2 l of methanol is heated at 65° C. with stirring for a period of 4 h. After cooling, the solvent is removed in vacuo, the residue is taken up in 2.5 l of diisopropyl ether, and the solid is removed. The solid is dissolved in a little water and subsequently extracted with ethyl acetate. The organic fractions are combined, dried over MgSO4 and evaporated in vacuo. Yield: 94.7% [GC] After cooling the solvent is removed in vacuo the solid is removed The solid is dissolved in a little water subsequently extracted with ethyl acetate dried over MgSO4 evaporated in vacuo

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

Procedure: A solution of 576.1 g (3.5 mol) of methyl 2-chloro-3-oxovalerate and 674.5 g (8.75 mol) of ammonium acetate in 1.2 l of methanol is heated at 65° C. with stirring for a period of 4 h. After cooling, the solvent is removed in vacuo, the residue is taken up in 2.5 l of diisopropyl ether, and the solid is removed. The solid is dissolved in a little water and subsequently extracted with ethyl acetate. The organic fractions are combined, dried over MgSO4 and evaporated in vacuo. Yield: 94.7% [GC] After cooling the solvent is removed in vacuo the solid is removed The solid is dissolved in a little water subsequently extracted with ethyl acetate dried over MgSO4 evaporated in vacuo

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

Procedure: Dry NH3 gas is passed through 48.9 g (0.30 mol) of methyl 2-chloro-3-oxovalerate at 70° C. for a period of 2 h. After removal of volatile constituents in vacuo, the crude product is dissolved in diisopropyl ether and washed with a little ice water. After drying over MgSO4, the solvent is removed in vacuo. Yield: 80.0% [GC] After removal of volatile constituents in vacuo the crude product is dissolved in diisopropyl ether washed with a little ice water After drying over MgSO4 the solvent is removed in vacuo

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

Procedure: Dry NH3 gas is passed through 48.9 g (0.30 mol) of methyl 2-chloro-3-oxovalerate at 70° C. for a period of 2 h. After removal of volatile constituents in vacuo, the crude product is dissolved in diisopropyl ether and washed with a little ice water. After drying over MgSO4, the solvent is removed in vacuo. Yield: 80.0% [GC] After removal of volatile constituents in vacuo the crude product is dissolved in diisopropyl ether washed with a little ice water After drying over MgSO4 the solvent is removed in vacuo

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

Procedure: A stirred solution of 2,4,6-trichlorophenylthiourea (scheme 1: (B)) (3.25 g, 12.72 mmoles) and methyl 2-chloro-3-oxopentanoate (Scheme 1: (C)) (1.92 mL, 1.1 equiv.) in ethanol (60 mL) was heated at reflux for 16 hours. The solvent was removed in vacuo and the product was recrystallized from methanol (4.49 g, 97%). H1 NMR (CDCl3) δ 1.15 (3H, t), 2.91 (2H, q), 3.75 (3H, s), 7.47 (2H, s), 9.10 (1H, br). at reflux for 16 hours The solvent was removed in vacuo the product was recrystallized from methanol (4.49 g, 97%)

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

Procedure: In a 500 ml Hastelloy-made autoclave having been purged with nitrogen were put 100 g (0.2886 mol) of the methyl 2-chloro-3-oxooctadecanoate (VII) prepared in (1) above, 2 ml of a methylene chloride solution of 260 mg (0.144 mol) of a ruthenium-optically active phosphine complex Ru2Cl4 [(+)-Tol-BINAP]2NEt3, and 300 ml of methanol, and the mixture was allowed to react at 50° C. under a hydrogen pressure of 30 atm for 18 hours. Methanol was removed by evaporation to give 95.8 g (0.275 mol; yield: 95.3%) of the title compound (VIII) (melting point: 39-40° C.). having been purged with nitrogen to react at 50° C. under a hydrogen pressure of 30 atm for 18 hours Methanol was removed by evaporation