1,3-dichloropropane

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:0.00; pressure:0.00; stir:

Conditions: temp:53.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To N-ethyl-p-toluenesulfonamide (5.01 g, 0.0251 mol) in DMF (50 mL) in a dry flask is added sodium hydride (80% in oil, 0.93 g, 0.031 mol). After gas evolution subsides, 1,3-dichloropropane (22.48 g, 0.199 mol) is added. The mixture is heated at 53° C. for 10 h then cooled and poured into ice water (300 mL), which is extracted twice with ether. The combined extracts are washed with 1% sodium bisulfite, water (3×), and brine. Removal of solvent by rotary evaporation then Kugelrohr distillation gives crude product, which is chromatographed on silica gel (30% hexane/CHCl3) to furnish 2.91 g product (42%) NMR (CDCl3) δ 1.15 (t, 3H), 1.9-2.2 (m, 2H), 2.44 (s, 3H), 3.11-3.35 (m, 4H), 3.6 (t, 2H), 7.3 (d, 2H), 7.74 (d, 2H). then cooled is extracted twice with ether The combined extracts are washed with 1% sodium bisulfite, water (3×), and brine Removal of solvent by rotary evaporation Kugelrohr distillation gives crude product, which is chromatographed on silica gel (30% hexane/CHCl3)

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

Procedure: To a suspension of 2.20 g (50 mmol) of 60% sodium hydride in 100 ml of DMF, a solution of 12.06 g (50 mmol) of 3,4-dihydro-2H-1,2-benzothiazin-4-one 1,1-dioxide ethylene acetal in 50 ml of DMF was added under ice cooling and stirring. The reaction mixture was stirred for 30 minutes at 0° C. and then for further one hour at room temperature. Under ice cooling, a solution of 16.95 g (150 mmol) of 1,3-dichloropropane in 50 ml of DMF was added to the reaction mixture, followed by stirring for 17 hours at room temperature. The post-treatment and purification were conducted as in Example 10, whereby 13.41 g of the title compound were obtained (yield: 84%). The reaction mixture was stirred for 30 minutes at 0° C. by stirring for 17 hours at room temperature The post-treatment and purification

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

Procedure: The title compound was prepared as described for 6-bromo-2,3-dimethylhexanoic acid from isobutyric acid (9.67 g, 109.8 mmol), and 1,3-dichloropropane (37.2 g, 329.2 mmol). The product was purified by flash chromatography (CHCl3) to provide the acid (0.9 g, 5%) as a oil, HRMS (M+Li)+ calcd for C7H13O2ClLi 171.0764, found 171.0766. The product was purified by flash chromatography (CHCl3)

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

Procedure: The sodium mercaptide of 2-mercaptoethanol was made by reacting 1 mole each of sodium methoxide and 2-mercaptoethanol in dry methanol under a nitrogen atmosphere. To this solution, 0.5 mole of 1,3-dichloropropane was added and the mixture was refluxed for 1 hour and filtered. The methanol filtrate was evaporated on a flash evaporator and traces of 2-mercaptoethanol were distilled off at high vacuum at room temperature. The yellow, oily residue was extracted with acetone, the solution filtered, and the acetone evaporated to give a 95 percent yield of the crude product. the mixture was refluxed for 1 hour filtered The methanol filtrate was evaporated on a flash evaporator and traces of 2-mercaptoethanol were distilled off at high vacuum at room temperature The yellow, oily residue was extracted with acetone the solution filtered the acetone evaporated

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

Procedure: The sodium mercaptide of 2-mercaptoethanol was made by reacting 1 mole each of sodium methoxide and 2-mercaptoethanol in dry methanol under a nitrogen atmosphere. To this solution, 0.5 mole of 1,3-dichloropropane was added and the mixture was refluxed for 1 hour and filtered. The methanol filtrate was evaporated on a flash evaporator and traces of 2-mercaptoethanol were distilled off at high vacuum at room temperature. The yellow, oily residue was extracted with acetone, the solution filtered, and the acetone evaporated to give a 95 percent yield of the crude product. the mixture was refluxed for 1 hour filtered The methanol filtrate was evaporated on a flash evaporator and traces of 2-mercaptoethanol were distilled off at high vacuum at room temperature The yellow, oily residue was extracted with acetone the solution filtered the acetone evaporated

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

Procedure: An amount of 1,3-bis[(2-pyridyl)(phenyl)phosphino]propane was prepared substantially in the same way as the diphosphine of Example 2, except that instead of dichloromethane, 1,3-dichloropropane was employed.

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of the potassium salt of 5-chloropyrimid-2-one (0.01 mol) and 1.3-dichloropropane (0.02 mol) in dimethylformamide (50 ml) was heated at 60° C. for 8 h. The reaction mixture was then evaporated (1 mm Hg) and the residue dissolved in chloroform (80 ml). This solution was washed with 1 N NaOH (2 ml) and water before drying and evaporation; yield 60%, m.p. 102°-104° C. (benzene/ligroin). (Found: C, 41.83; H, 3.02. Calc. for C7H6ClN2O: C, 41.01; H, 2.95). The reaction mixture was then evaporated (1 mm Hg) the residue dissolved in chloroform (80 ml) This solution was washed with 1 N NaOH (2 ml) and water before drying evaporation

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of the potassium salt of 5-chloropyrimid-2-one (0.01 mol) and 1.3-dichloropropane (0.02 mol) in dimethylformamide (50 ml) was heated at 60° C. for 8 h. The reaction mixture was then evaporated (1 mm Hg) and the residue dissolved in chloroform (80 ml). This solution was washed with 1 N NaOH (2 ml) and water before drying and evaporation; yield 60%, m.p. 102°-104° C. (benzene/ligroin). (Found: C, 41.83; H, 3.02. Calc. for C7H6ClN2O: C, 41.01; H, 2.95). The reaction mixture was then evaporated (1 mm Hg) the residue dissolved in chloroform (80 ml) This solution was washed with 1 N NaOH (2 ml) and water before drying evaporation