pentanoyl pentanoate

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

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

Procedure: By following in principle the appropriate procedures of Example 4, Parts A and B or Example 5, but substituting other acyl anhydrides for acetic anhydride and caproic anhydride, such as propionic anhydride, butyric anhydride or valeric anhydride, the following compounds are obtained:

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

Procedure: By following in principle the appropriate procedures of Example 4, Parts A and B or Example 5, but substituting other acyl anhydrides for acetic anhydride and caproic anhydride, such as propionic anhydride, butyric anhydride or valeric anhydride, the following compounds are obtained:

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

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

Procedure: A mixture of (1.0 g, 4.97 mmol, 1.0 eq) 4-[(3-amino-2-pyridinyl)amino]phenol in 25 ml of valeric anhydride was heated to reflux for 8 hours. The reaction mixture was cooled, poured into 150 ml of 0.5N HCl, stirred 10 minutes, and extracted twice with ether. The ether extracts were combined, washed three times with saturated NaHCO3, once with H2O, once with brine, dried over MgSO4, and concentrated to give an oil. The oil was taken up in 100 ml CH3 OH and treated with 60 ml of 2N NaOH and allowed to stir at room temperature for 1 hour. The mixture was concentrated, poured into 200 ml of H2O and washed twice with ether. The aqueous layer was neutralized, and extracted twice with ethyl acetate. The ethyl acetate extracts were combined, washed once with H2O, dried over MgSO4, and concentrated to give 0.7 g of a solid. Silica gel chromatography eluting with 10% CH3OH/CH2Cl2 gave 510 mg, 38%, of a solid. M.P.: 268°-2690° C. was heated to reflux for 8 hours The reaction mixture was cooled extracted twice with ether washed three times with saturated NaHCO3 once with H2O, once with brine, dried over MgSO4 concentrated to give an oil to stir at room temperature for 1 hour The mixture was concentrated poured into 200 ml of H2O washed twice with ether extracted twice with ethyl acetate washed once with H2O dried over MgSO4 concentrated

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

Procedure: A mixture of (1.0 g, 4.97 mmol, 1.0 eq) 4-[(3-amino-2-pyridinyl)amino]phenol in 25 ml of valeric anhydride was heated to reflux for 8 hours. The reaction mixture was cooled, poured into 150 ml of 0.5N HCl, stirred 10 minutes, and extracted twice with ether. The ether extracts were combined, washed three times with saturated NaHCO3, once with H2O, once with brine, dried over MgSO4, and concentrated to give an oil. The oil was taken up in 100 ml CH3 OH and treated with 60 ml of 2N NaOH and allowed to stir at room temperature for 1 hour. The mixture was concentrated, poured into 200 ml of H2O and washed twice with ether. The aqueous layer was neutralized, and extracted twice with ethyl acetate. The ethyl acetate extracts were combined, washed once with H2O, dried over MgSO4, and concentrated to give 0.7 g of a solid. Silica gel chromatography eluting with 10% CH3OH/CH2Cl2 gave 510 mg, 38%, of a solid. M.P.: 268°-2690° C. was heated to reflux for 8 hours The reaction mixture was cooled extracted twice with ether washed three times with saturated NaHCO3 once with H2O, once with brine, dried over MgSO4 concentrated to give an oil to stir at room temperature for 1 hour The mixture was concentrated poured into 200 ml of H2O washed twice with ether extracted twice with ethyl acetate washed once with H2O dried over MgSO4 concentrated

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

Procedure: A mixture of (1.0 g, 4.97 mmol, 1.0 eq) 4-[(3-amino-2-pyridinyl)amino]phenol in 25 ml of valeric anhydride was heated to reflux for 8 hours. The reaction mixture was cooled, poured into 150 ml of 0.5N HCl, stirred 10 minutes, and extracted twice with ether. The ether extracts were combined, washed three times with saturated NaHCO3, once with H2O, once with brine, dried over MgSO4, and concentrated to give an oil. The oil was taken up in 100 ml CH3 OH and treated with 60 ml of 2N NaOH and allowed to stir at room temperature for 1 hour. The mixture was concentrated, poured into 200 ml of H2O and washed twice with ether. The aqueous layer was neutralized, and extracted twice with ethyl acetate. The ethyl acetate extracts were combined, washed once with H2O, dried over MgSO4, and concentrated to give 0.7 g of a solid. Silica gel chromatography eluting with 10% CH3OH/CH2Cl2 gave 510 mg, 38%, of a solid. M.P.: 268°-2690° C. was heated to reflux for 8 hours The reaction mixture was cooled extracted twice with ether washed three times with saturated NaHCO3 once with H2O, once with brine, dried over MgSO4 concentrated to give an oil to stir at room temperature for 1 hour The mixture was concentrated poured into 200 ml of H2O washed twice with ether extracted twice with ethyl acetate washed once with H2O dried over MgSO4 concentrated

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

Procedure: By reacting each of the resulting products with acetic anhydride, propionic anhydride, n-butyric anhydride, valeric anhydride or caproic anhydride as discussed in Parts A and C of Preparation I, the corresponding 17 alpha-acetate, -propionate, -n-butyrate, valerate and caproate are preprepared. as discussed in Parts A and C of Preparation I

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

Procedure: The anhydride may be, but not limited to, acetic acid anhydride, propionic anhydride, butyric anhydride, pentanoic anhydride or hexanoic anhydride. Preferably, the anhydride is acetic acid anhydride. According to an embodiment, the esterification of 1,4-bunediol is performed with acetic acid anhydride to form CH3C(O)O—(CH2)4—OH.

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

Procedure: In a further process disclosed in EP-A 1 116 719, 5-nitro-2(3H)-benzofuranone is reacted in the presence of pentanoic acid and pentanoic anhydride to give 3-(1-hydroxypentylidene)-5-nitro-2(3H)-benzofuranone which reacts under acidic conditions to give 2-(n-butyl)-5-nitrobenzofuran. The disadvantage of this process is that 5-nitro-2(3H)-benzofuranone is used as precursor, which makes industrial application uneconomic.

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

Procedure: In a manner similar to Example 12, a mixture of 8-chloro-1-(hydroxymethyl)-6-phenyl-4H-s-triazolo[4,3-a][1,4]benzodiazepine and valeric anhydride were heated on the water bath to give 8-chloro-1-(hydroxymethyl)-6-phenyl-4H-s-triazolo[4,3-a][1,4]benzodiazepine valerate (ester).

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

Procedure: By following in principle the appropriate procedures of Example 4, Parts A and B or Example 5, but substituting other acyl anhydrides for acetic anhydride and caproic anhydride, such as propionic anhydride, butyric anhydride or valeric anhydride, the following compounds are obtained: