benzoyl benzoate

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:0.00; pressure:0.00; stir:

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

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

Procedure: Acetic anhydride, propanoic anhydride, benzoic anhydride, monochloroacetyl anhydride, dichloroacetyl anhydride and benzoyl chlorides are preferred acylation agents.

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

Procedure: To a solution of 50 mg (91.9 μmol) of 10-deacetylbaccatin III and 13 μL (1.5 eq.) of benzoic anhydride in 2.0 mL of freshly distilled tetrahydrofuran 100 μL of a solution of 5.8 mg of commercial ytterbium trifluoromethanesulfonate hydrate in 1.0 mL of tetrahydrofuran was added. The reaction mixture was stirred at room temperature for 48 hours. Usual workup and isolation of the product by means of preparative TLC (Silica 60, CH2Cl2/MeOH 10:1) afforded 11 mg unreacted 10-deacetylbaccatin III (22%) along with 29 mg of 10-benzoyl-10deacetylbaccatin III (62%), m.p. 154°-156° C. C36H40O11 calculated C 66.66% H 6.22% measured C 66.50% H 6.23%. 1H-NMR (300 MHz, CDCl3) δ (ppm)=1.18 (s, 3H), 1.25 (s, 3H), 1.69 (s, 3H), 1.80-1.93 (m, 1H), 2.09 (s, 3H), 2.16-2.23 (m, 2H), 2.29 (s, 3H), 2.53-2.61 (m, 1H), 3.95 (d, 1H, J=6.9), 4.17 (d, 1H, J=8.3), 4.32 (d, 1H, J=8.3), 4.55 (dd, 1H, J=6.6, 10.6), 4.91 (br t, 1H, J=7.9), 5.00 (d, 1H, J=9.2), 5.67 (d, 1H, J=6.9), 6.59 (s, 1H), 7.40-7.52 (m, 4H), 7.54-7.61 (m, 2H), 8.04-8.14 (m, 4H).

Conditions: temp:97.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The title compound is prepared from heating a mixture of ω-phenyl-6-hydroxy-2,3,4-trimethoxy-acetophenone (0.996 g, 3.3 mmol), benzoic anhydride (6 g, 13.3 mmol) and sodium benzoate (6.5 g, 22.5 mmol) at 180-190° C. for 6 hr according to the published procedure (Wu, E S C et al. J. Med. Chem. 1988, 32, 183-192). Similar to the preparation ω-phenylresacetophenone (Wu, E S C et al. J. Med. Chem. 1987, 30, 788-792), ω-phenyl-6-hydroxy-2,3,4-trimethoxy-acetophenone is, in turn, obtained from adding anhydrous zinc chloride to a solution of 3,4,5-trimethoxyphenol and benzyl cyanide in ethyl acetate followed by bubbling HCl into the reaction mixture at room temperature and then heating at 95-100° C. with water. from heating obtained by bubbling HCl into the reaction mixture at room temperature

Conditions: temp:97.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The title compound is prepared from heating a mixture of ω-phenyl-6-hydroxy-2,3,4-trimethoxy-acetophenone (0.996 g, 3.3 mmol), benzoic anhydride (6 g, 13.3 mmol) and sodium benzoate (6.5 g, 22.5 mmol) at 180-190° C. for 6 hr according to the published procedure (Wu, E S C et al. J. Med. Chem. 1988, 32, 183-192). Similar to the preparation ω-phenylresacetophenone (Wu, E S C et al. J. Med. Chem. 1987, 30, 788-792), ω-phenyl-6-hydroxy-2,3,4-trimethoxy-acetophenone is, in turn, obtained from adding anhydrous zinc chloride to a solution of 3,4,5-trimethoxyphenol and benzyl cyanide in ethyl acetate followed by bubbling HCl into the reaction mixture at room temperature and then heating at 95-100° C. with water. from heating obtained by bubbling HCl into the reaction mixture at room temperature

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

Procedure: To a suspension of cytidine (100 g, 0.411 mol) in DMF (2.06 L) is added benzoic anhydride (102.4 g, 0.452 mol). The mixture was stirred at room temperature for 20 h. The DMF was removed in vacuo and the residue was triturated with diethyl ether. The resulting solid was collected by suction filtration and washed with diethyl ether (2×200 mL). Further drying in vacuo at room temperature gave the N4 benzamide (140.6 g, 98.3%). A portion of this material (139.3 g, 0.401 mol) was dissolved in anhydrous pyridine (1.2 L) and was treated with 1,3-dichloro-1,1,3,3-tetraisopropyl-disiloxane (141.4 mL, 0.441 mol) at room temp. The solution was stirred at room temperature overnight. The mixture was concentrated to near dryness in vacuo and coevaporated with toluene (3×200 mL). The residue was treated with EtOAc (1.8 L) and washed with HCl (2×200 mL, 0.05 N), NaHCO3 (5%, 2×400 mL). The organic layer was washed, dried (Na2SO4), filtered, and evaporated to dryness. Compound 16-1 (Compound 4-1 from U.S. Pat. No. 7,429,572) (256.5 g, >100%) was isolated as a white foam and used without further purification. The DMF was removed in vacuo the residue was triturated with diethyl ether The resulting solid was collected by suction filtration washed with diethyl ether (2×200 mL) Further drying in vacuo at room temperature

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

Procedure: To a suspension of cytidine (100 g, 0.411 mol) in DMF (2.06 L) is added benzoic anhydride (102.4 g, 0.452 mol). The mixture was stirred at room temperature for 20 hours. The DMF was removed in vacuo and the residue was triturated with diethyl ether. The resulting solid was collected by suction filtration and washed with diethyl ether (2×200 mL). Further drying in vacuo at room temperature gave the N4 benzamide (140.6 g, 98.3%). A portion of this material (139.3 g, 0.401 mol) was dissolved in anhydrous pyridine (1.2 L) and was treated with 1,3-dichloro-1,1,3,3-tetraisopropyl-disiloxane (141.4 mL, 0.441 mol) at room temperature. The solution was stirred at room temperature overnight. The mixture was concentrated to near dryness in vacuo and coevaporated with toluene (3×200 mL). The residue was treated with EtOAc (1.8 L) and washed with HCl (2×200 mL, 0.05 N), NaHCO3 (5%, 2×400 mL). The organic layer was washed dried (Na2SO4), filtered, and evaporated to dryness. Compound 701 (256.5 g, >100%) was isolated as a white foam and used without further purification. The DMF was removed in vacuo the residue was triturated with diethyl ether The resulting solid was collected by suction filtration washed with diethyl ether (2×200 mL) Further drying in vacuo at room temperature