propanoyl bromide

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: Exhaustive acylation of 9-amino and 9-acylaminodibenzo[b,d]pyrans effects peracylation to afford 1-acyloxy-9-diacylamino-hexahydro-dibenzo[b,d]pyrans. Such peracylation can be effected by reacting either a 9-amino or a 9-acylamino-hexahydro-dibenzo[b,d]pyran with an excess of an acylating agent, for example from about 2 to 10 molar excess, as well as carrying out the reaction at an elevated temperature of about 60° to about 150° C. The peracylation is carried out in the presence of a strong base such as sodium hydride. As an illustration of peracylation, a compound such as dl-cis-1-hydroxy-3-(2-hexenyl)-9-acetamido-6a,7,8,9,10,10a-hexahydro-6H-dibenzo[b,d]pyran can be reacted with about a 5 molar excess of propionyl bromide in the presence of sodium hydride at about 100° C. for about seventy-two hours to afford dl-cis-1-propionoxy-3-(2-hexenyl)-9-(N-propionyl)acetamido-6a,7,8,9,10,10a-hexahydro-6H-dibenzo[b,d]pyran. the reaction at an elevated temperature of about 60° to about 150° C

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

Procedure: Exhaustive acylation of 9-amino and 9-acylaminodibenzo[b,d]pyrans effects peracylation to afford 1-acyloxy-9-diacylamino-hexahydro-dibenzo[b,d]pyrans. Such peracylation can be effected by reacting either a 9-amino or a 9-acylamino-hexahydro-dibenzo[b,d]pyran with an excess of an acylating agent, for example from about 2 to 10 molar excess, as well as carrying out the reaction at an elevated temperature of about 60° to about 150° C. The peracylation is carried out in the presence of a strong base such as sodium hydride. As an illustration of peracylation, a compound such as dl-cis-1-hydroxy-3-(2-hexenyl)-9-acetamido-6a,7,8,9,10,10a-hexahydro-6H-dibenzo[b,d]pyran can be reacted with about a 5 molar excess of propionyl bromide in the presence of sodium hydride at about 100° C. for about seventy-two hours to afford dl-cis-1-propionoxy-3-(2-hexenyl)-9-(N-propionyl)acetamido-6a,7,8,9,10,10a-hexahydro-6H-dibenzo[b,d]pyran. the reaction at an elevated temperature of about 60° to about 150° C

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

Procedure: The acylation of 1-(5-amino-2-chlorophenyl)-4-(4-bromo-2-fluorobenzyl)-3-n-butyl-1H-pyrazole-5-carbonitrile (from Step G) with propionyl bromide in the presence of DMAP followed the procedure of Example 1, Step J. Flash chromatography of the crude product on silica gel (gradient elution with 5:1 to 3:1 hexane-EtOAc) afforded a 73% yield of the title compound as a tacky oil; homogeneous by TLC in 3:1 hexane-EtOAc; mass spectrum (FAB) m/e 517, 519 (M+1)+. 400 MHz 1H NMR (CDCl3) δ0.87 (t, J=7.3 Hz, 3H), 1.22 (t, J=7.6 Hz, 3H), 1.32 (m, 2H), 1.54 (m, 2H, partially obscured by H2O peak), 2.38 (q, J=7.6 Hz, 2H), 2.55 (t, J=7.8 Hz, 2H), 3.92 (s, 2H), 7.02 (dd, J≈8, 8.5 Hz, 1 H), 7.22-7.26 (m, 2H), 7.4-7.5 (m, 2H), 7.90 (d, J=2.2 Hz, 1H).

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

Procedure: The acylation of 1-(5-amino-2-chlorophenyl)-4-(4-bromo-2-fluorobenzyl)-3-n-butyl-1H-pyrazole-5-carbonitrile (from Step G) with propionyl bromide in the presence of DMAP followed the procedure of Example 1, Step J. Flash chromatography of the crude product on silica gel (gradient elution with 5:1 to 3:1 hexane-EtOAc) afforded a 73% yield of the title compound as a tacky oil; homogeneous by TLC in 3:1 hexane-EtOAc; mass spectrum (FAB) m/e 517, 519 (M+1)+. 400 MHz 1H NMR (CDCl3) δ0.87 (t, J=7.3 Hz, 3H), 1.22 (t, J=7.6 Hz, 3H), 1.32 (m, 2H), 1.54 (m, 2H, partially obscured by H2O peak), 2.38 (q, J=7.6 Hz, 2H), 2.55 (t, J=7.8 Hz, 2H), 3.92 (s, 2H), 7.02 (dd, J≈8, 8.5 Hz, 1 H), 7.22-7.26 (m, 2H), 7.4-7.5 (m, 2H), 7.90 (d, J=2.2 Hz, 1H).

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

Procedure: Exhaustive acylation of 9-amino and 9-acylaminodibenzo[b,d]pyrans effects peracylation to afford 1-acyloxy-9-diacylamino-hexahydro-dibenzo[b,d]pyrans. Such peracylation can be effected by reacting either a 9-amino or a 9-acylamino-hexahydro-dibenzo[b,d]pyran with an excess of an acylating agent, for example from about 2 to 10 molar excess, as well as carrying out the reaction at an elevated temperature of about 60° to about 150° C. The peracylation is carried out in the presence of a strong base such as sodium hydride. As an illustration of peracylation, a compound such as dl-cis-1-hydroxy-3-(2-hexenyl)-9-acetamido-6a,7,8,9,10,10a-hexahydro-6H-dibenzo[b,d]pyran can be reacted with about a 5 molar excess of propionyl bromide in the presence of sodium hydride at about 100° C. for about seventy-two hours to afford dl-cis-1-propionoxy-3-(2-hexenyl)-9-(N-propionyl)acetamido-6a,7,8,9,10,10a-hexahydro-6H-dibenzo[b,d]pyran. the reaction at an elevated temperature of about 60° to about 150° C

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

Procedure: The acylation of 1-(5-amino-2-chlorophenyl)-4-(4-bromo-2-fluorobenzyl)-3-n-butyl-1H-pyrazole-5-carbonitrile (from Step G) with propionyl bromide in the presence of DMAP followed the procedure of Example 1, Step J. Flash chromatography of the crude product on silica gel (gradient elution with 5:1 to 3:1 hexane-EtOAc) afforded a 73% yield of the title compound as a tacky oil; homogeneous by TLC in 3:1 hexane-EtOAc; mass spectrum (FAB) m/e 517, 519 (M+1)+. 400 MHz 1H NMR (CDCl3) δ0.87 (t, J=7.3 Hz, 3H), 1.22 (t, J=7.6 Hz, 3H), 1.32 (m, 2H), 1.54 (m, 2H, partially obscured by H2O peak), 2.38 (q, J=7.6 Hz, 2H), 2.55 (t, J=7.8 Hz, 2H), 3.92 (s, 2H), 7.02 (dd, J≈8, 8.5 Hz, 1 H), 7.22-7.26 (m, 2H), 7.4-7.5 (m, 2H), 7.90 (d, J=2.2 Hz, 1H).

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

Procedure: The title compound was prepared by reaction of 2-[5-amino-2-(trifluoromethyl)phenyl]-5-n-butyl-4-[[2'-(N-t-butylsulfamoyl)-3-fluorobiphenyl-4-yl]methyl]-2,4-dihydro-3H-1,2,4-triazol-3-one (from Step A) with propionyl bromide (3 equivalents) in the presence of DMAP (1.1 equiv) following the method of Example 69. Chromatographic purification of the crude product on silica gel (elution with 0.8% MeOH in CH2Cl2) afforded a nearly quantitative yield of off-white, stiff foam; homogeneous by TLC in 95:5 CH2Cl2 --MeOH; mass spectrum (FAB) m/e 682 (M+Li)+. Chromatographic purification of the crude product on silica gel (elution with 0.8% MeOH in CH2Cl2) afforded a nearly quantitative yield of off-white, stiff foam

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

Procedure: The title compound was synthesized by reaction of 2-[5-amino-2-(trifluoromethyl)phenyl]-5-n-butyl-4-[[2'-[N-(2-chlorobenzoyl)sulfamoyl]-3-fluorobiphenyl-4-yl]methyl]-2,4-dihydro-3H-1,2,4-triazol-3-one (from Step G) with propionyl bromide (3 equivalents) and DBU (1.1 equiv) according to the method of Example 69. The material was obtained in 60% yield as a pale yellow solid, mp 181°-183° C.; homogeneous by TLC in 9:1 CH2Cl2 -MeOH; mass spectrum (FAB) m/e 796 (M+K)+. The material was obtained in 60% yield as a pale yellow solid, mp 181°-183° C.