N,N-dimethylbenzamide

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:80.01; pressure:0.00; stir:

Procedure: In an argon filled glove box, a 5.0 mL wheaton microreactor was charged with [Ir(cod)(OMe)]2 (1.98 mg, 1.5 mol%), L1 ligand (2.1 mg, 3.5 mol%), B2pin2 (50.8 mg, 1.0 equiv.), KOtBu (1.0 mg, 4.5 mol%) and dry THF (1.0 mL). The reaction mixture was stirred for 2 minutes at room temperature. To this mixture, N,N-dimethylbenzamide (29.8 mg, 0.2 mmol) was added. The microreactor was capped with a teflon pressure cap and placed into pre-heated aluminum block at 80 oC. The reaction mixture was stirred for 12 h. After completion (judged by GC/MS), THF was removed under reduced pressure and chromatographic separation with silica gel (20% ethyl acetate in hexane) gave the meta-borylated product 4a (39.1 mg, 71%) as white solid.

Conditions: temp:25.01; pressure:0.00; stir:

Conditions: temp:25.01; 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: To a solution of N,N-dimethylbenzamide (48.0 g, 0.32 mol) in 1,2-dichloroethane (500 mL) was added oxalyl chloride (48.0 g, 0.38 mol). The reaction mixture was stirred for 24 hours at room temperature. To the reaction mixture was then added pyrrole (22.0 g, 0.33 mol). The reaction mixture was again stirred for 24 hours at room temperature. Aqueous sodium acetate (20%, 200 mL) was added to the reaction mixture and vigorous stirring was continued for 24 hours at room temperature. The organic layer was filtered through a silica gel column and concentrated under reduced pressure to yield 2-benzoylpyrrole which was used without further purification. Yield 43.0 g (80%), mp 76°-77° C. The reaction mixture was again stirred for 24 hours at room temperature vigorous stirring was continued for 24 hours at room temperature The organic layer was filtered through a silica gel column concentrated under reduced pressure

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

Procedure: To a solution of N,N-dimethylbenzamide (48.0 g, 0.32 mol) in 1,2-dichloroethane (500 mL) was added oxalyl chloride (48.0 g, 0.38 mol). The reaction mixture was stirred for 24 hours at room temperature. To the reaction mixture was then added pyrrole (22.0 g, 0.33 mol). The reaction mixture was again stirred for 24 hours at room temperature. Aqueous sodium acetate (20%, 200 mL) was added to the reaction mixture and vigorous stirring was continued for 24 hours at room temperature. The organic layer was filtered through a silica gel column and concentrated under reduced pressure to yield 2-benzoylpyrrole which was used without further purification. Yield 43.0 g (80%). The reaction mixture was again stirred for 24 hours at room temperature vigorous stirring was continued for 24 hours at room temperature The organic layer was filtered through a silica gel column concentrated under reduced pressure

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

Procedure: To a solution of N,N-dimethylbenzamide (48.0 g, 0.32 mol) in 1,2-dichloroethane (500 mL) was added oxalyl chloride (48.0 g, 0.38 mol). The reaction mixture was stirred for 24 hours at room temperature. To the reaction mixture was then added pyrrole (22.0 g, 0.33 mol). The reaction mixture was again stirred for 24 hours at room temperature. Aqueous sodium acetate (20%, 200 mL) was added to the reaction mixture and vigorous stirring was continued for 24 hours at room temperature. The organic layer was filtered through a silica gel column and concentrated under reduced pressure to yield 2-benzoylpyrrole which was used without further purification. Yield 43.0 g (80%). The reaction mixture was again stirred for 24 hours at room temperature vigorous stirring was continued for 24 hours at room temperature The organic layer was filtered through a silica gel column concentrated under reduced pressure

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

Procedure: Table 1 lists the addition products of some typical small molecule amides. In the case of N,N-dimethylformamide (DMF), the double bond content nearly completely disappeared, after stirring for 3 days in the presence of DTBP at 125° C. to give a mixture of products 2a and 2b. Abstraction of the carbonyl-bonded hydrogen atom results in the formation of the N,N-dimethyl amide 2b (13C NMR: 171 ppm; IR: 1655 cm−1; >N—CO—CH2—). However, abstraction of the hydrogen atom of the nitrogen-bonded methyl group also yields N-propyl-N-methyl formamide 2a (13C NMR: 161 ppm; IR: 1684 cm−1; >N—CO—H). Solid state 13C NMR shows an approximately 1:1 ratio of a mixture which is consistent with the results reported for the similar small molecules [ ] Friedman and Schecter y1961 ibid]. Similarly, addition of N,N-dimethylacetamide and N,N-dimethylbenzamide to (vinyl)polystyrene gave only N-propyl-N-methylacetamide 3a and N-propyl-N-methylbenzamide 4a, respectively. Cyclic N-methylamide N-methylpyrrolidione (NMP) also gave good yields of the possible addition products 7a-c although the exact proportions could not be determined.20 N-methylacetamide, acetamide and formamide showed none of the addition products 5a and 8a respectively. Substituted ureas such as N,N,N′,N′-tetramethylurea and DMPU were succesful in adding to the residual vinyl groups although in moderately low yeilds of 6a and 9a and 9b. The addition of an N-acetyl α-amino acids was also performed (22).

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

Procedure: Table 1 lists the addition products of some typical small molecule amides. In the case of N,N-dimethylformamide (DMF), the double bond content nearly completely disappeared, after stirring for 3 days in the presence of DTBP at 125° C. to give a mixture of products 2a and 2b. Abstraction of the carbonyl-bonded hydrogen atom results in the formation of the N,N-dimethyl amide 2b (13C NMR: 171 ppm; IR: 1655 cm−1; >N—CO—CH2—). However, abstraction of the hydrogen atom of the nitrogen-bonded methyl group also yields N-propyl-N-methyl formamide 2a (13C NMR: 161 ppm; IR: 1684 cm−1; >N—CO—H). Solid state 13C NMR shows an approximately 1:1 ratio of a mixture which is consistent with the results reported for the similar small molecules [ ] Friedman and Schecter y1961 ibid]. Similarly, addition of N,N-dimethylacetamide and N,N-dimethylbenzamide to (vinyl)polystyrene gave only N-propyl-N-methylacetamide 3a and N-propyl-N-methylbenzamide 4a, respectively. Cyclic N-methylamide N-methylpyrrolidione (NMP) also gave good yields of the possible addition products 7a-c although the exact proportions could not be determined.20 N-methylacetamide, acetamide and formamide showed none of the addition products 5a and 8a respectively. Substituted ureas such as N,N,N′,N′-tetramethylurea and DMPU were succesful in adding to the residual vinyl groups although in moderately low yeilds of 6a and 9a and 9b. The addition of an N-acetyl α-amino acids was also performed (22).