2-methyl-1H-pyrrole

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

Procedure: The titled compound was prepared from 2-methylpyrrole (J. Org. Chem. 1956, 21, 918.) in an analogous manner to that of 4-(pyrrol-1-ylmethyl)phenyl iodide (EP 488 602 A1).

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

Procedure: The titled compound was prepared from 2-methylpyrrole (J. Org. Chem. 1956, 21, 918.) in an analogous manner to that of 4-(pyrrol-1-ylmethyl)phenyl iodide (EP 488 602 A1).

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

Procedure: 2-Methyl-1H-pyrrole (Intermediate 31, 10 g, 0.123 mmol) in anhydrous diethyl ether (30 ml) was added dropwise over 1 h to a stirred solution of trichloroacetyl chloride (29 g, 0.16 mmol) in anhydrous Et2O (100 ml). The mixture was stirred for a further 1 h then K2CO3 (10 g/30 ml) was added slowly through a dropping funnel. The organic phase was dried over Na2SO4 and treated with decolorizing charcoal (3 g) for 30 min at room temperature. The resulting purple solution was concentrated and triturated with n-hexanes to give the title compound as a purple solid. (16.72 g). NMR (CDCl3): 2.36 (s, 3H), 6.04 (dd, 1H), 7.45 (dd, 1H), 10.344 (s, 1H). The organic phase was dried over Na2SO4 treated with decolorizing charcoal (3 g) for 30 min at room temperature The resulting purple solution was concentrated triturated with n-hexanes

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

Procedure: 2-Methyl-1H-pyrrole (Intermediate 31, 10 g, 0.123 mmol) in anhydrous diethyl ether (30 ml) was added dropwise over 1 h to a stirred solution of trichloroacetyl chloride (29 g, 0.16 mmol) in anhydrous Et2O (100 ml). The mixture was stirred for a further 1 h then K2CO3 (10 g/30 ml) was added slowly through a dropping funnel. The organic phase was dried over Na2SO4 and treated with decolorizing charcoal (3 g) for 30 min at room temperature. The resulting purple solution was concentrated and triturated with n-hexanes to give the title compound as a purple solid. (16.72 g). NMR (CDCl3): 2.36 (s, 3H), 6.04 (dd, 1H), 7.45 (dd, 1H), 10.344 (s, 1H). The organic phase was dried over Na2SO4 treated with decolorizing charcoal (3 g) for 30 min at room temperature The resulting purple solution was concentrated triturated with n-hexanes

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

Procedure: Then 200 mL of CH2Cl2 was added to the reaction mixture and diluted, then rinsed by NaOH aqueous solution. Solvent was removed using a rotary evaporator, and the dipyrromethane product was purified over a silica gel column to give 1-(2,3,4,5,6-pentafluoro-1,1,-(2-pyrryl)methane (6.16 g, 97%). The dipyrromethane (99 μL, 0.8 mmol) thus obtained and 2,3,4,5,6-pentafluoro-benzaldehyde (250 mg, 0.8 mmol) were dissolved in CH2Cl2 (20 mL) in a 50 mL round-bottom flask under nitrogen atmosphere and was added 20 μL of 2.5M trifluoroborane etherate (BF3OEt2). After 2 hours, DDQ (280 mg) was added and the solution was stirred for one day. The solvent was removed using a rotary evaporator and the expanded porphyrin products were separated by a column chromatography. As shown in FIG. 2, only the expended polyphyrins with even pyrrole subunits were formed and the separation process was facilitated significantly. Yields of the expanded porphyrins are shown in Table 2. diluted rinsed by NaOH aqueous solution Solvent was removed a rotary evaporator the dipyrromethane product was purified over a silica gel column to give 1-(2,3,4,5,6-pentafluoro-1,1

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

Procedure: The titled compound was prepared from 2-methylpyrrole (J. Org. Chem. 1956, 21, 918.) in an analogous manner to that of 4-(pyrrol-1-ylmethyl)phenyl iodide (EP 488 602 A1).

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

Procedure: The titled compound was prepared from 2-methylpyrrole (J. Org. Chem. 1956, 21, 918.) in an analogous manner to that of 4-(pyrrol-1-ylmethyl)phenyl iodide (EP 488 602 A1).

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

Procedure: Pyridine (8.80 g.) in dry methylene chloride (100 ml.) was added dropwise to a stirred solution of oxalyl chloride (13.96 g.) in dry methylene chloride (300 ml.) at -70° to give a white precipitate. The mixture was stirred at -70° for 15 minutes and then a solution of 2-methylpyrrole (8.10 g.) in dry methylene chloride (75 ml.) was added over 30 minutes. The mixture was stirred at -70° for a further 3 hours and then allowed to warm up to -20° giving a clear solution. Ethanol (25 ml.) was added and the solution was allowed to reach room temperature. The solution was washed with N hydrochloric acid (3×100 ml.) followed by water (3×100 ml.) and then dried over sodium sulphate. Evaporation of the solvent gave a dark oil which solidified on standing. The solid was dissolved in hot petroleum ether (B.P. 60°-80°) and some insoluble material was filtered off. The solid which crystallized from the cooled filtrate was chromatographed on silica gel. Elution with a mixture of chloroform and petroleum ether (B.P. 60°-80°) (3:1) gave a solid which was crystallized from petroleum ether (B.P. 60°-80°) to give 5-methyl-2-pyrrolylglyoxylic acid ethyl ester (11.4 g.), M.P. 72°-74°. Found: C, 59.72; H, 6.54; N, 7.47. C9H11NO3 requires: C, 59.66; H, 6.16; N, 7.77%. to give a white precipitate The mixture was stirred at -70° for a further 3 hours to warm up to -20° giving a clear solution to reach room temperature The solution was washed with N hydrochloric acid (3×100 ml.) dried over sodium sulphate Evaporation of the solvent gave a dark oil which some insoluble material was filtered off The solid which crystallized from the cooled filtrate was chromatographed on silica gel Elution with a mixture of chloroform and petroleum ether (B.P. 60°-80°) (3:1) gave a solid which was crystallized from petroleum ether (B.P. 60°-80°)

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

Procedure: The titled compound was prepared from 2-methylpyrrole (J. Org. Chem. 1956, 21, 918.) in an analogous manner to that of 4-(pyrrol-1-ylmethyl)phenyl iodide (EP 488 602 A1).

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

Procedure: The titled compound was prepared from 2-methylpyrrole (J. Org. Chem. 1956, 21, 918.) in an analogous manner to that of 4-(pyrrol-1-ylmethyl)phenyl iodide (EP 488 602 A1).

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

Procedure: 2-Methyl-1H-pyrrole (Intermediate 31, 10 g, 0.123 mmol) in anhydrous diethyl ether (30 ml) was added dropwise over 1 h to a stirred solution of trichloroacetyl chloride (29 g, 0.16 mmol) in anhydrous Et2O (100 ml). The mixture was stirred for a further 1 h then K2CO3 (10 g/30 ml) was added slowly through a dropping funnel. The organic phase was dried over Na2SO4 and treated with decolorizing charcoal (3 g) for 30 min at room temperature. The resulting purple solution was concentrated and triturated with n-hexanes to give the title compound as a purple solid. (16.72 g). NMR (CDCl3): 2.36 (s, 3H), 6.04 (dd, 1H), 7.45 (dd, 1H), 10.344 (s, 1H). The organic phase was dried over Na2SO4 treated with decolorizing charcoal (3 g) for 30 min at room temperature The resulting purple solution was concentrated triturated with n-hexanes