7#,K@bJ=!/ |[kkpx"S s5*_555+7555555Supporting Information Rhodium Complex-Catalyzed Addition of Isonitriles with Carbonyl Compounds: Catalytic Synthesis of Pyrroles Hikaru Takaya, Sachiko Kojima, and Shun-Ichi Murahashi* Department of Chemistry, Graduate School of Engineering Science, Osaka University 1-3 Machikaneyama, Toyonaka, Osaka 560-8531, Japan General Melting points were determined on Yanagimoto micro melting point apparatus. Infrared spectra was recorded on a Shimadzu FTIR-4100 spectrometer. 1H and 13C NMR spectra were obtained on a Varian UNITY-INOVA-500 (1H at 500 MHz, 13C at 125 MHz) spectromater and JEOL JNM-GSX-270 (1H at 270 MHz, 13C at 68.5 MHz) spectrometer. Analytical GLC evaluation of product mixtures were also performed on Shimadzu Model GC-17A flame ionization chromatography by using a 30 m x 0.25 mm glass capillary column (Silicone DB-1). Mass spectra and high-resolution mass spectra (HRMS) were obtained on a JEOL JMS-DX303HF mass spectrometer and a Shimadzu GCMS QP-5000 mass spectrometer with a chemical bounded glass capillary column (Silicone DB-1, 30 m x 0.25 mm). Elemental analysis were performed on a Perkin Elmer 2400II CHN elemental analysis. Purification by column chromatography was performed with Merck silica gel, 7734. Preparative TLC was performed on a glass plates coated with E. Merck silica gel 60 PF254 (Art. 7749). Rhodium-Catalyzed Reactions of Ethyl Isocyanoacetate (2) with Ketones. Preparation of ethyl cyclohexylideneformamidoacetate (3). A mixture of ethyl isocyanoacetate (2) (113 mg, 1.0 mmol), cyclohexanone (196.3 mg, 2.0 mmol), and Rh4(CO)12 (1) (5.6 mg, 0.0075 mmol) in dry toluene (0.5 mL) was stirring at 80C for 4 h under argon atmosphere in a Teflon-cocked test tube. After removal of the solvent, the crude product was purified by column chromatography (SiO2) to give (E)- and (Z)-mixture of ethyl cyclohexylideneformamidoacetate (3) as colorless solid (179.6 mg, 85%, E/Z = 66/34). mp 89.0-90.2 C; IR (KBr) 3283 (s), 2990 (s), 1725 (s, CO), 1661 (s, CO), 1505 (s), 1391 (s), 1307 (s), 1208 (s), 1101 (s) cm-1. MS (EI, 70eV) m/z(%) 211(9), 165(49), 137(19), 108(100), 93(9), 81(20), 67(19), 53(32), 41(77). HRMS Calcd for C11H17NO3: 211.1208, Found: 211.1210.  Ethyl (E)-cyclohexylideneformamidoacetate: 1H NMR (500 MHz, CDCl3) d 1.29 (t, J = 7.5 Hz, 3 H, -OCH2CH3), 1.65 (m, 6H, -CH2CH2CH2CH2CH2-), 2.25 (t, J = 7.1 Hz, 2H, -CH2CH2CH2CH2CH2-), 2.73 (t, J = 7.1 Hz, 2H, -CH2CH2CH2CH2CH2-), 4.23 (q, J = 7.5, 2H, -OCH2CH3), 7.19 (br, 1H, -NHCHO), 8.19 (br, 1H, -NHCHO); 13C NMR (125 MHz, CDCl3) d 14.1 (-OCH2CH3), 26.0 (-CH2CH2CH2CH2CH2-), 27.2 (-CH2CH2CH2CH2CH2-), 27.7 (-CH2CH2CH2CH2CH2-), 30.4 (-CH2CH2CH2CH2CH2-), 31.6 (-CH2CH2CH2CH2CH2-), 60.9 (-OCH2CH3), 117.0 (C=C(NHCHO)CO2Et), 151.4 (C=C(NHCHO)CO2Et), 159.9 (-NHCHO), 164.8 (-CO2Et). Ethyl (Z)-cyclohexylidene-formamidoacetate: 1H NMR (500 MHz, CDCl3) d 1.31 (t, J = 7.5 Hz, 3 H, -OCH2CH3), 1.60 (m, 6H, -CH2CH2CH2CH2CH2-), 2.38 (t, J = 7.1 Hz, 2H, -CH2CH2CH2CH2CH2-), 2.80 (t, J = 7.1 Hz, 2H, -CH2CH2CH2CH2CH2-), 4.25 (q, J = 7.5, 2H, -OCH2CH3), 6.96 (br, 1H, -NHCHO), 7.94 (br, J = 11.1 Hz, 1H, -NHCHO); 13C NMR (125 MHz, CDCl3) d 14.1 (-OCH2CH3), 25.9 (-CH2CH2CH2CH2CH2-), 27.9 (-CH2CH2CH2CH2CH2-), 28.1 (-CH2CH2CH2CH2CH2-), 30.7 (-CH2CH2CH2CH2CH2-), 31.6 (-CH2CH2CH2CH2CH2-), 61.1 (-OCH2CH3), 118.0 (C=C(NHCHO)CO2Et), 154.0 (C=C(NHCHO)CO2Et), 159.9 (-NHCHO), 165.1 (-CO2Et). Preparation of ethyl 2-formamido-3-phenylbutenoate. A mixture of ethyl isocyanoacetate (2) (113 mg, 1.0 mmol), acetophenone (240.3 mg, 2.0 mmol), and Rh4(CO)12 (1) (5.6 mg, 0.0075 mmol) in dry toluene (0.5 mL) was stirring at 80C for 4 h under argon in a Teflon-cocked test tube. After removal of the solvent, the crude product was purified by column chromatography (SiO2) to give (Z,E)- and (Z,Z)-mixture of ethyl 2-formamido-3-phenylbutenoate as colorless solid (177.3 mg, 76%, Z,E/Z,Z= 51/49). mp 84.0-84.9C; IR (KBr) 3317 (s), 3022 (s), 2899 (s), 1700 (s, CO), 1626 (s, CO), 1506 (s), 1489 (s), 1388 (s), 1327 (s), 1217 (s), 1134 (s), 1014 (s), 849(s), 766 (S), 744 (s), 706 (s) cm-1. MS (EI, 70eV) m/z(%) 233(34), 205(43), 187(57), 176(44), 159(20), 131(100), 115(15), 103(54), 91(11), 77(27), 69(9), 51(12), 43(7). Anal. Calcd for C13H15NO3: C, 66.94; H, 6.48; N, 6.00. Found: C, 66.74; H, 6.46; N, 5.87. HRMS Calcd for C13H15NO3: 233.1052, Found: 233.1075.  Ethyl (Z,E)-2-formamido-3-phenylbutenoate: 1H NMR (500 MHz, CDCl3) d 0.91 (t, J = 7.3 Hz, 3 H, -OCH2CH3), 2.07 (s, 3H, CH3(Ph)C=), 3.91 (t, J = 7.3 Hz, 2H, -OCH2CH3), 7.18 (m, -C6H5), 7.31 (m, -C6H5), 7.43 (br, 1H, -NHCHO), 8.28 (br, 1H, -NHCHO); 13C NMR (125 MHz, CDCl3) d 14.0 (-OCH2CH3), 23.1 (CH3(Ph)C=), 123.0 (=C(NHCHO)CO2Et), 127.8 (o-Ph), 128.3 (p-Ph), 128.8 (m-Ph), 141.7 (i-Ph), 143.2 (CH3(Ph)C=), 160.0 (-NHCHO), 165.8 (-CO2Et). Ethyl (Z,Z)-2-formamido-3-phenylbutenoate: 1H NMR (500 MHz, CDCl3) d 0.95 (t, J = 7.3 Hz, 3 H, -OCH2CH3), 2.21 (s, 3H, CH3(Ph)C=), 3.93 (t, J = 7.3 Hz, 2H, -OCH2CH3), 7.18 (m, -C6H5), 7.31 (m, -C6H5), 7.43 (br, 1H, -NHCHO), 8.23 (br, 1H, -NHCHO); 13C NMR (125 MHz, CDCl3) d 14.1 (-OCH2CH3), 23.2 (CH3(Ph)C=), 123.9 (=C(NHCHO)CO2Et), 127.6 (o-Ph), 128.6 (p-Ph), 129.0 (m-Ph), 141.7 (i-Ph), 143.2 (CH3(Ph)C=), 160.0 (-NHCHO), 165.1 (-CO2Et). Rhodium-Catalyzed Synthesis of Pyrroles from Ethyl Isocyanoacetate (2) with 1,3-Dicarbonyl Compounds Ethyl 3,5-dimethylpyrrole-2-carboxylate (4). A mixture of Rh4(CO)12 (1) (5.6 mg, 0.0075 mmol), ethyl isocyanoacetate (2) (113.1 mg, 1.0 mmol), acetylacetone (200.3 mg, 2.0 mmol) and dry toluene (0.5 mL) was placed in a 15 mL Teflon-cocked test tube equipped with a magnetic stirring bar. After stirring the mixture for 4 h under argon atmosphere at room temperature, the solvent was removed under reduced pressure. The resulting dark orange mixture was purified by column chromatography (SiO2, hexane/ethyl acetate = 10/1) to afford the pyrrole 4 as a colorless solid. (151.5 mg, 84%). When the reaction carried out by using 5.0176 g of 2, 6.0087g of 4 can be obtained (yield 81%): mp 123.5C; IR (KBr) 3397 (s), 1660 (s, CO), 1455 (s), 1327 (m), 1273 (s) cm-1; 1H NMR (270 MHz, CDCl3) d 1.34 (t, J = 7.1 Hz, 3 H, -OCH2CH3), 2.24 (s, 3H, 5C-CH3), 2.32 (s, 3H, 3C-CH3), 4.29 (q, J = 7.1, 2H, -OCH2CH3), 5.78 (m, 1H, 4C-H), 8.83 (br, 1H, NH); 13C NMR (67.9 MHz, CDCl3) d 12.7 (5C-CH3), 13.0 (-OCH2CH3), 14.5 (3C-CH3), 59.6 (-OCH2CH3), 111.3 (4C), 117.8 (2C), 129.0 (3C), 132.4 (5C), 161.8 (-CO2Et); MS (EI, 70eV) m/z(%) 167(90), 138(39), 121(100), 93(51), 66(65), 39(45), 27(47). Anal. Calcd for C9H13NO2: C, 64.65; H, 7.83; N, 8.38. Found: C, 64.53; H, 7.62; N, 8.09.  General Procedure for the Rh4(CO)12 (1)-Catalyzed Reaction of Isonitriles with 1,3-Dicarbonyl Compounds. A mixture of ethyl isocyanoacetate (2) (113 mg, 1.0 mmol), 1,3-dicarbonyl compounds (2.0 mmol), rhodium catalyst, Rh4(CO)12 (1) (5.6 mg, 0.0075 mmol), and dry toluene (0.5 mL) was stirring at 80C for 4 h under argon in a Teflon-cocked test tube. After removal of the solvent, the crude product was purified by column chromatography (SiO2) to give the corresponding pyrroles. The representative results are shown in Table 1.  Ethyl 3,4,5-trimethylpyrrole-2-carboxylate (5a). mp 129.0C; IR (KBr) 3296 (s), 1666 (s, C=O), 1442 (s), 1277 (s) cm-1; 1H NMR (270 MHz, CDCl3) d 1.34 (t, J = 7.1 Hz, 3 H, -OCH2CH3), 1.91 (s, 3H, 4C-CH3), 2.18 (s, 3H, 5C-CH3), 2.25 (s, 3H, 3C-CH3), 4.29 (q, J = 7.1, 2H, CH2), 8.85 (br, 1H, NH); 13C NMR (67.9 MHz, CDCl3) d 8.7 (4C-CH3), 10.6 (3C-CH3), 11.3 (5C-CH3), 14.5 (-OCH2CH3), 59.5 (-OCH2CH3), 111.6 (2C), 117.0 (4C), 127.4 (3C), 129.5 (5C), 161.9 (-CO2Et); MS (EI, 70eV) m/z(%) 181(100), 135(97), 106(60), 92(34), 79(37), 65(25), 53(31), 39(32), 27(49). Anal. Calcd for C10H15NO2: C, 66.27; H, 8.34; N, 7.73. Found: C, 66.23; H, 8.38; N, 7.73. Ethyl 3,5-dimethyl-4-(2-cyanoethyl)pyrrole-2-carboxylate (5b). mp 142.5C; IR (KBr) 3314 (s), 2982 (w), 2241 (w, CN), 1676 (s,CO), 1286 (m), 1095 (m) cm-1; 1H NMR (270 MHz, CDCl3) d 1.35 (t, J = 7.1, -OCH2CH3), 2.26 (s, 3H, 5C-CH3), 2.27 (s, 3H, 3C-CH3), 2.43 (t, J = 7.1, 2H, -CH2CH2CN), 2.75 (t, J = 7.1, 2H, -CH2CH2CN), 4.30 (q, J = 7.1, 2H, -OCH2CH3), 8.65 (br, 1H, NH); 13C NMR (67.9 MHz, CDCl3) d 10.5 (3C-CH3), 11.5 (5C-CH3), 14.6 (-OCH2CH3), 18.7 (-CH2CH2CN), 20.4 (-CH2CH2CN), 59.8 (-OCH2CH3), 117.5 (-CN), 118.1 (2C), 119.4 (4C), 126.6 (3C), 130.0 (5C), 161.5 (-CO2Et). HRMS Calcd for C12H16N2O2: 220.1212, Found: 220.1208. Ethyl 3-methyl-5-phenylpyrrole-2-carboxylate (6a) and ethyl 5-methyl-3-phenylpyrrole-2-carboxylate (6b). A mixture of Rh4(CO)12 (1) (5.6 mg, 0.0075 mmol), ethyl isocyanoacetate (2) (113 mg, 1.0 mmol), 1-benzoylacetone (324.4 mg, 2.0 mmol) and dry toluene (0.5 mL) was stirring at 80 C for 17 h in a Teflon-cocked test tube under argon atmosphere. After removal of the solvent under reduced pressure, the residue was purified by column chromatography (SiO2, hexane/AcOEt = 25/1) to give the pyrrole 6a and 6b as a colorless solid. (6a: 117.17 mg, 52%, 6b: 16.4 mg, 7.3%). The structure of 6a and 6b were unequivocally determined by difference NOE, NOESY experiment, and X-ray structural analysis. 6a: mp 115.0C; IR (KBr) 3270 (s), 2980 (s), 1660 (s, CO), 1456 (s), 1292 (s), 1271 (s) 773 (s) cm-1; 1H NMR (270 MHz, CDCl3) d 1.38 (t, J = 7.1 Hz, 3 H, -OCH2CH3), 2.38 (s, 3H, 3C-CH3), 4.35 (q, J = 7.1, 2H, -OCH2CH3), 6.38 (dd, J = 2.9, 0.7, 4C-H), 7.28 (m, 1H, p-C6H5), 7.39 (m, 2H, m-C6H5), 7.53 (m, 2H, o-C6H5), 9.12 (br, 1H, NH); 13C NMR (67.9 MHz, CDCl3) d 12.9 (3C-CH3), 14.6 (-OCH2CH3), 60.1 (-OCH2CH3), 110.2 (4C), 120.0 (2C), 124.6 (o-C6H5), 127.6 (p-C6H5), 129.0 (m-C6H5) 129.4 (5C), 131.4 (3C), 135.1 (i-C6H5), 161.8 (-CO2Et); MS (EI, 70eV) m/z(%) 229(75), 183(100), 154(44), 140(37), 128(42), 115(38), 77(40), 51(27). Anal. Calcd for C14H15NO2: C, 73.3; H, 6.59; N, 6.11. Found: C, 73.05; H, 6.69; N, 6.09. 6b: mp 124.3C; IR (KBr) 3300 (s), 3090 (w), 1660 (s, C=O), 1431 (s), 1289 (s), 767 (s) cm-1; 1H NMR (270 MHz, CDCl3) d 1.23 (t, J = 7.1 Hz, 3H, -OCH2CH3), 2.32 (s, 3H, 5C-CH3), 4.23 (q, J = 7.1, 2H, -OCH2CH3), 6.06 (dd, J = 2.9, 0.7, 4C-H), 7.23 (m, 3H, m,p-C6H5), 7.47 (m, 2H, o-C6H5), 8.9 (br, 1H, NH); 13C NMR (67.9 MHz, CDCl3) d 13.0 (5C-CH3), 14.2 (-OCH2CH3), 60.0 (-OCH2CH3), 111.1 (4C), 116.6 (2C), 126.8 (o-C6H5), 127.5 (p-C6H5), 129.5 (m-C6H5), 132.5 (3C), 133.0 (5C), 135.4 (i-C6H5), 161.1 (-CO2Et); MS (EI, 70eV) m/z(%) 229(100), 183(84), 154(20), 140(18), 128(21), 115(9), 77(7), 51(3). Anal. Calcd for C14H15NO2: C, 73.3; H, 6.59; N, 6.11. Found: C, 73.3; H, 6.85; N, 5.91. Ethyl 3-methyl-5-tert-butylpyrrole-2-carboxylate (7). mp 75.5C; IR (KBr) 3340 (s), 2961 (w), 1662 (s), 1496(m), 1365 (m), 1273 (s), 1103 (m) cm-1; 1H NMR (270 MHz, CDCl3) d 1.29 (s, 9 H, -C(CH3)3), 1.34 (t, J = 7.1 Hz, 3 H, -OCH2CH3), 2.3 (s, 3H, 3C-CH3), 4.3 (q, J = 7.1, 2H, -OCH2CH3), 5.8 (dd, 1 H, 4C-H), 8.55 (br, 1H, NH); 13C NMR (67.9 MHz, CDCl3) d 12.9 (3C-CH3), 14.6 (-OCH2CH3), 30.1(-C(CH3)3), 31.5 (-C(CH3)3), 59.7 (-OCH2CH3), 108.0 (4C), 117.6 (2C), 128.3 (3C), 146.1 (5C), 162.0 (-CO2Et); MS (EI, 70eV) m/z(%) 209(19), 183(48), 164(7), 148(100), 120(5), 106(4), 91(9), 77(16), 51(12). Anal. Calcd for C12H19NO2: C, 68.87; H, 9.15; N, 6.69. Found: C, 68.86; H, 9.39; N, 6.69. Diethyl 5-methylpyrrole-2,3-dicarboxylate (8). mp. 61.1C; IR (KBr) 3296 (br), 1724 (s), 1666 (s, C=O), 1275 (s) cm-1; 1H NMR (500 MHz, CDCl3) d 1.36 (t, J = 7.0 Hz, 3 H, -OCH2CH3), 1.37 (t, J = 7.0 Hz, 3 H, -OCH2CH3), 2.29 (s, 3H, 5C-CH3), 4.28 (q, J = 7.0, 2H, -OCH2CH3), 4.35 (q, J = 7.0, 2H, -OCH2CH3), 6.35 (dd, J = 0.8, 2.8, 1H, 4C-H), 9.80 (br, 1H, NH); 13C NMR (125 MHz, CDCl3) d 12.7 (5C-CH3), 14.2 (-OCH2CH3), 14.2 (-OCH2CH3), 60.5 (-OCH2CH3), 60.9 (-OCH2CH3), 111.6 (4C), 120.8 (3C), 121.0 (2C), 131.9 (5C), 160.6 (-CO2Et), 164.4 (-CO2Et); MS (EI, 70eV) m/z(%) 225(100), 180(56), 152(54), 134(53), 107(64), 78(12), 53(10), 44(9). Anal. Calcd for C11H15F3NO4: C, 58.7; H, 6.7; N, 6.2. Found: C, 58.75; H, 6.68; N, 6.2. The structure of 8 was unequivocally determined by difference NOE, NOESY experiment, and X-ray structural analysis. Ethyl 4-fluoro-3,5-dimethylpyrrole-2-carboxylate (9). mp. 139.0C; IR (KBr) 3277 (s), 1670 (s, CO), 1277 (s), 1099 (s) cm-1; 1H NMR (270 MHz, CDCl3) d 1.36 (t, J = 7.3 Hz, 3H, -OCH2CH3), 2.22 (d, J = 0.9 Hz, 3H, 5C-CH3), 2.24 (s, 3H, 2C-CH3), 4.31 (q, J = 7.3 Hz, 2H, -OCH2CH3), 8.75 (br, 1H, NH); 13C NMR (67.9 MHz, CDCl3) d 8.1 (3C-CH3), 9.2 (d, JF-C = 1.0 Hz, 5C-CH3), 14.5 (-OCH2CH3), 60.0 (-OCH2CH3), 113.4 (d, JF-C = 5.3 Hz, 2C), 113.9 (d, JF-C = 15.3 Hz, 3C), 116.2 (d, JF-C = 27.3 Hz, 5C), 148.3 (d, JF-C = 237.4 Hz, 4C), 161.9 (-CO2Et); MS (EI, 70eV) m/z(%) 185(73), 157(14), 139(100), 111(20), 84(19), 71(12), 57(20), 40(81). HRMS Calcd for C9H12FNO2: 185.0852, Found: 185.0837. Ethyl 5-tert-butyl-3-(1,1,2,2,3,3,3-heptafluoropropyl)pyrrole-2-carboxylate (10). mp 91.0C; IR (KBr) 3320 (s), 2951 (s), 1682 (s, CO), 1506 (s) 1441 (s), 1371 (s), 1278 (s), 1197 (s), 1105 (s), 1047 (s), 897 (s), 873 (s), 897 (s), 821 (s), 742 (s) cm-1; 1H NMR (500 MHz, CDCl3) d 1.32 (s, 9 H, -C(CH3)3), 1.34 (t, J = 7.5 Hz, 3 H, -OCH2CH3), 4.35 (q, J = 7.5, 2H, -OCH2CH3), 6.23 (d, J = 4.0, 1H, 4C-H), 9.42 (br, 1H, NH); 13C NMR (125 MHz, CDCl3) d 14.2 (-OCH2CH3), 30.9 (-C(CH3)3), 32.7 (-C(CH3)3), 61.9 (-OCH2CH3), 108.0 (q, J = 4.2, 4C), 113.2 (2C), 115.3 (t, J = 37.4 Hz, -CF2CF2CF3), 116.6 (t, J = 37.4 Hz, -CF2CF2CF3), 117.5 (m, -CF2CF2CF3), 119.8 (d, J = 34.3, 2C), 120.7 (m, 3C), 146.2 (5C), 160.2 (-CO2Et); MS (EI, 70eV) m/z(%) 363(29), 348(79), 302(100), 282(45), 262(24), 127(22), 106(16), 91(16), 77(17), 59(12), 41(57). Anal. Calcd for C14H16F7NO2: C, 46.29; H, 4.44; N, 3.86. Found: C, 45.97; H, 4.45; N, 3.74. Synthesis of octamethylporphyrin from ethyl 3,4,5-trimethylpyrrole-2-carboxylate (5a). Oxidation of ethyl 3,4,5-trimethylpyrrole-2-carboxylate (5a) with Pb(OAc)4 gave ethyl 5-acetoxymethyl-3,4-dimethylpyrrole-2-carboxylate (18) and subsequent hydrolysis of 18 readily affords the corresponding 5-hydroxymethyl-3,4-dimethyl-2-pyrrolecarboxylic acid (19). The pyrrole 19 can be readily converted to octamethylporphyrin. The detailed experimental procedures and spectroscopic data for each compounds are described below. Ethyl 5-acetoxymethyl-3,4-dimethylpyrrole-2-carboxylate (18). In a 20 mL of round-bottomed flask, ethyl 3,4,5-trimethylpyrrole-2-carboxylate (5a) (512.9 mg, 2.45 mmol) was placed and dissolved in acetic acid (10 mL). Lead tetraacetate (1.167 g, 22.8 mmol) was added to the acetic acid solution of 5a in one portion, and the mixture was stirring for 2 h. The color of mixture was turned to be red from yellow. After stirring for 3 h at room temperature, the mixture was poured into 20 mL of cold water, giving pink precipitate. The resulting product was filtered and washed with cold water to give ethyl 5-acetoxymethyl-3,4-dimethylpyrrole-2-carboxylate (18) in 58% yield. mp 117.2C; IR (KBr) 3300 (s), 1736 (m), 1672 (s, CO), 1286 (m), 1246 (m) cm-1; 1H NMR (500 MHz, CDCl3) d 1.35 (t, J = 7.0 Hz, 3H, -OCH2CH3), 2.01 (s, 3H, 3C-CH3), 2.07 (s, 3H, CH3CO2CH2-), 2.25 (s, 3H, 4C-CH3), 4.31 (q, J = 7.0 Hz, 2H, -OCH2CH3), 5.02 (s, 2H, CH3CO2CH2-), 8.93 (br, 1H, NH); 13C NMR (125 MHz, CDCl3) d 8.58 (3C-CH3), 10.3 4C-CH3), 14.5 (-OCH2CH3), 20.8 (CH3CO2CH2-), 57.0 (-OCH2CH3), 59.9 (CH3CO2CH2-), 119.2 (2C), 120.1 (4C), 126.6 (3C), 126.8 (5C), 161.5 (-CO2Et), 171.5 (CH3CO2CH2-); MS (EI, 70eV) m/z(%) 239(20), 180(62), 168(36), 150(44), 134(87), 123(12), 107(47), 77(48), 65(35), 53(35), 43(100). HRMS Calcd for C12H17NO4: 239.1158, Found: 239.1145. 5-Hydroxymethyl-3,4-dimethylpyrrole-2-carboxylic acid (19). In a 25 mL of round-bottomed flask, a mixture of ethyl 5-acetoxymethyl-3,4-dimethylpyrrole-2-carboxylate (18) (383.1 mg, 1.6 mmol), potassium hydroxide (924.4 mg, 16.5 mmol) in methanol (7.0 mL) was refluxed over night. The color of the mixture was turned to be dark blown from yellow. After removal of the solvent under reduced pressure, the crude product was dissolved in 2 mL of water, and extract with diethyl ether (50 mL x 6). Then, 2 M of HCl solution was added to the water layer until blown precipitate was appeared. The precipitate was filtered to afford crude 5-hydroxymethyl-3,4-dimethylpyrrole-2-carboxylic (19) acid as blown solid (42 %). The crude product was used for next step without further purification, because the resultant pyrrole is readily decomposed by column chromatography, distillation, and recrystallization. 1H NMR (270 MHz, CDCl3) d 1.97 (s, 3H, 3C-CH3), 2.28 (s, 3H, 4C-CH3), 3.37 (s, 2H, HOCH2-), 8.89 (br, 1H, NH). Octamethylporphyrin. A mixture of potassium ferricyanide(III) (14.7 mg, 0.045 mmol) and 0.2 mL of acetic acid was heated at 100C. Then, crude 5-hydroxymethyl-3,4-dimethylpyrrole-2-carboxylic acid (19) (126.4 mg, 0.747 mmol) was added to the mixture, and stirred for 1 h at 100 C. The resulting mixture was stirring at room temperature over night. After removal of acetic acid under reduced pressure, octamethylporphyrin was obtained as purple solid (31.5 mg, 40%). Recrystallization from nitrobenzene follwed by addition of n-hexsane/benzene (1/1) gave pure octamethylporphyrin (13.4 mg, 17%). IR (KBr) 3478, 1676, 1197 cm-1; 1H NMR (500 MHz, CF3CO2D) d 10.32 (br, 4 H, meso-H), 3.43 (br, 24 H, -CH3). HRMS: Calcd for C28H30N4: 422.2469, Found: 422.2477. X-ray structure data for ethyl 3-methyl-5-phenylpyrrole-2-carboxylate (6a): crystal from benzene/hexane, C42H45N3O6 (Mr = 687.83); crystal dimensions 0.80 x 0.80 x 0.50 mm3; triclinic; space group P1(#2); a = 13.457(6), b = 13.702(7), c = 11.375(4) , a = 90.87(4), b = 103.91(3), g = 66.71(4), V = 1862(1) 3, Z = 2, rcalcd. = 1.226 gcm-3. The data were collected at 23C on a Rigaku AFC7R diffractometer using Mo-Ka (l = 0.71069 ). m(Mo-Ka) = 0.82 cm-1, scan type w-2q, 2qmax = 55.0, no. 8911 total reflections of which were 8553 unique (Rint = 0.013), The structure was solved by direct methods (MULTAN88), and refined (SHELXSL-97) by full-matrix least squares on F2 (all data), R1 = 0.048 for the 5179 observed data (I > 2s(I)) and wR2 = 0.218 for all data, GOF(F2) = 1.43. X-ray structure data for diethyl 5-methylpyrrole-2,3-carboxylate (8): crystal from methylene dicholoride/diethyl ether, C11H15NO4 (Mr = 225.24); crystal dimensions 0.10 x 0.50 x 0.50 mm3; monoclinic; space group C2/c(#15); a = 29.670(3), b = 7.4112(3), c = 10.377(1) , b = 92.577(3), V = 2279.7(4) 3, Z = 8, rcalcd. = 1.312 gcm-3. The data were collected at -60C on a Rigaku RAXIS-RAPID imaging plate diffractometer using Mo-Ka (l = 0.71069 ). m(Mo-Ka) = 1.00 cm-1, 2qmax = 55.0, no. 9035 total reflections of which were 2576 unique (Rint = 0.034), The structure was solved by direct methods (SAPI91), and refined by full-matrix least squares on F2 (all data), R1 = 0.048 for the 2073 observed data (I > 3s(I)) and wR2 = 0.224 for all data, GOF(F2) = 1.08. xJfJfJf hh[CHMD*yGrphbjcount   [currentpoint 192837465 ! currentpoint  [" save/chemsave exch def %%BeginProcSet: chemdict30 24 11 % ChemDraw Laser Prep % Copyright 1985-1997, CambridgeSoft Corp., All Rights Reserved userdict/chemdict30 210 dict put chemdict30 begin/version 24 def/sv 11 def/b{bind def}bind def/L{load def}b/R{null def}b/d/def L/a/add L/al/aload L/as/astore L/at/atan L/cp/closepath L/cv/curveto L/cw/currentlinewidth L/cpt/currentpoint L/dv/div L/D/dup L/e/exch L/F/false L/f/fill L/fa/forall L/g/get L/gi/getinterval L/gr/grestore L/gs/gsave L/ie/ifelse 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C $ "C  # C 6&O %%$$$$count   mcurrentpoint 192837465 ! currentpoint  m" save/chemsave exch def %%BeginProcSet: chemdict30 24 13 % ChemDraw Laser Prep % Copyright 1985-1997, CambridgeSoft Corp., All Rights Reserved userdict/chemdict30 210 dict put chemdict30 begin/version 24 def/sv 13 def/b{bind def}bind def/L{load def}b/R{null def}b/d/def L/a/add L/al/aload L/as/astore L/at/atan L/cp/closepath L/cv/curveto L/cw/currentlinewidth L/cpt/currentpoint L/dv/div L/D/dup L/e/exch L/F/false L/f/fill L/fa/forall L/g/get L/gi/getinterval L/gr/grestore L/gs/gsave L/ie/ifelse L/ix/index L/l/lineto L/mt/matrix L/M/moveto L/m/mul L/n/neg L/np/newpath L/pb/pathbbox L/P/pop L/r/roll L/rl/rlineto L/rm/rmoveto L/ro/rotate L/rp/repeat L/ru/round L/sc/scale L/sl/setlinewidth L/sm/setmatrix L/st/stroke L/sp/strokepath L/sq/sqrt L/s/sub L/T/true L/tr/transform L/xl/translate L/xc/exec L/A R/N R/St R/X R/Y R/aL R/bL R/bS R/bd R/bs R/cX R/cY R/ch R/co R/fB R/fI R/fS R/fZ R/fl R/ft R/iX R/iY R/idx R/lh R/llx 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7 ix 192837465 eq and{7 -1 r P 6 -2 r o o xl 7 -1 r s e 7 -1 r s e 5 -1 r dv neg e 5 -1 r dv neg e sc neg e neg e xl}{xl P P}ie 1 1 S dv D sc CMT currentmatrix P lW sl 4.0 setmiterlimit np}b end %%EndProcSet Z52 40 12 20 50 chemdict30 begin/hS x/sf x/lW x/bW x/cW x/sh T d 230 108 1 1 SPn/origstk x 65535 65535 65535 sBg "&("&("#* "&9"5G "&9"A "A "3S "5Q "5R"A";>"4#"%"" "%"4 "%" " "4"5"":"4"&(#"7"4 #"B "Q # "N"4 "4"7"4# "B "Q#"N"40.0000 0.0000 0.0000 1.0000 sk gs 800 756 M 697 578 ed l ed st gr gs 800 756 M 1139 756 ed l ed st gr gs 835 695 M 1104 695 ed l ed st gr gs 1139 756 M 1227 908 ed l ed st gr gs 1412 1050 M 1648 1050 ed l ed st gr gs 1139 756 M 1309 462 ed l ed st gr gs 1292 431 M 1528 431 ed l ed st gr gs 1292 493 M 1528 493 ed l ed st gr gs 1665 1021 M 1777 1213 ed l ed st gr gs 1614 1050 M 1725 1243 ed l ed st gr gs 1648 1050 M 1750 874 ed l ed st gr gs 1309 462 M 1207 285 ed l ed st gr gs 1235 1177 M 1225 1195 ed l ed st gr gs 3270 1033 M 3440 736 ed l ed st gr gs 3440 736 M 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