Embodiment
Embodiment 1: iron-5,10,15, synthetic (structural formula 1) of 20-four [(N-cyclohexyl)-2 '-pyridyl] porphyrin pentachloro-salt
10.7 gram 2-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, pure 5,10,15,20-four (2 '-pyridyl) porphyrin 1.74 grams.Productive rate 10%.
1 gram 5,10,15,20-four (2 '-pyridyl) porphyrin is dissolved in 10 milliliters of chlorocyclohexanes, refluxes 4 hours when 60 spend.After reaction is finished, the solution cool to room temperature.Under vacuum, steam excessive chlorocyclohexane and promptly get 5,10,15,20-four [(N-cyclohexyl)-2 '-pyridyl] porphyrin tetrachloro salt 1.8 grams, productive rate 99%.
1.8 restrain 5,10,15,20-four [(N-cyclohexyl)-2 '-pyridyl] porphyrin tetrachloro salt is dissolved in 100 ml waters, adds 0.33 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,10,15,20-four [(N-cyclohexyl)-2 '-pyridyl] porphyrin pentachloro-salt 1.79 grams, productive rate 95%.UV spectrum (aqueous solution, nanometer): 410,585.Mass spectrum: 201[(M-5Cl
-)
5+/ 5].Ultimate analysis: theoretical value: C, 65.01; H, 5.80; Cl, 14.99; Fe, 4.72; N, 9.48.Measured value: C, 64.7; H, 5.70; Cl, 15.5; Fe, 4.75; N, 9.35.
Embodiment 2: copper-5,10,15, synthetic (structural formula 2) of 20-four [(N-tetramethylene base)-3 '-pyridyl] porphyrin tetrachloro salt
10.7 gram 3-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, pure 5,10,15,20-four (3 '-pyridyl) porphyrin 2.6 grams.Productive rate 15%.
2 grams 5,10,15,20-four (3 '-pyridyl) porphyrin is dissolved in 30 milliliters of chloro tetramethylene, refluxes 4 hours when 60 spend.After reaction is finished, the solution cool to room temperature.Under vacuum, steam excess chlorine and promptly get 5,10,15,20-four [(N-tetramethylene base)-3 '-pyridyl] porphyrin tetrachloro salt 3.1 grams, productive rate 99% for tetramethylene.
3 grams 5,10,15,20-four [(N-tetramethylene base)-3 '-pyridyl] porphyrin tetrachloro salt is dissolved in 100 ml waters, adds 0.33 gram dichloride copper then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive dichloride copper, under vacuum, steam water and promptly get copper-5,10,15,20-four [(N-tetramethylene base)-3 '-pyridyl] porphyrin tetrachloro salt 3.03 grams, productive rate 95%.UV spectrum (aqueous solution, nanometer): 420,565.Mass spectrum: 214.5[(M-4Cl
-)
4+/4]。Ultimate analysis: theoretical value: C, 64.52; H, 5.03; Cl, 13.60; Cu, 6.10; N, 10.75.Measured value: C, 64.7; H, 5.13; Cl, 13.32, Cu, 6.05; N, 10.80
Embodiment 3: cobalt-5,10,15, synthetic (structural formula 3) of 20-four [(N-tetramethylene base)-4 '-pyridyl] porphyrin pentachloro-salt
10.7 gram 4-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, pure 5,10,15,20-four (4 '-pyridyl) porphyrin 4.3 grams, productive rate 25%.
4 grams 5,10,15,20-four (4 '-arsenic pyridine base) porphyrin is dissolved in 30 milliliters of chloro tetramethylene, refluxes 4 hours when 60 spend.After reaction is finished, the solution cool to room temperature.Under vacuum, steam excess chlorine and promptly get 5,10,15,20-four [(N-tetramethylene base)-4 '-pyridyl] porphyrin tetrachloro salt 6.1 grams, productive rate 99% for tetramethylene.
6 grams 5,10,15,20-four [(N-tetramethylene base)-4 '-pyridyl] porphyrin tetrachloro salt is dissolved in 100 ml waters, adds 1.2 gram cobalt dichlorides then.The gained mixture refluxed in air 12 hours.Add ammoniacal liquor and remove excessive cobalt dichloride, under vacuum, steam water and promptly get cobalt-5,10,15,20-four [(N-tetramethylene base)-4 '-pyridyl] porphyrin pentachloro-salt 6.05 grams, productive rate 92%.UV spectrum (aqueous solution, nanometer): 417,551.Mass spectrum: 179[(M-5Cl
-)
5+/ 5].Ultimate analysis: theoretical value: C, 62.67; H, 4.88; Cl, 16.52; Co, 5.49; N, 10.44.Measured value: C, 62.70; H, 4.85; Cl, 16.6; Co, 5.35; N, 10.50.
Embodiment 4: iron-5,10,15, synthetic (structural formula 4) of 20-four [(4 '-C-glucosyl group)-phenyl] porphyrin
28 gram (4 '-C-glucosyl group)-phenyl aldehydes and 6.7 restrain and are dissolved in 1 liter of propionic acid after pyrroles mix, and reflux was cooled to room temperature in 2 hours then in air.Steam propionic acid under vacuum, carry out silicagel column with the mixed solution of 80% chloroform and 20% methyl alcohol and separate, isolate 5,10,15,20-four [(4 '-C-glucosyl group)-phenyl] porphyrin 2.6 restrains.The gained porphyrin is dissolved in 50 ml methanol, adds 3 gram ferrous chloride.The gained mixture refluxed 2 hours under protection of nitrogen gas.Filter out excessive ferrous chloride, under vacuum, steam methyl alcohol and promptly get iron-5,10,15,20-four [(4 '-C-glucosyl group)-phenyl] porphyrin 2.4 grams.Mass spectrum: 1319[(M-Fe+3H)
+/ 1].Ultimate analysis: theoretical value: C, 63.35; H, 5.02; Fe, 4.09; N, 4.10; 0,23.44; Measured value: C, 62.73; H, 5.12; Fe, 4.1; N, 3.95; 0,24.1.
The synthetic of (4 '-C-glucosyl group)-phenyl aldehyde can be with reference to Pasetto, P. wait the people at J.Chem.Soc., Chem.Commun.2001, disclosed synthetic method in " Synthesis of hydrolytically stable porphyrinC-and S-glycoconjugates in high yields " among the 81-82.
Embodiment 5: manganese-5,10-two [(N-methyl)-4 '-pyridyl]-15, synthetic (structural formula 6) of 20-two (4 '-tolyl) porphyrin acetate
5.4 gram 4-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 5.3 gram phenyl aldehydes and 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5,10-two [4 '-pyridyl]-15,20-two (4 '-tolyl) porphyrin 0.54 gram.Productive rate 20%.
0.5 restrain 5,10-two [4 '-pyridyl]-15,20-two (4 '-tolyl) porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirs 24 hours.Under vacuum, steam excess iodine methane and promptly get 5,10-two [(N-methyl)-4 '-pyridyl]-15,20-two (4 '-tolyl) porphyrin two salt compounded of iodine 0.66 gram, productive rate 92%.
0.6 restrain 5,10-two [(N-methyl)-4 '-pyridyl]-15,20-two (4 '-tolyl) porphyrin two salt compounded of iodine are dissolved in 50 ml waters, add 0.4 gram manganese acetate then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive manganese acetate, under vacuum, steam water and promptly get manganese-5,10-two [(N-methyl)-4 '-pyridyl]-15,20-two (4 '-tolyl) porphyrin acetate 0.52 gram, productive rate 95%.UV spectrum (aqueous solution, nanometer): 435,605.Mass spectrum: 364[(M-2CH
3COO
-)
2+/ 2].Ultimate analysis: theoretical value: C, 71.00; H, 5.00; Mn, 6.50; N, 9.94; 0,7.57 measured value: C, 70.5; H, 4.95; Mn, 6.45; N, 9.84; 0,8.26.
Embodiment 6: iron-5,15-two [(N-methyl)-4 '-pyridyl]-10, synthetic (structural formula 7) of 20-two (4 '-tolyl) porphyrin three villaumites
5.4 gram 4-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 5.3 gram phenyl aldehydes and 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5,15-two [4 '-pyridyl]-10,20-two (4 '-tolyl) porphyrin 0.1 gram.Productive rate 3.5%.
0.1 restrain 5,15-two [4 '-pyridyl]-10,20-two (4 '-tolyl) porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirs 24 hours.Under vacuum, steam excess iodine methane and promptly get 5,10-two [(N-methyl)-4 '-pyridyl]-15,20-two (4 '-tolyl) porphyrin two salt compounded of iodine 0.13 gram, productive rate 90%.
0.1 restrain 5,15-two [(N-methyl)-4 '-pyridyl]-10,20-two (4 '-tolyl) porphyrin two salt compounded of iodine are dissolved in 50 ml waters, add 0.3 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,15-two [(N-methyl)-4 '-pyridyl]-10,20-two (4 '-tolyl) porphyrin three villaumites 0.08 gram, productive rate 90%.UV spectrum (aqueous solution, nanometer): 411,580.Mass spectrum: 364[(M-3Cl
-)
3+/ 3].Ultimate analysis: theoretical value: C, 66.17; H, 4.35; Cl, 12.74; Fe, 6.69; N, 10.06 measured values: C, 65.2; H, 4.10; Cl, 13.5; Fe, 7.7; N, 9.5.
Embodiment 7 :-4 '-pyridyl iron-5-[(N-methyl)]-10,15, synthetic (structural formula 8) of 20-three (4 '-tolyl) porphyrin two villaumites
5.4 gram 4-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 5.3 gram phenyl aldehydes and 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Products therefrom is the mixture of 6 kinds of different porphyrins.Carry out silicagel column with chloroform and separate, isolate pure 5-(4 '-pyridyl)-10,15,20-three (4 '-tolyl) porphyrin 0.82 gram.Productive rate 30%.
0.8 gram 5-(4 '-pyridyl)-10,15,20-three (4 '-tolyl) porphyrin is dissolved in 20 milliliters of methyl iodide, at room temperature stirs 24 hours.Under vacuum, steam excess iodine methane and promptly get the 5-[(N-methyl)-4 '-pyridyl]-10,15,20-three (4 '-tolyl) porphyrin one salt compounded of iodine 0.92 gram, productive rate 95%.
0.9-4 '-pyridyl gram 5-[(N-methyl)]-10,15,20-three (4 '-tolyl) porphyrin one salt compounded of iodine is dissolved in 50 ml waters, adds 2 then.5 gram iron trichlorides.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5-[(N-methyl)-4 '-pyridyl]-10,15,20-three (4 '-tolyl) porphyrin two villaumites 0.72 gram, productive rate 80%.UV spectrum (methyl alcohol, nanometer): 431,595.Mass spectrum 356[(M-2Cl
-)
2+/ 2].Ultimate analysis: theoretical value: C, 70.78; H, 4.55; Cl, 8.89; Fe, 7.00; N, 8.78 measured values: C, 69.8; H, 4.40; Cl, 9.35; Fe, 7.50; N, 8.95.
Embodiment 8: iron-5,10, synthetic (structural formula 9) of 15-three [(N-methyl)-4 '-pyridyl]-20-(4 '-tolyl) porphyrin tetrachloro salt
5.4 gram 4-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 5.3 gram phenyl aldehydes and 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Products therefrom is the mixture of 6 kinds of different porphyrins.Carry out silicagel column with the mixed solution of 90% chloroform and 10% methyl alcohol and separate, isolate pure 5,10,15-three (4 '-pyridyl)-20-(4 '-tolyl) porphyrin 0.52 gram.Productive rate 20%.
0.5 restrain 5,10,15-three (4 '-pyridyl)-20-(4 '-tolyl) porphyrin is dissolved in 20 milliliters of methyl iodide, at room temperature stirred 24 hours.Under vacuum, steam excess iodine methane and promptly get 5,10,15-three [(N-methyl)-4 '-pyridyl]-20-(4 '-tolyl) porphyrin three salt compounded of iodine 0.71 gram, productive rate 85%.
0.7 restrain 5,10,15-three [(N-methyl)-4 '-pyridyl]-20-(4 '-tolyl) porphyrin three salt compounded of iodine are dissolved in 50 ml waters, add 2.5 gram iron trichlorides then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,10,15-three [(N-methyl)-4 '-pyridyl]-20-(4 '-tolyl) porphyrin tetrachloro salt 0.47 gram, productive rate 85%.UV spectrum (aqueous solution, nanometer): 415,590.Mass spectrum: 182[(M-4Cl
-)
4+/ 4].Ultimate analysis: theoretical value: C, 61.95; H, 4.16; Cl, 16.25; Fe, 6.40; N, 11.24; Measured value: C, 62.2; H, 4.26; Cl, 16.39; Fe, 6.30; N, 10.85.
Embodiment 9: manganese-5,10-two [(N-methyl)-2 '-pyridyl]-15, synthetic (structural formula 10) of 20-two (2 '-tolyl) porphyrin acetate
5.4 gram 2-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 6.0 gram o-methyl-benzene formaldehyde and 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5,10-two [4 '-pyridyl]-15,20-two (2 '-tolyl) porphyrin 0.5 gram.Productive rate 18%.
0.5 restrain 5,10-two [2 '-pyridyl]-15,20-two (2 '-tolyl) porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirs 24 hours.Under vacuum, steam excess iodine methane and promptly get 5,10-two [(N-methyl)-2 '-pyridyl]-15,20-two (2 '-tolyl) porphyrin two salt compounded of iodine 0.64 gram, productive rate 90%.
0.6 restrain 5,10-two [(N-methyl)-2 '-pyridyl]-15,20-two (2 '-tolyl) porphyrin two salt compounded of iodine are dissolved in 50 ml waters, add 0.4 gram manganese acetate then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive manganese acetate, under vacuum, steam water and promptly get manganese-5,10-two [(N-methyl)-2 '-pyridyl]-15,20-two (2 '-tolyl) porphyrin acetate 0.52 gram, productive rate 95%.UV spectrum (aqueous solution, nanometer): 437,610.Mass spectrum: 364[(M-2CH
3COO
-)
2+/ 2].Ultimate analysis: theoretical value: C, 71.00; H, 5.00; Mn, 6.50; N, 9.94; 0,7.57 measured value: C, 70.3; H, 4.95; Mn, 6.65; N, 9.9; 0,8.2.
Embodiment 10: iron-5,15-two [(N-methyl)-2 '-pyridyl]-10, synthetic (structural formula 11) of 20-two (2 '-tolyl) porphyrin three villaumites
5.4 gram 2-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 6.0 gram o-methyl-benzene formaldehyde and 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5,15-two [2 '-pyridyl]-10,20-two (2 '-tolyl) porphyrin 0.2 gram.Productive rate 7%.
0.2 restrain 5,15-two [2 '-pyridyl]-10,20-two (2 '-tolyl) porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirs 24 hours.Under vacuum, steam excess iodine methane and promptly get 5,10-two [(N-methyl)-2 '-pyridyl]-15,20-two (2 '-tolyl) porphyrin two salt compounded of iodine 0.26 gram, productive rate 90%.
0.2 restrain 5,15-two [(N-methyl)-2 '-pyridyl]-10,20-two (2 '-tolyl) porphyrin two salt compounded of iodine are dissolved in 50 ml waters, add 0.3 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,15-two [(N-methyl)-2 '-pyridyl]-10,20-two (2 '-tolyl) porphyrin three villaumites 0.08 gram, productive rate 90%.UV spectrum (aqueous solution, nanometer): 411,580.Mass spectrum: 243[(M-3Cl
-)
3+/ 3].Ultimate analysis: theoretical value: C, 66.17; H, 4.35; Cl, 12.74; Fe, 6.69; N, 10.06 measured values: C, 65.2; H, 4.10; Cl, 13.5; Fe, 7.7; N, 9.5.
Embodiment 11 :-2 '-pyridyl iron-5-[(N-methyl)]-10,15, synthetic (structural formula 12) of 20-three (2 '-tolyl) porphyrin two villaumites
5.4 gram 2-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 6.0 gram o-methyl-benzene formaldehyde and 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Products therefrom is the mixture of 6 kinds of different porphyrins.Carry out silicagel column with chloroform and separate, isolate pure 5-(2 '-pyridyl)-10,15,20-three (2 '-tolyl) porphyrin 0.8 gram.Productive rate 29%.
0.8 gram 5-(2 '-pyridyl)-10,15,20-three (2 '-tolyl) porphyrin is dissolved in 20 milliliters of methyl iodide, at room temperature stirs 24 hours.Under vacuum, steam excess iodine methane and promptly get the 5-[(N-methyl)-2 '-pyridyl]-10,15,20-three (2 '-tolyl) porphyrin one salt compounded of iodine 0.9 gram, productive rate 93%.
0.9-2 '-pyridyl gram 5-[(N-methyl)]-10,15,20-three (2 '-tolyl) porphyrin one salt compounded of iodine is dissolved in 50 ml waters, adds 2 then.5 gram iron trichlorides.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5-[(N-methyl)-2 '-pyridyl]-10,15,20-three (2 '-tolyl) porphyrin two villaumites 0.7 gram, productive rate 77%.UV spectrum (methyl alcohol, nanometer): 430,596.Mass spectrum 356[(M-2Cl
-)
2+/ 2].Ultimate analysis: theoretical value: C, 70.78; H, 4.55; Cl, 8.89; Fe, 7.00; N, 8.78 measured values: C, 69.6; H, 4.60; Cl, 9.32; Fe, 7.53; N.8.95.
Embodiment 12: iron-5,10, synthetic (structural formula 13) of 15-three [(N-methyl)-2 '-pyridyl]-20-(2 '-tolyl) porphyrin tetrachloro salt
8.1 gram 2-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 3 then.0 gram o-methyl-benzene formaldehyde and 6.7 gram pyrroles.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5,10,15-three [(N-methyl)-2 '-pyridyl]-20-(2 '-tolyl) porphyrin 2.5 grams.With gained 2.5 grams 5,10,15-three [(N-methyl)-2 '-pyridyl]-20-(2 '-tolyl) porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirred 24 hours.Under vacuum, steam excess iodine methane and promptly get 5,10,15-three [(N-methyl)-2 '-pyridyl]-20-(2 '-tolyl) porphyrin three salt compounded of iodine 3.0 gram.3。0 gram 5,10,15-three [(N-methyl)-2 '-pyridyl]-20-(2 '-tolyl) porphyrin three salt compounded of iodine are dissolved in 100 ml waters, add 4 gram iron trichlorides then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,10,15-three [(N-methyl)-2 '-pyridyl]-20-(2 '-tolyl) porphyrin tetrachloro salt 2.1 gram, overall yield 9.6%。UV spectrum (aqueous solution, nanometer): 410,582.Mass spectrum: 182.5[(M-4Cl
-)
3+/4]。Ultimate analysis: theoretical value: C, 61.95; H, 4.16; Cl, 16.25; Fe, 6.40; N, 11.24 measured values: C, 62.5; H, 4.17; Cl, 16.03; Fe, 7.5; N, 9.8.
Embodiment 13: iron-5,10-two [(N-methyl)-3 '-pyridyl]-15, synthetic (structural formula 14) of 20-two (4 '-tolyl) porphyrin three villaumites
5.4 gram 3-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 6.0 gram p-tolyl aldehydes and 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5,10-two [3 '-pyridyl]-15,20-two (4 '-tolyl) porphyrin 0.4 gram.Productive rate 14%.
0.4 restrain 5,10-two [3 '-pyridyl]-15,20-two (4 '-tolyl) porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirs 24 hours.Under vacuum, steam excess iodine methane and promptly get 5,10-two [(N-methyl)-2 '-pyridyl]-15,20-two (4 '-tolyl) porphyrin two salt compounded of iodine 0.52 gram, productive rate 90%.
0.5 restrain 5,10-two [(N-methyl)-3 '-pyridyl]-15,20-two (4 '-tolyl) porphyrin two salt compounded of iodine are dissolved in 50 ml waters, add 0.3 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,10-two [(N-methyl)-3 '-pyridyl]-15,20-two (4 '-tolyl) porphyrin three villaumites 0.2 gram, productive rate 90%.UV spectrum (aqueous solution, nanometer): 409,582.Mass spectrum: 243[(M-3Cl
-)
3+/ 3].Ultimate analysis: theoretical value: C, 66.17; H, 4.35; Cl, 12.74; Fe, 6.69; N, 10.06 measured values: C, 65.3; H, 4.0; Cl, 13.7; Fe, 7.5; N, 9.5.
Embodiment 14: iron-5,15-two [(N-methyl)-3 '-pyridyl]-10, synthetic (structural formula 15) of 20-two (4 '-tolyl) porphyrin three villaumites
5.4 gram 3-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 6.0 gram p-tolyl aldehydes and 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5,15-two [3 '-pyridyl]-10,20-two (4 '-tolyl) porphyrin 0.25 gram.Productive rate 9%.
0.25 restrain 5,15-two [3 '-pyridyl]-10,20-two (4 '-tolyl) porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirs 24 hours.Under vacuum, steam excess iodine methane and promptly get 5,10-two [(N-methyl)-3 '-pyridyl]-15,20-two (4 '-tolyl) porphyrin two salt compounded of iodine 0.325 gram, productive rate 90%.
0.3 restrain 5,15-two [(N-methyl)-3 '-pyridyl]-10,20-two (4 '-tolyl) porphyrin two salt compounded of iodine are dissolved in 50 ml waters, add 0.3 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,15-two [(N-methyl)-3 '-pyridyl]-10,20-two (4 '-tolyl) porphyrin three villaumites 0.13 gram, productive rate 95%.UV spectrum (aqueous solution, nanometer): 413,585.Mass spectrum: 243[(M-3Cl
-)
3+/ 3].Ultimate analysis: theoretical value: C, 66.17; H, 4.35; Cl, 12.74; Fe, 6.69; N, 10.06 measured values: C, 65.7; H, 4.0; Cl, 13.3; Fe, 7.2; N, 9.6.
Embodiment 15 :-3 '-pyridyl iron-5-[(N-methyl)]-10,15, synthetic (structural formula 16) of 20-three (4 '-tolyl) porphyrin two villaumites
5.4 gram 3-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 6.0 gram p-tolyl aldehydes and 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Products therefrom is the mixture of 6 kinds of different porphyrins.Carry out silicagel column with chloroform and separate, isolate pure 5-(3 '-pyridyl)-10,15,20-three (4 '-tolyl) porphyrin 1.0 grams.Productive rate 36%.
1 gram 5-(3 '-pyridyl)-10,15,20-three (4 '-tolyl) porphyrin is dissolved in 20 milliliters of methyl iodide, at room temperature stirs 24 hours.Under vacuum, steam excess iodine methane and promptly get the 5-[(N-methyl)-3 '-pyridyl]-10,15,20-three (4 '-tolyl) porphyrin one salt compounded of iodine 1.2 grams, productive rate 94%.
1.2-3 '-pyridyl gram 5-[(N-methyl)]-10,15,20-three (4 '-tolyl) porphyrin one salt compounded of iodine is dissolved in 50 ml waters, adds 2 then.5 gram iron trichlorides.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5-[(N-methyl)-4 '-pyridyl]-10,15,20-three (4 '-tolyl) porphyrin two villaumites 1.1 grams, productive rate 90%.UV spectrum (methyl alcohol, nanometer): 427,594.Mass spectrum 356[(M-2Cl
-)
2+/ 2].Ultimate analysis: theoretical value: C, 70.78; H, 4.55; Cl, 8.89; Fe, 7.00; N, 8.78 measured values: C, 69.4; H, 4.80; Cl, 9.52; Fe, 7.45; N.8.83.
Embodiment 16: iron-5,10, synthetic (structural formula 17) of 15-three [(N-methyl)-3 '-pyridyl]-20-(4 '-tolyl) porphyrin tetrachloro salt
8.1 gram 3-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 3.0 gram p-tolyl aldehydes and 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5,10,15-three [(N-methyl)-3 '-pyridyl]-20-(4 '-tolyl) porphyrin 3 grams.With gained 3 grams 5,10,15-three [(N-methyl)-3 '-pyridyl]-20-(4 '-tolyl) porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirred 24 hours.Under vacuum, steam excess iodine methane and promptly get 5,10,15-three [(N-methyl)-3 '-pyridyl]-20-(4 '-tolyl) porphyrin three salt compounded of iodine 3.2 grams.3.2 restrain 5,10,15-three [(N-methyl)-3 '-pyridyl]-20-(4 '-tolyl) porphyrin three salt compounded of iodine are dissolved in 100 ml waters, add 5 gram iron trichlorides then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,10,15-three [(N-methyl)-3 '-pyridyl]-20-(4 '-tolyl) porphyrin tetrachloro salt 2.5 grams, overall yield 11.4%.UV spectrum (aqueous solution, nanometer): 412,583.Mass spectrum: 182.5[(M-4Cl
-)
3+/4]。Ultimate analysis: theoretical value: C, 61.95; H, 4.16; Cl, 16.25; Fe, 6.40; N, 11.24 measured values: C, 62.3; H, 4.10; Cl, 16.13; Fe, 7.7; N, 9.77.
Embodiment 17: iron-5,10,15,20-four [N-[(N-methyl)-2 '-pyridyl]-4 '-pyridyl] synthetic (structural formula 18) of porphyrin nine villaumites
1 gram 5,10,15,20-four (4 '-pyridyl) porphyrin is dissolved in 50 ml methanol, adds 10 gram 2-chloro-N-methyl-pyridine iodates then.At room temperature stirred 24 hours, and filtered out throw out.Throw out is water-soluble, add 0.5 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,10,15, and 20-four [the N-[(N-methyl)-2 '-pyridyl]-4 '-pyridyl] porphyrin nine villaumites 0.7 gram.UV spectrum (aqueous solution, nanometer): 408,575.Mass spectrum: 116[(M-9Cl
-)
9+/ 9].Ultimate analysis: theoretical value: C, 56.35; H, 3.84; Cl, 23.39; Fe, 4.09; N, 12.32; Measured value: C, 56.9; H, 3.66; Cl, 23.33, Fe, 3.75; N, 12.36.
Synthesizing of 2-chloro-N-methyl-pyridine iodate: 10 gram 2-chloro-pyridines are dissolved in 100 milliliters of methyl iodide stirring at room 24 hours.Steam methyl iodide then, promptly get product.
Embodiment 18: iron-5,10,15,20-four [N-[(N-methyl)-4 '-pyridyl]-4 '-pyridyl] synthetic (structural formula 19) of porphyrin nine villaumites
1 gram 5,10,15,20-four (4 '-pyridyl) porphyrin is dissolved in 50 ml methanol, adds 10 gram 4-chloro-N-methyl-pyridine iodates then.At room temperature stirred 24 hours, and filtered out throw out.Throw out is water-soluble, add 0.5 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,10,15, and 20-four [the N-[(N-methyl)-4 '-pyridyl]-4 '-pyridyl] porphyrin nine villaumites 1.1 grams.UV spectrum (aqueous solution, nanometer): 408,575.Mass spectrum: 116[(M-9Cl
-)
9+/ 9].Ultimate analysis: theoretical value: C, 56.35; H, 3.84; Cl, 23.39; Fe, 4.09; N, 12.32; Measured value: C, 57.1; H, 3.63; Cl, 23.16; Fe, 3.95; N, 12.16.
Synthesizing of 4-chloro-N-methyl-pyridine iodate: 10 gram 4-chloro-pyridines are dissolved in 100 milliliters of methyl iodide stirring at room 24 hours.Steam methyl iodide then, promptly get product.
Embodiment 19: iron-5,10,15, synthetic (structural formula 1) of 20-four [(N-diethylene glycol monomethyl ether base)-2 '-pyridyl] porphyrin pentachloro-salt
10.7 gram 2-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate 5,10,15,20-four (2-pyridyl) porphyrin 3.5 grams.3.5 grams 5,10,15,20-four (2-pyridyl) porphyrin is dissolved in 10 milliliters of chloro diethylene glycol monomethyl ethers, at room temperature stirs 24 hours.The gained reactant is dissolved in 20 ml waters, adds 1.5 gram iron trichlorides.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,10,15,20-four [(N-diethylene glycol monomethyl ether base)-2 '-pyridyl] porphyrin pentachloro-salt 5 grams.UV spectrum (aqueous solution, nanometer): 408,585.Mass spectrum: 217[(M-5Cl
-)
5+/ 5].Ultimate analysis: theoretical value: C, 57.09; H, 5.43; Cl, 14.04; Fe, 4.42; N, 8.88; 0,10.14.Measured value: C, 57.27; H, 5.35; Cl, 14.02; Fe, 4.34; N, 8.64; 0,10.38.
Synthesizing of chloro diethylene glycol monomethyl ether: 10 gram diethylene glycol monomethyl ethers are dissolved in 1 liter of chloroform, add phosphorus trichloride 20 grams, stirring at room 10 hours.Steam chloroform then. carry out the silicagel column separation with chloroform and promptly get product.
Embodiment 20: iron-5,10-two [(N-diethylene glycol monomethyl ether base)-2 '-pyridyl]-15, synthetic (structural formula 1) of 20-two [(N-cyclohexyl)-2 '-pyridyl] porphyrin pentachloro-salt
3 grams 5,10,15,20-four (2-pyridyl) porphyrin at room temperature stirred 24 hours in being dissolved in the mixture of 20 milliliters of chloro diethylene glycol monomethyl ethers and 20 milliliters of chlorocyclohexanes.Carry out silicagel column with methyl alcohol and separate, isolate 5,10-two [(N-diethylene glycol monomethyl ether base)-2 '-pyridyl]-15,20-two [(N-cyclohexyl)-2 '-pyridyl] porphyrin tetrachloro salt. products therefrom is dissolved in 20 ml waters, adds 1.5 gram iron trichlorides.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,10-two [(N-diethylene glycol monomethyl ether base)-2 '-pyridyl]-15,20-two [(N-cyclohexyl)-2 '-pyridyl] porphyrin pentachloro-salt 4.5 grams.UV spectrum (aqueous solution, nanometer): 410,587.Mass spectrum: 209[(M-5Cl
-)
5+/ 5].Ultimate analysis: theoretical value: C, 60.92; H, 5.61; Cl, 14.50; Fe, 4.57; N, 9.17; 0,5.24.Measured value: C, 60.77; H, 5.81; Cl, 14.30; Fe, 4.52; N, 9.14; 0,5.47.
Embodiment 21 :-2 '-pyridyl iron-5-[(N-pentamethylene base)]-10,15, synthetic (structural formula 1) of 20-three [(N-cyclohexyl)-2 '-pyridyl] porphyrin pentachloro-salt
3 grams 5,10,15,20-four (2-pyridyl) porphyrin at room temperature stirred 24 hours in being dissolved in the mixture of 10 milliliters of chlorocyclopentanes and 30 milliliters of chlorocyclohexanes.Carry out silicagel column with methyl alcohol and separate, isolate 5-[(N-pentamethylene base)-2 '-pyridyl]-10,15,20-three [(N-cyclohexyl)-2 '-pyridyl] porphyrin tetrachloro salt.Products therefrom is dissolved in 20 ml waters, adds 1.5 gram iron trichlorides.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5-[(N-pentamethylene base)-2 '-pyridyl]-10,15,20-three [(N-cyclohexyl)-2 '-pyridyl] porphyrin pentachloro-salt 4 grams.UV spectrum (aqueous solution, nanometer): 412,588.Mass spectrum: 198[(M-5Cl
-)
5+/ 5].Ultimate analysis: theoretical value: C, 64.76; H, 5.69; Cl, 15.17; Fe, 4.78; N, 9.59.Measured value: C, 64.96; H, 5.57; Cl, 15.39; Fe, 4.68; N, 9.39.
Embodiment 22 :-2 '-pyridyl iron-5-[(N-pentamethylene base)]-10,15-two [(N-cyclohexyl)-2 '-pyridyl]-20-[(N-diethylene glycol monomethyl ether base)-2 '-pyridyl] synthetic (structural formula 1) of porphyrin pentachloro-salt
3 the gram 5,10,15,20-four (2-pyridyl) porphyrin is dissolved in 10 milliliters of chlorocyclopentanes, in the mixture of 10 milliliters of chloro diethylene glycol monomethyl ethers and 20 milliliters of chlorocyclohexanes in, at room temperature stirred 24 hours.Carry out silicagel column with methyl alcohol and separate, isolate 5-[(N-pentamethylene base)-2 '-pyridyl]-10,15-two [(N-cyclohexyl)-2 '-pyridyl]-20-[(N-diethylene glycol monomethyl ether base)-2 '-pyridyl] porphyrin tetrachloro salt.Products therefrom is dissolved in 20 ml waters, adds 1.5 gram iron trichlorides.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5-[(N-pentamethylene base)-2 '-pyridyl]-10,15-two [(N-cyclohexyl)-2 '-pyridyl]-20-[(N-diethylene glycol monomethyl ether base)-2 '-pyridyl] porphyrin pentachloro-salt 4.8 grams.UV spectrum (aqueous solution, nanometer): 411,588.Mass spectrum: 202[(M-5Cl
-)
5+/ 5].Ultimate analysis: theoretical value: C, 62.66; H, 5.60; Cl, 14.92; Fe, 4.70; N, 9.43; 0,2.69.Measured value: C, 61.62; H, 6.10; Cl, 14.96; Fe, 5.21; N, 9.49; 0,2.62.
Embodiment 23: iron-5,10-two [(N-diethylene glycol monomethyl ether base)-3 '-pyridyl]-15, synthetic (structural formula 2) of 20-two [(N-cyclohexyl)-3 '-pyridyl] porphyrin pentachloro-salt
3 grams 5,10,15,20-four (3-pyridyl) porphyrin at room temperature stirred 24 hours in being dissolved in the mixture of 20 milliliters of chloro diethylene glycol monomethyl ethers and 20 milliliters of chlorocyclohexanes.Carry out silicagel column with methyl alcohol and separate, isolate 5,10-two [(N-diethylene glycol monomethyl ether base)-3 '-pyridyl]-15,20-two [(N-cyclohexyl)-3 '-pyridyl] porphyrin tetrachloro salt. products therefrom is dissolved in 20 ml waters, adds 1.5 gram iron trichlorides.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,10-two [(N-diethylene glycol monomethyl ether base)-3 '-pyridyl]-15,20-two [(N-cyclohexyl)-3 '-pyridyl] porphyrin pentachloro-salt 4.2 grams.UV spectrum (aqueous solution, nanometer): 410,587.Mass spectrum: 209[(M-5Cl
-)
5+/ 5].Ultimate analysis: theoretical value: C, 60.92; H, 5.61; Cl, 14.50; Fe, 4.57; N, 9.17; 0,5.24.Measured value: C, 61.17; H, 5.31; Cl, 14.80; Fe, 4.52; N, 8.74; 0.5.47.
Embodiment 24 :-3 '-pyridyl iron-5-[(N-pentamethylene base)]-10,15, synthetic (structural formula 2) of 20-three [(N-cyclohexyl)-3 '-pyridyl] porphyrin pentachloro-salt
3 grams 5,10,15,20-four (3-pyridyl) porphyrin at room temperature stirred 24 hours in being dissolved in the mixture of 10 milliliters of chlorocyclopentanes and 30 milliliters of chlorocyclohexanes.Carry out silicagel column with methyl alcohol and separate, isolate 5-[(N-pentamethylene base)-3 '-pyridyl]-10,15,20-three [(N-cyclohexyl)-3 '-pyridyl] porphyrin tetrachloro salt.Products therefrom is dissolved in 20 ml waters, adds 1.5 gram iron trichlorides.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5-[(N-pentamethylene base)-3 '-pyridyl]-10,15,20-three [(N-cyclohexyl)-3 '-pyridyl] porphyrin pentachloro-salt 5.2 grams.UV spectrum (aqueous solution, nanometer): 412,588.Mass spectrum: 198[(M-5Cl
-)
5+/ 5].Ultimate analysis: theoretical value: C, 64.76; H, 5.69; Cl, 15.17; Fe, 4.78; N, 9.59.Measured value: C, 65.36; H, 5.58; Cl, 14.99; Fe, 4.37; N, 9.69.
Embodiment 25 :-3 '-pyridyl iron-5-[(N-pentamethylene base)]-10,15-two [(N-cyclohexyl)-3 '-pyridyl]-20-[(N-diethylene glycol monomethyl ether base)-3 '-pyridyl] synthetic (structural formula 2) of porphyrin pentachloro-salt
3 the gram 5,10,15,20-four (3-pyridyl) porphyrin is dissolved in 10 milliliters of chlorocyclopentanes, in the mixture of 10 milliliters of chloro diethylene glycol monomethyl ethers and 20 milliliters of chlorocyclohexanes in, at room temperature stirred 24 hours.Carry out silicagel column with methyl alcohol and separate, isolate 5-[(N-pentamethylene base)-3 '-pyridyl]-10,15-two [(N-cyclohexyl)-3 '-pyridyl]-20-[(N-diethylene glycol monomethyl ether base)-3 '-pyridyl] porphyrin tetrachloro salt.Products therefrom is dissolved in 20 ml waters, adds 1.5 gram iron trichlorides.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5-[(N-pentamethylene base)-3 '-pyridyl]-10,15-two [(N-cyclohexyl)-3 '-pyridyl]-20-[(N-diethylene glycol monomethyl ether base)-3 '-pyridyl] porphyrin pentachloro-salt 4.8 grams.UV spectrum (aqueous solution, nanometer): 411,588.Mass spectrum: 202[(M-5Cl
-)
5+/ 5].Ultimate analysis: theoretical value: C, 62.66; H, 5.60; Cl, 14.92; Fe, 4.70; N, 9.43; 0,2.69.Measured value: C, 62.62; H, 6.60; Cl, 13.96; Fe, 5.41; N, 9.29; 0,2.12.
Embodiment 26: iron-5,10-two [(N-diethylene glycol monomethyl ether base)-4 '-pyridyl]-15, synthetic (structural formula 3) of 20-two [(N-cyclohexyl)-4 '-pyridyl] porphyrin pentachloro-salt
3 grams 5,10,15,20-four (4-pyridyl) porphyrin at room temperature stirred 24 hours in being dissolved in the mixture of 20 milliliters of chloro diethylene glycol monomethyl ethers and 20 milliliters of chlorocyclohexanes.Carry out silicagel column with methyl alcohol and separate, isolate 5,10-two [(N-diethylene glycol monomethyl ether base)-4 '-pyridyl]-15,20-two [(N-cyclohexyl)-4 '-pyridyl] porphyrin tetrachloro salt. products therefrom is dissolved in 20 ml waters, adds 1.5 gram iron trichlorides.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,10-two [(N-diethylene glycol monomethyl ether base)-4 '-pyridyl]-15,20-two [(N-cyclohexyl)-4 '-pyridyl] porphyrin pentachloro-salt 4.4 grams.UV spectrum (aqueous solution, nanometer): 410,587.Mass spectrum: 209[(M-5Cl
-)
5+/ 5].Ultimate analysis: theoretical value: C, 60.92; H, 5.61; Cl, 14.50; Fe, 4.57; N, 9.17; 0,5.24.Measured value: C, 61.2; H, 5.13; Cl, 14.72; Fe, 4.65; N, 8.70; 0,5.60.
Embodiment 27 :-4 '-pyridyl iron-5-[(N-pentamethylene base)]-10,15, synthetic (structural formula 3) of 20-three [(N-cyclohexyl)-4 '-pyridyl] porphyrin pentachloro-salt
3 grams 5,10,15,20-four (3-pyridyl) porphyrin at room temperature stirred 24 hours in being dissolved in the mixture of 10 milliliters of chlorocyclopentanes and 30 milliliters of chlorocyclohexanes.Carry out silicagel column with methyl alcohol and separate, isolate 5-[(N-pentamethylene base)-4 '-pyridyl]-10,15,20-three [(N-cyclohexyl)-4 '-pyridyl] porphyrin tetrachloro salt.Products therefrom is dissolved in 20 ml waters, adds 1.5 gram iron trichlorides.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5-[(N-pentamethylene base)-4 '-pyridyl]-10,15,20-three [(N-cyclohexyl)-4 '-pyridyl] porphyrin pentachloro-salt 5.5 grams.UV spectrum (aqueous solution, nanometer): 412,588.Mass spectrum: 198[(M-5Cl
-)
5+/ 5].Ultimate analysis: theoretical value: C, 64.76; H, 5.69; Cl, 15.17; Fe, 4.78; N, 9.59.Measured value: C, 65.22; H, 5.87; Cl, 14.92; Fe, 4.32; N, 9.67.
Embodiment 28 :-4 '-pyridyl iron-5-[(N-pentamethylene base)]-10,15-two [(N-cyclohexyl)-4 '-pyridyl]-20-[(N-diethylene glycol monomethyl ether base)-4 '-pyridyl] synthetic (structural formula 3) of porphyrin pentachloro-salt
3 the gram 5,10,15,20-four (4-pyridyl) porphyrin is dissolved in 10 milliliters of chlorocyclopentanes, in the mixture of 10 milliliters of chloro diethylene glycol monomethyl ethers and 20 milliliters of chlorocyclohexanes in, at room temperature stirred 24 hours.Carry out silicagel column with methyl alcohol and separate, isolate 5-[(N-pentamethylene base)-4 '-pyridyl]-10,15-two [(N-cyclohexyl)-4 '-pyridyl]-20-[(N-diethylene glycol monomethyl ether base)-4 '-pyridyl] porphyrin tetrachloro salt.Products therefrom is dissolved in 20 ml waters, adds 1.5 gram iron trichlorides.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5-[(N-pentamethylene base)-4 '-pyridyl]-10,15-two [(N-cyclohexyl)-4 '-pyridyl]-20-[(N-diethylene glycol monomethyl ether base)-4 '-pyridyl] porphyrin pentachloro-salt 4 grams.UV spectrum (aqueous solution, nanometer): 411,588.Mass spectrum: 202[(M-5Cl
-)
5+/ 5].Ultimate analysis: theoretical value: C, 62.66; H, 5.60; Cl, 14.92; Fe, 4.70; N, 9.43; 0,2.69.Measured value: C, 61.98; H, 6.75; Cl, 13.55; Fe, 5.43; N, 9.49; 0,2.8.
Embodiment 29: iron-5, synthetic (structural formula 6) of 10-two [(N-methyl)-4 '-pyridyl]-15-(4 '-tolyl)-20-(p-hydroxybenzene) porphyrin three villaumites
5.4 gram 4-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 3.0 gram p-tolyl aldehydes then, 3 gram p-Hydroxybenzaldehydes and 6.7 gram pyrroles.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5,10-two [4 '-pyridyl]-15-(4 '-tolyl)-20-(p-hydroxybenzene) porphyrin 0.15 gram.The gained porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirred 24 hours.Under vacuum, steam excess iodine methane. products therefrom is dissolved in 50 ml waters, adds 0.3 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,10-two [(N-methyl)-4 '-pyridyl]-15-(4 '-tolyl)-20-(p-hydroxybenzene) porphyrin three villaumites 0.1 gram.UV spectrum (aqueous solution, nanometer): 411,583.Mass spectrum: 243.3[(M-3Cl
-)
3+/ 3].Ultimate analysis: theoretical value: C, 64.57; H, 4.09; Cl, 12.71; Fe, 6.67; N, 10.04; 0,1.91; Measured value: C, 64.75; H, 4.04; Cl, 12.17; Fe, 6.76; N, 10.09; 0,1.91.
Embodiment 30: iron-5,10-two [(N-methyl)-4 '-pyridyl]-15, synthetic (structural formula 6) of 20-two (p-hydroxybenzene) porphyrin three villaumites
5.4 gram 4-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 6 gram p-Hydroxybenzaldehydes and 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5,10-two [4 '-pyridyl]-15,20-two (p-hydroxybenzene) porphyrin 0.25 gram.The gained porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirred 24 hours.Under vacuum, steam excess iodine methane. products therefrom is dissolved in 50 ml waters, adds 0.5 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,10-two [(N-methyl)-4 '-pyridyl]-15,20-two (p-hydroxybenzene) porphyrin three villaumites 0.22 gram.UV spectrum (aqueous solution, nanometer): 412,585.Mass spectrum: 244[(M-3Cl
-)
3+/ 3].Ultimate analysis: theoretical value: C, 62.99; H, 3.84; Cl, 12.68; Fe, 6.66; N, 10.02; 0,3.81; Measured value: C, 62.92; H, 3.71; Cl, 13.13; Fe, 6.27; N, 10.12; 0,3.85.
Embodiment 31: iron-5, synthetic (structural formula 7) of 15-two [(N-methyl)-4 '-pyridyl]-10-(4 '-tolyl)-20-(p-hydroxybenzene) porphyrin three villaumites
5.4 gram 4-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 3.0 gram p-tolyl aldehydes then, 3 gram p-Hydroxybenzaldehydes and 6.7 gram pyrroles.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5,15-two [4 '-pyridyl]-10-(4 '-tolyl)-20-(p-hydroxybenzene) porphyrin 0.17 gram.The gained porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirred 24 hours.Under vacuum, steam excess iodine methane. products therefrom is dissolved in 50 ml waters, adds 0.3 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,15-two [(N-methyl)-4 '-pyridyl]-10-(4 '-tolyl)-20-(p-hydroxybenzene) porphyrin three villaumites 0.2 gram.UV spectrum (aqueous solution, nanometer): 411,583.Mass spectrum: 243.3[(M-3Cl
-)
3+/ 3].Ultimate analysis: theoretical value: C, 64.57; H, 4.09; Cl, 12.71; Fe, 6.67; N, 10.04; 0,1.91; Measured value: C, 65.2; H, 4.11; Cl, 12.56; Fe, 6.34; N, 10.22; 0,1.57.
Embodiment 32: iron-5,15-two [(N-methyl)-4 '-pyridyl]-10, synthetic (structural formula 7) of 20-two (p-hydroxybenzene) porphyrin three villaumites
5.4 gram 4-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 6 gram p-Hydroxybenzaldehydes and 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5,15-two [4 '-pyridyl]-10,20-two (p-hydroxybenzene) porphyrin 0.22 gram.The gained porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirred 24 hours.Under vacuum, steam excess iodine methane. products therefrom is dissolved in 50 ml waters, adds 0.5 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,15-two [(N-methyl)-4 '-pyridyl]-10,20-two (p-hydroxybenzene) porphyrin three villaumites 0.27 gram.UV spectrum (aqueous solution, nanometer): 412,585.Mass spectrum: 244[(M-3Cl
-)
3+/ 3].Ultimate analysis: theoretical value: C, 62.99; H, 3.84; Cl, 12.68; Fe, 6.66; N, 10.02; 0,3.81; Measured value: C, 62.59; H, 3.88; Cl, 12.84; Fe, 6.66; N, 10.42; 0,3.61.
Embodiment 33 :-4 '-pyridyl iron-5-[(N-methyl)]-10-(4 '-tolyl)-15, synthetic (structural formula 8) of 20-two (p-hydroxybenzene) porphyrin two villaumites
2.7 gram 4-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 3.0 gram p-tolyl aldehydes then, 6 gram p-Hydroxybenzaldehydes and 6.7 gram pyrroles.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5-[4 '-pyridyl]-10-(4 '-tolyl)-15,20-two (p-hydroxybenzene) porphyrin 0.05 gram.The gained porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirred 24 hours.Under vacuum, steam excess iodine methane. products therefrom is dissolved in 50 ml waters, adds 0.3 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5-[(N-methyl)-4 '-pyridyl]-10-(4 '-tolyl)-15,20-two (p-hydroxybenzene) porphyrin two villaumites 0.04 gram.UV spectrum (aqueous solution, nanometer): 413,585.Mass spectrum: 365[(M-2Cl
-)
2+/ 2].Ultimate analysis: theoretical value: C, 67.43; H, 4.02; Cl, 8.85; Fe, 6.97; N, 8.74; 0,3.99; Measured value: C, 68.13; H, 3.92; Cl, 8.17; Fe, 6.54; N, 9.28; 0,3.96.
Embodiment 34 :-4 '-pyridyl iron-5-[(N-methyl)]-10-(p-hydroxybenzene)-15, synthetic (structural formula 8) of 20-two (4 '-tolyl) porphyrin two villaumites
2.7 gram 4-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 6 gram p-tolyl aldehydes then, 3 gram p-Hydroxybenzaldehydes and 6.7 gram pyrroles.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5-[4 '-pyridyl]-10-(p-hydroxybenzene)-15,20-two (4 '-tolyl) porphyrin 0.04 gram.The gained porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirred 24 hours.Under vacuum, steam excess iodine methane. products therefrom is dissolved in 50 ml waters, adds 0.5 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5-[(N-methyl)-4 '-pyridyl]-10-(p-hydroxybenzene)-15,20-two (4 '-tolyl) porphyrin two villaumites 0.02 gram.UV spectrum (aqueous solution, nanometer): 413,584.Mass spectrum: 364[(M-2Cl
-)
2+/ 2].Ultimate analysis: theoretical value: C, 69.10; H, 4.29; Cl, 8.87; Fe, 6.98; N, 8.76; 0,2.00; Measured value: C, 68.92; H, 4.39; Cl, 8.53; Fe, 6.95; N, 9.09; 0,2.12.
Embodiment 35: iron-5,10, synthetic (structural formula 9) of 15-three [(N-methyl)-4 '-pyridyl]-20-(p-hydroxybenzene) porphyrin tetrachloro salt
8.1 gram 4-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 3 gram p-Hydroxybenzaldehydes and 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5,10,15-three (4 '-pyridyl)-20-(p-hydroxybenzene) porphyrin 2.7 grams.The gained porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirred 24 hours.Under vacuum, steam excess iodine methane. products therefrom is dissolved in 50 ml waters, adds 1.3 gram iron trichlorides then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,10,15-three [(N-methyl)-4 '-pyridyl]-20-(p-hydroxybenzene) porphyrin tetrachloro salt 2.5 grams.UV spectrum (aqueous solution, nanometer): 412,585.Mass spectrum: 183[(M-4Cl
-)
4+/ 4].Ultimate analysis: theoretical value: C, 60.44; H, 3.92; Cl, 16.22; Fe, 6.39; N, 11.21; 0,1.83; Measured value: C, 59.81; H, 3.73; Cl, 17.28; Fe, 6.32; N, 10.95; 0,1.91.
Embodiment 36: iron-5, synthetic (structural formula 10) of 10-two [(N-methyl)-2 '-pyridyl]-15-(4 '-tolyl)-20-(p-hydroxybenzene) porphyrin three villaumites
5.4 gram 2-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 3.0 gram p-tolyl aldehydes then, 3 gram p-Hydroxybenzaldehydes and 6.7 gram pyrroles.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5,10-two [2 '-pyridyl]-15-(4 '-tolyl)-20-(p-hydroxybenzene) porphyrin 0.17 gram.The gained porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirred 24 hours.Under vacuum, steam excess iodine methane. products therefrom is dissolved in 50 ml waters, adds 0.3 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,10-two [(N-methyl)-2 '-pyridyl]-15-(4 '-tolyl)-20-(p-hydroxybenzene) porphyrin three villaumites 0.12 gram.UV spectrum (aqueous solution, nanometer): 410,583.Mass spectrum: 243.3[(M-3Cl
-)
3+/ 3].Ultimate analysis: theoretical value: C, 64.57; H, 4.09; Cl, 12.71; Fe, 6.67; N, 10.04; 0,1.91; Measured value: C, 64.05; H, 4.54; Cl, 12.31; Fe, 6.76; N, 10.09; 0,1.97.
Embodiment 37: iron-5,10-two [(N-methyl)-2 '-pyridyl]-15, synthetic (structural formula 10) of 20-two (p-hydroxybenzene) porphyrin three villaumites
5.4 gram 2-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 6 gram p-Hydroxybenzaldehydes and 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5,10-two [2 '-pyridyl]-15,20-two (p-hydroxybenzene) porphyrin 0.15 gram.The gained porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirred 24 hours.Under vacuum, steam excess iodine methane. products therefrom is dissolved in 50 ml waters, adds 0.5 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,10-two [(N-methyl)-2 '-pyridyl]-15,20-two (p-hydroxybenzene) porphyrin three villaumites 0.12 gram.UV spectrum (aqueous solution, nanometer): 411,585.Mass spectrum: 244[(M-3Cl
-)
3+/ 3].Ultimate analysis: theoretical value: C, 62.99; H, 3.84; Cl, 12.68; Fe, 6.66; N, 10.02; 0,3.81; Measured value: C, 63.1; H, 3.8; Cl, 13.21; Fe, 6.32; N, 10.24; 0,3.33.
Embodiment 38: iron-5, synthetic (structural formula 11) of 15-two [(N-methyl)-2 '-pyridyl]-10-(2 '-tolyl)-20-(p-hydroxybenzene) porphyrin three villaumites
5.4 gram 2-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 3.0 gram p-tolyl aldehydes then, 3 gram p-Hydroxybenzaldehydes and 6.7 gram pyrroles.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5,15-two [2 '-pyridyl]-10-(4 '-tolyl)-20-(p-hydroxybenzene) porphyrin 0.11 gram.The gained porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirred 24 hours.Under vacuum, steam excess iodine methane. products therefrom is dissolved in 50 ml waters, adds 0.3 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,15-two [(N-methyl)-2 '-pyridyl]-10-(4 '-tolyl)-20-(p-hydroxybenzene) porphyrin three villaumites 0.23 gram.UV spectrum (aqueous solution, nanometer): 410.5,583.Mass spectrum: 243.3[(M-3Cl
-)
3+/ 3].Ultimate analysis: theoretical value: C, 64.57; H, 4.09; Cl, 12.71; Fe, 6.67; N, 10.04; 0,1.91; Measured value: C, 65.11; H, 4.21; Cl, 12.43; Fe, 6.21; N, 10.44; 0,1.60.
Embodiment 39: iron-5,15-two [(N-methyl)-2 '-pyridyl]-10, synthetic (structural formula 11) of 20-two (p-hydroxybenzene) porphyrin three villaumites
5.4 gram 2-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 6 gram p-Hydroxybenzaldehydes and 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5,15-two [2 '-pyridyl]-10,20-two (p-hydroxybenzene) porphyrin 0.27 gram.The gained porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirred 24 hours.Under vacuum, steam excess iodine methane. products therefrom is dissolved in 50 ml waters, adds 0.5 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,15-two [(N-methyl)-2 '-pyridyl]-10,20-two (p-hydroxybenzene) porphyrin three villaumites 0.11 gram.UV spectrum (aqueous solution, nanometer): 411,587.Mass spectrum: 244[(M-3Cl
-)
3+/ 3].Ultimate analysis: theoretical value: C, 62.99; H, 3.84; Cl, 12.68; Fe, 6.66; N, 10.02; 0,3.81; Measured value: C, 62.95; H, 3.88; Cl, 12.48; Fe, 6.66; N, 10.24; 0,3.16.
Embodiment 40 :-2 '-pyridyl iron-5-[(N-methyl)]-10-(4 '-tolyl)-15, synthetic (structural formula 12) of 20-two (p-hydroxybenzene) porphyrin two villaumites
2.7 gram 2-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 3.0 gram p-tolyl aldehydes then, 6 gram p-Hydroxybenzaldehydes and 6.7 gram pyrroles.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5-[2 '-pyridyl]-10-(4 '-tolyl)-15,20-two (p-hydroxybenzene) porphyrin 0.04 gram.The gained porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirred 24 hours.Under vacuum, steam excess iodine methane. products therefrom is dissolved in 50 ml waters, adds 0.3 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5-[(N-methyl)-2 '-pyridyl]-10-(4 '-tolyl)-15,20-two (p-hydroxybenzene) porphyrin two villaumites 0.022 gram.UV spectrum (aqueous solution, nanometer): 413,585.Mass spectrum: 365[(M-2Cl
-)
2+/ 2].
Embodiment 41 :-2 '-pyridyl iron-5-[(N-methyl)]-10-(p-hydroxybenzene)-15, synthetic (structural formula 12) of 20-two (4 '-tolyl) porphyrin two villaumites
2.7 gram 2-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 6 gram p-tolyl aldehydes then, 3 gram p-Hydroxybenzaldehydes and 6.7 gram pyrroles.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5-[2 '-pyridyl]-10-(p-hydroxybenzene)-15,20-two (4 '-tolyl) porphyrin 0.045 gram.The gained porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirred 24 hours.Under vacuum, steam excess iodine methane. products therefrom is dissolved in 50 ml waters, adds 0.5 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5-[(N-methyl)-2 '-pyridyl]-10-(p-hydroxybenzene)-15,20-two (4 '-tolyl) porphyrin two villaumites 0.03 gram.UV spectrum (aqueous solution, nanometer): 411,586.Mass spectrum: 364[(M-2Cl
-)
2+/ 2].
Embodiment 42: iron-5,10, synthetic (structural formula 13) of 15-three [(N-methyl)-2 '-pyridyl]-20-(p-hydroxybenzene) porphyrin tetrachloro salt
8.1 gram 2-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 3 gram p-Hydroxybenzaldehydes and 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5,10,15-three (2 '-pyridyl)-20-(p-hydroxybenzene) porphyrin 3 grams.The gained porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirred 24 hours.Under vacuum, steam excess iodine methane. products therefrom is dissolved in 50 ml waters, adds 1.3 gram iron trichlorides then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,10,15-three [(N-methyl)-2 '-pyridyl]-20-(p-hydroxybenzene) porphyrin tetrachloro salt 2.8 grams.UV spectrum (aqueous solution, nanometer): 409,585.Mass spectrum: 183[(M-4Cl
-)
4+/ 4].
Embodiment 43: iron-5, synthetic (structural formula 14) of 10-two [(N-methyl)-3 '-pyridyl]-15-(4 '-tolyl)-20-(p-hydroxybenzene) porphyrin three villaumites
5.4 gram 3-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 3.0 gram p-tolyl aldehydes then, 3 gram p-Hydroxybenzaldehydes and 6.7 gram pyrroles.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5,10-two [3 '-pyridyl]-15-(4 '-tolyl)-20-(p-hydroxybenzene) porphyrin 0.18 gram.The gained porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirred 24 hours.Under vacuum, steam excess iodine methane. products therefrom is dissolved in 50 ml waters, adds 0.3 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,10-two [(N-methyl)-3 '-pyridyl]-15-(4 '-tolyl)-20-(p-hydroxybenzene) porphyrin three villaumites 0.15 gram.UV spectrum (aqueous solution, nanometer): 411,585.Mass spectrum: 243.3[(M-3Cl
-)
3+/ 3].
Embodiment 44: iron-5,10-two [(N-methyl)-3 '-pyridyl]-15, synthetic (structural formula 14) of 20-two (p-hydroxybenzene) porphyrin three villaumites
5.4 gram 3-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 6 gram p-Hydroxybenzaldehydes and 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5,10-two [3 '-pyridyl]-15,20-two (p-hydroxybenzene) porphyrin 0.15 gram.The gained porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirred 24 hours.Under vacuum, steam excess iodine methane. products therefrom is dissolved in 50 ml waters, adds 0.5 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,10-two [(N-methyl)-3 '-pyridyl]-15,20-two (p-hydroxybenzene) porphyrin three villaumites 0.14 gram.UV spectrum (aqueous solution, nanometer): 411,585.Mass spectrum: 244[(M-3Cl
-)
3+/ 3].
Embodiment 45: iron-5, synthetic (structural formula 15) of 15-two [(N-methyl)-3 '-pyridyl]-10-(2 '-tolyl)-20-(p-hydroxybenzene) porphyrin three villaumites
5.4 gram 3-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 3.0 gram p-tolyl aldehydes then, 3 gram p-Hydroxybenzaldehydes and 6.7 gram pyrroles.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5,15-two [3 '-pyridyl]-10-(4 '-tolyl)-20-(p-hydroxybenzene) porphyrin 0.17 gram.The gained porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirred 24 hours.Under vacuum, steam excess iodine methane. products therefrom is dissolved in 50 ml waters, adds 0.3 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,15-two [(N-methyl)-3 '-pyridyl]-10-(4 '-tolyl)-20-(p-hydroxybenzene) porphyrin three villaumites 0.27 gram.UV spectrum (aqueous solution, nanometer): 411,583.Mass spectrum: 243.3[(M-3Cl
-)
3+/ 3].
Embodiment 46: iron-5,15-two [(N-methyl)-3 '-pyridyl]-10, synthetic (structural formula 15) of 20-two (p-hydroxybenzene) porphyrin three villaumites
5.4 gram 3-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 6 gram p-Hydroxybenzaldehydes and 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5,15-two [3 '-pyridyl]-10,20-two (p-hydroxybenzene) porphyrin 0.35 gram.The gained porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirred 24 hours.Under vacuum, steam excess iodine methane. products therefrom is dissolved in 50 ml waters, adds 0.5 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,15-two [(N-methyl)-3 '-pyridyl]-10,20-two (p-hydroxybenzene) porphyrin three villaumites 0.16 gram.UV spectrum (aqueous solution, nanometer): 411,585.Mass spectrum: 244[(M-3Cl
-)
3+/ 3].
Embodiment 47 :-3 '-pyridyl iron-5-[(N-methyl)]-10-(4 '-tolyl)-15, synthetic (structural formula 16) of 20-two (p-hydroxybenzene) porphyrin two villaumites
2.7 gram 3-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 3.0 gram p-tolyl aldehydes then, 6 gram p-Hydroxybenzaldehydes and 6.7 gram pyrroles.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5-[3 '-pyridyl]-10-(4 '-tolyl)-15,20-two (p-hydroxybenzene) porphyrin 0.034 gram.The gained porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirred 24 hours.Under vacuum, steam excess iodine methane. products therefrom is dissolved in 50 ml waters, adds 0.3 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5-[(N-methyl)-3 '-pyridyl]-10-(4 '-tolyl)-15,20-two (p-hydroxybenzene) porphyrin two villaumites 0.032 gram.UV spectrum (aqueous solution, nanometer): 411,585.Mass spectrum: 365[(M-2Cl
-)
2+/ 2].
Embodiment 48 :-3 '-pyridyl iron-5-[(N-methyl)]-10-(p-hydroxybenzene)-15, synthetic (structural formula 16) of 20-two (4 '-tolyl) porphyrin two villaumites
2.7 gram 3-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 6 gram p-tolyl aldehydes then, 3 gram p-Hydroxybenzaldehydes and 6.7 gram pyrroles.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5-[3 '-pyridyl]-10-(p-hydroxybenzene)-15,20-two (4 '-tolyl) 0.04 gram.The gained porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirred 24 hours.Under vacuum, steam excess iodine methane. products therefrom is dissolved in 50 ml waters, adds 0.5 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5-[(N-methyl)-3 '-pyridyl]-10-(p-hydroxybenzene)-15,20-two (4 '-tolyl) porphyrin two villaumites 0.04 gram.UV spectrum (aqueous solution, nanometer): 411,586.Mass spectrum: 364[(M-2Cl
-)
2+/ 2].
Embodiment 49: iron-5,10, synthetic (structural formula 17) of 15-three [(N-methyl)-3 '-pyridyl]-20-(p-hydroxybenzene) porphyrin tetrachloro salt
8.1 gram 3-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 3 gram p-Hydroxybenzaldehydes and 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5,10,15-three (3 '-pyridyl)-20-(p-hydroxybenzene) porphyrin 3 grams.The gained porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirred 24 hours.Under vacuum, steam excess iodine methane. products therefrom is dissolved in 50 ml waters, adds 1.3 gram iron trichlorides then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,10,15-three [(N-methyl)-3 '-pyridyl]-20-(p-hydroxybenzene) porphyrin tetrachloro salt 2.5 grams.UV spectrum (aqueous solution, nanometer): 410,585.Mass spectrum: 183[(M-4Cl
-)
4+/ 4].
Embodiment 50: iron-5,10-two [(4 '-C-glucosyl group)-phenyl]-15, synthetic (structural formula 4) of 20-two [(4 '-N-glucosyl group)-phenyl] porphyrin
14 gram (4 '-C-glucosyl group)-phenyl aldehydes, 14 gram (4 '-N-glucosyl group)-phenyl aldehydes and 6.7 restrain and are dissolved in 1 liter of propionic acid after pyrroles mix, and reflux was cooled to room temperature in 2 hours then in air.Under vacuum, steam propionic acid, carry out silicagel column with the mixed solution of 80% chloroform and 20% methyl alcohol and separate, isolate 5,10-two [(4 '-C-glucosyl group)-phenyl]-15,20-two [(4 '-N-glucosyl group)-phenyl] porphyrin 0.5 restrains.The gained porphyrin is dissolved in 50 ml methanol, adds 3 gram ferrous chloride.The gained mixture refluxed 2 hours under protection of nitrogen gas.Filter out excessive ferrous chloride, under vacuum, steam methyl alcohol and promptly get iron-5,10-two [(4 '-C-glucosyl group)-phenyl]-15,20-two [(4 '-N-glucosyl group)-phenyl] porphyrin 0.45 gram.Mass spectrum: 1321[(M-Fe+3H)
+/ 1].
The synthetic of (4 '-N-glucosyl group)-phenyl aldehyde can be with reference to Pasetto, P. wait the people at J.Chem.Soc., Chem.Commun.2001, disclosed synthetic method in " Synthesis of hydrolytically stable porphyrinC-and S-glycoconjugates in high yields " among the 81-82.
Embodiment 51: iron-5,10-two [(4 '-C-glucosyl group)-phenyl]-15, synthetic (structural formula 4) of 20-two [(4 '-0-glucosyl group)-phenyl] porphyrin
14 gram (4 '-C-glucosyl group)-phenyl aldehydes, 14 gram (4 '-0-glucosyl group)-phenyl aldehydes and 6.7 restrain and are dissolved in 1 liter of propionic acid after pyrroles mix, and reflux was cooled to room temperature in 2 hours then in air.Under vacuum, steam propionic acid, carry out silicagel column with the mixed solution of 80% chloroform and 20% methyl alcohol and separate, isolate 5,10-two [(4 '-C-glucosyl group)-phenyl]-15,20-two [(4 '-0-glucosyl group)-phenyl] porphyrin 0.47 restrains.The gained porphyrin is dissolved in 50 ml methanol, adds 3 gram ferrous chloride.The gained mixture refluxed 2 hours under protection of nitrogen gas.Filter out excessive ferrous chloride, under vacuum, steam methyl alcohol and promptly get iron-5,10-two [(4 '-C-glucosyl group)-phenyl]-15,20-two [(4 '-0-glucosyl group)-phenyl] porphyrin 0.42 gram.Mass spectrum: 1323[(M-Fe+3H)
+/ 1].
The synthetic of (4 '-0-glucosyl group)-phenyl aldehyde can be with reference to Pasetto, P. wait the people at J.Chem.Soc., Chem.Commun.2001, disclosed synthetic method in " Synthesis of hydrolytically stable porphyrinC-and S-glycoconjugates in high yields " among the 81-82.
Embodiment 52: iron-5,10-two [(4 '-0-glucosyl group)-phenyl]-15, synthetic (structural formula 4) of 20-two [(4 '-N-glucosyl group)-phenyl] porphyrin
14 gram (4 '-0-glucosyl group)-phenyl aldehydes, 14 gram (4 '-N-glucosyl group)-phenyl aldehydes and 6.7 restrain and are dissolved in 1 liter of propionic acid after pyrroles mix, and reflux was cooled to room temperature in 2 hours then in air.Under vacuum, steam propionic acid, carry out silicagel column with the mixed solution of 80% chloroform and 20% methyl alcohol and separate, isolate 5,10-two [(4 '-0-glucosyl group)-phenyl]-15,20-two [(4 '-N-glucosyl group)-phenyl] porphyrin 0.6 restrains.The gained porphyrin is dissolved in 50 ml methanol, adds 3 gram ferrous chloride.The gained mixture refluxed 2 hours under protection of nitrogen gas.Filter out excessive ferrous chloride, under vacuum, steam methyl alcohol and promptly get iron-5,10-two [(4 '-0-glucosyl group)-phenyl]-15,20-two [(4 '-N-glucosyl group)-phenyl] porphyrin 0.55 gram.Mass spectrum: 1325[(M-Fe+3H)
+/ 1].
Embodiment 53: cobalt-5,10,15, synthetic (structural formula 1) of 20-four [(N-diethylene glycol monomethyl ether base)-2 '-pyridyl] porphyrin
10.7 gram 2-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate 5,10,15,20-four (2-pyridyl) porphyrin 3.5 grams.3.5 grams 5,10,15,20-four (2-pyridyl) porphyrin is dissolved in 10 milliliters of chloro diethylene glycol monomethyl ethers, at room temperature stirs 24 hours.The gained reactant is dissolved in 20 ml waters, adds 2.5 gram cobalt dichlorides.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive cobalt dichloride, under vacuum, steam water and promptly get cobalt-5,10,15,20-four [(N-diethylene glycol monomethyl ether base)-2 '-pyridyl] porphyrin 3 grams.Mass spectrum: 271 (M
4+/ 4).
Embodiment 54: cobalt-5,10,15, synthetic (structural formula 1) of 20-four [(N-5 '-imidazolyl)-2 '-pyridyl] porphyrin
10.7 gram 2-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate 5,10,15,20-four (2-pyridyl) porphyrin 3.5 grams.3.5 grams 5,10,15,20-four (2-pyridyl) porphyrin is dissolved in 10 milliliters of 5-chloro imidazoles, at room temperature stirs 24 hours.The gained reactant is dissolved in 20 ml waters, adds 2.5 gram cobalt dichlorides.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive cobalt dichloride, under vacuum, steam water and promptly get cobalt-5,10,15,20-four [(N-5 '-imidazolyl)-2 '-pyridyl] porphyrin 2.7 grams.Mass spectrum: 236 (M
4+/ 4).
Embodiment 55: zinc-5,10,15, synthetic (structural formula 1) of 20-four [(N-(N-ethylethylenediamine base)-2 '-pyridyl] porphyrin
10.7 gram 2-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate 5,10,15,20-four (2-pyridyl) porphyrin 3.5 grams.3.5 grams 5,10,15,20-four (2-pyridyl) porphyrin is dissolved in 10 milliliters of iodo N-ethylethylenediamine bases, at room temperature stirs 24 hours.The gained reactant is dissolved in 20 ml waters, adds 2.5 gram zinc dichloride.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive zinc dichloride, under vacuum, steam water and promptly get zinc-5,10,15,20-four [(N-(N-ethylethylenediamine base)-2 '-pyridyl) porphyrin 2.7 grams.Mass spectrum: 304 (M
4+/ 4).
Embodiment 56: the effect of small molecule antioxidant and DNA
Because small molecule antioxidant of the present invention all has positive charge, so they can both work with the DNA that has negative charge.When with DNA titration a kind of small molecule antioxidant of the present invention, the uv-absorbing generation red shift of porphyrin.Fig. 1 is with CT-DNA titration 5,10-two [(N-methyl)-4 '-pyridyl]-15, the ultra-violet absorption spectrum of 20-two (4 '-tolyl) porphyrin two villaumites in water.Along with the adding of DNA, porphyrin obviously descends and red shift in the absorption of Soret band.
Embodiment 57: the cobalt complex of porphyrin synthetic
At first the porphyrin with 1 gram is dissolved in 100 milliliters the chloroform, adds the rose vitriols of 2 grams then.Under protection of nitrogen gas, reaction refluxed 2 hours, then cool to room temperature.Cross and miss unreacted rose vitriol, under vacuum, steam chloroform then, promptly obtain the cobalt complex of porphyrin.
Experimental example 1: iron-5,10,15,20-four [(N-cyclohexyl)-2 '-pyridyl] porphyrin pentachloro-salt in the focal cerebral ischemia model to the provide protection of rat brain
24 bull Sprague-Dawley rats are become four groups by 6 one components.Cause the rat brain thrombus with the method for the artery in the brain being separated ligation, inject iron-5,10,15,20-four [(N-cyclohexyl)-2 '-pyridyl] porphyrin pentachloro-salt to two groups of rats wherein by the amount of 1 mg/kg after 5 minutes.The cerebral infarct size that compares four groups of rats after one hour.The average cerebral infarct size of medication group rat be control rats average cerebral infarct size 1/2nd.
Experimental example 2: iron-5,15-two [(N-methyl)-2 '-pyridyl]-10,20-two (2 '-tolyl) porphyrin three villaumites in rat anoxia anoxia model to the provide protection of rat brain
24 bull Sprague-Dawley rats are become four groups by 6 one components.Inject iron-5,15-two [(N-methyl)-2 '-pyridyl]-10,20-two (2 '-tolyl) porphyrin three villaumites to two groups of rats wherein by the dosage of 2 mg/kg.After one hour rat is placed in the bottle that fills nitrogen, takes out rapidly after one minute, observe the rats death number.The rats death number of medication group is 1/3rd of a control group.
Cerebral thrombosis is meant the constricted flow of blood in brain.Again dredge blood flow after the operation, can cause further infringement to brain, this is called again the infringement that oxygen supply causes.Many scientists think, cerebral thrombosis and again the infringement that causes of oxygen supply have at least a part to cause by free radical.The derivatives of porphyrin that has large-substituent of the present invention can be used as small molecule antioxidant and is used for treating cerebral thrombosis, alleviates because the death of the brain cell that causes of cerebral thrombosis and the infringement that causes of oxygen supply again, and consumption is a 0.5-100 mg/kg body weight.
Acute myocardial infarction, so-called heart failure.It is to cause heart tissue death to cause owing to the coronary flow of supplying heart blood is obstructed.Long-term or nonvolatil blood flow is obstructed and makes and finally cause myocardial cell's death by the part myocardial anoxia.If by nature or medical procedure get involved, blood flow is by very fast mediation, the infringement that infarct causes may be removed or alleviate.But the mediation again of blood flow also can damage myocardial cell and adjacent tissue cell thereof.This injury is called the ischemic infringement that causes of oxygen supply again.Studies have shown that free radical all plays an important role in blood flow the is obstructed infringement that causes and the ischemic infringement that oxygen supply causes again.Therefore, the derivatives of porphyrin that has large-substituent of the present invention can reduce tissue injury as small molecule antioxidant, and patient in heart failure is benefited.
Owing in the process of radiation treatment, produce a large amount of free radicals, thereby human body produced very big side effect.The derivatives of porphyrin that has large-substituent of the present invention can be treated owing to human body is accepted the sequela that radiation treatment causes as small molecule antioxidant.
Chronic bronchitis, asthma, rheumatic arthritis, senile dementia, Parkinson's formula disease, the shock that causes by septicemia, disease such as aging is also directly relevant with a large amount of generations of free radical.So the derivatives of porphyrin that has a large-substituent of the present invention also can be used for treating these diseases as small molecule antioxidant.
Experimental example 3: have the distribution coefficient of the derivatives of porphyrin of large-substituent at oil phase and aqueous phase
Measuring method: in 10 milliliters test tube, add 3 milliliters n-Octanol, add the 1-2 milligram derivatives of porphyrin that has different substituents of the present invention then.After the derivatives of porphyrin dissolving that has large-substituent, add 3 milliliters water again.Acutely shake test tube, place then and spend the night.Mensuration has the absorbancy of the derivatives of porphyrin of large-substituent at oil phase and aqueous phase respectively, and both ratio is distribution coefficient.Table 1 is that some of this invention have the distribution coefficient of the derivatives of porphyrin of large-substituent at oil phase and aqueous phase.
Table 1: small molecule antioxidant is at the distribution coefficient of oil phase and aqueous phase
Porphyrin |
R |
R’ |
R” |
R’” |
K (n-Octanol/water) |
1 |
OH |
Me |
Me |
PyMe+ |
>2500 |
2 |
OH |
Me |
PyMe+ |
PyMe+ |
7.23 |
3 |
OH |
PyMe+ |
Me |
PyMe+ |
16.5 |
4 |
OH |
OH |
PyMe+ |
PyMe+ |
4.02 |
5 |
OH |
PyMe+ |
OH |
PyMe+ |
6.25 |
6 |
OH |
OH |
OH |
PyMe+ |
>2500 |
7 |
Me |
Me |
PyMe+ |
PyMe+ |
>100 |
8 |
Me |
PyMe+ |
Me |
PyMe+ |
38.5 |
As can be seen from Table 1, the derivatives of porphyrin that has a large-substituent of the present invention is different at the distribution coefficient of oil phase and aqueous phase, according to this characteristic, the derivatives of porphyrin of different substituents can be used for the treatment of different diseases.