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Phenylsubstituted Porphyrins. 2. Synthesis of 5-Arylporphyrins
Ekaterina A. Kolodina,a Tatiana V. Lubimova,b Sergei A. Syrbu,a @ and Alexander S. Semeikina
aIvanovo State University of Chemistry and Technology, Ivanovo, 153000, Russia bInstitute of Solution Chemistry, Russian Academy of Science, 153045, Ivanovo, Russia @Corresponding author E-mail: syrbu@isuct.ru
The condensation ofbiladiene-a,c dihydrobromides with benzaldehyde gives 5-phenylporphyrins. The reaction conditions have been studied and optimized; it is shown that synthesis of biladiene-a,c dihydrobromides can be combined with their following condensation with benzaldehyde.
Keywords: 5-Arylporphyrins, biladiene-a,c dihydrobromides, benzaldehyde, condensation reaction.
Introduction
Investigation of porphyrins, that are widely present in the nature, is often carried out with the use of their synthetic analogs as model compounds. meso-Tetraarylporphyrins 1 containing different substituents on the phenyl rings can be easily prepared by condensation reaction of pyrrole with corresponding benzaldehydes in the acidic media.[1"3] Unlike natural species, meso-tetraarylporphyrins don't have any alkyl or pseudoalkyl substituents in the p-positions of porphyrin macrocycle but, oppositely, have aryl rings in the meso-positions which can contain different active substituents allowing their further structural modification. On the other hand, p-octaalkylporphyrins 2, being also available, contain no active groups what makes difficult their modification. That's why the porphyrins, combining the advantages of these two classes of porphyrins (i.e. 5-aryloctaalkylporphyrins 3) are of great interest.
Presently several synthetic methods for 5-aryloctaalkyl-porphyrins 3 are known. One of the approaches is condensation of meso-aiyl-3,3',4,4'-tetraalkyldipyrrolylmethanes 4 with 5,5'-diformyl-3,3',4,4'- tetraalkyldipyrrolylmethanes 5 in CH3OH or CH2Cl2 under the action of strong acids (HI, HClO4 or p-toluenesulfonic acid)[4-9] (Scheme 1). In this reaction atmospheric oxygen or derivatives of benzoquinone with electron-withdrawing substituents (p- or o-chloranil, 2,3-dichloro-5,6-dicyanobensoquinone (DDQ)) act as oxidizers of the intermediate porphodimethene 6.
In a similar manner 5-aryloctaalkylporphyrins can be obtained by condensation of meso-aryl substituted dipyrrolylmethanes 4 with hydro-bromides of 5,5'-dimethoxymethyl-3,3',4,4'-tetraalkyl-dipyrrolylmethenes 7 in refluxing benzene with following oxidation of the intermediate product 8 by benzoquinone derivatives (Scheme 2).[10]
Scheme 1.
' Paper 1. Syrbu S.A., Lubimova T.V., Semeikin A.S. Khim. Geterotsikl. Soedin. 2004, 1464-1472.
R H Ar R
R H Ar R
/
wNH HN-—y 4
MeOH2C + CH2OMe
Scheme 2.
However this method is complicated by the formation of rather great quantity of octaalkylporphyrins unsubstituted in weso-positions.[10]
Another method widely used in the synthesis of 5-aryloctaalkylporphyrins 3 is the condensation reaction of benzaldehydes with 1,19-unsubstituted biladienes-a,c in alcholols catalized by acids[9, 11-14] or bases[15] (Scheme 3).
H4" or OH" + ArCHO -► 3
Scheme 3.
The goal of the present work was optimization of syntesis of 5-aryloctaalkylporphyrins 3 by condensation of biladienes-a,c 9 with benzaldehydes. The condensation reaction of dihydrobromides of 2,3,7,13,17,18-hexamethyl-8,12-diethylbiladienes-a,c 12 (R = Rj = Me; R2 = Et) and 8,12-dibuthyl-2,3,7,13,17,18-hexamethylbiladienes-a,c 12 (R = Rj = Me; R2 = Bu) with benzaldehydes was chosen as a model reaction (Scheme 4).
Experimental part
The UV-vis spectra were recorded on Lambda 20 spectrophotometer. B NMR spectra were measured in CDCl3 on Bruker AC-200 spectrometer. The purity and individuality of substances were established by thin layer chromotography (Silufol). The data of elemental analyses corresponded closely to the calculated values.
Syntheses
3,3 '4,4'-Tetraalkyldipyrrolylmethanes 11a.
3,3'-Dimethyl-4,4'-diethyldipyrrolylmethane 11a (R1 = Me; R2 = Et). The mixture of 5,5'-dicarbethoxy-3,3'-dimethyl-4,4'-diethyldipyrrolylmethane[16] (5 g, 13.4 mmol), KOH (5 g, 89.3 mmol) and ethylene glycol (50 ml) was refluxed during 1 hour. Then the solution was poured into 200 ml of water; the precipitate was filtered, washed with water and dried at room temperature. Yield 2.7 g (88%).
3,3',4,4'-Tetramethyldipyrrolylmethane 11a (R1 = R2 = Me) and 4,4'-dibutyl-3,3'-dimethyl-dipyrrolylmethane 11a (R1 = Me; R2 = Bu) were prepared in the same way using 5,5'-dicarbethoxy-3,3',4,4'-tetramethyldipyrrolylmethane[16] (yield 89%) and 5,5'-dicarbethoxy-4,4'-dibutyl-3,3'-dimethyldipyrrolylmethane[16] (yield 91%), correspondingly.
5,5 '-Dicarboxy-3,3 '4,4 '-tetraalkyldipyrrolylmethanes 11b.
5,5'-Dicarboxy-3,3 '-dimethyl-4,4'-diethyldipyrrolyl-methane 11b (R1 = Me; R2 = Et) The solution of 5,5'-dicarbethoxy-3,3'-dimethyl-4,4'-diethyldipyrromethane[16] (5 g, 13.4 mmol) and potassium hydroxide (5 g, 89.3 mmol) in MeOH was refluxed during
11a (X = H) lib (X=COOH)
Scheme 4.
4 hours. Then the mixture was poured into 200 ml of water and slightly acidified by 5% HCl. The precipitate was filtered, washed by water and dried at room temperature. Yield 3.8 g (89%).
5,5'-Dicarboxy-3,3',4,4'-tetramethyldipyrrolyl-methane 11b (R1 = R2 = Me) and 5,5'-dicarboxy-4,4'-dibutyl-3,3'-dimethyldipyrrolylmethane 11b (R1 = Me; R2 = Bu) were obtained in a similar way using 5,5'-dicarbethoxy-3,3',4,4'-tetra-methyldipyrrolylmethane[16] (yield 92%) and 5,5'-dicarbethoxy-4,4'-dibuthyl-3,3',4,4'-tetramethyldipyrrolylmethane[16] (yield 87%), correspondingly.
2,3,7,8,12,13,17,18-Octaalkylbiladiene-a,c dihydrobromides
12.
Method A.
2,3,7,13,17,18-Hexamethyl-8,12-diethylbiladiene-a,c dihydrobromide 12 (R = Me; R1 = Me; R2 = Et). Concentrated HBr (2 ml) was added into solution of 5,5'-dicarboxy-3,3'-dimethyl-4,4'-diethyldipyrromethane (3 g, 9.43 mmol) and 2-formyl-3,4-dimethylpyrrole[17] (2.3 g, 18.9 mmol) in MeOH (50 ml) and the mixture was stirred 1 hour. The dark-violet crystal precipitate was washed with MeOH, ether and dried at room temperature. Yield 5.1 g (90%).
The same procedure was carried out for the syntheses of 7,8,12,13-tetramethylbiladiene-a,c dihydrobromide 12 (R = H; R1 = R2 = Me) from 5,5'-dicarboxy-3,3',4,4'-tetramethyldipyrrolyl-methane and 2-formylpyrrole (90% yield);
7,13-dimethyl-8,12-diethylbiladiene-a,c dihydrobromide 12 (R = H; R1 = Me; R2 = Et) from 5,5'-dicarboxy-3,3'-dimethyl-4,4'-diethyldipyrromethane and 2-formylpyrrole (87%);
2,3,7,8,12,13,17,18-octamethylbiladiene-a,c dihydrobromide 12 (R = R1 = R2 = Me) from 5,5'-dicarboxy-3,3',4,4'-tetramethyldipyrrolylmethane and 2-formyl-3,4-dimethylpyrrole (70%);
8,12-dibutyl-2,3,7,13,17,18-hexamethylbiladiene-a,c dihydrobromide 12 (R = R1 = Me; R2 = Bu) from 5,5'-dicarboxy-3,3'-dibutyl-4,4'-dimethylpyrrolyl-methane and 2-formyl-3,4-dimethylpyrrole (85%).
Method B.
2,3,7,13,17,18-Hexamethyl-8,12-diethylbiladiene-a,c dihydrobromide 12 (R = Me; R1 = Me; R2 = Et). 4,4'-Dimethyl-3,3'-diethyldipyrrolylmethane (2.6 g, 11.3 mmol) and 2-formyl-3,4-dimethylpyrrole (2.8 g, 22.8 mmol) were dissolved in 70 ml MeOH at stirring, then conc. HBr (3.5 ml) was added. The mixture was stirred for 1 hour at room temperature. The precipitate, containing biladiene, was filtered, washed with MeOH and ether and dried. Yield 6.2 g (91%). UV-vis Xmax (CHCl3) nm (lge): 451 (4.77), 521 (5.15).
The same procedure was carried out for the syntheses of 8,12-dibutyl-7,13-dimethylbiladiene-a,c dihydrobromide 12 (R = H; R1 = Me; R2 = Bu) using 4,4'-dibutyl-3,3'-dimethyldipyrrolylmethane and 2-formylpyrrole (yield 71%);
2,3,7,8,12,13,17,18-octamethylbiladiene-a, c dihydrobromide 12 (R = R1 = R2 = Me) from 3,3',4,4'-tetramethyldipyrrolylmethane and 2-formyl-3,4-dimethylpyrrole (72%);
8,12-dibutyl-2,3,7,13,17,18-hexamethylbiladiene-a,c dihydrobromide 12 (R = R1 = Me; R2 = Bu) from 3,3'-dibuthyl-4,4'-dimethyldipyrrolylmethane and 2-formyl-3,4-dimethylpyrrole (84%). UV-vis Xmax (CHCl3) nm (lge): 452 (4.79); 522 (5.10).
5-Phenyl-2,3,7,8,12,18-hexamethyl-13,17-diethylporphyn 13 (Ar = Ph; R = R1 = Me; R2 = Et)
Method A. The mixture of biladiene 12 (R = R1 = Me; R2 = Et) (0.25 g, 0.415 mmol), benzaldehyde (0.5 ml, 4.5 mmol), HBr (0.5 ml) and MeOH (50 ml) was refluxed with stirring during 4 hours. Then iodine (0.05 g, 0.20 mmol) was added and the mixture was refluxed for 15 min. The solution was poured into 200 ml of cold water and neutralized by aqueous NH3 solution. The precipitate was filtered, washed with water and dried at 70°C. The product
was purified by column chromotography on Al2O3 (Brockmann III degree, eluent-CHCl3). The first fraction containing porphyrin was collected and its volume was reduced to 5 ml solution, and the porphyrin was precipitated by methanol (30 ml). Yield 113 mg (52%).
Method B. To the solution of 4,4'-dimethyl-3,3'-diethyldipyrrolylmethane (1.1 g, 4.78 mmol) and 2-formyl-3,4-dimethylpyrrole (1.2 g, 9.76 mmol) in MeOH (50 ml) conc. HBr (3 ml) was added at stirring. The mixture was stirred at room temperatrure for 1 hour, then benzaldehyde (5.8 ml, 57.4 mmol) was added. The resulting solution was heated and refluxed for 4 hours. After cooling aqueou NH3 solution (3 ml) was added. The precipitate was filtered, dried, dissolved in CHCl3 and purified by chromotography on Al2O3 (Brockmann II degree). The porphyrin fraction was concentrated and the product was precipitated by MeOH. Yield 1.2 g (48%).
The other porphyrins with electron-donating substituents were prepared analogously (Table 1).
5-(4'-Nitrophenyl)-2,3,7,8,12,18-hexamethyl-13,17-diethylporphin 13 (Ar = 4-PhNO2; R = R1 = Me; R2 = Et).
Method A. The mixture of biladiene 12 (R = R1 = Me; R2 = Et) (0.25 g, 0.415 mmol), 4-nitrobenzaldehyde (0.75 g, 5 mmol), HBr (0.5 ml) and BuOH (50 ml) was refluxed for 4 hours; then iodine (0.05 g, 0.20 mmol) was added and the mixture was allowed to reflux for 15 min more. Then the mixture was poured into 200 ml of water, BuOH was distilled away with water steam. The precipitate formed was filtered, washed with water and dried at 70°C. Dry product was dissolved in CHCl3 and purified by column chromotography on Al2O3 (Brockmann III degree, eluent-CHCl3). The first porphyrin containing fraction was collected, reduced to 5 ml solution and the porphyrin was precipitated by 30 ml of MeOH. Yield 90 mg (38%).
Method B. To the solution of 4,4'-dimethyl-3,3'-diethyldipyrrolylmethane (0.6 g, 2.6 mmol) and 2-formyl-3,4-dimethylpyrrole (0.64 g, 5.2 mmol) in 30 ml of BuOH conc. HBr (3.0 ml) was added at stirring (the precipitate of biladiene has been formed). After 40 min 4-nitrobenzaldehide (2.0 g, 13.2 mmol) was added and the resulting mixture was refluxed for 4 hours. Then the mixture was cooled, diluted with water, and BuOH was distilled away with water steam. The precipitate was filtered, washed with water, dried on air at 70°C. The product was dissolved in CHCl3 and purified by column chromotography on Al2O3 (Brockmann II degree, eluent-CHCl3). The eluate was evaporated and the porphyrin was precipitated by MeOH, filtered and washed with MeOH and dried on the air at 70°C. Yield 0.52 g (35%).
The other porphyrins with electron-withdrawing substituents were prepared analogously (Table 1).
Results and Discussion
The initial biladienes-a,c 12 (R = Rj = Me; R2 = Et) and 12 (R = Rj = Me; R = Bu) were obtained by condensation of a-unsubstituted dipyrrolylmethanes 11a (X = H) or their 5,5'-dicarboxy derivatives 11b (X = COOH) with 2-formyl-3,4-dimethylpyrrole 10 (R = Me) in CH3OH in the presence of HBr as an acidic catalyst. 5,5'-Dicarboxydipyrrolylmethanes 11b were previously obtained by hydrolysis of 5,5'-dicarbethoxydipyrrolylmethanes 14 in KOH-CH3OH solution; and 5,5'-unsubstituted dipyrrolylmethanes 11a were prepared by hydrolysis of 14 accompanied by decarboxylation in solution of KOH in ethylene glycol (Scheme 5). The both derivatives give biladienes-a,c with practically the same yield. It should be noted that the carboxy derivatives 11b are quite stable and can be stored for some
Table 1. Influence of the reaction conditions on the yield of 5-phenyloctaalkylporphyrins 13 (R = R1 = Me; R2 = Bu)
Ar solvent catalyst oxidizer yield (%)
EtOH - - 51.2
EtOH - iodine 57.0
EtOH Py iodine 22.7*
EtOH HBr iodine 60.1
MeOH HBr iodine 63.2
MeOH HBr o-chloranil 55.9
4-methoxyphenyl BuOH Py 16.7*
-
BuOH HBr - 29.7
BuOH HBr iodine 53.3
acetic acid - iodine 6.3
CHCl3 HBr o-chloranil 6.5
DMSO (1000) - - 0
2-methoxyphenyl MeOH HBr iodine 45.9
MeOH HBr iodine 15.4*
EtOH HBr iodine 17.0*
PrOH HBr iodine 26.7*
BuOH - - 13.6*
BuOH Py - 19.3*
BuOH HBr - 20.0*
4-nitrophenyl BuOH HBr iodine 25.3*
pentanol HBr - 19.4*
pentanol HBr iodine 33.2*
acetic acid - - 19.8*
Py - - 16.2*
xylene ClCH2COOH - 11.3*
DMSO(1000) - - 10.9*
3- nitrophenyl BuOH HBr iodine 16.5*
2- nitrophenyl BuOH HBr iodine 18.0*
* - the parallel formation of corrole 15 (R = R1 = Me; R2 = Bu)
IIN
KDH
(CH2OH)2 HN
11a
R Ar R
1. KOH, MeOH HN
Scheme 5.
NH HN
Ri\ LI >Ri
R2 R2
15
Scheme 6.
time unlike to unstable a-unsubstituted dipyrrolylmethanes 11a, which should be used immediately after their synthesis. However, the preparation of the latter is more simple to execute experimentally.
We have found, that condensation of biladienes-a,c 12 with benzaldehydes proceeds with best results in alcohols (Table 1). The addition of mineral acid (HBr), which should suppress the porphyrin formation, on the contrary, increases the yield of 5-arylporphyrins 13, whereas the presence of the base (pyridine) decreases the porphyrin yield and the corresponding corrole 15 is always formed (Scheme 6). The ratio of porphyrin and corrole yields seems to be determined by relative rates of these competitive reactions. The proceeding of the reaction in acetic acid, as well as in chloroform, decreases drastically the porphyrin yield. In the highly polar solvent such as DMSO no porphyrin formation is observed. The addition of oxidizer agent to the reaction mixture influences the yield of the product as well.
The study of the conditions of condensation reaction of 12 (R = R1 = Me; R2 = Et) with ^-anisaldehyde (Scheme 4) has shown that the yield of porphyrin 13 (R = R1 = Me; R2 = Et; Ar=4-methoxyphenyl) is increased with the reaction duration; but after the 4 hours the yield is diminished possibly due to the oxidation processes which begin to dominate over the porphyrin formation (Figure 1).
It was found that the highest yield of porphyrin 13 is observed when 12-fold excess of benzaldehyde over biladiene-a,c 12 is used (Figure 2). So, the large excess of benzaldehyde is needed to suppress the formation of corrole 15 (R = R = Me; R2 = Et).
So, the optimal conditions for the synthesis of porphyrin 13 is condensation of biladiene-a,c 12 with 12-fold excess of benzaldehyde in MeOH during 4 hours in the presence of HBr addition and the equimolar quantity of iodine as oxidizing agent.
We have also studied the influence of position and electronic effects of the substituents in the benzaldehydes on the yield of porphyrin 13. It was found that the highest yield is observed in the case of ^-substituted benzaldehydes. The
decreasing of yield, when o-substituted benzaldehydes are used, is explained by the steric factors of o-substituents in the condensation reaction. The decreasing of the porphyrin 13 yield in the case of some ^-substituted species is still not fully clear (Tables 1, 2). The use of benzaldehydes with electron-withdrawing substituents results in drastic decreasing of the porphyrin 13 yields and formation of corroles 15 as by-products. However, the reaction in more highly boiling butanol enhances the yield and allows to avoid formation of corroles.
Using the methods devised we have also synthesized the porphyrins containing four alkyl substituents in the P-positions of the porphyrin macrocycle 13 (R = H) (Scheme 4). The yields of these porphyrins is much more lower then of their octaalkyl analogs 13 (R = Me), which can be connected with the decreasing of the electron-donating influence of alkyl groups.
The yields and some properties of the obtained porphyrins 13 are presented in Tables 2 and 3.
The long-wave shift of ca. 4-5 nm of all bands and considerable decreasing of intensity of I and III bands are observed in the UV-vis spectra of porphyrins 13 (Table 2) if compared with that of octaalkylporphyrins unsubstituted on weso-positions. This can be caused by electron-withdrawing influence of aryl substituent or porphyrin macrocycle distortion owing to aryl substituent.
Since synthesis of dihydrobromides of biladienes-a,c and their following condensation proceed in the similar conditions using alcohol as the solvent, we have carried out the one-pot synthesis of porphyrins 13 using dipyrrolylmethanes and formylpyrroles without isolation of intermediate biladienes-a,c. This approach allows simplification of the synthetic procedure and reduces the reaction time with practically the same yields relative to the initial reagents.
Acknowledgements. This work was supported by Russian Foundation of Basic Research (Grant 07-03-00818) and Program for leading scientific schools.
2 4 6 8 ¡0 n 14 [Benzaldehyde]/[Biladiene]
Figure 1. The dependence of porphyrin 13 (R = R1 = Me; R2 = Et; Ar = 4-methoxyphenyl) yield on the duration of condensation of biladiene-a,c dihydrobromide 12 (R = R1 = Me; R2 = Et) in 10-fold excess of anisaldehyde in MeOH.
Figure 2. The dependence of the yield of porphyrin 13 (R = R1 = Me; R2 = Et; Ar = 4-methoxyphenyl) on the concentration ratio of anisaldehyde and dihydrobromide of biladiene-a,c 12 (R = R1 = Me; R2 = Et) in MeOH during 4 hours reaction.
Phenylsubstituted Porphyrins
Table 2. The yields and some properties of porphyrins 13.
Porphyrin 13
Nr. Ar R R1 R2 Yield R ** ""f Silufol
(%)*
1 H H Me Me 7.2 0.26 (benzene-heptane 2:1)
2 phenyl H Me Me 14.0 0.78 (CHCl3) 0.15 (benzene-heptane 2:1)
3 H Н Ме Et 6.8
4 phenyl Н Ме Et 11.0(10.6)
5 4-methoxyphenyl Н Ме Et 13.0(13.8)
6 3-nitrophenyl Н Ме Et 11.0(14.9)**
7 H H Me Bu 13.5
8 phenyl Н Me Bu 27.0
9 2-methoxyphenyl H Me Bu 25.0 0.19 (benzene-heptane 2:1)
10 4-methoxyphenyl H Me Bu 43.0 0.75 (CHCl3)
11 2-nitrophenyl H Me Bu 7.6** 0.34 (CHCl3)
12 3-nitrophenyl H Me Bu 16.0** 0.80 (CHCl3)
13 4-nitrophenyl H Me Bu 14.0** 0.30 (benzene-heptane; 2:1)
14 4-pyridyl H Me Bu 10.3 0.20 (CHCl3)
15 phenyl Me Me Me 56.2 0.27 (CHCl3) 0.65 (benzene)
16 H Me Me Me 18.0
17 4-methoxyphenyl Me Me Me 35.0
18 4-nitrophenyl Me Me Me 17.0 0.24 (benzene)
19 H Me Me Et 22.3
20 phenyl Me Me Et 52.0 0.30 (benzene)
21 2-methoxyphenyl Me Me Et 65.0 0.40 (benzene)
22 3-methoxyphenyl Me Me Et 48.0 0.48 (benzene)
23 4-methoxyphenyl Me Me Et 74.0(65.6) 0.45 (benzene)
24 2-nitrophenyl Me Me Et 17.0 0.27 (benzene)
25 3-nitrophenyl Me Me Et 27.0(35.0)** 0.42 (benzene)
26 4-nitrophenyl Me Me Et 38.0(35.0)** 0.41 (benzene)
27 4-pyridyl Me Me Et 20.0(27.7)**
28 H Me Me Bu 38.2 0.87 (CHCl3) 0.37 (benzene-heptane; 2:1)
29 phenyl Me Me Bu 43.5 0.81 (CHCl3) 0.32 (benzene-heptane; 2:1)
30 2-methoxyphenyl Me Me Bu 47.7 0.29 (CHCl3)
31 3-methoxyphenyl Me Me Bu 20.2 0.67 (CHCl3)
32 4-methoxyphenyl Me Me Bu 60.6 0.89 (CHCl3)
33 2-nitrophenyl Me Me Bu 25.5** 0.66 (CHCl3)
34 3-nitrophenyl Me Me Bu 51.0** 0.53 (CHCl3)
35 4-nitrophenyl Me Me Bu 48.0** 0.81 (CHCl3)
36 4-pyridyl Me Me Bu 12.6** 0.95 (CHCl3-CH3OH; 5:1)
37*** - H Me Bu
38*** - Me Me Me 0.45 (CHCl3)
39*** - Me Me Et
40*** - Me Me Bu 0.28 (CHCl3)
* - the yield in brackets is given for synthesis without isolation of intermediate biladiene
** - the reaction was carried out in BuOH
UV-vis spectra in CHCl3: I /nm (lge) 3 max v o /
I II III IV Soret
616(3.20) 564(3.56) 528(3.54) 495(3.91) 397(5.08)
623(3.20) 570(3.80) 532(3.63) 501(4.20) 404(5.39)
621(3.39) 569(3.86) 531(3.73) 499(4.24) 403(5.38)
621(3.21) 570(3.80) 531(3.63) 501(4.20) 405(5.36)
622(3.32) 570(3.81) 533(3.69) 501(4.19) 404(5.26)
618(3.24) 564(3.57) 530(3.54) 496(4.00) 398(5.16)
623(3.18) 570(3.79) 534(3.62) 501(4.20) 404(5.39)
623(3.30) 570(3.85) 534(3.71) 501(4.26) 405(5.44)
623(3.23) 571(3.83) 534(3.65) 502(4.24) 406(5.43)
624(3.36) 571(3.83) 535(3.72) 503(4.21) 405(5.33)
623(3.32) 570(3.84) 535(3.72) 502(4.23) 406(5.32)
624(3.36) 571(3.83) 537(3.76) 504(4.21) 405(5.26)
623(3.34) 570(3.82) 534(3.72) 502(4.20) 404(5.38)
624(3.45) 571(3.81) 537(3.85) 504(4.16) 404(5.26)
620(3.65) 568(3.68) 535(3.96) 500(4.60) 400(5.61)****
623(3.56) 571(3.84) 538(3.86) 504(4.21) 405(5.28)
624(3.57) 572(3.81) 537(3.85) 504(4.11) 402(5.15)
620(3.73) 568(3.81) 533(3.96) 498(4.10) 398(5.12)
623(3.51) 571(3.83) 536(3.86) 502(4.15) 403(5.22)
624(3.54) 571(3.85) 537(3.89) 504(4.19) 404(5.28)
623(3.52) 571(3.86) 537(3.90) 504(4.19) 404(5.28)
623(3.47) 571(3.83) 537(3.86) 503(4.17) 404(5.33)
627(3.48) 574(3.81) 539(3.81) 506(4.19) 404(5.21)
624(3.56) 573(3.87) 538(3.94) 505(4.20) 403(5.22)
624(3.50) 573(3.82) 537(3.87) 505(4.15) 403(5.18)
623(3.65) 571(3.92) 536(3.98) 503(4.25) 403(5.33)
620(3.78) 566(3.87) 533(4.04) 498(4.17) 398 (5.22)
624(3.51) 571(3.85) 538(3.89) 504(4.20) 404(5.29)
624(3.54) 571(3.85) 537(3.90) 504(4.18) 405(5.27)
624(3.48) 571(3.85) 538(3.88) 505(4.20) 406(5.30)
627(3.49) 574(3.74) 539(3.79) 506(4.06) 404(5.09)
626(3.57) 573(3.86) 539(3.94) 506(4.20) 404(5.22)
624(3.54) 573(3.86) 538(3.90) 506(4.20) 404(5.22)
624(3.56) 573(3.86) 538(3.93) 504(4.20) 404(5.29)
595(4.23) 550(4.17) - - 397(5.13)
593(4.14) 549(4.11) 539(4.13) shoulder 396(5.06)
593(4.06) shoulder 537(4.04) shoulder 397(4.99)
593(4.29) 550(4.22) 537(4.23) shoulder 397(5.16)
*** - corroles 15
**** - trichloroethylene
Table 3. The data of 'H NMR spectra of porphyrins 13, 5, ppm (CDCl3).
Nr. Ar R R1 R2 meso-CH NH
2 8.18m (2H) o-H 7.74m (3H) m,p-H 8.96d (2H) 9.20d (2H) 3.48s (12H) 3.48s (12H) 10.02s (2H) 9.83s (1H) -3.45bs (2H)
4 8.25m (2H) o-H 7.78m (2H) m,p-H 9.29d (2H) 9.04d (2H) 3.62s (6H) 4.04q (4H) CH2 1.89t (6H) CH3 10.16s (2H) 10.03s (1H) -3.37bs (2H)
4.04q (4H) CH2
8 8.25m (2H) o-H 7.79m (3H) m,p-H 9.02d (2H) 9.29d (2H) 3.61s (6H) 2.28qv (4H) CH2 1.75sc (4H) CH2 1.13t (6H) CH3 10.14s (2H) 10.01s (1H) -3.38bs (2H)
8.01d (1H) 6-H 7.78t (1H) 5-H 7.37t (2H) 3,4-H 4.04t (4H) CH2
9 8.95d (2H) 9.26d (2H) 3.60s (6H) 2.28qv (4H) CH2 1.75sc (4H) CH2 1.12t (6H) CH3 10.12s (2H) 10.00s (1H) -3.39bs (2H)
11 8.42m (1H) 6H 8.29m (1H) 5-H 7.96m (2H) 3,4-H 8.81d (2H) 9.28d (2H) 3.59s (6H) 4.04t (4H) CH2 2.28qv (4H) CH2 1.74sc (4H) CH2 1.12t (6H) CH3 10.14s (2H) 10.04s (1H) -3.39bs (2H)
13 8.62d (2H) o-H 8.42d (2H) m-H 8.91d (2H) 9.33d (2H) 3.60s (6H) 4.03t (4H) CH2 2.28qv (4H) CH2 1.79sc (4H) CH2 1.13t (6H) CH3 10.12s (2H) 10.05s (1H) -3.46bs (2H)
15 8.03m (2H) o-H 7.76m (3H) m,p-H 2.46s (6H) 3.51s (6H) 3.58s (6H) 3.61s (6H) 10.13s (2H) 9.92s (1H) -3.20bs (1H) -3.30bs (1H)
8.96d (2H) o-H 2.03s (6H) 3.14s(12H) 10.09s (2H) 9,90s (1H)
17* 8.51d (2H) m-H 4.12s (3H) OCH3 3.14s (12H) 3.19s (6H) -2.85bs (4H)
20 8.03d (2H) o-H 7.75m (3H) m,p-H 2.43s (6H) 3.52s (6H) 3.63s (6H) 4.04q (4H) CH2 1.86t (6H) CH3 10.15s (2H) 9.94s (1H) -3.28bs (2H)
25 8.99s (1H) 2-H 8.64d (1H) 4-H 8.48d (1H) 6-H 7.93t (1H) 5-H 2.40s (6H) 3.53s (6H) 3.64s (6H) 4.12q (4H) CH2 1.88t (6H) CH3 10.18s (2H) 9.99s (1H) -3.33bs (2H)
8.15d (2H) o-H 7.42d (2H) m-H 4.10s (3H) OCH3 3.92t (4H) CH2
32* 2.20s (6H) 3.19s (6H) 3.48s (6H) 2.05qv (4H)CH2 1.62sc (4H)CH22 1.02t (6H) CH3 10.22s (2H) 10.05s (1H) -1.34s (2H) -2.72s (2H)
33 8.37d (2H) o-H 7.94m (3H) m,p-H 2.43s (6H) 3.51s (6H) 3.60s (6H) 4.02t (4H) CH2 2.25qv (4H) CH2 1.76sc (4H) CH2 1.10t (6H) CH3 10.13s (2H) 9.94s (1H) -3.23bs (2H)
34 8.98s (1H) o-H 8.67d (1H) p-H 8.36d (1H) o-H 7.90t (1H) m-H 2.39s (6H) 3.52s (6H) 3.62s (6H) 4.03t (4H) CH2 2.27qv (4H) CH2 1.78sc (4H) CH2 1.12t (6H) CH3 10.16s (2H) 9.97s (1H) -3.25bs(2H)
35* 8.73d (2H) o-H 8.57d (2H) m-H 2.18s (6H) 3.22s (6H) 3.50s (6H) 3.94t (4H) CH2 2.04qv (4H) CH2 1.58sc (4H) CH2 1.00t (6H) CH3 10.31s (2H) 10.17s (1H) -1.53s (2H) -2.79s 5(2H)
3.80t (4H) CH2
40** - 3,14s (6H) 3,25s (6H) 3.35s (6H) 2.17qv (4H) CH2 1.74sc (4H) CH2 1.14t (6H) CH3 8.98s (3H) -3.96bs (3H)
* - in CDCl3+5% trifluoroacetic acid
** - for corrole 15 (R = R1 = Me; R2 = Bu)
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Received 17.06.2008 Accepted 16.10.2008 First published on the web 04.02.2009
