Interaction of N and O donor group containing phthalocyanines with boron derivatives

Practical use of phthalocyanines in particular is wider than porphyrazine and its derivatives. Phthalocyanines are used as quality dyes and pigments. In recent years, phthalocyanines have been extensively studied for photodynamic treatment of viruses and tumors, as well as applications in the laser technology as stain, electrochromic and electrophotographic materials, as catalysts. The phthalocyanine word was derived from the Greek equivalents of the words "naphtha (rock oil)" and "cyanine (dark blue)" and the name "phthalocyanine" (Pc) was first discovered in 1933 by Professor Reginald P. Linstead of Imperial College of Science and Technology, and their derivatives. Phthalocyanines were first discovered in 1907 by Braun and Tcherniac in the South Metropolitan Gas Company, while being the first new chromophoric derivatives discovered in the 20th century. They were obtained as a dark insoluble by-product during the synthesis of o-cyanobenzamide from acetic anhydride and phthalimide. The structure of this unsubstituted iron phthalocyanine was elucidated by Linstead and Robertson a quarter century later by the X-ray diffraction method. Many studies have been done on tetrapyrrole-derived macrocyclic compounds up to now and these studies have revealed many properties of tetrapyrols. One of the characteristics of porphyrin and phthalocyanines is the accumulation capacity in tumor tissues, one of the important points to be emphasized. On the other hand, Boron Neutron Capture Therapy, which is defined as BNCT, has been developed as a result of researches for tumor treatment. The thermal neutrons of 10 isotopes have been recognized as one of the most important and interesting ideas up to now in the scientific world, based on the fact that the energy released from the reaction is the destruction of the cell it is on. The use of tetrapyrrole derivatives such as phthalocyanine and porphyrin for this method is due to the fact that more than one substituent group can be attached to this structure. Thus, the target cell can be boron loaded at high concentration. As a country with more than 70% of the world boron reserves, boron should be investigated much more intensively in every aspect of our country. Moreover, since boron is used in many areas of the industry, it is important to focus on this issue. In the present study, new compounds were designed to combine these two important important compounds, and the synthesis and characterization of these compounds were aimed. Although there have been a number of studies on phthalocyanines, there has been little interest in boron-containing phthalocyanines and their derivatives other than carbene phthalocyanines and subphthalocyanines. In the first part of the study; firstly the tirozin-boc amino acid (1) compound and the 4-nitrophthalonitrile compound were protected with the tert-boc compound. In the second step, tirozin-boc phthalonitrile (2) was obtained by the reaction of 1 and 4-nitrophthalonitrile in DMF. In the third step, the tirozin phthalonitrile (3) compound was obtained by subjecting 2 of the compounds to TFA with 5 h of distillation. The esterification reaction of the 3-nitro compound with diphenyl boronic acid afforded the resultant compound 4. The most significant difference in the IR spectrum of compound 1 is the dominant aliphatic -CH groups coming from tertiary butyl groups at 2981-2846 cm-1. It was also observed at 3321 cm-1 for the -NH group and at 1673 cm-1 for the amide C = O pike from the protecting group. The -CN stretching vibrations in the IR spectrum of compound 2 appeared at 2235 cm-1, indicating that this peak has the desired effect. The spectrum of the aliphatic -CH groups belonging to the protons of the protecting groups in the 1 H-NMR spectrum of compound 2 was observed at 1.38 ppm. In the 13 C-NMR spectrum, it was understood that the peak nitrile group observed at 115.64 ppm belonged to the carbon atom. The visible change in the IR spectrum of compound 3 is the disappearance of the peak at 2846 cm-1 and the disappearance of the peak at C = O 1673 cm-1 from the protecting group. The peak at 1.38 ppm in 1H NMR and the aliphatic -CH group at 29 ppm in 13 C-NMR disappeared. The -COOH group existing in 3 compounds in the FT-IR spectrum of compound No. 4 disappeared and the frequencies of B-O and B-N were observed at 1419 cm-1 and 1277 cm-1, respectively. Proton from diphenyl borinic acid in the 1 H NMR spectrum of the 4-nitro compound was observed at a range of 8.11-7.25 ppm. In the 13C-NMR spectrum, the signal of the carbons in the diphenyl borinic acid was 136.88-130.62-127.26 ppm. The 11B NMR spectrum at 8.02 ppm proved the formation of 4 compounds with tetracoordination. In the second part of the study, tirozin boc phthalocyanine (5); tirozin-boc phthalonitrile was obtained by boiling the compound (2) with zinc (II) acetate and DBU in N, N (dimethylamino) ethanol for 24 hours at 140°C. In the fourth step, tyrosine phthalocyanine (6) was obtained by cleavage of the resultant boc compound by mixing 5 compounds with TFA for 5 hours. In the last step, the boronic acid (7) compound of the resulting tirozin phthalocyanine was obtained by boiling 6 compounds in DMSO solvent with diphenylboronic acid. 2235 cm-1 peak of the nitrile group disappeared in the IR spectrum of compound 5. The Q and B bands of the 5 composition in the DMSO absorption spectrum were observed at 680 nm and 350 nm, respectively. Compund 5 is similar to the spectrum of the precursor compound 2 in the 1H-NMR spectrum. In the IR spectrum of compound 6, 1673 peaks of the aliphatic-CH groups of the tert-butyl group at 2846 cm-1 and of the C = O group of BOC disappeared. In the 1H-NMR spectrum, the peak at 1.40 ppm of the aliphatic -CH of the protecting groups in the precursor 5 compounds is lost. The main difference of the compound 5 with the compound 6 is the absence of the broad peak of the COOH group of compound 7 observed in the IR spectra. In the UV-Vis spectrum of compound 7, the Q band appeared at 677 nm and the B band at 348 nm. The peak of the 11B-NMR spectrum at 21.675 ppm showed that the boron atom of phthalocyanine 7 was either tricoordinated or by interacting with the solvent pyridine-d5 used in NMR experiment a tetra-coordinated boron is formed. In the third part of the work, compound 8 was obtained by reduction of 4- [bis [2- (acetyloxy) ethyl] amino] -benzaldehyde with (NH4)2CO3 and NaBH4. In the next step, compound 9 was obtained after 72 hours at room temperature in the presence of potassium carbonate in dry DMF. In the last step, for synthesis of compound 10, 9 is added in N, N dimethylaminoethanol and 2-3 drops of 1,8-diazobicyclo [5,4,0] undec-7-ene (DBU) at 4 hours at 120oC with the addition of anhydrous zinc II acetate. The stretching band of the -OH group in the IR spectrum was increased to 3455 cm-1 with reducting of the compound 8. The peak of -CH2 in the alcohol group in the 1H NMR spectrum of compound 8 was observed at 4.61 ppm. The peak at 2.06 ppm was identified as the peak of the -CH3 groups at the ends. The characteristic peak for the carbon atom in the group -CH2OH of alcohol in the 13C NMR spectrum of compound 8 was observed at 65.15 ppm. The peak of the -CN group, which is characteristic of the FT-IR spectrum of compound 9 was found at 2232 cm-1. In compound 8 the tension band at 3455 cm-1 which is acid for the -OH group, was not observed in the compound 9. The aromatic ring protons in the 1H NMR spectra of compound 9 are in the range of 7.77-7.71-7.48 ppm, and in the 13C NMR spectra 161.90-135.14-125.51-123-85-119.95 -115.30-111.28 ppm. Aromatic protons in the 1 H NMR spectrum of the 10-position compound; 7.70-7.08-6.94-6.63-6.56 ppm. The protons in the -OCH2 group appeared at 4.1 ppm while the -CH2 protons bound to the -OH in the substituent were observed at 3.73 ppm. The protons of the -CH2 group due to the nitrogen atom in the substituent were observed at 4.28 ppm. The expected Q and B bands in DMF absorption of phthalocyanine compund 10 appeared at 685 nm and 354 nm.