Design and synthesis of tetraazachlorins, tetraazabacteriochlorins and tetraazaisobacteriochlorins

Abstract

Three approaches to the synthesis of reduced derivatives of tetraazaporphine such as tetraazachlorin, tetraazabacteriochlorin, and tetraazaisobacteriochlorin are reviewed. The fi rst synthesis of alkyl-substituted tetraazachlorins was achieved by the catalytic hydrogenation of magnesium complexes of tetraazaporphines. Two other synthesis approaches for reduced tetraazaporphines based on the mixed condensation of the precursors with different hydrogenation levels and β-β addition reactions have been developed in the last decade. The use of tetramethylsuccinonitrile as the saturated component in the mixed condensation with derivatives of aromatic and heteroaromatic dicarboxylic acids enable the synthesis of oxidation-resistant benzo-; 1,2-and 2,3-naphtho-; pyrazino-; 2,3-and 3,4-pyridinofused tetraazachlorins, tetraazabacteriochlorins, and tetraazaisobacteriochlorins. Fullerene conjugates of reduced tetraazaporphine derivatives were obtained using 1,2-dicyanofullerene as the source of the hydrogenated sites. Tetraazaporphine can act as dienophile in Diels-Alder reaction with dienes of the anthracene and cyclopentadiene series and also as dipolarophile in 1,3-dipolar cycloadditions with azomethine ylides and nitrones. In addition, the effect of the reduction of peripheral double bonds in tetraazaporphine macrocycle alone, and in combination with annelation of benzene or heterocyclic rings on the absorption spectra is discussed.

The fluorescence and electronic structure of phenyl-substituted tetraazachlorin molecules

“…From the theoretical standpoint, interaction of the conjugated systems of the porphyrazine macrocycle with phenyl rings is of interest. It is significant that phenylation does not disrupt the planarity of the porphyrazine macrocycle, as was demonstrated by the quantum chemical optimization of molecular geometry, as dis tinct from what was observed for 2, 3,7,8,12,13,17,18 octaphenylporphine, for which geometry optimiza tion by the same method indicates that the planes con taining three nearest neighbor atoms deviate from the mean plane of the macrocycle (tetrapyrrole with methine bridges) by a few degrees (<4°). EXPERIMENTAL H 2 Ph 6 TAC tm was synthesized by mixed condensa tion between diphenylmaleonitrile and tetramethyl succinonitrile in boiling dimethylaminoethanol in the presence of lithium dimethylaminoethoxide [8].…”

“…Since 1999 [1], the Organic Intermediates and Dyes Institute has been synthesizing and investigating hydro derivatives of tetraazaporphine (porphyrazin, Н 2 TAP) that are tetraaza analogues of chlorin and bacteriochlorin (see earlier reviews [2,3]). Our research team has carried out a number of studies on the correlation between the photophysics and struc ture of these molecules.…”

Synthetic approaches to asymmetric phthalocyanines and their analogues

“…[213][214][215][216] Depending on the reaction temperature and the nature of the diene, tetraazachlorins (TACs), tetraazabacteriochlorins (TABs), and tetraazaisobacteriochlorins (TAiBs) could be isolated from the reaction mixture (Schemes 21, 22). [213][214][215] For instance, the Diels-Alder reaction between unsubstituted porphyrazine 50 and anthracene derivatives at 130 o C results in the selective formation of tetraazachlorins 51, while raising the reaction temperature leads to the formation of tetraazabacteriochlorins 52 and tetraazaisobacteriochlorins 53 as the major products (Scheme 21); 213 similar results were obtained in the cyclopentadiene series. 216 Similarly, [3+2] cycloaddition reaction between tetraazaporphyrins 50, 54 or 56 and generated in situ dipolar reactants results in formation of respective tetraazachlorins 55, 57, or 59 along with tetraazabacteriochlorins 60 and 61 or tetraazaisobacteriochlorin 58 (Scheme 22).…”

Spectral-luminescent properties of substituted tetraazachlorins solubilized in solutions of nonionic surfactants

“…В работе использовали ряд ТАС (Рисунок 1): β,β,β',β'-тет раметилт ри(4-трет-бу т и л бе н з о ) т е т р а а з а х л о р и н ( [10][11][12] В качестве солюбилизаторов применяли следующие НПАВ: Pluronic F-68 (Sigma) -блок-сополимер этиленоксида и пропиленоксида (PlF68), [13] Cremophor EL (Fluka) -полиэтоксилированное касто-ровое масло (CrEL), [17] Эмуксол 3 (ФГУП «ГНЦ «НИОПИК») -полигликолевый эфир α-токоферола (Emu3). [16] В качестве рас-творителей использовали толуол (ГОСТ 5789-78), бензол (для спектрофотометрии), дистиллированную воду, фильтрованную через систему Milli-Q (Millipore).…”

“…[9] К таким перспективным гидрофобным фотосенсибилизаторам относятся представители нового класса гидрированных производных порфиразина -безметальные конденсиро-ванные замещенные тетраазахлорины (ТАС). [10][11][12] Однако они нуждаются в средствах доставки к клеткам опухоли, которыми могут служить неионогенные ПАВ (НПАВ) и высокомолекулярные соединения. [13][14][15] Настоящая работа является продолжением иссле-дования агрегации β,β,β',β'-тетраметилтрибензотетра-азахлорина (H 2 TBTAC), [16] солюбилизированного в рас-творах НПАВ, применительно к другим замещенным тетраазахлоринам, обладающим различной растворимо-стью.…”