89-40-7Relevant academic research and scientific papers
Post‐modification of phthalocyanines via isocyanide-based multicomponent reactions: Highly dispersible peptidomimetic metallophthalocyanines as potent photosensitizers
Afshari, Ronak,Ghasemi, Vahid,Shaabani, Shabnam,Shaabani, Ahmad,Aladaghlo, Zolfaghar,Fakhari, Ali Reza
, p. 49 - 59 (2019)
In this work, one-step synthesis of highly dispersible phthalocyanines containing carboxamide moieties via four-component Ugi reaction was demonstrated for the first time. These pseudopeptide-modified-phthalocyanines were characterized by means of IR, NMR, CHN and UV–Vis spectroscopy. Additionally, the purity of the pseudopeptide phthalocyanines was confirmed by capillary zone electrophoresis. Most of the synthesized phthalocyanines showed good dispersity in common organic solvents and especially in water. The in vitro photodynamic activities of water-soluble phthalocyanine 5k upon MCF-7 cancer cells were investigated and revealed that the cell viability was high in dark conditions, while the compound was phototoxic at visible light and the intensity of damage was directly related to its concentration. Also, phthalocyanine 5k showed high cellular uptake and more killing cells after the modification with Ugi-4CR. Since, many potent phthalocyanine photosensitizers are hydrophobic and poorly water-soluble, which limit their therapeutic applications, the novel phthalocyanines which modified through Ugi approach could be introduced as potent hydrophilic, nonaggregated and biocompatible sensitizers which can able to improve the effectiveness of photodynamic therapy.
Compound herbicide based on dichloro quinolinic acid
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Paragraph 0014; 0031; 0037; 0041; 0047; 0051; 0057, (2021/11/21)
The invention discloses a compound herbicide based on quinclorac, which comprises 20 - 30 parts of quinclorac. Dichloromethane 3-8 parts, synergist 10 - 20 parts, wetting agent 1.5 - 4.5 parts, dispersing agent 1-3 parts, defoaming agent 0.5 - 2.5 parts and water 50 - 70 parts. The synergist inhibits the growth of cells by hindering the synthesis of the protein, and the sprouts of monocotyledonous plants are obtained through young buds of plants. The lower endoderm of the dicotyledonous plant is absorbed and conducted upwards, the seeds and roots absorb conduction, the absorption amount is low, the conduction speed is slow, the growth of young buds and roots is inhibited.
Synthesis of new zinc(II) phthalocyanine conjugates with block copolymers for cancer therapy
Lamch, ?ukasz,Tsirigotis-Maniecka, Marta,Kulbacka, Julita,Wilk, Kazimiera A.
supporting information, p. 433 - 445 (2021/02/03)
Synthetic routes towards new conjugates of hydrophilic zinc(II) phthalocyanine (ZnPc) with poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) (Pluronic P123) and poly(L-lactide) (PLLA), are described. The main semiproduct ZnPc was obtained by heating 4-nitrophthalimide with urea and zinc chloride, followed by the reduction step. Steglich esterification was used to synthesize two ZnPc-conjugated block copolymers, further utilized in fabrication of polymeric micelles (PMs) - functionalized with the zinc(II) phthalocyanine-type moiety. Biological evaluation of the PMs indicated an acceptable biocompatibility level in accord with requirements in the field of nanotheranostics and nanomedicine.
Clean production method 4 - nitrophthalimide
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Paragraph 0015-0025, (2021/09/15)
The invention discloses a clean production method 4 -nitrophthalimide, which adopts 4 -nitrophthalic acid and urea to aminate in a solvent. A closed loop gives 4 -nitrophthalimide. The molar yield of the invention can reach above 85%. Product purity reaches 98% or more. After the reaction is finished, the reaction is cooled, the product is crystallized and precipitated, and the product is obtained through filtration. The filtered filtrate can be applied to the next batch without any treatment. To the method, the reaction substrate is changed, a new synthetic route is reconstructed, a large amount of waste acid due to nitration and acid mixing is avoided, the dangerous process of nitration reaction is avoided, the production management cost is reduced, and the production safety is greatly improved. , The production efficiency and the product quality are improved, and the cleanness of 4 -nitrophthalimide is realized. .
Azomethine phthalimides fluorescent E→Z photoswitches
Georgiev, Anton,Yordanov, Dancho,Dimov, Deyan,Zhivkov, Ivailo,Nazarova, Dimana,Weiter, Martin
, (2020/03/03)
Herein, we report the synthesis and E→Z photoswitching behavior of two 4-substituted azomethine phthalimides containing anthracenyl and 4-(dimethylamino)phenyl moieties (EAMP1 and EAMP2). These compounds represent newly synthesized and unstudied photoswitches with dual fluorescence properties as E-isomers and at photostationary state (PSS) depending on the solvent polarity. Steady-state fluorescence measurements were performed in various solvents and the results show strong sensitivity on the environmental polarity. The kinetics of E→Z photoswitching to PSS was studied in AcCN by visible light activation at 410 nm (EAMP1) and long wavelength UV-light activation at 350 nm (EAMP2). The quantitative and qualitative performance of the switching behavior was evaluated by the degree of photoisomerization (R) and the rate constant (k). It was found for EAMP1 R = 6.95 %, k = 8.87 × 10?4 s?1 and EAMP2 R = 88.72 %, k = 4.00 × 10?4 s?1, respectively. The reason for the lower photoconversion of EAMP1 compared to the EAMP2 was analyzed through optimization of the molecular geometry of E- and Z-isomers in the ground state (S0) and first excited state (S1) by DFT/TD-DFT calculations with B3LYP/6-31+G(d,p) level of theory using IEFPCM in AcCN. It was found that E-isomers in the S0 have nonplanar conformation, while the Z-isomer of EAMP1 prefers twisted conformation and the Z-isomer of EAMP2 T-shaped conformation is energetically advantageous compared to the twisted one. The reason is the weak H….π noncovalent interaction (NCI) between 4-(dimethylamino)phenyl moiety and phthalimide ring. Moreover, the Z-isomer of EAMP2 is unusual stable up to 600 min at room temperature in dark compared to the EAMP1, which undergoes full Z→E relaxation for less than 60 min at the same conditions. The Z→E relaxation of EAMP2 is achieved for 90 min at 60 °C. The fluorescence E→Z switching behavior was studied by emission measurements in AcCN and 1,4-DOX as E-isomers and at PSS in room and liquid nitrogen (77 K) temperatures. In the polar and nonpolar solvents, red-shifted emissions with increased fluorescence quantum (Φfl) yields have been observed at PSS compared to the E-isomers. The molecular rotor behavior was studied in the binary mixture of glycerol:ethanol and the results show a sensitivity of the emission bands depending on the environmental viscosity. Time-resolved fluorescence decay measurements were performed in AcCN and 1,4-DOX as E-isomers and at PSS to estimate the mechanism of fundamental fluorescence bands. We found that dyes at PSS have longer lifetime (τ) compared to the E-isomers, especially in less polar 1,4-DOX.
Indirect solvent assisted tautomerism in 4-substituted phthalimide 2-hydroxy-Schiff bases
Antonov, Liudmil,Crochet, Aurelien,Deneva, Vera,Fromm, Katharina M.,Georgiev, Anton,Yordanov, Dancho
, (2020/05/08)
The paper presents the synthesis and characterization of two 4-substituted phthalimide 2-hydroxy-Schiff bases containing salicylic (4) and 2-hydroxy-1-naphthyl (5) moieties. The structural differences of 2-hydroxyaryl substituents, resulting in different enol/keto tautomeric behaviour, depending on the solvent environment were studied by absorption UV–Vis spectroscopy. Compound 5 is characterized by a solvent-dependent tautomeric equilibrium (KT in toluene = 0.12, acetonitrile = 0.22 and MeOH = 0.63) while no tautomerism is observed in 4. Ground state theoretical DFT calculations by using continuum solvation in MeOH indicate an energy barrier between enol/keto tautomer 5.6 kcal mol?1 of 4 and 0.63 kcal mol?1 of 5, which confirms the experimentally observed impossibility of the tautomeric equilibrium in the former. The experimentally observed specific solvent effect in methanol is modeled via explicit solvation. The excited state intramolecular proton transfer (ESIPT) was investigated by steady state fluorescence spectroscopy. Both compounds show a high rate of photoconversion to keto tautomers hence keto emissions with large Stokes shifts in five alcohols (MeOH, EtOH, 1-propanol, 1-butanol, and 1-pentanol) and various aprotic solvents (toluene, dichlormethane, acetone, AcCN). According to the excited state TDDFT calculations using implicit solvation in MeOH, it was found that enol tautomers of 4 and 5 are higher in energy compared to the keto ones, which explains the origin of the experimentally observed keto form emission.
Palladium(II) phthalocyanines efficiently promote phosphine-free Sonogashira cross-coupling reaction at room temperature
Platonova, Yana B.,Tomilova, Larisa G.,Volov, Alexander N.
, p. 224 - 228 (2020/09/17)
Herein we report that exceptionally simple and inexpensive Pd(II) complexes of phthalocyanines efficiently catalyze direct formation of diphenylacetylenes at ambient conditions with low loading of catalyst (0.5 mol%). Results of this study demonstrate that terminal alkynes reacted mildly with p-substituted aryl bromides at room temperature under Pd and Cu-cocatalysis to give the corresponding phenylacetylenes in yields up to 98%. Also we have examined this catalyst in Sonogashira cross-coupling with aryl chlorides and it was very effective and this reaction at room temperature that there is no examples in recent articles. This protocol represents the first use of palladium phthalocyanine as homogeneous catalyst in the Pd/Cu-promoted Sonogashira reaction. The palladium(II) phthalocyanine complex is significantly more active in Sonogashira cross-coupling between aryl halides and terminal alkynes as compared with traditional catalysts because of absence of palladium black formation through agglomeration of metal particles and deactivation of catalyst.
Preparation of new biologically active and water soluble dyes: Characterization, aggregation and extraction of metal ions from solutions
Touj, Nedra,Al-Ayed, Abdullah Sulaiman,Hamdi, Naceur
, p. 1398 - 1404 (2019/06/10)
The synthesis of metallo-phthalocyanines complexes (M = Co, Ni, Cu, Zn) containing azo dye were described in this study. The metallophthalocyanines have been supported by elemental analysis, UV-visible, FT-IR and NMR. The aggregation of phthalocyanine compounds was investigated in different solvents and concentrations. The newly synthesized metallophthalocyanines possess modest antibacterial activity against various Gram-positive and Gram-negative bacteria. Moreover, these complexes have been tested as antioxidant and presented remarkable activities by two different in vitro chemical assays. They were able to reduce DPPH % radical with IC50 values ranging from 3.8 to 7.5 μmol L-1 and some of them also reduced ABTS % radical cation.
Synthesizing method of 5-fluoro-3-methyl isobenzofuran-1(3H)-ketone
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Paragraph 0039-0042, (2019/01/23)
The invention relates to the technical field of medicine and relates to a synthesizing method of 5-fluoro-3-methyl isobenzofuran-1(3H)-ketone. The 5-fluoro-3-methyl isobenzofuran-1(3H)-ketone is synthesized by subjecting the initial raw material phthalimide to 8 steps such as nitration, reduction, cyclizing, diazotization, bromination and esterification. The method has the advantages that the preparation of the 5-fluoro-3-methyl isobenzofuran-1(3H)-ketone which is the key intermediate of the antitumor drug Lorlatinib (PF-06463922), total yield can reach 7.0% or above, and the method is simpleto operate, convenient in post-processing, low in time consumption, low in cost and beneficial to industrialization; the Lorlatinib is synthesized by subjecting the intermediate and 1-methyl-3-(( methylamino)methyl)-1H-pyrazol-5-nitrile to ammonolysis, substitution, coupling, chiral resolution and the like, and a new method is provided for the synthesizing of the antitumor drug Lorlatinib.
Development of three ways molecular logic gate based on water soluble phenazine fluorescent ‘selective ion’ sensor
Daniel Thangadurai,Nithya,Rakkiyanasamy
supporting information, p. 132 - 140 (2018/12/13)
New hydrophilic fluorescent selective ion sensor based on phenazine and phthalazine moieties, 1,1′-(phenazine-2,3-diyl)-bis(3-(1,4-dihydroxyphthalazin-6-yl)urea) (1), has been designed, synthesized and characterized. Interestingly, sensor 1 exhibits prominent “turn-on” and “turn-off” fluorogenic signaling at 580 nm towards Fe2+ & AcO? and Sr2+ & Cu2+, respectively. The fluorescence titration experiments shed light on the nature of the interaction between 1 and guest molecules (Fe2+, Sr2+, Cu2+ and AcO?), which divulge that 1 is flexible enough to orient itself according to the size of the guest molecule. Water mediated excited-state intramolecular proton transfer (ESIPT) and photo-induced electron transfer (PET) mechanisms are responsible for the dual behavior of 1, which binds with guest molecules in 1:1 stoichiometry. Based on the significant duplex fluorescence response of 1, a molecular logic gate keypad lock with sixteen “on” passwords for a storage system has been developed.
