36323-32-7

Upstream product

• 121-91-5 isophthalic acid 
• 100-58-3 phenylmagnesium bromide 
• 3770-82-9 1,3-dibenzoylbenzene 
• 626-19-7 Isophthalaldehyde 
• 108-86-1 bromobenzene 
• 99-63-8 benzene-1,3-dicarbonyl dichloride 

Downstream Products

• 3770-82-9 1,3-dibenzoylbenzene 
• 1453107-50-0 (13,14-diethyl-6,21-diphenylbenziporphyrinato)palladium-(II) 
• 1453107-46-4 1,3-bis-[phenyl(2-pyrrolyl)methyl]benzene 

Relevant academic research and scientific papers

Tetraphenylbenziporphyrin - A ligand for organometallic chemistry

6,11,16,21-Tetraphenylbenziporphyrin (TPBPH)H, an analogue of tetraphenylporphyrin with one of the pyrrole groups replaced by a benzene ring, is formed in good yield in the condensation of the appropriate precursor with pyrrole and benzaldehyde. (TPBPH)H

Light-driven MPV-type reduction of aryl ketones/aldehydes to alcohols with isopropanol under mild conditions

Alcohols are versatile structural motifs of pharmaceuticals, agrochemicals and fine chemicals. With respect to green chemistry, the development of more sustainable and cost-efficient processes for converting ketones/aldehydes to alcohols is highly desired. Herein, a direct light-driven strategy for reducing ketones/aldehydes to alcohols using isopropanol as the reducing agent and solvent, in the presence of t-BuOLi, under an air atmosphere at room temperature is developed. This operationally simple light-promoted Meerwein-Ponndorf-Verley (MPV) type reduction can be used to produce various benzylic alcohol derivatives as well as applied to bioactive molecules and PEEK model compounds, demonstrating its application potential.

Autocatalytic Carbonyl Arylation through In Situ Release of Aryl Nucleophiles from N-Aryl-N′-Silyldiazenes

A method for the catalytic generation of functionalized aryl alkali metals is reported. These highly reactive intermediates are liberated from silyl-protected aryl-substituted diazenes by the action of Lewis basic alkali metal silanolates, resulting in desilylation and loss of N2. Catalytic quantities of these Lewis bases initiate the transfer of the aryl nucleophile from the diazene to carbonyl and carboxyl compounds with superb functional-group tolerance. The aryl alkali metal can be decorated with electrophilic substituents such as methoxycarbonyl or cyano as well as halogen groups. The synthesis of a previously unknown cyclophane-like [4]arene macrocycle from a 1,3-bisdiazene combined with a 1,4-dialdehyde underlines the potential of the approach.

Near-infrared luminescent material of boron difluoride coordination-based ring-expanding porphyrin coordination compound

The invention provides a near-infrared luminescent material of boron difluoride coordination-based benzo ring-expanding porphyrin, wherein in the boron difluoride coordination compound of benzo ring-expanding porphyrin, a benzene ring substitutes a pyrrole ring, so that the stability of benzo ring-expanding porphyrin macrocyclic molecules is greatly improved. According to the invention, the emission wavelength of the benzo ring-expanding porphyrin boron difluoride coordination compound near-infrared luminescent material is in a red light range, and the material can emit strong light and is a good red light luminescent material; and compared with other benzene ring substituted porphyrins, the molecules in the near-infrared luminescent material of the invention obviously generate large red shift, so that the near-infrared luminescent material is widely applied to photodynamic research, nuclear magnetic imaging contrast agents and the like.

Synthesis of Nonaromatic and Aromatic Dithia Benzisapphyrins

A series of [24?€] dithia meta-benzisapphyrins and [22?€] dithia para-benzisapphyrins were synthesized by 3 + 2 condensation of appropriate benzitripyrrane with bithiophene diol under mild acid catalyzed conditions. The dithia m-benzisapphyrins and dithia p-benzisapphyrins were thoroughly characterized by HR-MS, 1D and 2D NMR, absorption, and electrochemical techniques. Our studies showed that dithia m-benzisapphyrins are nonaromatic, whereas the dithia p-benzisapphyrins are aromatic in nature. Thus, we demonstrated here that the dithiabenzisapphyrins can be made aromatic by replacing the m-phenylene moiety of the benzisapphyrin macrocycle with a p-phenylene unit. Furthermore, the studies also indicated that the aromaticity of the dithia p-benzisapphyrins was relatively more compared to the reported heterosapphyrins. The structural and spectral characteristics including aromaticity of the m-benzisapphyrins and p-benzisapphyrins were also discussed with the help of DFT, NICS, and TD-DFT studies.

Synthesis of Selenium and Tellurium Core-Modified Azuliporphyrinogens and Benziporphyrinogens and Corresponding Carbaporphyrinoids

The synthesis of selenium and tellurium core-modified carbaporphyrinogens was carried out by the reaction of functional selenophene/tellurophene diols with azulene or a benzitripyrrane in the presence of acid. The products were obtained in moderate yields and were characterized by using 1H and 13C NMR, UV-vis, FT-IR, CV, and HRMS spectroscopic techniques. Further, oxidation of the obtained core-modified carbaporphyrinogens in the presence of DDQ in CHCl3 afforded the corresponding carbaporphyrins in good yields. Benziporphyrins showed no indication of a ring current or macrocyclic aromaticity as confirmed by using proton NMR spectroscopy, but the addition of TFA gave rise to the formation of weakly diatropic dications.

Synthesis of benziporphyrins and heterobenziporphyrins and an assessment of the diatropic characteristics of the protonated species

Benzitripyrranes were prepared by reacting diphenyl-substituted benzenedicarbinols with excess pyrrole in the presence of BF3· Et2O. These dipyrrolic compounds underwent acid-catalyzed condensations with a pyrrole dialdehyde to afford good yields of diphenylbenziporphyrins, and further reaction with palladium(II) acetate gave stable organometallic derivatives. The X-ray crystal structure of a palladium(II) benziporphyrin showed that the system deviates significantly from planarity. Although the benzitripyrranes failed to give stable macrocyclic products with furan or thiophene dialdehydes, they afforded tetraphenyl heterobenziporphyrins upon reaction with diphenyl-substituted furan- or thiophenedicarbinols and BF3·Et2O. Benziporphyrins and their heteroanalogues showed no indication of a diamagnetic ring current by proton NMR spectroscopy, but addition of TFA gave rise to the formation of weakly diatropic dications.

Improved syntheses of meso-tetraarylbenziporphyrins and observations of substituent effects on the diatropic characteristics of these formally nonaromatic carbaporphyrinoids

Carbaporphyrinoid systems are widely investigated but improved routes to these systems are needed. A fairly direct route to tetraphenylbenziporphyrin has been reported previously starting from isophthalaldehyde and this approach has been adapted to make use of more easily accessible isophthalic acids. Isophthalic acid and 5-tert-butylisophthalic acid were converted into the related diacyl chlorides and reacted with excess benzene or chlorobenzene to give a series of diketones. These were reduced with sodium borohydride to give the corresponding dialcohols in virtually quantitative yields and this route allows the synthesis of >10 g quantities of these key intermediates. Reaction of these dicarbinols with pyrrole and benzaldehyde or 4-chlorobenzaldehyde in the presence of BF3·Et2O in dichloromethane, followed by oxidation with DDQ, gave a series of eight-different tetraarylbenziporphyrins in up to 32% yield. Although benziporphyrins are generally considered to be nonaromatic, they may exhibit trace amounts of global diatropic character and this appears to be enhanced by the presence of a tert-butyl group on the benzene moiety or the introduction of 4-chlorophenyl substituents. Addition of TFA to the NMR solutions generated dications that exhibit an unambiguous ring current effect where the internal CH proton NMR resonances appear upfield in the range of 5.05-5.65 ppm, while the external pyrrolic resonances show concomitant downfield shifts to give values between 7.08 and 7.86 ppm. A tert-butyl substituent again increased the diatropic character of the macrocycle, although replacement of meso-phenyl groups with more electron-withdrawing 4-chlorophenyl units had the opposite effect in this case. These results are consistent with the aromatic characteristics deriving from canonical forms that have [18]annulene substructures. Two examples of palladium(II) benziporphyrin complexes were prepared and these results demonstrate that the presence of 4-chlorophenyl or tert-butyl groupings do not have a negative impact on the formation of organometallic derivatives. The improved yields for the reported synthetic methodology and the new information that can be obtained by systematically altering the substitution patterns around the macrocyclic periphery will facilitate further development of the chemistry of benziporphyrins.

Tetraaryldimethoxybenziporphyrins. At the edge of carbaporphyrinoid aromaticity

(Chemical Equation Presented) A series of eight dimethoxybenziporphyrins were prepared in three steps from 1,3-dimethoxybenzene or 2,6-dimethoxytoluene. Dibromination, followed by lithium-halogen exchange and reaction with benzaldehyde gave dicarbinol int