57955-18-7

Upstream product

• 4539-51-9 2-aminocarbazole 
• 151-50-8 potassium cyanide 
• 56-23-5 tetrachloromethane 
• 86-74-8 9H-carbazole 
• 75898-34-9 2'-nitro-[1,1'-biphenyl]-4-carbonitrile 
• 10537-08-3 2-chloro-9H-carbazole 
• 57-13-6 urea 
• 3652-90-2 2-bromo-9H-carbazole 
• 124-38-9 carbon dioxide 
• 870703-52-9 9H-carbazol-2-yl trifluoromethanesulfonate 
• 109-74-0 propyl cyanide 
• 615-43-0 2-iodophenylamine 
• 75898-35-0 2'-amino-[1,1'-biphenyl]-4-carbonitrile 
• 126747-14-6 4-cyanophenylboronic acid 

Downstream Products

• 51094-28-1 9H-carbazole-2-carboxylic acid 
• 1395093-43-2 9-(3-(1-(2,6-diisopropylphenyl)-1H-imidazol-2-yl)phenyl)-9H-carbazole-2-carbonitrile 
• 1395093-45-4 2-(1-(2,6-diisopropylphenyl)-1H-imidazol-2-yl)-9-(3-(1-(2,6-diisopropylphenyl)-1H-imidazol-2-yl)phenyl)-9H-carbazole 
• 1395093-44-3 N-(2,6-diisopropylphenyl)-9-(3-(1-(2,6-diisopropylphenyl)-1H-imidazol-2-yl)phenyl)-9H-carbazole-2-carboximidamide 

Relevant academic research and scientific papers

Visible-light-driven Cadogan reaction

Visible-light-driven photochemical Cadogan-type cyclization has been discovered. The organic D-A type photosensitizer 4CzIPN found to be an efficient mediator to transfer energy from photons to the transient intermediate that breaks the barriers of deoxygenation in Cadogan reaction and enables a mild metal-free access to carbazoles and related heterocycles. DFT calculation results indicate mildly endergonic formation of the intermediate complex of nitrobiarenes and PPh3, which corresponds with experimental findings regarding reaction temperature. The robust synthetic capacity of the photoredox Cadogan reaction systems has been demonstrated by the viable productivity of a broad range of carbazoles and related N-heterocycles with good tolerance of various functionalities.

NaI/PPh3-Mediated Photochemical Reduction and Amination of Nitroarenes

A mild transition-metal- and photosensitizer-free photoredox system based on the combination of NaI and PPh3 was found to enable highly selective reduction of nitroarenes. This protocol tolerates a broad range of reducible functional groups such as halogen (Cl, Br, and even I), aldehyde, ketone, carboxyl, and cyano. Moreover, the photoredox catalysis with NaI and stoichiometric PPh3 provides also an alternative entry to Cadogan-type reductive amination when o-nitrobiarenes were used.

Reductive cyanation of organic chlorides using CO2 and NH3 via Triphos–Ni(I) species

Cyano-containing compounds constitute important pharmaceuticals, agrochemicals and organic materials. Traditional cyanation methods often rely on the use of toxic metal cyanides which have serious disposal, storage and transportation issues. Therefore, there is an increasing need to develop general and efficient catalytic methods for cyanide-free production of nitriles. Here we report the reductive cyanation of organic chlorides using CO2/NH3 as the electrophilic CN source. The use of tridentate phosphine ligand Triphos allows for the nickel-catalyzed cyanation of a broad array of aryl and aliphatic chlorides to produce the desired nitrile products in good yields, and with excellent functional group tolerance. Cheap and bench-stable urea was also shown as suitable CN source, suggesting promising application potential. Mechanistic studies imply that Triphos-Ni(I) species are responsible for the reductive C-C coupling approach involving isocyanate intermediates. This method expands the application potential of reductive cyanation in the synthesis of functionalized nitrile compounds under cyanide-free conditions, which is valuable for safe synthesis of (isotope-labeled) drugs.

Catalytic Cyanation Using CO2 and NH3

Li and co-workers describe the catalytic cyanation of organic halides with CO2 and NH3. In the presence of Cu2O/DABCO as the catalyst, a variety of aromatic bromides and iodides were transformed to the desired nitrile products with broad functional-group tolerance. Both 13C- and/or 15N-labeled nitriles were obtained conveniently with appropriately isotope-labeled CO2 and NH3. Construction of functionalized chemical compounds from small molecules in a highly selective and efficient manner is crucial for sustainable development. The chemical-based manufacturing sector of the future should aim to produce chemicals from very simple and abundant resources, just as nature uses CO2 and N2 to generate sugars, amino acids, and so forth. In practice, however, the utilization of CO2 for the generation of industrial products, such as drugs and related intermediates, still remains a major challenge. Here, we describe the facile cyanide-free production of high-value nitriles with CO2 and NH3 as the sole sources of carbon and nitrogen, respectively. This practical and catalytic methodology provides a unique strategy for the utilization of small molecules for sustainable and cost-effective applications. Selective cyanation of aryl halides was achieved with CO2 and NH3 as the only sources of carbon and nitrogen, respectively. In the presence of Cu catalysts under low pressure (3 atm), a variety of aromatic iodides and bromides were transformed to the desired nitrile products without the use of toxic metal cyanides. Notably, olefins, esters, amides, alcohols, and amino groups were tolerated. Mechanistic studies suggest that Cu(III)-aryl insertion by isocyanate intermediates is involved. [13C,15N]-labeled nitriles were conveniently accessible from the respective isotope-labeled CO2 and NH3 via this methodology.

Cyaniding method for preparing nitrile compound

The invention provides a cyaniding method for preparing a nitrile compound. Organic halide or pseudohalide, CO2 and NH3 which are low in price and are easily obtained and a reducing agent react, a selective cyaniding reaction is conducted in the presence of a transition metal catalyst, and the target product namely organic the nitrile compound is obtained. According to the cyaniding method for preparing the nitrile compound, a new reaction route is used, through a CO2 and NH3 reaction of metal catalysis, dehalogenation cyaniding or quasi halide cyaniding of halide or pseudohalide is directly achieved through a one-pot method, the problem is solved that a traditional cyanation reaction needs equivalent toxic cyanide, a new direct and convenient method for preparing isotope-labeled nitrile compounds is provided at the same time, and the method can be applied to medicine, tracing, biology and medicine research and development.

Photochemical intramolecular amination for the synthesis of heterocycles

Polycyclic heterocycles can be formed in good to excellent yields via photochemical conversion of the corresponding substituted aryl azides under irradiation with purple LEDs in a continuous flow reactor. The experimental set-up is tolerant to UV-sensitive functional groups while affording diverse carbazoles, as well as an indole and pyrrole framework, in short reaction times. The photochemical method is presumed to progress through a mechanism differing from the other methods of azide activation involving transition metal catalysis.

Nickel-Catalyzed Cyanation of Aryl Chlorides and Triflates Using Butyronitrile: Merging Retro-hydrocyanation with Cross-Coupling

We describe a nickel-catalyzed cyanation reaction of aryl (pseudo)halides that employs butyronitrile as a cyanating reagent instead of highly toxic cyanide salts. A dual catalytic cycle merging retro-hydrocyanation and cross-coupling enables the conversion of a broad array of aryl chlorides and aryl/vinyl triflates into their corresponding nitriles. This new reaction provides a strategically distinct approach to the safe preparation of aryl cyanides, which are essential compounds in agrochemistry and medicinal chemistry.

NEW DIBENZOFURANS AND DIBENZOTHIOPHENES

The present invention relates to compounds of formula (I) which are characterized in that they are substituted by at least one nitrile substituted carbazolyl group and their use in electronic devices, especially electroluminescent devices. When used as el

Rh(I)-catalyzed decarbonylation synthesis of carbazoles via C-N cleavage

A one-pot Rh(I)-catalyzed synthesis of 9-H carbazoles via C-N bond cleavage by activation of aldehyde C-H bonds is reported. This protocol offers good yields and tolerates a broad range of functional groups. Based on the extensive control experiments, we propose a plausible decarbonylation mechanism.

Synthesis of carbazoles by copper-catalyzed intramolecular C-H/N-H coupling

A Cu-catalyzed intramolecular C-H amination for the synthesis of carbazoles has been developed. The key to success is the installation of the picolinamide-based directing group, which is spontaneously removed after the coupling event. The Cu catalysis proceeded smoothly under Pd- and I(III)-free conditions, and its mild oxidation aptitude enables the rapid and concise construction of heteroatom-incorporated carbazole core π-systems.