Month: October 2022

In 2022,Bawden, Joseph C.; Francis, Paul S.; DiLuzio, Stephen; Hayne, David J.; Doeven, Egan H.; Truong, Johnny; Alexander, Richard; Henderson, Luke C.; Gomez, Daniel E.; Massi, Massimiliano; Armstrong, Blake I.; Draper, Felicity A.; Bernhard, Stefan; Connell, Timothy U. published an article in Journal of the American Chemical Society. The title of the article was 《Reinterpreting the Fate of Iridium(III) Photocatalysts-Screening a Combinatorial Library to Explore Light-Driven Side-Reactions》.Electric Literature of C7H3BrFN The author mentioned the following in the article:

Photoredox catalysts are primarily selected based on ground and excited state properties, but their activity is also intrinsically tied to the nature of their reduced (or oxidized) intermediates. Catalyst reactivity often necessitates an inherent instability, thus these intermediates represent a mechanistic turning point that affords either product formation or side-reactions. In this work, we explore the scope of a previously demonstrated side-reaction that partially saturates one pyridine ring of the ancillary ligand in heteroleptic iridium(III) complexes. Using high-throughput synthesis and screening under photochem. conditions, we identified different chem. pathways, ultimately governed by ligand composition The ancillary ligand was the key factor that determined photochem. stability. Following photoinitiated electron transfer from a sacrificial tertiary amine, the reduced intermediate of complexes containing 1,10-phenanthroline derivatives exhibited long-term stability. In contrast, complexes containing 2,2′-bipyridines were highly susceptible to hydrogen atom transfer and ancillary ligand modification. Detailed characterization of selected complexes before and after transformation showed differing effects on the ground and excited state reduction potentials dependent on the nature of the cyclometalating ligands and excited states. The implications of catalyst stability and reactivity in chem. synthesis was demonstrated in a model photoredox reaction. The results came from multiple reactions, including the reaction of 4-Bromo-2-fluorobenzonitrile(cas: 105942-08-3Electric Literature of C7H3BrFN)

4-Bromo-2-fluorobenzonitrile(cas:105942-08-3) is used as a reagent in the synthesis of picolinamide derivatives as a novel class of 11β-hydroxysteroid dehydrogenase type 1 (11β-HSD1) inhibitors.Electric Literature of C7H3BrFN 4-Bromo-2-fluorobenzonitrile is also used in the preparation of fluorinated CB2 receptor agonists for PET imaging.

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Reference of 2,4,6-Tris(diphenylamino)-3,5-difluorobenzonitrileOn October 6, 2021 ,《Photocatalytic Hydroaminoalkylation of Styrenes with Unprotected Primary Alkylamines》 was published in Journal of the American Chemical Society. The article was written by Askey, Hannah E.; Grayson, James D.; Tibbetts, Joshua D.; Turner-Dore, Jacob C.; Holmes, Jake M.; Kociok-Kohn, Gabriele; Wrigley, Gail L.; Cresswell, Alexander J.. The article contains the following contents:

A solution to these problems using organophotoredox catalysis, enabling a direct, modular and sustainable preparation of α-(di)substituted γ-arylamines, including challenging electron-neutral and moderately electron-rich aryl groups was reported. A broad range of functionalities were tolerated, and the reactions was run on multigram scale in continuous flow. The method was applied to a concise, protecting-group-free synthesis of the blockbuster drug Fingolimod, as well as a phosphonate mimic of its in-vivo active form (by iterative α-C-H functionalization of ethanolamine). The reaction was sequenced with an intramol. N-arylation to provided a general and modular access to valuable (spirocyclic) 1,2,3,4-tetrahydroquinolines and 1,2,3,4-tetrahydronaphthyridines. Mechanistic and kinetic studies supportes an irreversible hydrogen atom transfer activation of the alkylamine by the azidyl radical and some contribution from a radical chain. The reaction was photon-limited and exhibits a zero-order dependence on amine, azide, and photocatalyst, with a first-order dependence on styrene. In the experimental materials used by the author, we found 2,4,6-Tris(diphenylamino)-3,5-difluorobenzonitrile(cas: 1403850-00-9Reference of 2,4,6-Tris(diphenylamino)-3,5-difluorobenzonitrile)

2,4,6-Tris(diphenylamino)-3,5-difluorobenzonitrile(cas: 1403850-00-9) is cyanoarene-based donor-acceptor photocatalyst developed by the Zeitler group. While this catalyst has a balanced redox profile, allowing for its use in a variety of transformations, it stands out as the most reducing catalyst of the family.Reference of 2,4,6-Tris(diphenylamino)-3,5-difluorobenzonitrile

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

COA of Formula: C10H7BrN2On November 3, 1993 ,《Novel applications of vinylogous Mannich reactions. Total synthesis of rugulovasines A and B》 appeared in Journal of the American Chemical Society. The author of the article were Martin, Stephen F.; Liras, Spiros. The article conveys some information:

The total syntheses of the Ergot alkaloids rugulovasines A (I, R = MeNH, R1 = H) and B (R = H, R1 = MeNH) were completed in a concise sequence requiring only eight reactions from com. available 4-bromoindole. The two key steps of the synthesis were the vinylogous Mannich reaction of the iminium salt of II with the furan III and the cyclization of IV by a SRN1 reaction. Thus, 4-bromoindole was converted in a straightforward manner to the 3-acetaldehyde derivative, which after treatment with benzylmethylamine provided the intermediate enamine II. Treatment of II with silyloxyfuran III in the presence of acid produced IV via a vinylogous Mannich reaction. A photostimulated SRN1 reaction of IV was employed to construct the spirocyclic lactone moiety followed by hydrogenolysis gave rugulovasines A and B. The experimental process involved the reaction of 2-(4-Bromo-3-indolyl)acetonitrile(cas: 89245-35-2COA of Formula: C10H7BrN2)

2-(4-Bromo-3-indolyl)acetonitrile(cas: 89245-35-2) is a member of nitriles. Nitriles have been reduced to amines by many methods, especially by catalytic hydrogenation and by metal hydrides. Aliphatic and aromatic nitriles have also been reduced to nitro derivatives using hydrazinium monoformate in the presence of Raney-nickel.COA of Formula: C10H7BrN2

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Garcia-Monroy, Ricardo; Gonzalez-Calderon, Davir; Ramirez-Villalva, Alejandra; Mastachi-Loza, Salvador; Aguirre-de Paz, Jose G.; Fuentes-Benites, Aydee; Gonzalez-Romero, Carlos published their research in Journal of the Mexican Chemical Society in 2021. The article was titled 《Synthesis of novel benzylic 1,2,3-triazole-4-carboxamides and their in vitro activity against clinically common fungal species》.Formula: C9H7NO The article contains the following contents:

A library of novel benzylic 1,2,3-triazole-4-carboxamides I (R = Ph, 4-methylphenyl, 4-phenylphenyl; R1 = 4-methoxyphenyl, 2,6-dichlorophenyl, 2H-1,3-benzodioxol-5-yl, etc.) were obtained with acceptable yields via a one-pot procedure. The series of compounds I was screened for fungicidal activity and evaluated in vitro against four filamentous fungi and four Candida species. The former consisted of Aspergillus fumigatus, Trichosporon cutaneum, Rhizopus oryzae and Mucor hiemalis, and the latter consisted of C. krusei, C. albicans, C. utilis and C. glabrata. According to the in vitro assays, I (R = Ph, R1 = 2,6-dichlorophenyl; R = Ph, R1 = 2H-1,3-benzodioxol-5-yl) were the most efficient fungicidal agents (of all the test compounds) against R. oryzae, even better than the reference drug (itraconazole). Thus, I (R = Ph, R1 = 2,6-dichlorophenyl; R = Ph, R1 = 2H-1,3-benzodioxol-5-yl) represent important scaffolds that can be modified to increase antifungal activity. Addnl., they are candidates for complementary studies on the inhibition of clin. infections produced by Rhizopus spp. strains.3-Oxo-3-phenylpropanenitrile(cas: 614-16-4Formula: C9H7NO) was used in this study.

3-Oxo-3-phenylpropanenitrile(cas: 614-16-4) has been used to produce 2-benzoyl-3-furan-2-yl-acrylonitrile. It is an active methylene compound, useful in heterocyclic synthesis, e.g. polyfunctional pyridines and pyrimidines.Formula: C9H7NO

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Murugesan, Kathiravan; Donabauer, Karsten; Koenig, Burkhard published an article in 2021. The article was titled 《Visible-Light-Promoted Metal-Free Synthesis of (Hetero)Aromatic Nitriles from C(sp3)-H Bonds》, and you may find the article in Angewandte Chemie, International Edition.Quality Control of 4-Bromobenzonitrile The information in the text is summarized as follows:

The metal-free activation of C(sp3)-H bonds to value-added products is of paramount importance in organic synthesis. We report the use of the com. available organic dye 2,4,6-triphenylpyrylium tetrafluoroborate (TPP) for the conversion of methylarenes to the corresponding aryl nitriles via a photocatalytic process. Applying this methodol., a variety of cyanobenzenes have been synthesized in good to excellent yield under metal- and cyanide-free conditions. We demonstrate the scope of the method with over 50 examples including late-stage functionalization of drug mols. (celecoxib) and complex structures such as L-menthol, amino acids, and cholesterol derivatives Furthermore, the presented synthetic protocol is applicable for gram-scale reactions. In addition to methylarenes, selected examples for the cyanation of aldehydes, alcs. and oximes are demonstrated as well. Detailed mechanistic investigations have been carried out using time-resolved luminescence quenching studies, control experiments, and NMR spectroscopy as well as kinetic studies, all supporting the proposed catalytic cycle.4-Bromobenzonitrile(cas: 623-00-7Quality Control of 4-Bromobenzonitrile) was used in this study.

4-Bromobenzonitrile(cas: 623-00-7) has been used in the synthesis of 4-iodobenzonitrile via photo-induced aromatic Finkelstein iodination reaction.Quality Control of 4-Bromobenzonitrile It can also be used as an aryl halide test compound in developing greener reaction conditions for Suzuki cross-coupling between aryl halides and phenyl boronic acid.

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Marcin, Lawrence R.; Higgins, Mendi A.; Zusi, F. Christopher; Zhang, Yunhui; Dee, Michael F.; Parker, Michael F.; Muckelbauer, Jodi K.; Camac, Daniel M.; Morin, Paul E.; Ramamurthy, Vidhyashankar; Tebben, Andrew J.; Lentz, Kimberley A.; Grace, James E.; Marcinkeviciene, Jovita A.; Kopcho, Lisa M.; Burton, Catherine R.; Barten, Donna M.; Toyn, Jeremy H.; Meredith, Jere E.; Albright, Charles F.; Bronson, Joanne J.; Macor, John E.; Thompson, Lorin A. published an article in Bioorganic & Medicinal Chemistry Letters. The title of the article was 《Synthesis and SAR of indole- and 7-azaindole-1,3-dicarboxamide hydroxyethylamine inhibitors of BACE-1》.Recommanded Product: 3-Formyl-1H-indole-6-carbonitrile The author mentioned the following in the article:

Heterocyclic replacement of the isophthalamide Ph ring in hydroxyethylamine (HEA) BACE-1 inhibitors was explored. A variety of indole-1,3-dicarboxamide HEAs I (X = CH; R1 = R2 = Et, n-Pr, n-Bu; R1 = n-Bu, R2 = H, Me; R3 = H, F, CN; R4 = H, F, Cl, CF3, CO2H, etc.; R5 = 3-MeOC6H4CH2; R6 = H, F) exhibited potent BACE-1 enzyme inhibition, but displayed poor cellular activity. Improvements in cellular activity and aspartic protease selectivity were observed for 7-azaindole-1,3-dicarboxamide HEAs I (X = N; R1 = Bu, n-pentyl, isopentyl, MeOCH2CH2, R2 = Me; R1 = cyclopropylmethyl, R2 = n-Pr; R1R2N = 2-ethoxymethyl-1-piperidinyl, etc.; R3 = R4 = H; R5 = 3-MeOC6H4CH2, 3-MeOC6H4CO, cyclopropyl, etc.; R6 = H, F). A methylprolinol-bearing azaindole I [X = N; R1R2N = (R)-2-methoxymethyl-1-pyrrolidinyl; R3 = R4 = H; R5 = 3-MeOC6H4CH2; R6 = F] demonstrated robust reductions in rat plasma Aβ levels, but did not lower rat brain Aβ due to poor central exposure. The same compound exhibited a high efflux ratio in a bidirectional Caco-2 assay and was likely a substrate of the efflux transporter P-glycoprotein. X-ray crystal structures are reported for two indole HEAs in complex with BACE-1. In the experiment, the researchers used many compounds, for example, 3-Formyl-1H-indole-6-carbonitrile(cas: 83783-33-9Recommanded Product: 3-Formyl-1H-indole-6-carbonitrile)

3-Formyl-1H-indole-6-carbonitrile(cas: 83783-33-9) is a member of nitriles. Nitriles have been reduced to amines by many methods, especially by catalytic hydrogenation and by metal hydrides. Aliphatic and aromatic nitriles have also been reduced to nitro derivatives using hydrazinium monoformate in the presence of Raney-nickel.Recommanded Product: 3-Formyl-1H-indole-6-carbonitrile

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

In 2014,Mahtab, Reena; Srivastava, Ashish; Gupta, Nishi; Kushwaha, Sandeep Kumar; Tripathi, Aradhna published 《Synthesis of novel 2-benzylbenzo[d] thiazole-6-sulfonamide derivatives as potential anti inflammatory agent》.Journal of Chemical and Pharmaceutical Sciences published the findings.Formula: C8H6BrN The information in the text is summarized as follows:

The benzothiazole derivatives such as substituted 2-benzylbenzo[d]thiazole-6-sulfonamides I [R = H, 2-HO, 2-MeO, 3-Br] were synthesized by using sulfa drugs from substituted benzyl bromides. All the newly synthesized benzothiazole derivatives showed considerable anti-inflammatory activity. The chem. structures of the synthesized compounds were confirmed by means of IR, 1H-NMR, mass spectral and elemental anal. These compounds were screened for anti-inflammatory activity by carrageenan induced paw edema method in rats at a dose of 100 mg/kg body weight Among the tested compounds of benzothiazole derivatives, compounds I [R = 2-OH, 2-OMe, 2,5-(F)2, 4-Br] exhibited some anti-inflammatory activity but compounds I [R = H, 2-F, 4-F, 4-Cl, 3-Br] were more potent when compared to standard drug celecoxib. The experimental part of the paper was very detailed, including the reaction process of 2-(3-Bromophenyl)acetonitrile(cas: 31938-07-5Formula: C8H6BrN)

According to other reports, 2-(3-Bromophenyl)acetonitrile(cas: 31938-07-5) is used in the preparation of diarylpyrimidines (DAPYs) as HIV-1 non-nucleoside reverse transcriptase inhibitors.Formula: C8H6BrN

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

In 2017,Hammann, Jeffrey M.; Lutter, Ferdinand H.; Haas, Diana; Knochel, Paul published 《A Robust and Broadly Applicable Cobalt-Catalyzed Cross-Coupling of Functionalized Bench-Stable Organozinc Pivalates with Unsaturated Halides》.Angewandte Chemie, International Edition published the findings.Name: 4-Bromo-2-fluorobenzonitrile The information in the text is summarized as follows:

We report a robust and broadly applicable CoCl2-catalyzed cross-coupling between functionalized aryl and heteroaryl zinc pivalates and various electron-poor aryl and heteroaryl halides (X=Cl, Br, I). Couplings with (E)- or (Z)-bromo- or iodo-alkenes proceed with retention of configuration. Also, alkynyl bromides react with arylzinc pivalates providing arylated alkynes. The results came from multiple reactions, including the reaction of 4-Bromo-2-fluorobenzonitrile(cas: 105942-08-3Name: 4-Bromo-2-fluorobenzonitrile)

4-Bromo-2-fluorobenzonitrile(cas:105942-08-3) is used as a OLED intermediate, Pharmaceutical, electronic and chemical intermediate.Name: 4-Bromo-2-fluorobenzonitrile It is used in the synthesis of heterocycles and liquid crystals.

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts