Month: January 2023

N-Demethylation of N,N-Dimethylanilines by the Benzotriazole N-Oxyl Radical: Evidence for a Two-Step Electron Transfer-Proton Transfer Mechanism was written by Baciocchi, Enrico;Bietti, Massimo;Lanzalunga, Osvaldo;Lapi, Andrea;Raponi, Daniele. And the article was included in Journal of Organic Chemistry in 2010.COA of Formula: C9H10N2 This article mentions the following:

The reaction of the benzotriazole N-oxyl radical (BTNO) with a series of 4-X-N,N-dimethylanilines (X = CN, CF₃, CO₂CH₂CH₃, CH₃, OC₆H₅, OCH₃) has been investigated in CH₃CN. Product anal. shows that the radical, 4-X-C₆H₄N(CH₃)CH₂^·, is first formed, which can lead to the N-demethylated product or the product of coupling with BTNO. Reaction rates were found to increase significantly by increasing the electron-donating power of the aryl substituents (ρ⁺ = -3.8). With electron-donating substituents (X = CH₃, OC₆H₅, OCH₃), no intermol. deuterium kinetic isotope effect (DKIE) and a substantial intramol. DKIE are observed With electron-withdrawing substituents (X = CN, CF₃, CO₂CH₂CH₃), substantial values of both intermol. and intramol. DKIEs are observed These results can be interpreted on the basis of an electron-transfer mechanism from the N,N-dimethylanilines to the BTNO radical followed by deprotonation of the anilinium radical cation (ET-PT mechanism). By applying the Marcus equation to the kinetic data for X = CH₃, OC₆H₅, OCH₃ (rate-determining ET), a reorganization energy for the ET reaction was determined (λ_BTNO/DMA = 32.1 kcal mol^-1). From the self-exchange reorganization energy for the BTNO/BTNO^– couple, a self-exchange reorganization energy value of 31.9 kcal mol^-1 was calculated for the DMA^·1/DMA couple. In the experiment, the researchers used many compounds, for example, 4-(Ethylamino)benzonitrile (cas: 4714-63-0COA of Formula: C9H10N2).

4-(Ethylamino)benzonitrile (cas: 4714-63-0) belongs to nitriles. Nitriles are polar, as indicated by high dipole moments. As liquids, they have high relative permittivities, often in the 30s. Alkyl nitriles are sufficiently acidic to undergo deprotonation of the C-H bond adjacent to the CN group.Strong bases are required, such as lithium diisopropylamide and butyl lithium. The product is referred to as a nitrile anion. COA of Formula: C9H10N2

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

General Reductive Amination of Aldehydes and Ketones with Amines and Nitroaromatics under H₂ by Recyclable Iridium Catalysts was written by Sui, Dejun;Mao, Fei;Fan, Haipeng;Qi, Zhengliang;Huang, Jun. And the article was included in Chinese Journal of Chemistry in 2017.Computed Properties of C14H12N2 This article mentions the following:

Heterogeneous iridium catalysts were prepared and applied for the reductive amination of aldehydes and ketones with nitroaroms. and amines using H₂. The iridium catalysts were prepared by pyrolysis of ionic liquid 1-methyl-3-cyanomethylimidazoulium chloride ([MCNI]Cl) with iridium chloride (IrCl₃) in activated carbons. Iridium particles were well dispersed and stable in the N-doped carbon materials from [MCNI]Cl with activated carbon. The Ir@NC(600-2h) catalyst was found to be highly active and selective for the reductive amination of aldehydes and ketones using H₂ and a variety of nitrobenzenes and amines were selectively converted into the corresponding secondary and tertiary amines. The Ir@NC(600-2h) catalyst was reusable several times without evident deactivation. In the experiment, the researchers used many compounds, for example, 4-(Benzylamino)benzonitrile (cas: 10282-32-3Computed Properties of C14H12N2).

4-(Benzylamino)benzonitrile (cas: 10282-32-3) belongs to nitriles. Trimerization of aromatic nitriles requires harsh reaction conditions, high temperatures, long reaction times, and pressure. Asymmetric bioreduction of nitriles is an attractive route to produce optically active nitriles as current metal-catalyzed hydrogenations tend to have low reactivity.Computed Properties of C14H12N2

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Simple, efficient catalyst system for the palladium-catalyzed amination of aryl chlorides, bromides, and triflates was written by Wolfe, John P.;Tomori, Hiroshi;Sadighi, Joseph P.;Yin, Jingjun;Buchwald, Stephen L.. And the article was included in Journal of Organic Chemistry in 2000.Electric Literature of C14H12N2 This article mentions the following:

Palladium complexes supported by (2-PhC₆H₄)P(CMe₃)₂ (I) or (2-PhC₆H₄)PCy₂ (II; Cy = cyclohexyl) are efficient catalysts for the catalytic amination of a wide variety of aryl halides and triflates. Use of ligand I allows for the room-temperature catalytic amination of many aryl chloride, bromide, and triflate substrates, while ligand II is effective for the amination of functionalized substrates or reactions of acyclic secondary amines. The catalysts perform well for a large number of different substrate combinations at 80-110°, including chloropyridines and functionalized aryl halides and triflates using 0.5-1.0 mol% Pd; some reactions proceed efficiently at low catalyst levels (0.05 mol% Pd). These ligands are effective for almost all substrate combinations that have been previously reported with various other ligands, and they represent the most generally effective catalyst system reported to date. I and II are air-stable, crystalline solids that are com. available. Their effectiveness is due to a combination of steric and electronic properties that promote oxidative addition, Pd-N bond formation, and reductive elimination. In the experiment, the researchers used many compounds, for example, 4-(Benzylamino)benzonitrile (cas: 10282-32-3Electric Literature of C14H12N2).

4-(Benzylamino)benzonitrile (cas: 10282-32-3) belongs to nitriles. There has been no report on the microbial biosynthesis of nitriles and the physiological function of such enzymes, nor was it not even known whether aliphatic and aromatic nitriles are biological compounds or just petrochemicals. Nitrile groups in organic compounds can undergo a variety of reactions depending on the reactants or conditions. A nitrile group can be hydrolyzed, reduced, or ejected from a molecule as a cyanide ion.Electric Literature of C14H12N2

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Base-promoted N-alkylation using formamides as the N-sources in neat water was written by Chen, Wen-Xin;Zhang, Cai-Yun;Shao, Li-Xiong. And the article was included in Tetrahedron in 2014.Related Products of 37812-51-4 This article mentions the following:

An efficient catalyst-free, alternative method for the C-N bond formation reaction of alkyl electrophiles using formamides as the N-sources was achieved under mild conditions. The reaction possesses the advantages of a broad range of substrates scope and wide functional group tolerance. It should also be noted that this process was performed using the environmentally benign water as the sole solvent, and high yield can also be achieved in ten-gram scale. In the experiment, the researchers used many compounds, for example, 4-(Morpholinomethyl)benzonitrile (cas: 37812-51-4Related Products of 37812-51-4).

4-(Morpholinomethyl)benzonitrile (cas: 37812-51-4) belongs to nitriles. The electronic structure of nitriles is very similar to that of an alkyne with the main difference being the presence of a set of lone pair electrons on the nitrogen. Nitriles are susceptible to hydrogenation over diverse metal catalysts. The reaction can afford either the primary amine (RCH2NH2) or the tertiary amine ((RCH2)3N), depending on conditions.Related Products of 37812-51-4

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

ZrCl₄/[bmim]BF₄-Catalyzed condensation of salicylaldehydes and malononitrile: Single-step synthesis of 3-cyanocoumarin derivatives was written by Valizadeh, Hassan;Mahmoodian, Manzar;Gholipour, Hamid. And the article was included in Journal of Heterocyclic Chemistry in 2011.Computed Properties of C14H14N2O2 This article mentions the following:

A versatile and efficient single-step route to 3-cyanocoumarins via Knoevenagel condensation of salicylaldehydes and malononitrile using ZrCl₄ as the catalyst (15 mol %) in ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate as reaction medium and catalyst is described. The novel procedure features single step, short reaction time, good yields, and simple workup. J. Heterocyclic Chem., (2011). In the experiment, the researchers used many compounds, for example, 7-(Diethylamino)-2-oxo-2H-chromene-3-carbonitrile (cas: 51473-74-6Computed Properties of C14H14N2O2).

7-(Diethylamino)-2-oxo-2H-chromene-3-carbonitrile (cas: 51473-74-6) belongs to nitriles. The R-C-N bond angle in and nitrile is 180° which give a nitrile functional group a linear shape. Both the carbon and the nitrogen are sp hydridized which leaves them both with two p orbitals which overlap to form the two π bond in the triple bond. Some nitriles are manufactured by heating carboxylic acids with ammonia in the presence of catalysts. This process is used to make nitriles from natural fats and oils, the products being used as softening agents in synthetic rubbers, plastics, and textiles and for making amines.Computed Properties of C14H14N2O2

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

“On-Water” Palladium-Catalyzed Tandem Cyclization Reaction for the Synthesis of Biologically Relevant 4-Arylquinazolines was written by Yuan, Shuo;Yu, Bin;Liu, Hong-Min. And the article was included in Chemistry – A European Journal in 2019.Safety of 2-Amino-3,5-dibromobenzonitrile This article mentions the following:

The quinazoline scaffold is prevalent in pharmaceutically relevant mols. that show diverse biol. activities. An efficient “on-water” palladium-catalyzed tandem cyclization reaction from com. available arylboronic acids RB(OH)₂ (R = Ph, 3-nitrophenyl, naphthalen-1-yl, etc.) and benzonitriles (E)-2-CN-R¹C₆H₄N=C(R²)N(Me)₂ [R¹ = H, 5-Me, 4,5-(OMe)₂, etc.; R² = H, Me] that enable the rapid access to 4-arylquinazoline scaffolds I [R³ = H, 7-Me, 6,7-(OMe)₂, etc.] in good to excellent yields (45 examples, up to 98% yield) was reported. This protocol has shown good functional group tolerance and broad substrate scope. The reaction was also performed on a gram scale and successfully applied to the synthesis of the highly potent and selective PI3Kδ inhibitor II, showing the practicability and synthetic utility of the protocol. In this reaction, the quinazoline scaffold I is efficiently constructed with the simultaneous formation of one C-C bond and one C-N bond. Collectively, the protocol could serve as an alternative strategy to synthesize biol. important quinazoline scaffolds. In the experiment, the researchers used many compounds, for example, 2-Amino-3,5-dibromobenzonitrile (cas: 68385-95-5Safety of 2-Amino-3,5-dibromobenzonitrile).

2-Amino-3,5-dibromobenzonitrile (cas: 68385-95-5) belongs to nitriles. The R-C-N bond angle in and nitrile is 180° which give a nitrile functional group a linear shape. Both the carbon and the nitrogen are sp hydridized which leaves them both with two p orbitals which overlap to form the two π bond in the triple bond. Nitriles are susceptible to hydrogenation over diverse metal catalysts. The reaction can afford either the primary amine (RCH2NH2) or the tertiary amine ((RCH2)3N), depending on conditions.Safety of 2-Amino-3,5-dibromobenzonitrile

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Stable and reusable nanoscale Fe₂O₃-catalyzed aerobic oxidation process for the selective synthesis of nitriles and primary amides was written by Murugesan, Kathiravan;Senthamarai, Thirusangumurugan;Sohail, Manzar;Sharif, Muhammad;Kalevaru, Narayana V.;Jagadeesh, Rajenahally V.. And the article was included in Green Chemistry in 2018.Application In Synthesis of 3-Methylthiophene-2-carbonitrile This article mentions the following:

The sustainable introduction of nitrogen moieties in the form of nitrile or amide groups in functionalized mols. is of fundamental interest because nitrogen-containing motifs are found in a large number of life science mols., natural products and materials. Hence, the synthesis and functionalization of nitriles and amides from easily available starting materials using cost-effective catalysts and green reagents is highly desired. In this regard, herein the nanoscale iron oxide-catalyzed environmentally benign synthesis of nitriles and primary amides from aldehydes and aqueous ammonia in the presence of 1 bar O₂ or air was reported. Under mild reaction conditions, this iron-catalyzed aerobic oxidation process proceeds to synthesize functionalized and structurally diverse aromatic, aliphatic and heterocyclic nitriles. Addnl., applying this iron-based protocol, primary amides have also been prepared in a water medium. In the experiment, the researchers used many compounds, for example, 3-Methylthiophene-2-carbonitrile (cas: 55406-13-8Application In Synthesis of 3-Methylthiophene-2-carbonitrile).

3-Methylthiophene-2-carbonitrile (cas: 55406-13-8) belongs to nitriles. Nitrile function is a very important functional group because it can be manipulated to other functional groups such as carboxylic acid by hydrolysis or amine by reduction, respectively. Some nitriles are manufactured by heating carboxylic acids with ammonia in the presence of catalysts. This process is used to make nitriles from natural fats and oils, the products being used as softening agents in synthetic rubbers, plastics, and textiles and for making amines.Application In Synthesis of 3-Methylthiophene-2-carbonitrile

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Synthesis, characterization, and SAR of arylated indenoquinoline-based cholinesterase and carbonic anhydrase inhibitors was written by Ekiz, Makbule;Tutar, Ahmet;Oekten, Salih;Buetuen, Burcu;Kocyigit, Uemit M.;Taslimi, Parham;Topcu, Guelacti. And the article was included in Archiv der Pharmazie (Weinheim, Germany) in 2018.Product Details of 68385-95-5 This article mentions the following:

The authors report the synthesis of bromoindenoquinolines (15a-f) by Friedlander reactions in low yields (13-50%) and the conversion of the corresponding phenyl-substituted indenoquinoline derivatives 16-21 in high yields (80-96%) by Suzuki coupling reactions. To explore the structure-activity relationship (SAR), their inhibition potentials to inhibit acetylcholinesterase (AChE), butyrylcholinesterase (BChE), and human carbonic anhydrase cyctosolic (hCA I and II) enzymes were determined Monophenyl (16-18) indenoquinolines significantly inhibited the AChE and BChE enzymes in ranges of IC₅₀ 37-57 nM and 84-93 nM, resp., compared with their starting materials 15a-c and reference compounds (galanthamine and tacrine). These novel arylated indenoquinoline-based derivatives were effective inhibitors of the BChE, hCA I and II, BChE and AChE enzymes with K_i values in the range of 37±2.04 to 88640±1990 nM for AChE, 120.94±37.06 to 1150.95±304.48 nM for hCA I, 267.58±98.05 to 1568.16±438.67 nM for hCA II, and 84±3.86 to 144120±2910 nM for BChE. As a result, monophenyl indenoquinolines 16-18 may have promising anti-Alzheimer drug potential and 3,8-dibromoindenoquinoline amine (15f) can be novel hCA I and hCA II enzyme inhibitors. In the experiment, the researchers used many compounds, for example, 2-Amino-3,5-dibromobenzonitrile (cas: 68385-95-5Product Details of 68385-95-5).

2-Amino-3,5-dibromobenzonitrile (cas: 68385-95-5) belongs to nitriles. Trimerization of aromatic nitriles requires harsh reaction conditions, high temperatures, long reaction times, and pressure. In addition, Nitriles can react with alkynes, which leads to an increase in carbon chain length (carbocyanation).Product Details of 68385-95-5

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Lewis acid-base integrated robust metal-organic framework and reconfigurable composite for solvent-free Biginelli condensation and tandem catalysis with size selectivity was written by Seal, N.;Neogi, S.. And the article was included in Materials Today Chemistry in 2022.Safety of 2-(Anthracen-9-ylmethylene)malononitrile This article mentions the following:

Aiming at environmentally benign catalyzes with less energy consumption, reduction in chem. usage and minimization of wastes, metal-organic frameworks (MOFs) combining basic functionality enriched pores and unsaturated metal centers (UMCs) is most promising. Alternatively, astute tuning of channel dimension in these materials can benefit much anticipated size-exclusive catalysis, whereas fabrication of flexible MOF-composite is imperative considering facile applicability over real-life platforms. The pillar-bilayered and hydrolytically robust MOF, built from tri-carboxylate ligand, linear linker and solvent-bound [Cd₃(COO)₆] secondary building unit exhibits N-functionality enriched porous channels and activation-driven generation of open metal sites. Benefiting from unique bifunctional character, the MOF acts as excellent solvent-free catalyst toward one-pot Biginelli reaction and deacetalization-Knoevenagel condensation under mild condition. Both the reactions transpire with broad substrate scope, high recyclability and superior activity to contemporary materials, wherein single-crystal X-ray diffraction is first time applied as product characterization tool. Judiciously designed control experiments validate individual catalytic routes, thereby substantiating the importance of contrasting pore-functionalities at the interface of structure-property synergism. To the best of three-component coupling and acid-base tandem catalysis, substrates with incompatible mol. dimension to that of the twofold interpenetration generated optimized pores exhibit insignificant conversion and demonstrate unprecedented pore-fitting-actuated size selectivity. In view of practically advanced and eco-friendly substrate design, reconfigurable MOF-cotton fiber composite is fabricated via in situ growth, which delivered excellent yields for both these reactions with comparable reusability to that of pristine framework, delineating a paradigm shift to smart, futuristic and green strategy in synergistic catalysis. In the experiment, the researchers used many compounds, for example, 2-(Anthracen-9-ylmethylene)malononitrile (cas: 55490-87-4Safety of 2-(Anthracen-9-ylmethylene)malononitrile).

2-(Anthracen-9-ylmethylene)malononitrile (cas: 55490-87-4) belongs to nitriles. Nitrile compounds can be prepared by the incorporation of a cyanide source through C–C bond formation or by dehydration of primary carboxamides. In conventional organic reductions, nitrile is reduced by treatment with lithium aluminium hydride to the amine. Reduction to the imine followed by hydrolysis to the aldehyde takes place in the Stephen aldehyde synthesis, which uses stannous chloride in acid.Safety of 2-(Anthracen-9-ylmethylene)malononitrile

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Anil Synthesis in the Design of Push-Pull Systems. Synthesis of 2- and 4-(4-Styrylphenyl)-substituted Diphenylpyrimidines was written by Harutyunyan, A. A.;Panosyan, H. A.;Safaryan, M. S.;Gukasyan, G. T.;Danagulyan, G. G.. And the article was included in Russian Journal of Organic Chemistry in 2020.Product Details of 5203-15-6 This article mentions the following:

The potential of anil synthesis for the preparation of 2,4,6-triaryl-substituted pyrimidines I (R = H, OMe, i-Pr; R¹ = H; RR¹ = -OCH₂O-) and II (R² = H, isobutoxy) with an extended chain of delocalized π-bonds was studied. The reaction of (E)-3-phenyl-1-arylprop-2-en-1-ones 4-R³ C₆H₄C(O)CH=CHC(O)C₆H₅ (R³ = H, Me) with benzamidine hydrochlorides 4-R²C₆H₄C(NH₂)=NH.HCl in ethanol in the presence of KOH gave pyrimidines III. The synthesized pyrimidines III were reacted with (E)-N-(phenyl- or 2-chlorophenyl)-1-arylmethanimines 4-R-5-R¹C₆H₃CH=N(2-R⁴C₆H₄) (R⁴ = H, 2-Cl) in DMF in the presence of a KOH/LiH mixture to obtain (E)-4,6-diphenyl-2-(4-styrylphenyl)pyrimidines I and (E)-2,6-diphenyl-4-(4-styrylphenyl)pyrimidines II. In the experiment, the researchers used many compounds, for example, 4-iso-Butoxybenzonitrile (cas: 5203-15-6Product Details of 5203-15-6).

4-iso-Butoxybenzonitrile (cas: 5203-15-6) belongs to nitriles. Trimerization of aromatic nitriles requires harsh reaction conditions, high temperatures, long reaction times, and pressure. In addition, Nitriles can react with alkynes, which leads to an increase in carbon chain length (carbocyanation).Product Details of 5203-15-6

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts