Month: January 2023

New ligands for nickel catalysis from diverse pharmaceutical heterocycle libraries was written by Hansen, Eric C.;Pedro, Dylan J.;Wotal, Alexander C.;Gower, Nicholas J.;Nelson, Jade D.;Caron, Stephane;Weix, Daniel J.. And the article was included in Nature Chemistry in 2016.Computed Properties of C7H6N2O This article mentions the following:

Ligands are essential for controlling the reactivity and selectivity of reactions catalyzed by transition metals. Access to large phosphine ligand libraries has become an essential tool for the application of metal-catalyzed reactions industrially, but these existing libraries are not well suited to new catalytic methods based on non-precious metals (for example, Ni, Cu and Fe). The development of the requisite nitrogen- and oxygen-based ligand libraries lags far behind that of the phosphines and the development of new libraries is anticipated to be time consuming. Here we show that this process can be dramatically accelerated by mining for new ligands in a typical pharmaceutical compound library that is rich in heterocycles. Using this approach, we were able to screen a structurally diverse set of compounds with minimal synthetic effort and identify several new ligand classes for nickel-catalyzed cross-electrophile coupling. These new ligands gave improved yields for challenging cross-couplings of pharmaceutically relevant substrates compared with those of those of previously published ligands. In the experiment, the researchers used many compounds, for example, 4-methoxypicolinonitrile (cas: 36057-44-0Computed Properties of C7H6N2O).

4-methoxypicolinonitrile (cas: 36057-44-0) belongs to nitriles. Nitrile carbon shifts are in the range of 115�25 ppm whereas in isonitriles the shifts are around 155�65 ppm. 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.Computed Properties of C7H6N2O

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Study of the microwave-assisted hydrolysis of nitriles and esters and the implementation of this system in rapid microwave-assisted Pd-catalyzed amination was written by Van Baelen, Gitte;Maes, Bert U. W.. And the article was included in Tetrahedron in 2008.Name: 4-(Benzylamino)benzonitrile This article mentions the following:

Microwave-assisted hydrolysis of benzonitriles and Me benzoates has been studied using a toluene/concentrated aqueous KOH two phase system in the presence and absence of phase transfer catalyst. Conditions to allow and avoid smooth hydrolysis could be identified. Based on the latter, the first microwave protocol which allows the rapid Pd-catalyzed amination of aliphatic amines with chlorobenzenes containing sensitive functional groups has been developed. In the experiment, the researchers used many compounds, for example, 4-(Benzylamino)benzonitrile (cas: 10282-32-3Name: 4-(Benzylamino)benzonitrile).

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. Industrially, the main methods for producing nitriles are ammoxidation and hydrocyanation. Both routes are green in the sense that they do not generate stoichiometric amounts of salts.Name: 4-(Benzylamino)benzonitrile

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Heterometallic coordination polymers: syntheses, structures and heterogeneous catalytic applications was written by Bansal, Deepak;Pandey, Saurabh;Hundal, Geeta;Gupta, Rajeev. And the article was included in New Journal of Chemistry in 2015.Recommanded Product: 2-(Anthracen-9-ylmethylene)malononitrile This article mentions the following:

A metalloligand Na[Co(L)₂] (1) of the ligand H₂L (N²,N⁶-bis(4,5-dihydrothiazol-2-yl)pyridine-2,6-dicarboxamide) offering appended thiazoline rings has been used for the synthesis of one-dimensional {Co³⁺L₂Zn²⁺(H₂O)₂}·ClO₄ (2), {Co³⁺L₂Cd²⁺}·ClO₄ (3) and {Co³⁺L₂Hg²⁺Cl} (4) coordination polymers. 1 Offers appended thiazoline rings having both soft sulfur and hard nitrogen donors. The crystal structures of 2 and 3 display the coordination of hard thiazoline-N donors to Zn²⁺ and Cd²⁺ ions. 4 Illustrates the bonding through both hard thiazoline-N and soft thiazoline-S donors. The three heterometallic coordination polymers have been used as reusable heterogeneous catalysts for the ring-opening reactions of oxiranes and thiairanes; Knoevenagel condensation of benzaldehydes and benzothialdehydes; and cyanation reactions of aldehydes and carbothialdehydes. The authors’ results demonstrate that the relative size and Lewis acidity of secondary metals potentially control the catalytic outcome via preferential interaction with the substrates. In the experiment, the researchers used many compounds, for example, 2-(Anthracen-9-ylmethylene)malononitrile (cas: 55490-87-4Recommanded Product: 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. 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.Recommanded Product: 2-(Anthracen-9-ylmethylene)malononitrile

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

New Green, Recyclable Magnetic Nanoparticles Supported Amino Acids as Simple Heterogeneous Catalysts for Knoevenagel Condensation was written by Girija, D.;Bhojya Naik, H. S.;Kumar, B. Vinay;Sudhamani, C. N.;Harish, K. N.. And the article was included in Letters in Organic Chemistry in 2013.SDS of cas: 51473-74-6 This article mentions the following:

Coumarin derivatives were synthesized using magnetically recoverable iron oxide nanoparticles supported amino acids as heterogeneous catalysts via one-pot multi component reaction using MW irradiation Easy recovery of the catalyst using an external magnet, efficient recycling, and reusable without significant loss of their catalytic efficiency makes the protocol greener and sustainable. In the experiment, the researchers used many compounds, for example, 7-(Diethylamino)-2-oxo-2H-chromene-3-carbonitrile (cas: 51473-74-6SDS of cas: 51473-74-6).

7-(Diethylamino)-2-oxo-2H-chromene-3-carbonitrile (cas: 51473-74-6) belongs to nitriles. Trimerization of aromatic nitriles requires harsh reaction conditions, high temperatures, long reaction times, and pressure. 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.SDS of cas: 51473-74-6

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Ruthenium(II) bis(hydrazone) complexes derived from 1,3,4-oxadiazoles: Synthesis, crystal structure and catalytic application in N-alkylation reactions was written by Prakash, Govindan;Ramachandran, Rangasamy;Nirmala, Muthukumaran;Viswanathamurthi, Periasamy;Sanmartin, Jesus. And the article was included in Inorganica Chimica Acta in 2015.Electric Literature of C14H12N2 This article mentions the following:

1,3,4-Oxadiazoles (A-C) were derived via a series of reactions between isoniazid and salicylaldehydes. While reacting the oxadiazoles with [RuHCl(CO)(PPh₃)₃] in the presence of NaOH, mononuclear ruthenium(II) complexes bearing ‘salen’ type N,N’-bis(salicylidene)hydrazone ligands (1–3) were obtained. The oxadiazoles and ruthenium(II) complexes were characterized by anal. and spectral methods. The single crystal XRD analyses of complexes 1 and 2 suggested an octahedral geometry around ruthenium(II) ions in which the bis(hydrazone) act as mononeg. bidentate ligands. Also the presence of an intramol. hydrogen bonding between the hydroxyl proton and one of the azomethine nitrogens in all the complexes. Further, the complexes were proved as versatile catalysts for the N-alkylation of amines with alcs. under optimized reaction conditions. 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. Trimerization of aromatic nitriles requires harsh reaction conditions, high temperatures, long reaction times, and pressure. Industrially, the main methods for producing nitriles are ammoxidation and hydrocyanation. Both routes are green in the sense that they do not generate stoichiometric amounts of salts.Electric Literature of C14H12N2

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

La-Mg mixed oxide as a highly basic water resistant catalyst for utilization of CO₂ in the synthesis of quinazoline-2,4(1H,3H)-dione was written by Rasal, Kalidas B.;Yadav, Ganapati D.. And the article was included in RSC Advances in 2016.Application In Synthesis of 2-Amino-3-chlorobenzonitrile This article mentions the following:

The synthesis of quinazoline-2,4(1H,3H)-dione was done by direct utilization of CO₂ in the cyclization of 2-aminobenzonitrile (2-ABN) using lanthanum magnesium mixed oxide (La-Mg MO) as a strong basic catalyst under mild reaction conditions in water. It gave a conversion of~92% with 100% selectivity at 140 °C in 14 h. La-Mg MO was prepared by hydrothermal method using urea as homogeneous precipitating agent. The catalyst was characterized by different anal. techniques like BET, XRD, FT-IR, scanning electron microscope, and TGA, and the basicity by CO₂-TPD and acidity by NH₃ TPD. Various reaction parameters were studied to predict the reaction mechanism and kinetics. The reaction follows the Langmuir-Hinshelwood-Hougen-Watson (LHHW) type kinetics model with an apparent activation energy of 23.3 kcal mol^-1. The catalyst was recycled three times with an insignificant change in activity. The overall process is clean and green. In the experiment, the researchers used many compounds, for example, 2-Amino-3-chlorobenzonitrile (cas: 53312-77-9Application In Synthesis of 2-Amino-3-chlorobenzonitrile).

2-Amino-3-chlorobenzonitrile (cas: 53312-77-9) belongs to nitriles. Nitriles are polar, as indicated by high dipole moments. As liquids, they have high relative permittivities, often in the 30s. 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.Application In Synthesis of 2-Amino-3-chlorobenzonitrile

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Nickel-catalyzed cross-coupling of unactivated alkyl halides using bis(pinacolato)diboron as reductant was written by Xu, Hailiang;Zhao, Chenglong;Qian, Qun;Deng, Wei;Gong, Hegui. And the article was included in Chemical Science in 2013.Recommanded Product: 4-methoxypicolinonitrile This article mentions the following:

(Pinacolato)diboron was used as the terminal reductant which allowed the efficient Ni-catalyzed coupling of unactivated secondary and primary alkyl halides, generating the C(sp³)-C(sp³) coupling products in good yields. The mild catalytic conditions displayed an excellent functional group tolerance and good chemoselectivities which required only 1.5 equivalent of primary bromides for the coupling with secondary bromides. Mechanistic studies suggest that an in-situ organoborane/Suzuki process was not likely and was proved that the base and ligand had more profound impact on selecting this reductive coupling pathway. The good chemoselectivity appears to be evoked by the formation of Ni-Bpin catalytic intermediates which demands matched sizes and reactivities of the alkyl halide coupling partners for optimal coupling efficiency. In the experiment, the researchers used many compounds, for example, 4-methoxypicolinonitrile (cas: 36057-44-0Recommanded Product: 4-methoxypicolinonitrile).

4-methoxypicolinonitrile (cas: 36057-44-0) 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. Asymmetric bioreduction of nitriles is an attractive route to produce optically active nitriles as current metal-catalyzed hydrogenations tend to have low reactivity.Recommanded Product: 4-methoxypicolinonitrile

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Preparation of N-substituted amidines was written by Cooper, F. C.;Partridge, M. W.. And the article was included in Journal of the Chemical Society in 1953.Application of 5203-15-6 This article mentions the following:

PhNH₂ (I) (10.1 g.), 25.4 g. 4-MeC₆H₄CN (II), 5 g. powd. Na, and 100 cc. PhMe-free C₆H₆ (III) refluxed 3 days and worked up as described by Lottermoser [J. prakt. Chem. 54, 113(1896)] gave 95% 4-MeC₆H₄C(:NH)NHPh (IV) (analyses indicated 88% CN^– and 75% PhMe based on the equation: 2 RCN + ArNH₂ + 2 Na â†?RC(:NAr)NH^– Na⁺ + RH + NaCN). I (20.2 g.), 25.4. g. II, 5 g. powd. Na, and 100 mL. III as in the previous example gave 96% IV and 0.5% kyanphenin (V). I (9.3 g.), 3.9 g. finely powd. NaNH₂ and 100 cc. C₆H₆ refluxed about 1.25 h., 10.3 g. PhCN (VI) added, and the whole refluxed 2.25 h. gave 12.6 g. PhC(:NH)NHPh (VII), m. 114-15°; with granular NaNH₂, the yield of VII was 57%, and with PhNMe₂ as solvent, 23%. I (9.3 g.), 2.3 g. Na, 10.3 g. VI, and 100 cc. dry C₆H₆ refluxed 27 h. evolved no permanent gas; the products were VII, PhCH₂NH₂ (VIII) (identified as benzylammonium picrate), and BzH; I and Na in boiling C₆H₆ gave about 2% PhNHNa; VII and Na in boiling C₆H₆ gave no permanent gas and small amounts of VIII and I; I and VI refluxed 8 h. gave a trace of PhC(:NPh)NHPh. Two procedures were used to prepare the following compounds in procedure A, 0.1 mol each of powd. Na, the amine, and the nitrile in 100 cc. dry C₆H₆ were refluxed 20-30 h., 15 cc. EtOH was added, the base extracted into aqueous MeCH(OH)CO₂H, isolated by addition of aqueous NH₃, and crystallized from petr. ether; in Procedure B, granular NaNH₂ was used in place of the Na of Procedure A (R, R’ in RC(:NH)NHR’, procedure, % yield, m. p., and m.p. of picrate): 4-MeC₆H₄, Ph, A, 65, 151-2°, 152-3°; 4-MeOC₆H₄, Ph, A, 51, 147-8°, 129-30°; 4-ClC₆H₄, Ph, A, 64, 140-1°, 175-6°; 4-sec-BuOC₆H₄, Ph, A, 63, 116.0-16.5°, 138-40°; Ph, 2-MeC₆H₄, A, 61, 109-10°, 152-3°; Ph, 4-MeOC₆H₄, A, 73, 115.5-16.5°, 171-3°; Ph, 2-C₁₀H₇, A, 39 (Procedure B gave 54%), 128.5-9.5°, 216.5-18.0°; Ph, 2-C₅H₄N, A, 65, 98.5-9.5°, 206-7°; Ph, cyclohexyl, A, 43, 115-16°, 142-3°; 2-MeC₆H₄, Ph, B, 47 122-3°, 175-6°; 4-PhOC₆H₄, Ph, A, 83, 183.5-4.5°, 145-6°; Ph, 2-thiazolyl, B, 6, 90-1°, 162-3°; PhCH₂, Ph, B, 64, 140-1°, 109-10°; Me, Ph, B, 36, -, 190-1°; 2-phenylbenzimidazole, B, 72, 299-301°, 275-6° (decomposition). The following were prepared incidental to the above: p-ClC₆H₄NHCPh:NH.HCl.2H₂O, needles, m. 103-6° (decomposition) (from H₂O) {base, m. 114-15° [acetate, needles, m. 131-2° (from C₆H₆); picrate, m. 180-1°]}; N-(2-hydroxyethyl)benzamidinium picrate, prisms, m. 140-2°, solidifies and remelts at 180-215° (decomposition); 4-sec-BuOC₆H₄CN, b_1.3 109-11°, n²⁰_D 1.5256; 4-HOC₆H₄(NHPh):NH.HO₃SPh, m. 180-2°, (picrate, m. 82-4° (from aqueous iso-PrOH), base, small needles, m. 182.5-3.0°). In the experiment, the researchers used many compounds, for example, 4-iso-Butoxybenzonitrile (cas: 5203-15-6Application of 5203-15-6).

4-iso-Butoxybenzonitrile (cas: 5203-15-6) 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. Industrially, the main methods for producing nitriles are ammoxidation and hydrocyanation. Both routes are green in the sense that they do not generate stoichiometric amounts of salts.Application of 5203-15-6

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Highly enantioselective bioreduction of prochiral ketones by stem and germinated plant of Brassica oleracea variety italica was written by Mohammadi, Mehdi;Yousefi, Maryam;Habibi, Zohreh. And the article was included in Biocatalysis and Biotransformation in 2011.Category: nitriles-buliding-blocks This article mentions the following:

An eco-friendly and environmentally benign asym. reduction of a broad range of prochiral ketones employing Brassica oleracea variety italica (stems and germinated plant) as a novel biocatalyst was developed. It was found that B. oleracea variety italica could be used effectively for enantioselective bioreduction in aqueous medium with moderate to excellent chem. yield and enantiomeric excess (ee). This process is more efficient and generates less waste than conventional chem. reagents or microorganisms. Both R- and S-configurations were obtained by these asym. reactions. The best ee were achieved for pyridine derivatives (92-99%). The ee in germinated plant reactions were significantly higher than those of stem reactions. The low cost and the easy availability of these biocatalysts suggest their possible use for large scale preparations of important chiral alcs. In the experiment, the researchers used many compounds, for example, (R)-4-(1-Hydroxyethyl)benzonitrile (cas: 101219-69-6Category: nitriles-buliding-blocks).

(R)-4-(1-Hydroxyethyl)benzonitrile (cas: 101219-69-6) belongs to nitriles. Trimerization of aromatic nitriles requires harsh reaction conditions, high temperatures, long reaction times, and pressure. 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.Category: nitriles-buliding-blocks

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Rational Design, Synthesis, and Characterization of Deep Blue Phosphorescent Ir(III) Complexes Containing (4′-Substituted-2′-pyridyl)-1,2,4-triazole Ancillary Ligands was written by Park, Hea Jung;Kim, Ji Na;Yoo, Hyun-Ji;Wee, Kyung-Ryang;Kang, Sang Ook;Cho, Dae Won;Yoon, Ung Chan. And the article was included in Journal of Organic Chemistry in 2013.SDS of cas: 36057-44-0 This article mentions the following:

On the basis of the results of frontier orbital considerations, 4-substituted-2′-pyridyltriazoles were designed to serve as ancillary ligands in 2-phenylpyridine main ligand containing heteroleptic iridium(III) complexes that display deep blue phosphorescence emission. The iridium(III) complexes, Ir1–Ir7, prepared using the new ancillary ligands, were found to display structured, highly quantum efficient (Φ_p = 0.20-0.42) phosphorescence with emission maxima in the blue to deep blue 448-456 nm at room temperature In accord with predictions based on frontier orbital considerations, the complexes were observed to have emission properties that are dependent on the electronic nature of substituents at the C-4 position of the pyridine moiety of the ancillary ligand. Importantly, placement of an electron-donating Me group at C-4′ of the pyridine ring of the 5-(pyridine-2′-yl)-3-trifluoromethyl-1,2,4-triazole ancillary ligand leads to an iridium(III) complex that displays a deep blue phosphorescence emission maximum at 448 nm in both the liquid and film states at room temperature Finally, an OLED device, constructed using an Ir-complex containing the optimized ancillary ligand as the dopant, was found to emit deep blue color with a CIE of 0.15, 0.18, which is close to the perfect goal of 0.15, 0.15. In the experiment, the researchers used many compounds, for example, 4-methoxypicolinonitrile (cas: 36057-44-0SDS of cas: 36057-44-0).

4-methoxypicolinonitrile (cas: 36057-44-0) belongs to nitriles. Nitrile carbon shifts are in the range of 115�25 ppm whereas in isonitriles the shifts are around 155�65 ppm. 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. SDS of cas: 36057-44-0

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts