Category: nitriles-buliding-blocks

Chiral Bidentate Boryl Ligand Enabled Iridium-Catalyzed Enantioselective C(sp³)-H Borylation of Cyclopropanes was written by Shi, Yongjia;Gao, Qian;Xu, Senmiao. And the article was included in Journal of the American Chemical Society in 2019.COA of Formula: C8H5BrFN This article mentions the following:

The authors herein report an Ir-catalyzed enantioselective C(sp³)-H borylation of cyclopropanecarboxamides using a chiral bidentate boryl ligand for the 1st time. A variety of substrates with α-quaternary C centers could be compatible in this reaction to provide β-borylated products with good to excellent enantioselectivities. Also the borylated products can be used as versatile precursors engaging in stereospecific transformations of C-B bonds, including the synthesis of a bioactive compound Levomilnacipran. In the experiment, the researchers used many compounds, for example, 2-(3-Bromo-4-fluorophenyl)acetonitrile (cas: 501420-63-9COA of Formula: C8H5BrFN).

2-(3-Bromo-4-fluorophenyl)acetonitrile (cas: 501420-63-9) 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. 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.COA of Formula: C8H5BrFN

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Improved method for the synthesis of 4-methylanthranilic acid was written by Takatori, Kichitaro;Asano, Shingo;Usui, Fumio. And the article was included in Gifu Yakka Daigaku Kiyo in 1958.Electric Literature of C8H8N2 This article mentions the following:

An improved synthetic method of synthesis of 4-methylanthranilic acid, effective for the treatment of Yoshida sarcoma, is studied. p-Toluidine (30 g.), 60 cc. alc., and 90 cc. 10% KOH is refluxed 1 hr. to give 97% 3-nitro-p-toluidine (I), orange columns, m. 113-14° (60% alc. or ligroine). I (50 g.) in 135 cc. 50% H₂SO₄ is cooled, treated with 25 g. NaNO₂ and 70 cc. H₂O at -10°, and stirred to give a reddish orange solution containing 3-nitro-p-toluene-diazonium sulfate. This solution is added to warmed (50°) Cu(CN)₂ solution gradually, kept 20 min. more, cooled, and the separated mass extracted with C₆H₆ to give 76% 3-nitro-p-tolunitrile (II), colorless to light yellow needles, m. 96-8° (H₂O). II (20 g.) in 20 g. AcOH is reduced with 90 cc. concentrated HCl and 200 g. leafy Pb at 55-60° to 43%, 3-amino-p-tolunitrile (III), plates, m. 92-4.5° (30% alc.). III (10 g.) and 50 cc. 10% KOH solution is boiled 7 hrs., cooled, neutralized with dilute AcOH, and the precipitate recrystallized from alc. to give 67% 4-methylanthranilic acid (IV), columns, m. 177-8°, violet fluorescence in alc. When this reaction is stopped after boiling only 2 hrs., 2-amino-p-toluamide, plates, m. 144-7°, is obtained. In the experiment, the researchers used many compounds, for example, 3-Amino-4-methylbenzonitrile (cas: 60710-80-7Electric Literature of C8H8N2).

3-Amino-4-methylbenzonitrile (cas: 60710-80-7) belongs to nitriles. Nitriles are polar, as indicated by high dipole moments. As liquids, they have high relative permittivities, often in the 30s. 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.Electric Literature of C8H8N2

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

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

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

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

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

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

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

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