Category: nitriles-buliding-blocks

Rh^III– and Ir^III-catalyzed asymmetric transfer hydrogenation of ketones in water was written by Wu, Xiaofeng;Li, Xiaohong;Zanotti-Gerosa, Antonio;Pettman, Allan;Liu, Jianke;Mills, Allan James;Xiao, Jianliang. And the article was included in Chemistry – A European Journal in 2008.Recommanded Product: (R)-4-(1-Hydroxyethyl)benzonitrile This article mentions the following:

Asym. transfer hydrogenation (ATH) of ketones by formate in neat water is shown to be viable with Rh-TsDPEN and Ir-TsDPEN catalysts, derived in situ from [Cp^*MCl₂]₂ (M = Rh, Ir) and TsDPEN. A variety of ketones were reduced, including non-functionalized aryl ketones, heteroaryl ketones, keto esters, and unsaturated ketones. In comparison with Ir-TsDPEN and the related Ru^II catalyst, the Rh^III catalyst is most efficient in water, affording enantioselectivities of up to 99% ee at substrate/catalyst (S/C) ratios of 100-1000 even without working under an inert atm. The aqueous phase reduction is shown to be highly pH-dependent; the optimum pH windows for TOF greater than 50 molmol^-1h^-1 for Rh- and Ir-TsDPEN are 5.5-10.0 and 6.5-8.5, resp. Outside the pH window, the reduction becomes slow or stagnant depending on the pH. However, the enantioselectivities erode only under acidic conditions. At a higher S/C ratio, the aqueous ATH by Rh-TsDPEN is shown to be product – as well as byproduct – inhibited; the product inhibition appears to stem at least partly from the reaction being reversible. The aqueous phase reduction is simple, efficient and environmentally benign, thus presenting a viable alternative for asym. reduction In the experiment, the researchers used many compounds, for example, (R)-4-(1-Hydroxyethyl)benzonitrile (cas: 101219-69-6Recommanded Product: (R)-4-(1-Hydroxyethyl)benzonitrile).

(R)-4-(1-Hydroxyethyl)benzonitrile (cas: 101219-69-6) 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. 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. Recommanded Product: (R)-4-(1-Hydroxyethyl)benzonitrile

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Nitriles in heterocyclic synthesis: novel routes to cyclopentenothienopyridines, cyclopentenothienopyrimidenes and cyclopentenopyrrolopyrazoles was written by Harb, Abdel Fattah Ali. And the article was included in Egyptian Journal of Pharmaceutical Sciences in 1992.Safety of 2-Amino-5,6-dihydro-4H-cyclopenta[b]thiophene-3-carbonitrile This article mentions the following:

Aminocyclopentenothiophenecarbonitrile I prepared via an extension to the Gewald reaction, was converted into the cyclopentenothienopyridines II (R = H, NH₂) and III by treatment with acrylonitrile, malononitrile and Et cyanoacetate. I was converted into the corresponding cyclopentenothienopyrimidines IV (X = S, R¹ = NHPh; X = O, R¹ = Me, H) on treatment with Ph isothiocyanate, acetic anhydride and triethylorthoformate resp. Also the corresponding cyclopentenopyrrolopyrazole V was obtained by treating I with hydrazine hydrate. In the experiment, the researchers used many compounds, for example, 2-Amino-5,6-dihydro-4H-cyclopenta[b]thiophene-3-carbonitrile (cas: 70291-62-2Safety of 2-Amino-5,6-dihydro-4H-cyclopenta[b]thiophene-3-carbonitrile).

2-Amino-5,6-dihydro-4H-cyclopenta[b]thiophene-3-carbonitrile (cas: 70291-62-2) belongs to nitriles. Trimerization of aromatic nitriles requires harsh reaction conditions, high temperatures, long reaction times, and pressure. 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. Safety of 2-Amino-5,6-dihydro-4H-cyclopenta[b]thiophene-3-carbonitrile

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Ketene gem-dithiols; a convenient one-step procedure from aliphatic active methylenes: reactions and synthesis of polyfunctionally substituted thia- and azaheteroaromatics was written by Zayed, Salem E.. And the article was included in Phosphorus, Sulfur and Silicon and the Related Elements in 1996.Application of 58168-20-0 This article mentions the following:

It has been reported in the current literature that the isolation of certain ketene gem dithiols has failed due to dimerization. Generation of ketene gem-dithiols via trapping with other reactants led to formation of pyridine, pyrrole, pyridothiadiazole and pyrazolone derivatives In the experiment, the researchers used many compounds, for example, Ethyl 5-amino-4-cyano-3-(2-ethoxy-2-oxoethyl)thiophene-2-carboxylate (cas: 58168-20-0Application of 58168-20-0).

Ethyl 5-amino-4-cyano-3-(2-ethoxy-2-oxoethyl)thiophene-2-carboxylate (cas: 58168-20-0) 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.Application of 58168-20-0

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

SAR study of 5-alkynyl substituted quinazolin-4(3H)-ones as phosphoinositide 3-kinase delta (PI3Kδ) inhibitors was written by Wei, Manman;Zhang, Xi;Wang, Xiang;Song, Zilan;Ding, Jian;Meng, Ling-Hua;Zhang, Ao. And the article was included in European Journal of Medicinal Chemistry in 2017.Electric Literature of C5H3ClN4 This article mentions the following:

PI3Kδ is a key component in the aberrant signaling transduction in B cell malignancy, therefore specific targeting PI3Kδ has become an attractive molecularly targeted therapy for chronic lymphocytic leukemia (CLL). Herein, we describe the discovery and optimization of a series of 5-alkynyl substituted PI3Kδ inhibitors based on the first FDA-approved inhibitor idelalisib. Compound 8d bearing the 1-morpholinohex-5-yn-1-one moiety as the C5-substituent was identified to have high potency against PI3Kδ (3.82 nM) and SU-DHL-6 cells (7.60 nM), resp. It was 154-fold selective over PI3Kα, 133-fold selective against PI3Kβ, and 24-fold selective against PI3Kγ. Treatment of MOLT-4 and SU-DHL-6 cells with compound 8d for 1 h resulted in reduction of phosphorylation of both Akt (S473) and its downstream S6k1 (T389) in a concentration-dependent manner. Compound 8d showed potent anti-proliferative activity as well against T lymphoblast MOLT-4, suggesting its potential activity in T-cell leukemia. In the experiment, the researchers used many compounds, for example, 4-Amino-6-chloropyrimidine-5-carbonitrile (cas: 60025-09-4Electric Literature of C5H3ClN4).

4-Amino-6-chloropyrimidine-5-carbonitrile (cas: 60025-09-4) 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. 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. Electric Literature of C5H3ClN4

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Tris(2-cyanoethyl)amine was written by Xu, An-Wu;Cai, Yue-Peng;Su, Cheng-Yong;Liu, Hong-Ke. And the article was included in Acta Crystallographica, Section C: Crystal Structure Communications in 2000.COA of Formula: C9H12N4 This article mentions the following:

In the title compound, N(CH₂CH₂CN)₃, (I), the three cyanoethyl groups adopt a conformation with the CN groups (I) oriented in the same direction, suggesting the compound may behave as a potential tripodal ligand. Crystallog. data are given. In the experiment, the researchers used many compounds, for example, 3,3′,3”-Nitrilotripropanenitrile (cas: 7528-78-1COA of Formula: C9H12N4).

3,3′,3”-Nitrilotripropanenitrile (cas: 7528-78-1) 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.COA of Formula: C9H12N4

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Nickel Catalyzed Regiodivergent Cross-Coupling Alkylation of Aryl Halides with Redox-Active Imines was written by Huang, Long;Kancherla, Rajesh;Rueping, Magnus. And the article was included in ACS Catalysis in 2022.Formula: C11H13N This article mentions the following:

Herein, a visible light nickel-catalyzed protocol for the deaminative cross-coupling of redox-active imines with various electrophiles that allow for the rapid construction of C(sp³) enriched arene Ar(t-Bu)/Me₂CH₂Ar [Ar = 4-NCC₆H₄, 4-Ph(CO)C₆H₄, 3-NCC₆H4, etc.]/AcAr [Ar = 4-((Me)₂(Et))CC₆H₄, 4-(C(O)OEtCH₂(Me)₂)CC₆H₄, 4-((PhCH₂CH₂)(Me)₂)CC₆H₄, etc.] in a regiodivergent manner. Key to the success of this protocol was the combination of a readily available organic photocatalyst and a Lewis acid additive. As an addnl. approach to alkylarenes, also showcased that the nature of electrophiles dictates the regiochem. outcome. In the experiment, the researchers used many compounds, for example, 3-(tert-Butyl)benzonitrile (cas: 154532-34-0Formula: C11H13N).

3-(tert-Butyl)benzonitrile (cas: 154532-34-0) 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 addition, Nitriles can react with alkynes, which leads to an increase in carbon chain length (carbocyanation).Formula: C11H13N

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Reaction of 4-(diethylamino)salicylaldehyde with malononitrile was written by Tkach, I. I.;Reznichenko, A. V.;Luk’yanets, E. A.. And the article was included in Khimiya Geterotsiklicheskikh Soedinenii in 1992.Name: 7-(Diethylamino)-2-oxo-2H-chromene-3-carbonitrile This article mentions the following:

Treating 4-(diethylamino)salicylaldehyde (I) with CH₂(CN)₂ in AcOH gave 27% coumarin derivative II and 6.2% coumarin III; in polyphosphoric acid 53% amide IV was obtained; and in Ac₂O 49% dicyanovinyl derivative V was obtained. Addnl. obtained were thione VI and benzopyranonaphthyridines VII (R = H, Et). In the experiment, the researchers used many compounds, for example, 7-(Diethylamino)-2-oxo-2H-chromene-3-carbonitrile (cas: 51473-74-6Name: 7-(Diethylamino)-2-oxo-2H-chromene-3-carbonitrile).

7-(Diethylamino)-2-oxo-2H-chromene-3-carbonitrile (cas: 51473-74-6) 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. 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.Name: 7-(Diethylamino)-2-oxo-2H-chromene-3-carbonitrile

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Direct oxidative esterification of alcohols and hydration of nitriles catalyzed by a reusable silver nanoparticle grafted onto mesoporous polymelamine formaldehyde (AgNPs@mPMF) was written by Ghosh, Kajari;Iqubal, Asif Md.;Molla, Rostam Ali;Mishra, Ashutosh;Kamaluddin;Islam, Sk Manirul. And the article was included in Catalysis Science & Technology in 2015.Related Products of 55406-13-8 This article mentions the following:

A nitrogen-rich mesoporous organic polymer was synthesized as a novel support. A silver nanoparticle was synthesized and grafted onto it. The prepared catalyst (AgNPs@mPMF) was characterized by powder X-ray diffraction (XRD), SEM(SEM) and energy dispersive X-ray spectrometry (EDS), thermogravimetric anal. (TGA), high-resolution transmission electron microscopy (HRTEM), UV-vis diffuse reflectance spectroscopy (DRS), N₂ adsorption, Raman spectroscopy and EPR study. The catalytic activity was evaluated for the oxidative esterification reaction of alcs. and hydration of nitriles. The oxidative esterification reaction was carried out for various activated alcs. giving excellent yields of the corresponding ester products. The catalyst was also efficient in the hydration of nitriles. Both reactions were optimized by varying the bases, temperatures and solvents. The catalyst can be facilely recovered and reused six times without a significant decrease in its activity and selectivity. In the experiment, the researchers used many compounds, for example, 3-Methylthiophene-2-carbonitrile (cas: 55406-13-8Related Products of 55406-13-8).

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. 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.Related Products of 55406-13-8

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

New Insights into the Reaction Capabilities of Ionic Organic Bases in Cu-Catalyzed Amination was written by Lo, Quintin A.;Sale, David;Braddock, D. Christopher;Davies, Robert P.. And the article was included in European Journal of Organic Chemistry in 2019.Application In Synthesis of 4-(Benzylamino)benzonitrile This article mentions the following:

The application of ionic organic bases in the copper-catalyzed amination reaction (Ullmann reaction) has been studied at rt, with sub-mol-% catalyst loadings, and with amines at elevated temperatures The cation present in the base has been shown to have little effect on the reaction at standard catalyst and ancillary ligand loadings, whereas the choice of anion is crucial for good reactivity. A substrate scope carried out at rt with the best performing bases, TBAM (bis[tetrabutylammonium]malonate) and bis(tetra-(n-butyl)phosphonium) malonate (TBPM), showed both bases to be highly effective under these mild reaction conditions. Moreover, under sub-mol % catalyst loadings and rt conditions, TBPM gave good yields for a number of different amines and aryl iodides. By using more forceful conditions (120°) moderate to excellent yields of cross-coupled products. As part of this work a study on the stability of the organic bases at 120° was undertaken. TBAM is shown to decompose to give nBu₃N and mono-butylmalonate at higher temperatures, and this can be correlated to a decrease in performance in the coupling reaction. The phosphonium cations in TBPM did not undergo analogous reactivity but were shown instead to experience some degree of deprotonation at the α-CH₂ to generate phosphonium ylides. This however did not lead to a significantly degradation in the activity of the TBPM in the cross-coupling reaction. In the experiment, the researchers used many compounds, for example, 4-(Benzylamino)benzonitrile (cas: 10282-32-3Application In Synthesis of 4-(Benzylamino)benzonitrile).

4-(Benzylamino)benzonitrile (cas: 10282-32-3) belongs to nitriles. Nitrile carbon shifts are in the range of 115–125 ppm whereas in isonitriles the shifts are around 155–165 ppm. 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 4-(Benzylamino)benzonitrile

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Regioselective Borylation of the C-H Bonds in Alkylamines and Alkyl Ethers. Observation and Origin of High Reactivity of Primary C-H Bonds Beta to Nitrogen and Oxygen was written by Li, Qian;Liskey, Carl W.;Hartwig, John F.. And the article was included in Journal of the American Chemical Society in 2014.Formula: C12H14N2O This article mentions the following:

Borylation of aliphatic C-H bonds in alkylamines and alkyl ethers to form primary aminoalkyl and alkoxyalkyl boronate esters and studies on the origin of the regioselectivity of these reactions are reported. The products of these reactions can be used directly in Suzuki-Miyaura cross-coupling reactions or isolated as air-stable potassium trifluoroborate salts. Selective borylation of the terminal C-H bond at the positions β to oxygen and nitrogen occurs in preference to borylation of the other terminal C-H bonds. Exptl. studies and computational results show that C-H bond cleavage is the rate-determining step of the current borylation reactions. The observed higher reactivity of C-H bonds at the terminal position of ethylamines and ethers results from a combination of attractive Lewis acid-base and hydrogen-bonding interactions, as well as typical repulsive steric interactions, in the transition state. In this transition state, the heteroatom lies directly above the boron atom of one boryl ligand, creating a stabilizing interaction between the weak Lewis acid and Lewis base, and a series of C-H bonds of the substrate lie near the oxygen atoms of the boryl ligands, participating in a set of weak C-H···O interactions that lead to significant stabilization of the transition state forming the major product. In the experiment, the researchers used many compounds, for example, 4-(Morpholinomethyl)benzonitrile (cas: 37812-51-4Formula: C12H14N2O).

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. In addition, Nitriles can react with alkynes, which leads to an increase in carbon chain length (carbocyanation).Formula: C12H14N2O

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts