Tag: 200-300

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

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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

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9-Amino-5,7-dibromo-1,2,3,4-tetrahydroacridine hemihydrate was written by Celik, Ismail;Akkurt, Mehmet;Ekiz, Makbule;Okten, Salih;Tutar, Ahmet;Ersanli, Cem Cuneyt. And the article was included in IUCrData in 2017.Safety of 2-Amino-3,5-dibromobenzonitrile This article mentions the following:

The asym. unit of the title compound, C₁₃H₁₂Br₂N₂·0.5H₂O, includes two mols. of 5,7-dibromo-1,2,3,4-tetrahydroacridin-9-amine and one water mol. In the crystal, C-H···O, N-H···N, N-H···O and O-H···N hydrogen bonds connect the mols., forming a two-dimensional network parallel to (010). The two-dimensional sheets are further assembled into a three-dimensional structure through C-H···π and π-π stacking interactions [centroid-centroid distance = 3.719 (2) Å]. 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. 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.Safety of 2-Amino-3,5-dibromobenzonitrile

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Nitrile – Wikipedia,
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Structure-activity relationships in the formation of amides from substituted N-benzylanilines was written by Ulgen, M.;Gorrod, J. W.;Barlow, D.. And the article was included in Xenobiotica in 1994.HPLC of Formula: 10282-32-3 This article mentions the following:

The in vitro hepatic microsomal metabolism of certain substituted N-benzylanilines was studied in the male hamster to establish the mechanism(s) and process(es) involved in the formation of the corresponding amides. N-benzyl-2,4,6-trihalogeno, N-benzyl-4-cyano- and N-benzyl-4-nitroanilines were only metabolized by N-debenzylation. However, N-benzyl-4-methyl- and N-benzyl-2,4,6-trimethylanilines gave rise to both the corresponding amide and nitrone metabolites together with dealkylation products. These latter two substrates also produced hydroxymethyl metabolites as major products. Metabolism of N-(2,4,6-trimethylbenzyl)aniline also led to the formation of an amide metabolite. The dealkylation products, the corresponding imine and an unknown metabolite, probably an hydroxylated products were also detected with this substrate. N-(2,4-dichlorobenzyl) and N-(2,6-dichlorobenzyl)anilines yielded the corresponding nitrone metabolites; but no amide metabolite was detected. Oxidative dealkylation leading to the formation of the corresponding primary anilines and aldehydes, together with para hydroxylation of aniline rings, were established as major routes of metabolism for both compounds Similarly, neither N-(2,4,6-trifluorobenzyl) nor N-(4-nitrobenzyl)anilines produced any amide metabolite although dealkylation products were detected. The pattern of amide formation observed for these N-benzylsubstituted anilines is discussed in terms of the steric and electronic effects of their aromatic substituents. In the experiment, the researchers used many compounds, for example, 4-(Benzylamino)benzonitrile (cas: 10282-32-3HPLC of Formula: 10282-32-3).

4-(Benzylamino)benzonitrile (cas: 10282-32-3) 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. HPLC of Formula: 10282-32-3

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Imidazolium-based phosphinite ionic liquid (IL-OPPh₂) as reusable catalyst and solvent for the Knoevenagel condensation reaction was written by Valizadeh, Hassan;Gholipour, Hamid. And the article was included in Synthetic Communications in 2010.Electric Literature of C14H14N2O2 This article mentions the following:

A task-specific ionic liquid (IL), which bears a weak Lewis base (OPPh₂) in an imidazolium cation, efficiently catalyzed the Knoevenagel condensation of aryl aldehydes with H₂C(CN)₂, H₂C(CO₂Me)₂, H₂C(CO₂Et)₂, and NCCH₂CO₂Et. This IL played a dual role as both the reaction medium and also catalyst, and it could be easily recovered and reused in several runs. Satisfactory results were obtained with good yields, short reaction time, and simplicity in the exptl. procedure. A variety of coumarin derivatives were synthesized in this procedure. In the experiment, the researchers used many compounds, for example, 7-(Diethylamino)-2-oxo-2H-chromene-3-carbonitrile (cas: 51473-74-6Electric Literature 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. In addition, Nitriles can react with alkynes, which leads to an increase in carbon chain length (carbocyanation).Electric Literature of C14H14N2O2

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Nitrile – Wikipedia,
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An Air-Stable Nickel(0) Phosphite Precatalyst for Primary Alkylamine C-N Cross-Coupling Reactions was written by Kampmann, Sven S.;Skelton, Brian W.;Wild, Duncan A.;Koutsantonis, George A.;Stewart, Scott G.. And the article was included in European Journal of Organic Chemistry in 2015.Synthetic Route of C14H12N2 This article mentions the following:

In this report we describe the design and preparation of a new air-stable nickel phosphite based catalyst for unique C-N bond forming processes. Specifically, (BINAP)Ni[P(OPh)₃]₂, is presented as an effective catalyst for a range of amination reactions between aryl halides and primary alkylamines. The results are supported by relevant kinetic studies, DFT calculations and a catalytic cycle indicating possible reaction intermediates. In the experiment, the researchers used many compounds, for example, 4-(Benzylamino)benzonitrile (cas: 10282-32-3Synthetic Route 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. 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.Synthetic Route of C14H12N2

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Synthesis of Benzotriazine and Aryltriazene Derivatives Starting from 2-Azidobenzonitrile Derivatives was written by Nakhai, Azadeh;Stensland, Birgitta;Svensson, Per H.;Bergman, Jan. And the article was included in European Journal of Organic Chemistry in 2010.Name: 2-Amino-3,5-dibromobenzonitrile This article mentions the following:

3-Substituted 3,4-dihydro-4-imino-1,2,3-benzotriazine derivatives 7 (e. g. I) were formed from 2-azidobenzonitriles as starting materials on treatment with Grignard or lithium organic reagents. In some cases these procedures gave aryltriazenes, e. g. II and III, as products. All compounds were identified by NMR spectroscopy and the structures of three products, namely I, II and III, were corroborated by X-ray crystallog. In the experiment, the researchers used many compounds, for example, 2-Amino-3,5-dibromobenzonitrile (cas: 68385-95-5Name: 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. 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.Name: 2-Amino-3,5-dibromobenzonitrile

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Nitrile – Wikipedia,
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An Efficient and Selective Nickel-Catalyzed Direct N-Alkylation of Anilines with Alcohols was written by Vellakkaran, Mari;Singh, Khushboo;Banerjee, Debasis. And the article was included in ACS Catalysis in 2017.Electric Literature of C14H12N2 This article mentions the following:

Herein, we developed an efficient and selective nickel-catalyzed monoalkylation of various primary alcs. with aryl and heteroaryl amines together with diols and amino alc. derivatives Notably, the catalytic protocol consisting of an earth-abundant and non-precious NiBr₂/L1 (L1 = 1,10-phenanthroline) system enables the transformations in the presence of hydroxyl, alkene, nitrile, and nitro functionalities. As a highlight, we have demonstrated the alkylation of diamine, intramol. cyclization to N-heterocycles, and functionalization of complex vitamin E, an (±)-α-tocopherol derivative Preliminary mechanistic studies revealed the participation of a benzylic C-H bond in the rate-determining step. 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. Nitrile carbon shifts are in the range of 115�25 ppm whereas in isonitriles the shifts are around 155�65 ppm. Asymmetric bioreduction of nitriles is an attractive route to produce optically active nitriles as current metal-catalyzed hydrogenations tend to have low reactivity.Electric Literature of C14H12N2

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Highly efficient amination in neat water of benzyl chlorides with dialkylformamides catalyzed by N-heterocyclic carbene-palladium(II)-1-methylimidazole complex was written by Chen, Wen-Xin;Zhang, Cai-Yun;Lu, Jian-Mei. And the article was included in Journal of Chemical Research in 2013.Safety of 4-(Morpholinomethyl)benzonitrile This article mentions the following:

N,N-dialkylbenzylamines were synthesized from substituted benzyl chlorides and dialkylformamides in good to almost quant. yields in a eco-friendly solvent, water, in the presence of NHC-Pd(II)-Im complex. In the experiment, the researchers used many compounds, for example, 4-(Morpholinomethyl)benzonitrile (cas: 37812-51-4Safety of 4-(Morpholinomethyl)benzonitrile).

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. 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.Safety of 4-(Morpholinomethyl)benzonitrile

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Synthesis, evaluation and structure-activity relationships of 5-alkyl-2,3-dihydroimidazo[1,2-c]quinazoline, 2,3-dihydroimidazo[1,2-c]quinazolin-5(6H)-thiones and their oxo-analogues as new potential bronchodilators was written by Bahekar, Rajesh H.;Rao, A. Raghu Ram. And the article was included in Arzneimittel-Forschung in 2001.Computed Properties of C7H4Br2N2 This article mentions the following:

With an aim to obtain potent bronchodilators, 2 series of 5-alkyl-2,3-dihydroimidazo[1,2-c]quinazolines (Va-1), 2,3-dihydroimidazo[1,2-c]quinazolin-5-(6H)-thiones (VIIIa-d) and their oxo-analogs (IXa-d) were designed. The compounds Va-1 were synthesized by two alternative routes. The former (Method A) based on the dehydrocyclization of 4-(1-hydroxyethyl)aminoquinazoline (IV) and the latter (Method B) involves the usage of 2-aminobenzonitrile (VI) which on reaction with ethylenediamine leads to the formation of the key intermediate 2-(2-aminophenyl)-4,5-dihydro-1H-imidazoles (VII). Finally the intermediate VII on condensation with different acid anhydrides yielded the title compound V. In general, method-A resulted the compound V in quantatively higher yields. 2,3-Dihydroimidazo[1,2-c]quinazolin-5 (6H)-thiones (VIII) were obtained by condensing VIi with carbon disulfide and a further oxidation of VIII gave their corresponding oxo-analogs (IX). The title compounds V, VIII and IX were evaluated for their bronchodilator activity using in vitro and in vivo (standard animal models) methods. All the test compounds exhibited bronchodilator activity. The structure activity relationship studies indicated good correlation between the nature of the substituent and bronchodilator activity. In the 5-alkyl substituted compounds V, a longer alkyl chain showed higher bronchodilator activity. Compounds VIII and IX were less potent and replacement of sulfur with oxygen showed no significant effect on the biol. activity. The presence of halogens altered the biol. activity in both the series. Among the compounds tested, 9-iodo-5-(propyl)-2,3-dihydroimidazo[1,2-c]quinazoline (VI) was the most potent (percentage protection = 87.1%; relative activity = 1.1 compared to the standard aminophylline). In the experiment, the researchers used many compounds, for example, 2-Amino-3,5-dibromobenzonitrile (cas: 68385-95-5Computed Properties of C7H4Br2N2).

2-Amino-3,5-dibromobenzonitrile (cas: 68385-95-5) 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 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.Computed Properties of C7H4Br2N2

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Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts