Category: nitriles-buliding-blocks

Mechanistic investigation of the iridium-catalysed alkylation of amines with alcohols was written by Fristrup, Peter;Tursky, Matyas;Madsen, Robert. And the article was included in Organic & Biomolecular Chemistry in 2012.Quality Control of 4-(Benzylamino)benzonitrile This article mentions the following:

The [Cp*IrCl₂]₂-catalyzed alkylation of amines with alcs. was investigated using a combination of exptl. and theor. methods. A Hammett study involving a series of para-substituted benzyl alcs. resulted in a line with a neg. slope. This clearly documents that a pos. charge is built up in the transition state, which in combination with the measurement of a significant kinetic isotope effect determines hydride abstraction as being the selectivity-determining step under these conditions. A complementary Hammett study using para-substituted anilines was also carried out. Again, a line with a neg. slope was obtained suggesting that nucleophilic attack on the aldehyde is selectivity-determining A computational investigation of the entire catalytic cycle with full-sized ligands and substrates was performed using d. functional theory. The results suggest a catalytic cycle where the intermediate aldehyde stays coordinated to the iridium catalyst and reacts with the amine to give a hemiaminal which is also bound to the catalyst. Dehydration to the imine and reduction to the product amine also takes place without breaking the coordination to the catalyst. The fact that the entire catalytic cycle takes place with all the intermediates bound to the catalyst is important for the further development of this synthetic transformation. In the experiment, the researchers used many compounds, for example, 4-(Benzylamino)benzonitrile (cas: 10282-32-3Quality Control of 4-(Benzylamino)benzonitrile).

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.Quality Control of 4-(Benzylamino)benzonitrile

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Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Ethylene diamine grafted nanoporous UiO-66 as an efficient basic catalyst in the multi-component synthesis of 2-aminothiophenes was written by Erfaninia, N.;Tayebee, R.;Dusek, M.;Amini, M. M.. And the article was included in Applied Organometallic Chemistry in 2018.Application of 70291-62-2 This article mentions the following:

This study demonstrates ED-UiO-66 as a novel and effective solid nanoporous basic catalyst prepared through the amine grafting onto the pores of UiO-66. The manufactured nanoparticles were identified by FT-IR, XRD, TGA, FESEM, TEM, CHN and BET and the characterization results certified formation of a single phase nanoporous substance with the medium grain size less than 90 nm. The synthesized material was employed as an efficient catalyst for the preparation of 2-aminothiophenes I [R = 4,5-(-CH₂-)₅, 5-CH₃, 5-C₆H₅] through the Gewald method. This thermochem. stable nanocatalyst was environmentally safe, reusable and economic. Therefore, this methodol. can be simply extended for industrial goals. In the experiment, the researchers used many compounds, for example, 2-Amino-5,6-dihydro-4H-cyclopenta[b]thiophene-3-carbonitrile (cas: 70291-62-2Application of 70291-62-2).

2-Amino-5,6-dihydro-4H-cyclopenta[b]thiophene-3-carbonitrile (cas: 70291-62-2) 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.Application of 70291-62-2

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Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Photocatalytic C-H Amination of Aromatics Overcoming Redox Potential Limitations was written by Morofuji, Tatsuya;Ikarashi, Gun;Kano, Naokazu. And the article was included in Organic Letters in 2020.Computed Properties of C8H8N2O This article mentions the following:

The photocatalytic C-H amination of aromatics overcoming redox potential limitations was reported. Radical cations of aromatic compounds were generated photocatalytically using Ru(phen)₃(PF₆)₂, which had a reduction potential at a high oxidation state (E_red(Ru^III/Ru^II) = +1.37 V vs SCE) lower than the oxidation potentials of aromatic substrates (E_ox = +1.65 to +2.27 V vs SCE). The radical cations were trapped with pyridine to give N-arylpyridinium ions, which were converted to aromatic amines. In the experiment, the researchers used many compounds, for example, 3-Amino-4-methoxybenzonitrile (cas: 60979-25-1Computed Properties of C8H8N2O).

3-Amino-4-methoxybenzonitrile (cas: 60979-25-1) 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.Computed Properties of C8H8N2O

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Nitrile – Wikipedia,
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Oxidation of alcohols by transition metal complexes. Part III. The reduction of aldimines by hydrogen transfer from propan-2-ol catalyzed by rhodium complexes was written by Grigg, Ronald;Mitchell, Thomas R. B.;Tongpenyai, Ngampong. And the article was included in Synthesis in 1981.Category: nitriles-buliding-blocks This article mentions the following:

Benzaldimines 4-RC₆H₄CH:NCH₂Ph (R = H, Me, MeO, Cl, CF₃) and I (R¹ = H, MeO, Cl, CF₃, cyano; R² = H, MeO, Cl, CF₃, cyano) reacted with Me₂CHOH and a Rh complex to yield the resp. 4-RC₆H₄CH₂NHCH₂Ph and II. A mixture of PhCH:NCH₂Ph, RhCl(PPh₃)₃, and Na₂CO₃ in Me₂CHOH was refluxed 60 min to give ∼90% (Ph₂CH₂)₂NH. In the experiment, the researchers used many compounds, for example, 4-(Benzylamino)benzonitrile (cas: 10282-32-3Category: nitriles-buliding-blocks).

4-(Benzylamino)benzonitrile (cas: 10282-32-3) 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. 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. Category: nitriles-buliding-blocks

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Nitrile – Wikipedia,
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Synthesis, Characterization, Antimicrobial Activity Screening, and Molecular Docking Study of Pyrimidine Carbonitrile Derivatives was written by Bhat, Radhika;Begum, Noor Shahina. And the article was included in Russian Journal of Organic Chemistry in 2021.Computed Properties of C5H3ClN4 This article mentions the following:

The synthesis of pyrimidine carbonitrile derivatives I [R = 1-piperidyl, 2-phenylethylamino, 2-(1H-indol-3-ylmethylene)hydrazino, etc.] was described. The compounds I were characterized by FT-IR and ¹H and ¹³C- NMR spectroscopy and mass spectrometry. All the compounds I were evaluated for in-vitro antimicrobial activity against different bacterial and fungal strains. The min. inhibitory concentrations (MICs) of all the compounds I were validated. Compounds I [R = 2-[(3,4-dimethoxyphenyl)methylene]hydrazino, 1-piperidyl], which had the lowest MIC values were selected for cell leakage anal. and bacterial growth curve study. It was found that both the compounds I [R = 2-[(3,4-dimethoxyphenyl)methylene]hydrazino, 1-piperidyl] have potential to induce bacterial cell membrane rupture and disintegration. Field emission scanning electron microscopic anal. confirmed the effect of the selected compounds on the morphol. of both Gram-pos. (S. aureus) and Gram-neg. (E. coli) bacteria. The mechanism of interaction between the drug and the target protein of S. aureus and E. coli was studied by mol. docking. In the experiment, the researchers used many compounds, for example, 4-Amino-6-chloropyrimidine-5-carbonitrile (cas: 60025-09-4Computed Properties of C5H3ClN4).

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

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Charge localization in the retro-Diels-Alder fragmentation of tetralins was written by Lightner, David A.;Steinberg, Frank S.. And the article was included in Organic Mass Spectrometry in 1970.SDS of cas: 29809-13-0 This article mentions the following:

The electron-impact induced retro-Diels-Alder reaction of 5- and 6-substituted tetralins has been examined Most electron-donating groups at C-5 retard the fragmentation relative to tetralin; whereas, electron-withdrawing groups slightly increase the fragmentation. In the experiment, the researchers used many compounds, for example, 5,6,7,8-Tetrahydronaphthalene-1-carbonitrile (cas: 29809-13-0SDS of cas: 29809-13-0).

5,6,7,8-Tetrahydronaphthalene-1-carbonitrile (cas: 29809-13-0) 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. 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.SDS of cas: 29809-13-0

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Nitrile – Wikipedia,
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Cp*Co(III) and Cu(OAc)₂ bimetallic catalysis for Buchwald-type C-N cross coupling of aryl chlorides and amines under base, inert gas & solvent-free conditions was written by Srivastava, Avinash K.;Sharma, Charu;Joshi, Raj K.. And the article was included in Green Chemistry in 2020.Formula: C14H12N2 This article mentions the following:

A strategy involving bimetallic catalysis with a combination of Cp*Co(CO)I₂ and Cu(OAc)₂ was used for performing Buchwald-type C-N coupling reactions of aryl chlorides RCl (R = Ph, pyridin-2-yl, 4-cyanophenyl, etc.) with amines R¹NHR² (R¹ = H, Et; R² = Pr, benzyl, 4-methoxyphenyl, etc.; R¹R² = -(CH₂)₄– and -(CH₂)₅-). The reactions proceeded at 100°C to produce excellent yields of many of the desired C-N coupled products R¹N(R)R², in 4 h, under aerobic reaction conditions. The reactions were shown to run under base-free and solvent-free conditions, enabling this strategy to work efficiently for electron-withdrawing and base-sensitive functionalities. The presented methodol. was found to be equally efficient for electron-donating functionalities as well as for primary (1°) and secondary (2°) aromatic and aliphatic amines. Moreover, the products were easily separated through the extractions of the organic aqueous layer, with this process chromatog. separations are not required. In the experiment, the researchers used many compounds, for example, 4-(Benzylamino)benzonitrile (cas: 10282-32-3Formula: C14H12N2).

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. 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.Formula: C14H12N2

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Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Action of stilbene on tetrachloro-ο-benzoquinone was written by Schonberg, Alexander;Latif, Nazih. And the article was included in Journal of the American Chemical Society in 1950.COA of Formula: C8H13N This article mentions the following:

Tetrachloro-ο-quinone (I) (1 g.) and (PhCH:)₂ (II) in 30 cc. C₆H₆, exposed 13 days to sunlight, give 2,3-diphenyl-5,6,7,8-tetrachloro-1,4-benzodioxan (III), m. about 172°; III results in 70% yield on boiling 1.2 g. I and 0.9 g. II in C₆H₆ 15 hrs. in the dark. I (0.6 g.) and 0.5 g. (p-MeC₆H₄CH:)₂, exposed 10 days to sunlight, give 2-phenyl-3-(p-tolyl)-5,6,7,8-tetrachloro-1,4-benzodioxan, m. 132°. III, heated 15 min. in a C₆H₄(CO₂Et)₂ bath (oil-pump vacuum), gives II. III does not react with ο-C₆H₄(NH₂)₂ (refluxed 2 hrs. in 90% AcOH). In the experiment, the researchers used many compounds, for example, 2-Cyclohexylacetonitrile (cas: 4435-14-7COA of Formula: C8H13N).

2-Cyclohexylacetonitrile (cas: 4435-14-7) 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: C8H13N

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Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Synthesis of novel fused thienodiazaphosphorine derivatives from 2-amino-3-cyanothiophenes and Lawesson’s reagent was written by Khalladi, Khaoula;Touil, Soufiane. And the article was included in Journal of Sulfur Chemistry in 2012.Formula: C8H8N2S This article mentions the following:

In a simple one-pot procedure, treatment of 2-amino-3-cyanothiophenes with Lawesson’s reagent led to the new thieno[2,3-d][1,3,2]diazaphosphorine-6-thione-2-sulfides in good to excellent yields. A possible reaction mechanism, involving a Dimroth-type rearrangement, was proposed. The structure of obtained products was confirmed by NMR (¹H, ³¹P, and ¹³C) and IR spectroscopies and by mass spectrometry. In the experiment, the researchers used many compounds, for example, 2-Amino-5,6-dihydro-4H-cyclopenta[b]thiophene-3-carbonitrile (cas: 70291-62-2Formula: C8H8N2S).

2-Amino-5,6-dihydro-4H-cyclopenta[b]thiophene-3-carbonitrile (cas: 70291-62-2) 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. Asymmetric bioreduction of nitriles is an attractive route to produce optically active nitriles as current metal-catalyzed hydrogenations tend to have low reactivity.Formula: C8H8N2S

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Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Organic catalysts. XL. Synthetic dehydrogenases. 8 was written by Mix, Hermann;Krause, Hans Walter. And the article was included in Chemische Berichte in 1956.Synthetic Route of C8H8N2 This article mentions the following:

Some isatins, CMe:CH.CH:CR.C:C.NH.CO.CO (I), and N-(7-methylisatin-4-carbonyl)amino acid Et esters (II), substituted in the 4-position, are prepared and tested for their dehydrogenase activity. Treating p-MeC₆H₄CO₂H with fuming HNO₃ yields 4,3-Me(O₂N)C₆H₃CO₂H, m. 188-9°, which, reduced with Raney Ni in dioxane at 120° and 100 atm., gives 90% 4,3-Me(H₂N)C₆H₃CO₂H (III), m. 162°. Heating 5 g. III in 150 cc. H₂O containing 2 cc. concentrated H₂SO₄ with 5.5 g. CCl₃CHO.H₂O (IV) and 6.5 g. (HONH₂)₂.H₂SO₄ (V) yields 3-isonitrosoacetamido-4-methylbenzoic acid which (10 g.), heated in 22 cc. concentrated H₂SO₄ at 85-90° and kept 0.5 hr. at 95-100°, gives 72% I (R = CO₂H) (VI), yellow-red needles, m. 278-80°; Et ester, prepared by heating 5 g. VI in 150 cc. EtOH-HCl 0.5 hr. on a water bath and chromatographing over Al₂O₃, orange rods, m. 205°. Heating 5 g. 4,3-Me(H₂N)C₆H₃CN, m. 81°, 6.3 g. IV, and 7.5 g. V in 430 cc. H₂O and 3 cc. concentrated H₂SO₄ gives 2-2.5 g. isonitroso compound which, heated with concentrated H₂SO₄, yields I (R = CONH₂), brick-red crystals, decompose above 270°. Adding 0.94 cc. ClCO₂Et dropwise to a solution of 2 g. VI and 2.28 g. Bu₃N in 20 cc. CHCl₃ at -5°, stirring the mixture 0.5 hr. at -5°, then adding 900 mg. PhNH₂, and stirring the mixture 12 hrs. give I (R = CONHPh), small red rods, m. 308°; I (R = CONEt₂), light red leaflets, m. 192°. The following II are prepared (amino acid given): alanine, light red rods, m. 254°; norvaline, light red leaflets, m. 220°; α-aminobutyric acid, red leaflets, m. 218-19°; glutamic di-Et ester, red needles, m. 171-2°; glutamic mono-Et ester, long red needles, m. 186-7°; phenylalanine, red needles, m. 225-6°; tryptophan Me ester, purple crystals, m. 254°. Treating 1.2 g. 2,4-Me₂C₆H₃NH₂ in 30 cc. H₂O and 1.16 g. concentrated H₂SO₄ with 1.7 g. IV and 1.9 g. V yields isonitrosoacetamido-p-xylene which, added to 10 cc. concentrated H₂SO₄ at 65-7° and the mixture heated 20 min. at 65-70°, gives 4,7-dimethylisatin, yellow-red precipitate, m. 261°. Reduction of 4,3-Me(O₂N)C₆H₃NHAc with Raney Ni at 120° and 100 atm. gives 100% 3,4-Me(H₂N)C₆H₃NHAc, m. 159°, which (6 g.), stirred 4-5 hrs. at 36-40° with 6 g. IV and 7.2 g. V, yields 3-isonitrosoacetamido-4-methylacetanilide. Heating the latter 45 min. in 10 cc. concentrated H₂SO₄ at 95-100° gives 4-amino-7-methylisatin, light red needles, charring above 310°. The dehydrogenase activity of these compounds has been tested by measuring the time required to decolorize a solution of 2 × 10^-5 moles methylene blue and 2.25 × 10^-4 moles DL-alanine in 71% HCONMe₂ at 40°. The results, given in a table, show that V is the most active catalyst. The introduction of the Me group at the 7-position has no effect on the dehydrogenation velocity. For the calculation of the partial velocities of the catalysis the P_S curves of some of the compounds are given. In the experiment, the researchers used many compounds, for example, 3-Amino-4-methylbenzonitrile (cas: 60710-80-7Synthetic Route of C8H8N2).

3-Amino-4-methylbenzonitrile (cas: 60710-80-7) 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.Synthetic Route of C8H8N2

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts