Month: January 2023

Efficient Access to 2,6,8-Trisubstituted 4-Aminoquinazolines through Microwave-Assisted One-Pot Chemoselective Tris-Suzuki-Miyaura or S_NAr/Bis-Suzuki-Miyaura Reactions in Water was written by Kabri, Youssef;Crozet, Maxime D.;Terme, Thierry;Vanelle, Patrice. And the article was included in European Journal of Organic Chemistry in 2015.Application In Synthesis of 2-Amino-3,5-dibromobenzonitrile This article mentions the following:

An efficient, sequential, one-pot strategy for synthesizing polyfunctionalized quinazoline derivatives is presented. After selective amination of 6,8-dibromo-2,4-dichloroquinazoline at the C-4 position, 2,6,8-trisubstituted 4-aminoquinazoline derivatives I (R = 4-MeOC₆H₄, 4-ClC₆H₄, pyridin-3-yl, etc.) were prepared through one-pot chemoselective sequential tris-Suzuki-Miyaura or S_NAr/bis-Suzuki-Miyaura reactions under microwave irradiation in an aqueous medium. This approach, used with a variety of boronic acids, affords polysubstituted quinazoline derivatives in good to excellent yields in only a few steps and in the environmentally benign solvent water. In the experiment, the researchers used many compounds, for example, 2-Amino-3,5-dibromobenzonitrile (cas: 68385-95-5Application In Synthesis of 2-Amino-3,5-dibromobenzonitrile).

2-Amino-3,5-dibromobenzonitrile (cas: 68385-95-5) 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. Application In Synthesis of 2-Amino-3,5-dibromobenzonitrile

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Cytochrome P450 Catalyzed Oxidative Hydroxylation of Achiral Organic Compounds with Simultaneous Creation of Two Chirality Centers in a Single C-H Activation Step was written by Roiban, Gheorghe-Doru;Agudo, Ruben;Reetz, Manfred T.. And the article was included in Angewandte Chemie, International Edition in 2014.Reference of 24056-34-6 This article mentions the following:

Regio- and stereoselective oxidative hydroxylation of achiral or chiral organic compounds mediated by synthetic reagents, catalysts, or enzymes generally leads to the formation of one new chiral center that appears in the resp. enantiomeric or diastereomeric alcs. By contrast, when subjecting appropriate achiral compounds to this type of C-H activation, the simultaneous creation of two chiral centers with a defined relative and absolute configuration may result, provided that control of the regio-, diastereo-, and enantioselectivity is ensured. The present study demonstrates that such control is possible by using wild-type (wt) or mutant forms of the monooxygenase cytochrome P 450 BM3 as catalysts in the oxidative hydroxylation of methylcyclohexane and seven other monosubstituted cyclohexane derivatives In the experiment, the researchers used many compounds, for example, 4-Hydroxycyclohexanecarbonitrile (cas: 24056-34-6Reference of 24056-34-6).

4-Hydroxycyclohexanecarbonitrile (cas: 24056-34-6) 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. 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.Reference of 24056-34-6

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Electrochemical oxidation of acylsilanes and their tosylhydrazones was written by Yoshida, Junichi;Itoh, Masanori;Matsunaga, Shinichiro;Isoe, Sachihiko. And the article was included in Journal of Organic Chemistry in 1992.Recommanded Product: 2-Cyclohexylacetonitrile This article mentions the following:

Oxidation potentials of acylsilanes were much less pos. than those of ketones and aldehydes. The effect of silicon is attributed to the rise of the HOMO level by the interaction between the C-Si σ orbital and the nonbonding p orbital of the carbonyl oxygen which in turn favors the electron transfer. Preparative electrochem. oxidation of acylsilanes proceeded smoothly, giving rise to facile cleavage of the C-Si bond and the introduction of nucleophiles such as alcs., water, and carbamates onto the carbonyl carbon. Electrochem. properties of tosylhydrazones of acylsilanes were also investigated. A decrease in oxidation potential of tosylhydrazones caused by silyl substitution was smaller than that for carbonyl compounds Preparative electrochem. oxidation of tosylhydrazones of acylsilanes gave the corresponding nitriles with consumption of a catalytic amount of electricity. In the experiment, the researchers used many compounds, for example, 2-Cyclohexylacetonitrile (cas: 4435-14-7Recommanded Product: 2-Cyclohexylacetonitrile).

2-Cyclohexylacetonitrile (cas: 4435-14-7) 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.Recommanded Product: 2-Cyclohexylacetonitrile

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Synthesis, photophysical characterization and DFT studies on fluorine-free deep-blue emitting Pt(II) complexes was written by Sanning, Jan;Stegemann, Linda;Nyenhuis, Marvin;Daniliuc, Constantin G.;Doltsinis, Nikos L.;Strassert, Cristian A.. And the article was included in Zeitschrift fuer Naturforschung, B: A Journal of Chemical Sciences in 2016.Synthetic Route of C7H6N2O This article mentions the following:

Herein authors show that cyclometalated, square planar Pt(II) complexes can be tuned to achieve deep-blue phosphorescent emitters. For this purpose, the introduction of an electron-donating moiety on two different bidentate NN and NO fluorine-free luminophores, namely 2-(1H-tetrazol-5-yl)pyridine and picolinic acid, was carried out. The remaining two coordination sites of the Pt(II) metal center were filled by a sterically demanding cyclometallating unit, namely a tertiary phosphite CP ligand. This ancillary ligand avoids aggregation and provides high solubility in organic solvents. Based on this approach, we were able to blue-shift the emission of the complexes down to 411 nm, and to achieve a maximal photoluminescence quantum yield of 56% in the solid state. In the experiment, the researchers used many compounds, for example, 4-methoxypicolinonitrile (cas: 36057-44-0Synthetic Route of C7H6N2O).

4-methoxypicolinonitrile (cas: 36057-44-0) 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. 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.Synthetic Route of C7H6N2O

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

A facile, choline chloride/urea catalyzed solid phase synthesis of coumarins via Knoevenagel condensation was written by Harishkumar, Hosanagara N.;Mahadevan, Kittappa M.;Kiran Kumar, Hittalumane C.;Satyanarayan, Nayak D.. And the article was included in Organic Communications in 2011.Related Products of 51473-74-6 This article mentions the following:

The influence of choline chloride/urea ionic liquid in solid phase on the Knoevenagel condensation is demonstrated. The active methylene compounds such as meldrum acid, diethylmalonate, Et cyanoacetate, dimethylmalonate, were efficiently condensed with various salicylaldehydes in presence of choline chloride/urea ionic liquid without using any solvents or addnl. catalyst. The reaction is remarkably facile because of the air and water stability of the catalyst, and needs no special precautions. The reactions were completed within 1 h with excellent yields (95%). The products formed were sufficiently pure, and can be easily recovered. The use of ionic liquid choline chloride/urea in solid phase offered several significant advantages such as low cost, greater selectivity and easy isolation of products. In the experiment, the researchers used many compounds, for example, 7-(Diethylamino)-2-oxo-2H-chromene-3-carbonitrile (cas: 51473-74-6Related Products of 51473-74-6).

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. 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. Related Products of 51473-74-6

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Design, synthesis, AChE/BChE inhibitory activity, and molecular docking of spiro[chromeno[4,3-b]thieno[3,2-e]pyridine]-7-amine tacrine hybrids was written by Kappenberg, Yuri G.;Nogara, Pablo A.;Stefanello, Felipe S.;Moretto, Luis Henrique;Santos, Patricia M.;Rocha, Joao. B. T.;Zanatta, Nilo;Martins, Marcos. A. P.;Bonacorso, Helio G.. And the article was included in Journal of Molecular Structure in 2022.Synthetic Route of C8H8N2S This article mentions the following:

A new series of 12 examples of spiro[chromeno[4,3-b]thieno[3,2-e]pyridine]-7-amines tacrine hybrids were designed and synthesized as cholinesterase inhibitors. These new compounds were synthesized at 20-33% yields by a one-pot two-step cyclocondensation reaction of 2-aminothiophene-3-carbonitriles with spiro[chroman-2,10-cycloalkan]-4-ones using AlCl₃ as the catalyst without solvent and under conventional thermal heating. Subsequently, these new tacrine hybrids were subjected to AChE and BChE inhibitory activity evaluation and mol. docking studies. In vitro cholinesterase assays and in silico docking indicated that all new tacrine analgs were not AChE inhibitors. However, the mols. without a carbocyclic moiety geminated to the thiophene ring, i.e., spiro scaffolds that originated from cyclopentanone , cyclohexanone , and cycloheptanone showed the highest inhibitory potency against the BChE enzyme, thereby proving to be promising candidates for evaluation in Alzheimer’s disease synthetic models. In the experiment, the researchers used many compounds, for example, 2-Amino-5,6-dihydro-4H-cyclopenta[b]thiophene-3-carbonitrile (cas: 70291-62-2Synthetic Route of C8H8N2S).

2-Amino-5,6-dihydro-4H-cyclopenta[b]thiophene-3-carbonitrile (cas: 70291-62-2) 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 C8H8N2S

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Substrate profiling of the cobalt nitrile hydratase from Rhodococcus rhodochrous ATCC BAA 870 was written by Mashweu, Adelaide R.;Chhiba-Govindjee, Varsha P.;Bode, Moira L.;Brady, Dean. And the article was included in Molecules in 2020.Reference of 1753-48-6 This article mentions the following:

The aromatic substrate profile of the cobalt nitrile hydratase from Rhodococcus rhodochrous ATCC BAA 870 was evaluated against a wide range of nitrile containing compounds (>60). To determine the substrate limits of this enzyme, compounds ranging in size from small (90 Da) to large (325 Da) were evaluated. Larger compounds included those with a bi-aryl axis, prepared by the Suzuki coupling reaction, Morita-Baylis-Hillman adducts, heteroatom-linked diarylpyridines prepared by Buchwald-Hartwig cross-coupling reactions and imidazo[1,2-a]pyridines prepared by the Groebke-Blackburn-Bienayme multicomponent reaction. The enzyme active site was moderately accommodating, accepting almost all of the small aromatic nitriles, the diarylpyridines and most of the bi-aryl compounds and Morita-Baylis-Hillman products but not the Groebke-Blackburn-Bienayme products. Nitrile conversion was influenced by steric hindrance around the cyano group, the presence of electron donating groups (e.g., methoxy) on the aromatic ring, and the overall size of the compound In the experiment, the researchers used many compounds, for example, 2-Aminopyrimidine-5-carbonitrile (cas: 1753-48-6Reference of 1753-48-6).

2-Aminopyrimidine-5-carbonitrile (cas: 1753-48-6) belongs to nitriles. Nitrile carbon shifts are in the range of 115–125 ppm whereas in isonitriles the shifts are around 155–165 ppm. Asymmetric bioreduction of nitriles is an attractive route to produce optically active nitriles as current metal-catalyzed hydrogenations tend to have low reactivity.Reference of 1753-48-6

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Chemically Robust and Bifunctional Co(II)-Framework for Trace Detection of Assorted Organo-toxins and Highly Cooperative Deacetalization-Knoevenagel Condensation with Pore-Fitting-Induced Size-Selectivity was written by Seal, Nilanjan;Palakkal, Athulya S.;Singh, Manpreet;Goswami, Ranadip;Pillai, Renjith S.;Neogi, Subhadip. And the article was included in ACS Applied Materials & Interfaces in 2021.Synthetic Route of C18H10N2 This article mentions the following:

Acute detection of assorted classes of organo-toxins in a practical environment is an important sustainable agenda, whereas cooperative and recyclable catalysis can mitigate hazards by minimizing energy requirements and reducing waste generation. The authors constructed an acid-/base-stable Co(II)-framework with a network topol., (Me)₂NH₂·[Co₃(L)₂(_μ2-OH)(bpy)_1.5(H₂O)₃] (bpy = 4,4′-bipyridine, H₃L = 4,4′,4”-tricarboxytriphenylamine) with unidirectional porous channels decorated by anionic [Co₂(μ₂-OH)(COO)₄(H₂O)₃] secondary building units and neutral [CoN₂(COO)₂] nodes. Intense luminescent of the hydrolytically robust framework is harnessed for selective, fast-responsive, and regenerable detection of two detrimental organo-aromatics, 4-aminophenol (4-AP) and 2,4,6-trinitrophenol (TNP). Alongside remarkable quenching, their nanomolar detection limits (4-AP: 99.5 nM; TNP: 67.2 nM) rank among the lowest reported values in H₂O and corroborate their ultra-sensitivity. D. functional theory (DFT) calculations verify the electron-transfer route of sensing through portraying redistribution of energy levels of MOs in a three-dimensional network by each analyte and further envisages noncovalent host-guest interactions. Benefiting from the concurrent existence of an open-metal site and a triphenylamine-moiety-functionalized ligand, the activated framework acts as an outstandingly cooperative heterogeneous catalyst in deacetalization-Knoevenagel condensation under mild conditions. The acid-base dual catalysis is detailed for the 1st time from combined inputs of control experiments and DFT validations. To the best of tandem reaction, larger-sized substrate exhibits insignificant conversion, and certifies rarest pore-fitting induced size-selectivity. In the experiment, the researchers used many compounds, for example, 2-(Anthracen-9-ylmethylene)malononitrile (cas: 55490-87-4Synthetic Route of C18H10N2).

2-(Anthracen-9-ylmethylene)malononitrile (cas: 55490-87-4) 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. 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.Synthetic Route of C18H10N2

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Challenging nickel-catalysed amine arylations enabled by tailored ancillary ligand design was written by Lavoie, Christopher M.;MacQueen, Preston M.;Rotta-Loria, Nicolas L.;Sawatzky, Ryan S.;Borzenko, Andrey;Chisholm, Alicia J.;Hargreaves, Breanna K. V.;McDonald, Robert;Ferguson, Michael J.;Stradiotto, Mark. And the article was included in Nature Communications in 2016.HPLC of Formula: 60710-80-7 This article mentions the following:

An operationally simple and air-stable ligand/nickel(II) pre-catalyst that accommodated the broadest combination of C(sp²)-N coupling partners reported to date for any single nickel catalyst, without the need for a precious-metal co-catalyst was reported. Key to the unprecedented performance of this pre-catalyst was the application of the new, sterically demanding yet electron-poor bisphosphine PAd-DalPhos. Featured were the first reports of nickel-catalyzed room temperature reactions involving challenging primary alkylamine and ammonia reaction partners employing an unprecedented scope of electrophiles, including transformations involving sought-after (hetero)aryl mesylates for which no capable catalyst system was known. In the experiment, the researchers used many compounds, for example, 3-Amino-4-methylbenzonitrile (cas: 60710-80-7HPLC of Formula: 60710-80-7).

3-Amino-4-methylbenzonitrile (cas: 60710-80-7) 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.HPLC of Formula: 60710-80-7

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Tetrahydro-ar-1-(and 2)-naphthoic acids and their derivatives was written by Sergievskaya, S. I.;Nikhamkina, E. G.. And the article was included in Zhurnal Obshchei Khimii in 1945.Name: 5,6,7,8-Tetrahydronaphthalene-1-carbonitrile This article mentions the following:

ar-1-Aminotetralin (45 g.), 75 cc. concentrated HCl, and 200 cc. water were mixed and treated with sufficient water to dissolve the HCl salt; diazotization by 22.5 g. NaNO₂ in 300 cc. water at -5°, followed by addition to 56 g. NaCN in 500 cc. water, 80 cc. 10% NH₄OH, and 33 g. CuCl, stirring for 2-3 hrs., and steam distillation gave 5,6,7,8-tetrahydro-1-naphthonitrile (35.7%), b₅ 130-1°, b₁₇ 156-7°. Heating 15.7 g. of above with 19.8 g. NaOH, 75 cc. EtOH, and 5 cc. water at reflux gave 13 g. of the corresponding acid (I), m. 139-40° (after crystallization, m. 150-1°; solvent not given) and 0.5 g. amide (no m.p.); the hydrolysis may be conducted in a sealed tube at 140° for 8 hrs., using concentrated HCl, although the yield is lowered (ca. 50%); the same acid was obtained after alc. KOH hydrolysis of the hydrogenation product of Et 1-naphthoate. I (5 g.), 17 cc. absolute EtOH, and 1.5 cc. concentrated H₂SO₄, heated 6 hrs., yielded the Et ester, b₄128-9°; hydrogenation of Et 1-naphthoate in EtOH, using Raney Ni at 130° and 50 atm., gave the same ester, b₁₈ 165-70°. Chloride of I, obtained by heating 12 g. I with 100 g. SOCl₂, b₃ 122-3°. Treatment of this with NH₄OH gave the amide, m. 181-2° (from EtOH). The chloride (1.8 g.) in dry benzene and 2 g. Et₂NCH₂CH₂OH were refluxed for 2 hrs., and after the usual treatment, treated with Et₂O-HCl to give 2-diethylaminoethyl 5,6,7,8-tetrahydro-1-naphthoate-HCl, m. 161-2° (from benzene). Similar procedures were used in the preparation of 5,6,7,8-tetrahydro-2-naphthonitrile (from ar-2-aminotetralin), b₄ 103-4° (36%); acid, m. 153° (from EtOH) (96%); Et ester, b₄ 135.5°, b₈ 147°; chloride, b₃ 115-16°; amide, m. 140-1° (from EtOH); 2-diethylaminoethyl ester-HCl, m. 152-3° (from benzene). The alkylamino esters are weak anesthetics. In the experiment, the researchers used many compounds, for example, 5,6,7,8-Tetrahydronaphthalene-1-carbonitrile (cas: 29809-13-0Name: 5,6,7,8-Tetrahydronaphthalene-1-carbonitrile).

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

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts