Month: January 2023

3-Substituted 7-(diethylamino)coumarins as molecular scaffolds for the bottom-up self-assembly of solids with extensive π-stacking was written by Arcos-Ramos, Rafael;Maldonado-Dominguez, Mauricio;Ordonez-Hernandez, Javier;Romero-Avila, Margarita;Farfan, Norberto;Carreon-Castro, Maria del Pilar. And the article was included in Journal of Molecular Structure in 2017.Electric Literature of C14H14N2O2 This article mentions the following:

In this study, a set of mol. crystals derived from 3-substituted 7-(diethylamino)-2H-chromen-2-ones 1-8 were studied to sample the aggregation of coumarins into ordered solids. Crystals of parent compound 1a and its brominated derivative 2 were obtained and solved in the P-1 and C2/c space groups, resp. All the crystalline coumarins studied display extensive π-stacking in the solid-state. Theor. valence-conduction band gaps for derivatives 3b and 5 are close to crystalline rubrene, highlighting the importance of cooperativity and periodicity of π-stacking, in organic semiconductors; given their synthetic accessibility, electronic tunability and self-assembly via stacking, dipolar and H-bonding interactions, these systems arise as candidates for the bottom-up construction of organic crystals with extensive π-stacking and high polarizability. 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. Nitriles are polar, as indicated by high dipole moments. As liquids, they have high relative permittivities, often in the 30s. 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 C14H14N2O2

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Epiphyseal plate lesions, degenerative arthritis, and dissecting aneurysms of the aorta produced by aminonitriles was written by Wawzonek, S.;Ponseti, I. V.;Shepard, R. S.;Wiedenmann, L. G.. And the article was included in Science (Washington, DC, United States) in 1955.Formula: C9H12N4 This article mentions the following:

β-Aminopropionitrile (I) fed to weanling rats at concentrations of 0.1, 0.4, and 1.0% in their diet produced widening and extensive disruption of the epiphyseal plates, widespread periosteal new bone formations, loosening and detachment of the ligamentous and tendinous insertions, degenerative arthritis, and dissecting aneurysms of the aorta. The severity of the epiphyseal plate lesions and periosteal new bone formation was in direct proportion to the concentration administered. Histologically these lesions appeared to be identical to the lesions observed in rats fed diets containing 50% Lathyrus odoratus seeds (cf. Federation Proc. 13, 473(1954)). Following the method of Dupuy and Lee (C.A. 48, 4182h) the compound β-(γ-L-glutamylamino)propionitrile was isolated from these germinating seeds and found to be active in producing the skeletal lesions when fed at a 1% level. In order to determine the active moiety of this compound weanling rats were fed the following diet: 1% β-alanine plus 1% L-glutamic acid, 1 and 2% propionitrile, 1 and 2% acetonitrile, 1% indoleacetonitrile, 0.4 and 1% bis(2-cyanoethyl)amine (II); 0.4 and 1% tris(2-cyanoethyl)amine, and 0.1, 0.4, and 1% I. Only II produced death (1% concentration for 16 days), or skeletal lesions (0.4% concentration for 50 days). In order to determine the mode of action of I, weanling rats were fed 0.1 and 0.4% acrylonitrile and were injected subcutaneously with sublethal doses of KCN. Neither of these produced skeletal lesions. Investigators of other aminonitriles revealed that aminoacetonitrile at the 0.2% level produced extremely severe skeletal lesions 2 weeks after feeding, and at the 1% level killed within 6 days. α-Aminopropionitrile at 1.0 and 0.2% levels stunted the rats but did not produce detectable skeletal lesions. γ-Aminobutyronitrile (0.2% level) had no abnormal effect. In the experiment, the researchers used many compounds, for example, 3,3′,3”-Nitrilotripropanenitrile (cas: 7528-78-1Formula: C9H12N4).

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

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Substituent dependency of the dihydroazulene ⇄ vinylheptafulvene photochromism: steric and electronic effects of 9-anthryl compounds- new access to condensed hydropentalenes was written by Gierisch, Sebastian;Bauer, Walter;Burgemeister, Thomas;Daub, Joerg. And the article was included in Chemische Berichte in 1989.Electric Literature of C18H10N2 This article mentions the following:

The synthesis of 2-(9-anthryl)-1,8a-dihydro-1,1-azulenedicarbonitrile (I) from 8-methoxyheptafulvene (II) by [8+2] cycloaddition reaction via tetrahydroazulene III and elimination of MeOH is described. On irradiation with visible light I is transformed to the vinylheptafulvene IV, which reconverts to I under thermal conditions. The steric congestion caused by the 9-anthryl substituent determines the rate of the [8+2] cycloaddition reaction as well as the kinetics of the thermal back reaction IV → I and causes thermochromic behavior of I. By intramol. electrophilic substitution, III yields the condensed hydropentalene V, which on oxidation leads to the condensed polycycle VI. The stereochem. assignments of the 9-anthryl compounds were made mainly by one- and two-dimensional ¹H-NMR spectroscopy. In the experiment, the researchers used many compounds, for example, 2-(Anthracen-9-ylmethylene)malononitrile (cas: 55490-87-4Electric Literature 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. 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 C18H10N2

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Base strengths of cyanoamines was written by Stevenson, Geo. W.;Williamson, Dallas. And the article was included in Journal of the American Chemical Society in 1958.Product Details of 7528-78-1 This article mentions the following:

Conjugate acids of cyanoamines have the following pK_a: Et₂NCN -2.0 ± 0.3, Et₂NCH₂CN 4.55, Et₂N(CH₂)₂CN 7.65, Et₂N(CH₂)₃CN 9.29, Et₂N(CH₂)₄CN 10.08, Et₂N(CH₂)₅CN 10.46, Et₂NCMe₂CN 9.13, HN(CH₂CN)₂ 0.2 ± 0.1, EtN(CH₂CN)₂ -0.6 ± 0.1, HN(CH₂CH₂CN)₂ 5.26, EtN(CH₂CH₂CN)₂ 4.55, N(CH₂CH₂CN)₃ 1.1 ± 0.1, H₂NCH₂CN 5.34, piperidinoacetonitrile 4.55, α-piperidinoisobutyronitrile 9.22, β-(N-amphetamine)propionitrile 7.23, β-(N-methamphetamine)propionitrile 6.95, and β-(N-norcodeine)propionitrile 5.68. The cyano group has a base-weakening effect attributed to inductive and field effects. Hall’s equations (C.A. 52, 1735f) were used to estimate σ^* values for the cyanoalkyl groups. pK_a was determined by potentiometric titration of the strong bases with HCl or of salts of weaker bases with NaOH. For the very weak bases titration curves were determined spectrophotometrically at 210 mμ, the bases showing considerable absorption at this wave length and the salts very little. In the experiment, the researchers used many compounds, for example, 3,3′,3”-Nitrilotripropanenitrile (cas: 7528-78-1Product Details of 7528-78-1).

3,3′,3”-Nitrilotripropanenitrile (cas: 7528-78-1) 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. 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.Product Details of 7528-78-1

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Half-sandwich (η⁵-Cp*)Rh(III) complexes of pyrazolated organo-sulfur/selenium/tellurium ligands: efficient catalysts for base/solvent free C-N coupling of chloroarenes under aerobic conditions was written by Sharma, Charu;Srivastava, Avinash Kumar;Sharma, Kamal Nayan;Joshi, Raj Kumar. And the article was included in Organic & Biomolecular Chemistry in 2020.SDS of cas: 10282-32-3 This article mentions the following:

Three new pyrazolated chalcogenoether ligated Rh(III) half-sandwich complexes [Cp*RhCl(PhECH₂CH₂Pz-Br)] (1–3; Pz-Br = 4-bromo-1-pyrazolyl-κN²; E = S, Se, Te) were synthesized by the thermal reaction of chalcogenoether (S, Se and Te) substituted 1H-pyrazole ligands (L1-L3) and [(η⁵-C₅Me₅)RhCl]₂ in methanol. The complexes were fully characterized by various spectroscopic techniques, and the mol. structures of complexes 1 and 2 were also established through single crystal X-ray crystallog. anal., which indicates a pseudo-octahedral half-sandwich piano-stool geometry around the rhodium metal. All three complexes were found to be thermally stable and insensitive towards air and moisture. One mol% of Rh(III) complexes 1–3 along with 10 mol% of Cu(OAc)₂ were explored for the Buchwald-Hartwig type C-N coupling reactions of amine and aryl chloride. Good to excellent yields (89-92%) of the coupling products were obtained with seleno- and thio-ether functionalized pyrazolated Rh(III) complexes (1 and 2), while an average yield (39%) was obtained with the telluro-ether functionalized complex (3). In contrast to the previously reported C-N coupling reactions the present reaction works under solvent- and base-free conditions, and the coupling reaction is accomplished in just 6 h with a high yield of the coupling product. The present methodol. was also found to be efficient for a wide variety of functionalized aryl halides, and aliphatic or aromatic amines (1° and 2°). Moreover, the reaction also enables the C-N coupling of electron-withdrawing substrates and base-sensitive functionalities. In the experiment, the researchers used many compounds, for example, 4-(Benzylamino)benzonitrile (cas: 10282-32-3SDS of cas: 10282-32-3).

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.SDS of cas: 10282-32-3

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Discovery of a Phosphoinositide 3-Kinase (PI3K) β/δ Inhibitor for the Treatment of Phosphatase and Tensin Homolog (PTEN) Deficient Tumors: Building PI3Kβ Potency in a PI3Kδ-Selective Template by Targeting Nonconserved Asp856 was written by Perreault, Stephane;Chandrasekhar, Jayaraman;Cui, Zhi-Hua;Evarts, Jerry;Hao, Jia;Kaplan, Joshua A.;Kashishian, Adam;Keegan, Kathleen S.;Kenney, Thomas;Koditek, David;Lad, Latesh;Lepist, Eve-Irene;McGrath, Mary E.;Patel, Leena;Phillips, Bart;Therrien, Joseph;Treiberg, Jennifer;Yahiaoui, Anella;Phillips, Gary. And the article was included in Journal of Medicinal Chemistry in 2017.Synthetic Route of C5H2Cl2N4 This article mentions the following:

Phosphoinositide 3-kinase (PI3K) beta signaling is required to sustain cancer cell growth in which the tumor suppressor phosphatase and tensin homolog (PTEN) has been deactivated. This manuscript describes the discovery, optimization, and in vivo evaluation of a novel series of PI3Kbeta/delta inhibitors in which PI3Kbeta potency was built in a PI3Kdelta-selective template. This work led to the discovery of a highly selective PI3Kbeta/delta inhibitor displaying excellent pharmacokinetic profile and efficacy in a human PTEN-deficient LNCaP prostate carcinoma xenograft tumor model. In the experiment, the researchers used many compounds, for example, 2-Amino-4,6-dichloropyrimidine-5-carbonitrile (cas: 1277179-33-5Synthetic Route of C5H2Cl2N4).

2-Amino-4,6-dichloropyrimidine-5-carbonitrile (cas: 1277179-33-5) 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.Synthetic Route of C5H2Cl2N4

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Steric effects in the phototransposition reactions of dialkylbenzenes was written by Gonzalez, C. M.;Pincock, J. A.. And the article was included in Canadian Journal of Chemistry in 2006.Related Products of 29809-13-0 This article mentions the following:

The photochem., photophys. properties, and temperature dependence (-25 to +65 °) of fluorescence by quantum yields and excited singlet state lifetimes in acetonitrile have been examined for three sets of dialkylbenzene derivatives: Set 1 – ortho-xylene (10), tetralin (11), and indan (12); Set 2 – 2,3-dimethylbenzonitrile (9-23), 5-cyanotetralin (T-23), and 4-cyanoindan (I-23); and Set 3 – 3,4-dimethylbenzonitrile (9-34), 6-cyanotetralin (T-34), and 5-cyanoindan (I-34). Phototransposition reactions occur for 10, 9-23, 9-34, and T-34. Fitting of the temperature-dependent fluorescence data to an Arrhenius expression gave A and E_a values for all substrates studied except I-23 and I-34. The fluorescence intensity of these two compounds was essentially independent of temperature For the other compounds, the data revealed that the activation barrier separating the excited singlet state (S₁) from the reactive intermediate, a prefulvene biradical, was the important one in determining the reaction efficiency. The dominant mode of decay of the reactive intermediate was internal return to the starting material. Moreover, the general observation was made that nitrile substitution ortho to one of the alkyl groups in these dialkylbenzene derivatives reduced the rate at which they were converted to the reactive intermediate and, therefore, also the efficiency of the phototransposition reactions. In the experiment, the researchers used many compounds, for example, 5,6,7,8-Tetrahydronaphthalene-1-carbonitrile (cas: 29809-13-0Related Products of 29809-13-0).

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

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

A novel palladium-catalyzed amination of aryl halides with amines using rac-P-Phos as the ligand was written by Chen, Huansheng;Wang, Quanrui;Tao, Fenggang. And the article was included in Chinese Journal of Chemistry in 2009.Related Products of 10282-32-3 This article mentions the following:

An efficient palladium-catalyzed amination of aryl halides with amines, using rac-P-Phos as the ancillary ligand and Pd(OAc)₂ as the palladium source is developed. The ligand and all of the synthetic intermediates are stable to air and moisture, allowing easy handling. Aromatic amines, e.g. R¹C₆H₄NR²R³ (R¹ = H, 4-MeO, 4-Ph, etc.; R² = H, Me; R³ = PhCH₂, 4-MeC₆H₄, Ph; R²R³ = N-morpholinyl, N-indolyl), were obtained in high yields. In the experiment, the researchers used many compounds, for example, 4-(Benzylamino)benzonitrile (cas: 10282-32-3Related Products of 10282-32-3).

4-(Benzylamino)benzonitrile (cas: 10282-32-3) 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 10282-32-3

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Covalently Interlocked Cyclohexa-m-phenylenes and Their Assembly: En Route to Supramolecular 3D Carbon Nanostructures was written by Dumslaff, Bastian;Reuss, Anna N.;Wagner, Manfred;Feng, Xinliang;Narita, Akimitsu;Fytas, George;Muellen, Klaus. And the article was included in Angewandte Chemie, International Edition in 2017.Application In Synthesis of 3-(tert-Butyl)benzonitrile This article mentions the following:

In our search to cluster as many phenylene units as possible in a given space, we have proceeded to the three-dimensional world of benzene-based mols. by employing covalently interlocked cyclohexa-m-phenylenes, as present in the unique paddlewheel-shaped polyphenylene 10. A precursor was conceived, in which freely rotating m-chlorophenylene units provide sufficient solubility along with the necessary proximity for the final ring closure to give 10. Monitoring the assembly of solubilized tert-Bu derivatives of 10 into supramol. carbon nanostructures by dynamic light scattering (DLS) and Brillouin light scattering (BLS) revealed the dimensions of the initially formed aggregates as well as the amorphous character of the solid state. In the experiment, the researchers used many compounds, for example, 3-(tert-Butyl)benzonitrile (cas: 154532-34-0Application In Synthesis of 3-(tert-Butyl)benzonitrile).

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. 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 In Synthesis of 3-(tert-Butyl)benzonitrile

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Enantioselective Reduction of Ketones Induced by a C₂-Symmetrical Chiral Hydroxyamide/Titanium(IV) Complex was written by Phothongkam, Supannee;Uang, Biing-Jiun. And the article was included in Asian Journal of Organic Chemistry in 2015.Safety of (R)-4-(1-Hydroxyethyl)benzonitrile This article mentions the following:

An efficient catalytic system based on the use of a chiral titanium complex generated in situ for the enantioselective reduction of ketones as acetophenone, 1-tetralone, etc. using catecholborane as a reducing agent was developed. The reaction employed the chiral β-hydroxyamide ligand, which can be easily prepared from inexpensive and com. available starting materials, in combination with titanium tetraisopropoxide to achieve enantioenriched secondary alcs. such as (R)-1-tetralol, (R)-1-(2-thienyl)ethanol, etc. in good yields and with up to >99% ee. In the experiment, the researchers used many compounds, for example, (R)-4-(1-Hydroxyethyl)benzonitrile (cas: 101219-69-6Safety of (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. 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.Safety of (R)-4-(1-Hydroxyethyl)benzonitrile

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts