Author: Jessica.F

C-H chlorination of (hetero)anilines via photo/organo co-catalysis was written by Xie, Wuchen;Wang, Meng;Yang, Siyu;Chen, Yadong;Feng, Jie;Huang, Yatian. And the article was included in Organic & Biomolecular Chemistry in 2022.SDS of cas: 53312-77-9 This article mentions the following:

Herein, a photo-redox and organo co-catalyzed chlorination method for anilines to gave chloro-anilines ArNR¹R² [Ar = 4-ClC₆H₄, 3,4-di-Cl-5-FC₆H₂, 4-Cl-2,5-di-FC₆H₂, etc.; R¹ = H, Me; R² = H, Me, C(O)Me, Ph, pyrimidin-2-yl; R¹R² = (CH₂)₂N(CH₃)(CH₂)₂] was disclose. This method had great substrate generality and excellent mono-chlorination selectivity. Another merit of this method was the late-stage modification of drug mols., which would be useful in medicinal chem. In the experiment, the researchers used many compounds, for example, 2-Amino-3-chlorobenzonitrile (cas: 53312-77-9SDS of cas: 53312-77-9).

2-Amino-3-chlorobenzonitrile (cas: 53312-77-9) belongs to nitriles. Nitriles are polar, as indicated by high dipole moments. As liquids, they have high relative permittivities, often in the 30s. 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.SDS of cas: 53312-77-9

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Thiophene/thiazole-benzene replacement on guanidine derivatives targeting α₂-Adrenoceptors was written by Flood, Aoife;Trujillo, Cristina;Sanchez-Sanz, Goar;Kelly, Brendan;Muguruza, Carolina;Callado, Luis F.;Rozas, Isabel. And the article was included in European Journal of Medicinal Chemistry in 2017.Reference of 70291-62-2 This article mentions the following:

Searching for improved antagonists of α₂-adrenoceptors, a thorough theor. study comparing the aromaticity of phenyl-, pyridinyl-, thiophenyl- and thiazolylguanidinium derivatives were carried out [at M06-2X/6-311++G(p,d) computational level] confirming that thiophene and thiazole were good ‘ring equivalent’ to benzene in these guanidinium systems. Based on these results, a small but chem. diverse library of guanidine derivatives were synthesized to explore the effect that the bioisosteric change has on affinity and activity at α₂-adrenoceptors in comparison with our previously studied Ph derivatives All compounds were tested for their α₂-adrenoceptor affinity and unsubstituted guanidinothiophenes displayed the strongest affinities in the same range as the Ph analogs. In the case of cycloalkyl systems, thiophenes with 6-membered rings showed the largest affinities, while for the thiazoles the 5-membered analog presented the strongest affinity. From all the compounds tested for noradrenergic activity, only one compound exhibited agonistic activity, while two compounds showed very promising antagonism of α₂-adrenoceptors. In the experiment, the researchers used many compounds, for example, 2-Amino-5,6-dihydro-4H-cyclopenta[b]thiophene-3-carbonitrile (cas: 70291-62-2Reference of 70291-62-2).

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. 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.Reference of 70291-62-2

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Straightforward conversion of arene carboxylic acids into aryl nitriles by palladium-catalyzed decarboxylative cyanation reaction was written by Ouchaou, Kahina;Georgin, Dominique;Taran, Frederic. And the article was included in Synlett in 2010.Reference of 55406-13-8 This article mentions the following:

A one-pot procedure to convert aromatic carboxylic acids into aromatic nitriles was described. The methodol. is based on a palladium(II)-catalyzed decarboxylative cyanation reaction using cyanohydrins as soluble cyanide sources. The described reaction worked on a panel of substrates and is addnl. of particular interest for the straightforward preparation of ¹³C- or ¹⁴C-labeled compounds In the experiment, the researchers used many compounds, for example, 3-Methylthiophene-2-carbonitrile (cas: 55406-13-8Reference of 55406-13-8).

3-Methylthiophene-2-carbonitrile (cas: 55406-13-8) 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.Reference of 55406-13-8

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A CaO catalyzed facile one-pot synthesis of 2-aminothiophenes using Gewald reaction was written by Durgareddy, G. A. N. K.;Ravikumar, R.;Ravi, S.;Adapa, Srinivas R.. And the article was included in Pharma Chemica in 2013.Formula: C8H8N2S This article mentions the following:

A series of 2-aminothiophene derivatives I [R¹ = H, Me, Ph, etc.; R² = H, Me, COOEt, etc.; X = COOEt, CN] was synthesized via heterogeneous CaO catalyzed Gewald reaction of an active nitrile or Et ester with ketones in presence of elemental sulfur in ethanol. The present protocol offers several advantages such as low cost material CaO as a catalyst with good yields, shorter reaction time, simple exptl. procedures and low catalyst loading. 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. Nitrile compounds can be prepared by the incorporation of a cyanide source through C–C bond formation or by dehydration of primary carboxamides. 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.Formula: C8H8N2S

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Synthesis, Characterization, and Reactivity of Arylpalladium Cyanoalkyl Complexes: Selection of Catalysts for the α-Arylation of Nitriles was written by Culkin, Darcy A.;Hartwig, John F.. And the article was included in Journal of the American Chemical Society in 2002.HPLC of Formula: 5351-07-5 This article mentions the following:

A new coupling process, the Pd-catalyzed α-arylation of nitriles, was developed by exploring the structure and reactivity of arylpalladium cyanoalkyl complexes. Complexes L₂Pd(Ar)(RR¹CCN) (L₂ = DPPBz Ar = C₆H₄Bu-t-4 R = R¹ = H (1), Ar = C₆H₄Me-4, R = H R¹ = Pr-i (2), Ph (3), R = R¹ = Me (4); L₂ = DⁱPrPF, Ar = C₆H₄Bu-t-4, R = H R¹ = Ph (5); L₂ = BINAP, Ar = C₆H₄Bu-t-4, R = H R¹ = Pr-i (7), R = R¹ = Me (8)) or (DⁱPrPF)Pd(C₆H₄Bu-t-4)(N:C:C(CH₃)₂) (6) where DPPBz = 1,2-bis(diphenylphosphino)benzene, DⁱPrPF = 1,1′-bis(diisopropylphosphino)ferrocene, BINAP = (±)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl, and {Pd(PPh₂Et)(C₆H₄Me-4)(μ-CMe₂CN)}₂ (9) were prepared The mol. structures of 4, 6, and 9 were determined by single crystal x-ray anal. Coordination to Pd through the α-C was observed for DPPBz-ligated complexes and for complexes of primary and benzylic nitrile anions. However, the anion of isobutyronitrile was coordinated to Pd through the cyano-N when the complex was ligated by DⁱPrPF. The isobutyronitrile anion displaced a phosphine ligand to form a C,N-bridged dimer when generated from PPh₂Et-ligated Pd. These results suggest that the nitrile anion preferentially coordinates to Pd through the C atom in the absence of steric effects. Thermolysis of the arylpalladium cyanoalkyl complexes led to reductive elimination that formed α-aryl nitriles. The high yields and short reaction times observed for BINAP-ligated complexes suggested that BINAP-ligated Pd catalysts might be appropriate for the arylation of nitriles. Initial results on a Pd-catalyzed process for the direct coupling of aryl bromides and primary, benzylic, and secondary nitrile anions to form α-aryl nitriles in good yields are reported. E.g., addition of a toluene solution containing Me₂CHCN and the base NaN(SiMe₃)₂ to a suspension of Pd(OAc)₂, BINAP, and 4-NCC₆H₄Br in toluene gave 4-NCC₆H₄CMe₂CN in 99% yield after being stirred for 1 h at 100°. In the experiment, the researchers used many compounds, for example, 2-(4-Methoxyphenyl)-2-methylpropanenitrile (cas: 5351-07-5HPLC of Formula: 5351-07-5).

2-(4-Methoxyphenyl)-2-methylpropanenitrile (cas: 5351-07-5) 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. Asymmetric bioreduction of nitriles is an attractive route to produce optically active nitriles as current metal-catalyzed hydrogenations tend to have low reactivity.HPLC of Formula: 5351-07-5

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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

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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

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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

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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

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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