Category: nitriles-buliding-blocks

Moon, Lomary S. published the artcileChiral Solvating Agents for Cyanohydrins and Carboxylic Acids, SDS of cas: 13312-84-0, the publication is Journal of Organic Chemistry (2010), 75(16), 5487-5498, database is CAplus and MEDLINE.

A structure as simple as an ion pair of (R)- or (S)-mandelate and dimethylamminopyridinium ions possesses structural features that are sufficient for NMR enantiodiscrimination of cyanohydrins. Also, ¹H NMR data of cyanohydrins of known configuration obtained in the presence of the mandelate-dimethylaminopyridinium ion pair point to the existence of a correlation between chem. shifts and absolute configuration of cyanohydrins. Mandelate-DMAPH⁺ ion pair and mandelonitrile form a 1:1 complex with an association constant of 338 M^-1 (ΔG⁰, -3.4 kcal/mol) for the (R)-mandelonitrile/(R)-mandelate-DMAPH⁺ and 139 M^-1 (ΔG⁰, -2.9 kcal/mol) for the (R)-mandelonitrile/(S)-mandelate-DMAPH⁺ complex. To understand the origin of enantiodiscrimination, the geometry optimization and energy minimization of the models of ternary complexes of (S)-mandelonitrile/(R)-mandelate/DMAPH⁺ and (S)-mandelonitrile/(S)-mandelate/DMAPH⁺ complexes was performed using DFT methodol. (B3LYP) with the 6-31+G(d) basis set in Gaussian 3.0. Further, anal. of optimized mol. model obtained from theor. studies suggested that (i) DMAP may be replaced with other amines, (ii) the hydroxyl group of mandelic acid is not necessary for stabilization of ternary complex and may be replaced with other groups such as Me, (iii) the ion pair should form a stable ternary complex with any hydrogen-bond donor, provided its OH bond is sufficiently polarized, and (iv) α-H of racemic mandelic acid should also get resolved with optically pure mandelonitrile. These inferences were exptl. verified, which not only validated the proposed model but also led to development of a new chiral solvating agent for determination of ee of carboxylic acids and absolute configuration of aryl but not alkyl carboxylic acids.

Journal of Organic Chemistry published new progress about 13312-84-0. 13312-84-0 belongs to nitriles-buliding-blocks, auxiliary class Chloride,Nitrile,Benzene,Alcohol,Benzene Compounds, name is 2-(2-Chlorophenyl)-2-hydroxyacetonitrile, and the molecular formula is C8H6ClNO, SDS of cas: 13312-84-0.

Referemce:
https://en.wikipedia.org/wiki/Nitrile,
Nitriles – Chemistry LibreTexts

Zhang, Zhi-Jun published the artcileSignificant enhancement of (R)-mandelic acid production by relieving substrate inhibition of recombinant nitrilase in toluene-water biphasic system, Computed Properties of 13312-84-0, the publication is Journal of Biotechnology (2011), 152(1-2), 24-29, database is CAplus and MEDLINE.

The enantioselective hydrolysis of mandelonitrile with whole cells of a recombinant Escherichia coli expressing nitrilase activity was severely inhibited by the substrate at high concentrations (>300 mM), which resulted in a low yield of the target product (R)-(-)-mandelic acid. To relieve the substrate inhibition and to enhance the (R)-(-)-mandelic acid productivity, eight water-organic solvent biphasic systems were attempted in this work. Toluene was found to be the most suitable solvent as the organic phase among the solvents tested. Various parameters were systematically examined and optimized in shake flasks. The phase volume ratio, buffer pH and reaction temperature were shown to be sensitive parameters affecting both the yield and the enantiopurity of product in the biphasic system. Under the optimized conditions, significant enhancement of substrate tolerance from 200 mM to 500 mM and average productivity from 179.6 g L^-1 d^-1 to 352.6 g L^-1 d^-1 were achieved. Subsequently, the biocatalytic hydrolysis of mandelonitrile was successfully carried out in a stirred reactor (2-L scale) by repeated use of the calcium alginate entrapped cells for 5 batches, affording 110.7 g (R)-(-)-mandelic acid in 98.0% ee (enantiomeric excess) and a specific production of 13.8 g (mandelic acid) g^-1 (cell), resp.

Journal of Biotechnology published new progress about 13312-84-0. 13312-84-0 belongs to nitriles-buliding-blocks, auxiliary class Chloride,Nitrile,Benzene,Alcohol,Benzene Compounds, name is 2-(2-Chlorophenyl)-2-hydroxyacetonitrile, and the molecular formula is C14H26O2, Computed Properties of 13312-84-0.

Referemce:
https://en.wikipedia.org/wiki/Nitrile,
Nitriles – Chemistry LibreTexts

Parekh, Hansa published the artcilePreparation and resolution of (+-)-p-(α-cyanoarylamino)benzoic acid, Synthetic Route of 13312-84-0, the publication is Indian Journal of Chemistry (1973), 11(5), 501-3, database is CAplus.

α-Amino nitriles (±)-RCH(CN)NHC6H4COOH-p [(±)I:R = Ph, o-ClC6H4, p-MeOC6H4] were prepared by condensing an aldehyde cyanhydrin with p-aminobenzoic acid. The resolution of (±)(I) into optical isomers was accomplished through fractional crystallization of the brucine salts to give the resp. (-)-nitriles. With (±)-I (R = p-MeOC6H4), the (+)-nitrile was also obtained. The introduction of Cl in the Ph nucleus at the ortho-position enhanced the optical activity, while the MeO group at the paraposition decreased the optical activity.

Indian Journal of Chemistry published new progress about 13312-84-0. 13312-84-0 belongs to nitriles-buliding-blocks, auxiliary class Chloride,Nitrile,Benzene,Alcohol,Benzene Compounds, name is 2-(2-Chlorophenyl)-2-hydroxyacetonitrile, and the molecular formula is C8H6ClNO, Synthetic Route of 13312-84-0.

Referemce:
https://en.wikipedia.org/wiki/Nitrile,
Nitriles – Chemistry LibreTexts

Kai, Shumpei published the artcileQuantitative Analysis of Self-Assembly Process of a Pd₂L₄ Cage Consisting of Rigid Ditopic Ligands, Product Details of C10H12F6N4O6PdS2, the publication is Chemistry – A European Journal (2018), 24(3), 663-671, database is CAplus and MEDLINE.

The self-assembly process of a Pd₂L₄ cage complex consisting of rigid ditopic ligands, in which two 3-pyridyl groups are connected to a benzene ring through acetylene bonds and Pd^II ions was revealed by a recently developed quant. anal. of self-assembly process (QASAP), with which the self-assembly process of coordination assemblies can be investigated by monitoring the evolution with time of the average composition of all the intermediates. QASAP revealed that the rate-determining steps of the cage formation are the intramol. ligand exchanges in the final stage of the self-assembly: [Pd₂L₄Py*₂]⁴⁺→[Pd₂L₄Py*₁]⁴⁺+Py* and [Pd₂L₄Py*₁]⁴⁺→[Pd₂L₄]⁴⁺+Py* (Py*: 3-chloropyridine, which was used as a leaving ligand on the metal source). The energy barriers for the two reactions were determined to be 22.3 and 21.9 kcal mol^-1, resp. DFT calculations of the transition-state (TS) structures for the two steps indicated that the distortion of the trigonal-bipyramidal Pd^II center at the TS geometries increases the activation free energy of the two steps.

Chemistry – A European Journal published new progress about 68569-14-2. 68569-14-2 belongs to nitriles-buliding-blocks, auxiliary class Palladium, name is Tetrakis(acetonitrile)palladium(II) Ditriflate, and the molecular formula is C10H12F6N4O6PdS2, Product Details of C10H12F6N4O6PdS2.

Referemce:
https://en.wikipedia.org/wiki/Nitrile,
Nitriles – Chemistry LibreTexts

Frias, Maria published the artcileAsymmetric Synthesis of Rauhut-Currier type Products by a Regioselective Mukaiyama Reaction under Bifunctional Catalysis, Safety of (E)-4-(2-Nitrovinyl)benzonitrile, the publication is Journal of the American Chemical Society (2017), 139(2), 672-679, database is CAplus and MEDLINE.

The reactivity and the regioselective functionalization of silyl-diene enol ethers under a bifunctional organocatalyst provokes a dramatic change in the regioselectivity, from the 1,5- to the 1,3-functionalization. This variation makes possible the 1,3-addition of silyl-dienol ethers to nitroalkenes, giving access to the synthesis of tri- and tetrasubstituted double bonds in Rauhut-Currier type products. The process takes place under smooth conditions, nonanionic conditions, and with a high enantiomeric excess. A rational mechanistic pathway is presented based on DFT and mechanistic experiments

Journal of the American Chemical Society published new progress about 5153-73-1. 5153-73-1 belongs to nitriles-buliding-blocks, auxiliary class Nitrile,Alkenyl,Nitro Compound,Benzene, name is (E)-4-(2-Nitrovinyl)benzonitrile, and the molecular formula is C9H6N2O2, Safety of (E)-4-(2-Nitrovinyl)benzonitrile.

Referemce:
https://en.wikipedia.org/wiki/Nitrile,
Nitriles – Chemistry LibreTexts

Smyth, Lynette A. published the artcileSynthesis and reactivity of 3-amino-1H-pyrazolo[4,3-c]pyridin-4(5H)-ones: development of a novel kinase-focussed library, HPLC of Formula: 57663-05-5, the publication is Tetrahedron (2010), 66(15), 2843-2854, database is CAplus.

3-Amino-1H-pyrazolo[4,3-c]pyridin-4(5H)-ones represent a potentially attractive heteroaromatic scaffold for drug-discovery chem. In particular, the arrangement of hydrogen bond donor and acceptor groups in the bicyclic core can fulfil the requirements for ATP competitive binding to kinase enzymes. Efficient and regioselective routes from simple starting materials to novel functionalized 3-amino-1H-pyrazolo[4,3-c]pyridin-4(5H)-ones and related 3-amino-2H-pyrazolo[4,3-c]pyridines were explored and adapted for parallel synthesis, resulting in a library of compounds suitable for screening against kinases and other cancer drug targets. Methods for substituent variation at five distinct positions around the bicyclic core were devised to generate sets of compounds containing two- or three-point diversity.

Tetrahedron published new progress about 57663-05-5. 57663-05-5 belongs to nitriles-buliding-blocks, auxiliary class Fused/Partially Saturated Cycles,Tetrahydropyrimidins, name is 6-Methyl-4-(methylthio)-2-oxo-1,2-dihydropyridine-3-carbonitrile, and the molecular formula is C14H31NO2, HPLC of Formula: 57663-05-5.

Referemce:
https://en.wikipedia.org/wiki/Nitrile,
Nitriles – Chemistry LibreTexts

Campbell, Neil published the artcilePreparation of the halophenylacetic acids, Quality Control of 13312-84-0, the publication is Journal of the Chemical Society (1948), 1251-5, database is CAplus.

Gränacher’s synthesis (C.A. 16, 3898; 17, 2424) has been applied to the preparation of XC₆H₄CH₂CO₂H; the method depends on a satisfactory preparation of rhodanine (I), which is discussed. The yield of I depends upon the yield of H₂NCSSNH₄ (II) in the 1st stage of the reaction; the yield of II, as compared with that of CS(SNH₄)₂ (III), is a function of the NH₃ concentration which, in turn, is dependent on the temperature The more concentrated the NH₃ solution, the greater is the yield of III; the best yield of II is obtained at 10-15°; the yield of I from II is 44%. When the temperature is kept below 0%, III is the main product. Methods of distinguishing between II and III are given. Mol. quantities of aldehyde and I in AcOH (5 cc. per g. aldehyde), refluxed 0.5 h. with fused AcONa (twice the weight of I), give the following benzylidenerhodanines (IV): ο-Cl, pale yellow, m. 192°, 97% (Andreasch, C.A. 22, 3410, gives 169°); m-Cl, pale yellow, m. 233°, 93%; p-Cl, yellow, m. 231-2°, 93%; ο-Br, orange, m. 183.5°, 80%; m-Br, yellow, m. 238°, 90%; p-Br, yellow, m. 237-8°, 84%. IV were transformed into β-phenyl-α-thiopyruvic acids (V) by heating with 8 cc. 8% NaOH (per g. IV) at 50-5° until a clear or nearly clear solution resulted, cooling in an ice-salt bath, and acidifying rapidly with 3 N HCl; the crude acid in cold EtOH is precipitated with 1-2 volumes cold H₂O and recrystallized from MeOH, petr. ether, etc.; however, the crude acids were used in the next step. ο-Cl, m. 134-5°, 72% (A. gives 119-20°); m-Cl, straw-colored, m. 134°, 84%; p-Cl, yellow, m. 169-71°, 84% [a byproduct is probably α,α’-dithiobis(m-chlorocinnamic acid), yellow, m. 221-2°]; ο-Br, lemon-yellow, m. 142-3°, 70%; m-Br, pale yellow, m. 133-4°, 81%; p-Br, m. 165-80°, 75% (could not be purified further). α-Isonitroso-β-(halophenyl)propionic acids (VI) were prepared from V by refluxing (about 0.5 h.) in alc. containing 3 mols. NH₂OH (until H₂S evolution ceases); the crude acid is precipitated from dilute NaOH solution with concentrated HCl. ο-Cl, m. 156°, 83%; m-Cl, m. 149° (decomposition), 100%; p-Cl, m. 170° (decomposition) (1 sample m. 182°), 100%; ο-Br, m. 150° (decomposition), 100%; m-Br, m. 151°, 93%; p-Br, m. 173°, 85% (yields are of crude products). VI, refluxed 10 min. with Ac₂O (4 cc. per g. VI), the Ac₂O removed in vacuo, and the residue extracted with ether, give the (halophenyl)acetonitriles (VII): ο-Cl, b₁₁ 123-5°, 64%; m-Cl, b₁₀ 134-6°, 55%; p-Cl, b₁₂ 137-9°, m. 31-2°, 80%; ο-Br, b₁₃, 140-1°, 88%; m-Br, b₁₀ 145-7°, m. 27-8°, 70%; p-Br, b_10-12 152-6°, m. 48°, 72%. The over-all yields of the VII from the aldehydes were: ο-, m-, and p-Cl, 57, 47, 62%; ο-, m-, and p-Br, 49, 44, 38%; further losses, sometimes considerable, occur in the next step. VII were hydrolyzed by boiling with 60% H₂SO₄ or, preferably, with 20% EtOH-KOH, giving RC₆H₄CH₂CO₂H (R given): ο-Cl, m. 93-5° (p-nitrobenzyl ester, m. 70-1°); m-Cl, m. 77° (p-nitrobenzyl ester, m. 74-5°; p-toluidide, m. 138°); p-Cl, m. 104-6° (p-nitrobenzyl ester, m. 117°); ο-Br, m. 104-5° (p-nitrobenzyl ester, m. 74-5°; p-toluidide, m. 183-4°; anilide, m. 153-4°); m-Br, m. 102-3° (p-nitrobenzyl ester, m. 75-6°; p-toluidide, m. 135°); p-Br, m. 113-15° (p-nitrobenzyl ester, m. 128-9°; anilide, m. 174-6°; p-toluidide, m. 203°). The results show that this method leaves much to be desired. The crystalline compound from 20 g. p-BrC₆H₄CHO, 80 cc. NaHSO₃, and 5 cc. EtOH, stirred 2 h. with 10 g. KCN in 20 cc. H₂O, gives 12.5 g. p-bromomandelonitrile, m. 78-9°; 11 g. and 46 cc. HI (d. 1.94), refluxed 1 h. give 1.5 g. p-BrC₆H₄CH₂CO₂H; an unknown compound, m. 126-7°, is a byproduct. ο-ClC₆H₄CHO, through ο-ClC₆H₄CH(OH)CN, yields the benzoate (no properties given); refluxing with Pt black in tetralin did not give ο-ClC₆H₄CH₂CN. p-MeOC₆H₄CH₂CN was obtained in 39% yield (yield of intermediate benzoate 74 and 92% in 2 experiments). Other methods were tried without much success. A mixture of ο- and p-BrC₆H₄CH₂CO₂H could not be separated by fractional distillation of the acid chlorides or Et esters; chromatog. separation of the anilides, p-toluidides, and 2-naphthalides was only partially successful (they fluoresce in C₆H₆ but not on the Al₂O₃ column). α-(ο-Bromophenyl)aceto-2-naphthalide, m. 188-9°; p-isomer, m. 203-4°. α-Phenylaceto-2-naphthalide m. 162-3°. In the preparation of the naphthalides by heating the acids with 2-C₁₀H₇NH₂, (2-C₁₀H₇)₂NH is obtained, the catalyst presumably being the halo acid. 2-C₁₀H₇NH₂ and PhNH₂ give 2-C₁₀H₇NHPh, and p-MeC₆H₄NH₂ gives 2-C₁₀H₇NHC₆H₄Me-p, but ο- or m-ClC₆H₄NH₂ gives only (2-C₁₀H₇)₂NH. 2-C₁₀H₇NH₂ and its derivatives are more strongly adsorbed than the corresponding 1-derivatives

Journal of the Chemical Society published new progress about 13312-84-0. 13312-84-0 belongs to nitriles-buliding-blocks, auxiliary class Chloride,Nitrile,Benzene,Alcohol,Benzene Compounds, name is 2-(2-Chlorophenyl)-2-hydroxyacetonitrile, and the molecular formula is C8H6ClNO, Quality Control of 13312-84-0.

Referemce:
https://en.wikipedia.org/wiki/Nitrile,
Nitriles – Chemistry LibreTexts

Henze, Henry R. published the artcileHydantoins containing a tetrahydropyranyl substituent, Computed Properties of 30431-99-3, the publication is Journal of the American Chemical Society (1942), 1672-4, database is CAplus.

Refluxing a mixture of 155 g. NCCH₂CO₂Et and 97 g. (ClCH₂CH₂)₂O with 31.5 g. of Na in 450 cc. EtOH for 3 h. gives 31% of the Et ester, b₁₆ 135°, n_D²⁰ 1.4539, d₄²⁰ 1.1109, γ²⁰ 37.4, of 4-cyanotetrahydro-4-pyrancarboxylic acid; heating the acid at 180-200° gives 90% of tetrahydro-4-pyrancarbonitrile (I), b₁₀ 82-3°, n_D²⁰ 1.4521, d₄²⁰ 1.0343, γ²⁰ 40.7. 4-Acyltetrahydropyrans, RCOCH(CH₂.CH₂)₂O, were prepared by addition of a mol. proportion of I in absolute ether to 1.2-2 M proportions of the Grignard reagent (R is given): Me, b₁₄₄ 205-7°, n_D²⁰ 1.4530, d₄²⁰ 1.0243, γ²⁰ 35.8, MR 33.98, 53% yield (semicarbazone, m. 178° (all m. ps. corrected)); Et, b₂₀ 101°, n 1.4541, d. 1.0016, γ 37.2, MR, 38.60, 72% (semicarbazone, m. 151°); Pr, b₅ 85-8°, n 1.4545, d. 0.9828, 57% (semicarbazone, m. 145-6°); Bu, b₅ 100°, n 1.4551, d. 0.9700, 67% (semicarbazone, m. 180°; 2,4-dinitrophenylhydrazone, m. 99°); iso-Bu, b₆ 90-2°, n 1.4545, d. 0.9648, γ 33.2, MR 47.83, 69% (semicarbazone, m. 187-8°; 2,4-dinitrophenylhydrazone, m. 122°); Am, b₅ 106-7°, n 1.4573, d. 0.9589, γ 33.3, MR 52.45, 64% (semicarbazone, m. 117°; 2,4-dinitrophenylhydrazone, m. 89-90°); iso-Am, b₇ 116-17°, n 1.4567, d. 0.9562, γ 32.9, MR 52.45, 65% (semicarbazone, m. 158-9°; 2,4-dinitrophenylhydrazone, m. 134-5°); hexyl, b₆ 134-5°, n 1.4569, d. 0.9446, MR 57.07, 61% (semicarbazone, m. 161°); cyclohexyl, b₅ 142°, n 1.4839, d. 1.0262, MR 54.87, 46% (semicarbazone, m. 213-14°); Ph, m. 57-8°, 67%. The ketone with 1.8 molar equivalents of KCN and 3.6 molar equivalents of (NH₄)₂CO₃ in about 150 cc. 50% EtOH heated 12 h. at 58-60° gives 5-substituted 5-(tetrahydro-4-pyranyl)hydantoins, HN.CO.NH.CO.CRCH(CH₂.CH₂)₂O (R given): Me, m. 250°, 51%; Et, m. 246°, 70%; Pr, m. 223°, 66%; Bu, m. 195°, 49%; iso-Bu, m. 222°, 53%; Am, m. 171-2°, 79%; iso-Am, m. 195-6°, 68%; hexyl, m. 169°, 48%; cyclohexyl, m. 304-6°, 65%; Ph, m. 253°, 72%. The iso-Am and Ph derivatives exhibit mild anticonvulsant activity and are devoid of any hypnotic action.

Journal of the American Chemical Society published new progress about 30431-99-3. 30431-99-3 belongs to nitriles-buliding-blocks, auxiliary class Tetrahydropyran,Nitrile,Ester, name is Ethyl 4-cyanotetrahydro-2H-pyran-4-carboxylate, and the molecular formula is C9H13NO3, Computed Properties of 30431-99-3.

Referemce:
https://en.wikipedia.org/wiki/Nitrile,
Nitriles – Chemistry LibreTexts

Genokhova, N. S. published the artcileSynthesis of metallic complexes of 1,19-dimethyloctadehydrocorrins with electron acceptor β-substituents, SDS of cas: 26187-28-0, the publication is Zhurnal Obshchei Khimii (1977), 47(1), 121-9, database is CAplus.

I (M = Co, Ni, R = Me, CH2CO2H, R’ = CH2CH2CO2H; R = CO2Et, CN, R’ = Me) were prepared by the oxidative cyclization of hexamethylbiline derivatives in the presence of Ni and Co ions. The hexamethylbiline derivatives were also prepared The complexes and the ligands were characterized by electronic and NMR spectra.

Zhurnal Obshchei Khimii published new progress about 26187-28-0. 26187-28-0 belongs to nitriles-buliding-blocks, auxiliary class Pyrrole,Nitrile, name is 2,4-Dimethyl-1H-pyrrole-3-carbonitrile, and the molecular formula is C7H8N2, SDS of cas: 26187-28-0.

Referemce:
https://en.wikipedia.org/wiki/Nitrile,
Nitriles – Chemistry LibreTexts

Silva, Daniel published the artcileSynthesis, biological evaluation, and molecular modeling of nitrile-containing compounds: Exploring multiple activities as anti-Alzheimer agents, Recommanded Product: 2-Aminomalononitrile 4-methylbenzenesulfonate, the publication is Drug Development Research (2020), 81(2), 215-231, database is CAplus and MEDLINE.

Based on the monoamine oxidase (MAO) inhibition properties of aminoheterocycles with a carbonitrile group we have carried out a systematic exploration to discover new classes of carbonitriles endowed with dual MAO and AChE inhibitory activities, and Aβ anti-aggregating properties. Eighty-three nitrile-containing compounds, 13 of which are new, were synthesized and evaluated. In vitro screening revealed that 31, a new compound, presented the best lead for trifunctional inhibition against MAO A (0.34μM), MAO B (0.26μM), and AChE (52μM), while 32 exhibited a lead for selective MAO A (0.12μM) inhibition coupled to AChE (48μM) inhibition. Computational anal. revealed that the malononitrile group can find an advantageous position with the aromatic cleft and FAD of MAO A or MAO B. However, the total binding energy can be handicapped by an internal penalty caused by twisting of the ligand mol. and subsequent disruption of the conjugation (32 in MAO B compared to the conjugated 31). Conjugation is also important for AChE as well as the hydrophilic character of malononitrile that allows this group to be in close contact with the aqueous environment as seen for 83. Although the effect of 31 and 32 against Aβ_1-42, was very weak, the effect of 63 and 65, and of the new compound 75, indicated that these compounds were able to disaggregate Aβ_1-42 fibrils. The most effective was 63, a (phenylhydrazinylidene)propanedinitrile derivative that also inhibited MAO A (1.65μM), making it a potential lead for Alzheimer’s disease application.

Drug Development Research published new progress about 5098-14-6. 5098-14-6 belongs to nitriles-buliding-blocks, auxiliary class Nitrile,Salt,Sulfonic acid,Amine,Benzene, name is 2-Aminomalononitrile 4-methylbenzenesulfonate, and the molecular formula is C12H16BN3O2, Recommanded Product: 2-Aminomalononitrile 4-methylbenzenesulfonate.

Referemce:
https://en.wikipedia.org/wiki/Nitrile,
Nitriles – Chemistry LibreTexts