Category: nitriles-buliding-blocks

Quan, Xue-Jing published the artcilep-Toluenesulfonic Acid Mediated 1,3-Dipolar Cycloaddition of Nitroolefins with NaN₃ for Synthesis of 4-Aryl-NH-1,2,3-triazoles, Safety of (E)-4-(2-Nitrovinyl)benzonitrile, the publication is Organic Letters (2014), 16(21), 5728-5731, database is CAplus and MEDLINE.

A p-TsOH-mediated 1,3-dipolar cycloaddition of nitroolefins and sodium azide for the synthesis of 4-aryl-NH-1,2,3-triazoles has been developed. p-TsOH was discovered as a vital additive in this type of 1,3-dipolar cycloaddition This novel cycloaddition reaction is a good method for the rapid synthesis of valuable 4-aryl-NH-1,2,3-triazoles in high yields.

Organic Letters 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

Quan, Xue-Jing published the artcilep-Toluenesulfonic Acid Mediated 1,3-Dipolar Cycloaddition of Nitroolefins with NaN₃ for Synthesis of 4-Aryl-NH-1,2,3-triazoles [Erratum to document cited in CA161:682131], Name: (E)-4-(2-Nitrovinyl)benzonitrile, the publication is Organic Letters (2015), 17(2), 393, database is CAplus and MEDLINE.

On page 5730, structure 4a in Scheme 2 was published incorrectly, and subsequent text corresponding to this Structure is also incorrect; the correct structure, name, and text are given.

Organic Letters 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, Name: (E)-4-(2-Nitrovinyl)benzonitrile.

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

Leowanawat, Pawaret published the artcileZero-Valent Metals Accelerate the Neopentylglycolborylation of Aryl Halides Catalyzed by NiCl₂-Based Mixed-Ligand Systems, Application In Synthesis of 214360-44-8, the publication is Journal of Organic Chemistry (2010), 75(22), 7822-7828, database is CAplus and MEDLINE.

The highly active mixed-ligand catalytic system NiCl₂(dppp)/dppf combined with the reducing effect of zerovalent Zn and of other metals was used to demonstrate a method for the dramatic acceleration of the rate and for the enhancement of the yield of Ni-catalyzed neopentylglycolborylation of aryl halides. A diversity of electron-rich and electron-deficient aryl iodides, bromides, and chlorides were efficiently neopentylglycolborylated, typically in 1 h or less. This acceleration is particularly remarkable for the generally less reactive aryl bromides and chlorides and for all ortho-substituted aryl halides. By accelerating the rate of borylation and reducing its reaction time to complete conversion, pathways leading to protodeborylated or hydrodehalogenated side products have a reduced impact on the outcome of the overall reaction. Although Zn powder was the reducing agent of choice, compatibility of this technique with more readily recoverable Zn chips, as well as other metals such as Mn, Mg, Fe, Al, and Ca, demonstrated the broad scope of this synthetic method.

Journal of Organic Chemistry published new progress about 214360-44-8. 214360-44-8 belongs to nitriles-buliding-blocks, auxiliary class Nitrile,Boronic acid and ester,Benzene,Boronic Acids,Boronic acid and ester, name is 4-(5,5-Dimethyl-1,3,2-dioxaborinan-2-yl)benzonitrile, and the molecular formula is C12H14BNO2, Application In Synthesis of 214360-44-8.

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

Perez-Garcia, Raul M. published the artcileMild, organo-catalysed borono-deamination as a key to late-stage pharmaceutical precursors and ¹⁸F-labelled radiotracers, Synthetic Route of 214360-44-8, the publication is Frontiers in Chemistry (Lausanne, Switzerland) (2022), 884478, database is CAplus and MEDLINE.

A tris(pentafluorophenyl)borane catalyzed method for the synthesis of boronic acid esters from aromatic amines in yields of up to 93% was devised. Mild conditions, benign reagents, short reaction times, low temperatures and a wide substrate scope characterize the method. The reaction was found applicable to the synthesis of boronic acid ester derivatives of complex drug mols. in up to 86% isolated yield and high purity suitable for labeling. These boronates were subsequently labeled with [18F] fluoride ion in radiochem. yields of up to 55% with and even without isolation of the boronate-intermediate.

Frontiers in Chemistry (Lausanne, Switzerland) published new progress about 214360-44-8. 214360-44-8 belongs to nitriles-buliding-blocks, auxiliary class Nitrile,Boronic acid and ester,Benzene,Boronic Acids,Boronic acid and ester, name is 4-(5,5-Dimethyl-1,3,2-dioxaborinan-2-yl)benzonitrile, and the molecular formula is C12H14BNO2, Synthetic Route of 214360-44-8.

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

Fischer, H. published the artcilePyrrolenitriles and some of their transformations, Related Products of nitriles-buliding-blocks, the publication is Berichte der Deutschen Chemischen Gesellschaft [Abteilung] B: Abhandlungen (1930), 2249-57, database is CAplus.

2,4-Dimethyl-3-cyano-5-carbethoxypyrrole, MeC:C(CN).CMe:CR.NH (I, R = CO₂Et) is saponified to the 5-CO₂H acid (II) (I, R =CO₂H) without the CN group being hydrolyzed, and distillation in vacuo gives 2,4-dimethyl-3-cyanopyrrole (III). The CN group is materially stabilized by its position on the nucleus, whereas when it is on a side chain, as in 2,4-dimethyl-3-Ω-cyano-Ω-carbetboxy-vinyl-5-carbethoxypyrrole, it can be hydrolyzed with extraordinary ease, the β-position being attacked first and then the α-position. III can be obtained still more easily by the Knorr pyrrole synthesis from AcCH₂CO₂Et and AcCH₂CONH₂, and AcCH₂NH₂.HCl instead of AcCH₂CO₂Et-NaNO₂ gives an even better yield. With HCHO and a little HCl III readily yields 3,3′,5,5′-tetramethyl-4,4′-dicyanopyrrometliane (IV) which, surprisingly enough, cannot be converted with either FeCl₃ or Br into the corresponding methene (V) although the V.HBr is obtained in good yield, with elimination of CO₂, from II with HCO₂H and 48% HBr on the H₂O bath. NH₄OH readily gives the free V in red needles which form metal complexes. III and HCN readily give an aldehyde (VI) (1, R = CHO), whose oxime yields with AC₂O 2,4-dimethyl-3,5-dicyanopyrrole (VII). With boiling HCl VI yields V.HCl. The CHO group in VI is reduced to Me by the Wolff-Kishner method, giving 2,4,5-trimethyl-3-eyanopyrrole, together with some 2,4,5-trimethylpyrrole. From VI and 2,3,4-trimethylpyrrole, cryptopyrrole and crypto-pyrrolecarboxylic acid were obtained 3,3′,4,5,5′-pentamethyl- (VII), 3,3′,5,5′-tetramethyl-4-ethyl- (VIII) and 3,3′,5,5′-ietramethyl-4-propionic acid-4′-cyanopyrromethene-HBr (IX), resp.; VIII was also obtained from cryptopyrrolealdehyde with III. These cyanomethenes were synthesized with the object of preparing porphyrins with CN groups on the nucleus but numerous attempts to do this failed. Porphyrin formation took place but only etioporphyrin II could be isolated. This negative result is perhaps due to the unreactiveness of the α-Me groups. Bromination of the 3 methenes could not be effected either and I (R = CO₂Et) is likewise unreactive toward Br, although with Br and NaBrO₃ 3 Br atoms can be introduced into the α-Me group, with simultaneous oxidation of the α-Me group, the product being 2-tribromomethyl-3-cyano-4-hydroxymethyl-5-carbethoxypyrrole (X). III can also be brominated on the nucleus in the α-position. With SO₂Cl₂ I gave a yellow oil yielding with H₂O 2-hydroxymethyl-3-cyano-4-methyl-5-carbethoxypyrrole (XI). With higher concentrations, 6 atoms Cl are introduced: the product is probably 2,4-bistrichloromethyl-3-cyano-5-carbethoxypyrrole (XII). II (about 40 g. from 60 g. I with boiling aqueous NaOH), m. 250°; 8 g. in vacuo at 150° gives 4 g. III, m. 107°. 2,4-Dimethyl-3-carboxamide-5-carbethoxypyrrole (1.8 g. from 12 g. AcCH₂-CO₂Et, NaNO₂, AcCH₂CONH₂ and Zn dust), m. 173°; 0.5 g. gives with boiling NaOAc-Ac₂O 0.3 g. I, which is obtained in 1 g. yield from 1.5 g. ACCH₂NH₂.HCl and AcCH-CONH₂ in NaOH. V.HBr (13-5 g. from 20 g. II), golden yellow, in. 242° (decomposition). V.HCl (1 g. from 2 g. II), m. 225° (decomposition). Free V, ruby-red, m. 280°(decomposition); Cu complex, C₃0H₂6N₈C₁1 crystals with metallic green surface luster, soluble in most solvents with red color; Co complex, green; On complex, 2C₃0H₂6N₈Zn.Zn(OAc)₂, pink, contains 2 active H atoms (Chugaev-Zerevitinov). XI, reddens and sinters 145-°, m. around 195-6°. XII (2.8 g. from 5 g. I, 20 g. SO₂Cl₂ and 20 cc. Et₂O), m. around 98°. X (about 20%), m. 183°, easily soluble in dilute alkalies, the yellow solution becoming dark brown and finally black (in 20% NaOH it at once darkens and decomposes), regenerates I on long boiling with Zn dust in AcOH. 2,4-Dimethyl-3-cyano-5-formylpyrrole (VI) (9-10 g. from 15 g. III in CHCl₃-Et₂O with anhydrous HCN), m. 223° oxime, m. 206°; semicarbazone, turns yellow 250° and gradually darkens and sinters; phenylhydrazone, m. 175°. VII, m. 209°. 2,4-Dimethyl-3-cya-no-5-bromopyrrole (0-5 g. from 0.4 g. III with Br-AcOH), darkens 130° and sinters without melting. VII (1.3g. from 0.75g. VI), yellow, decomposes 230°. VIII (80%), orange-red, darkens 190°, m. 241° IX, golden yellow, m. 240° (decomposition).

Berichte der Deutschen Chemischen Gesellschaft [Abteilung] B: Abhandlungen 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, Related Products of nitriles-buliding-blocks.

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

Plaza, Manuel published the artcileHeterocyclization and Spirocyclization Processes Based on Domino Reactions of N-Tosylhydrazones and Boronic Acids Involving Intramolecular Allylborylations of Nitriles, Quality Control of 238088-16-9, the publication is Chemistry – A European Journal (2018), 24(55), 14836-14843, database is CAplus and MEDLINE.

Polycyclic mols. featuring all-carbon quaternary bridgehead centers were synthesized through domino cyclizations between N-tosylhydrazones and boronic acids. Variations of the general cascade have been applied for the preparation of 3-quinuclidinones and related alkaloid-like scaffolds through transannular heterocyclizations. Moreover, the employment of 3-cyanopropyl and 4-cyanobutylboronic acids and α,β-unsaturated N-tosylhydrazones led to spirocycles through unprecedented formal [n+1] cyclizations, including the stereoselective spirocyclization of the Hajos-Parrish ketone. The common feature of all the new reactions described is the creation of an all-carbon quaternary center by formation of two Csp³-C bonds on the hydrazonic carbon atom. DFT-based calculations suggested the occurrence of cascade processes, which involve a diazo compound carboborylation followed by a 1,3-borotropic rearrangement on an intermediate allylboronic acid and a novel bora-aza-ene cyclization.

Chemistry – A European Journal published new progress about 238088-16-9. 238088-16-9 belongs to nitriles-buliding-blocks, auxiliary class Nitrile,Boronic acid and ester,Aliphatic cyclic hydrocarbon,Boronic Acids,Boronate Esters, name is 4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)butanenitrile, and the molecular formula is C10H18BNO2, Quality Control of 238088-16-9.

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

Back, Jisu published the artcileTriazenyl Radicals Stabilized by N-Heterocyclic Carbenes, COA of Formula: C10H12F6N4O6PdS2, the publication is Journal of the American Chemical Society (2017), 139(43), 15300-15303, database is CAplus and MEDLINE.

Notwithstanding the notable progress in the synthesis of N-heterocyclic carbene-stabilized radicals, aminyl radicals, supported by NHCs or otherwise, were scarcely studied due to synthetic challenges. Triazenyl radical is a particular form of aminyl radical that contains three adjacent N atoms, and offers intriguing possibilities for unique reactivity and phys. properties stemming from expected delocalization of the spin d. over the NNN moiety and its conjugated substituents. Here, the authors report the synthesis and full characterization of the 1st NHC-stabilized triazenyl radicals, obtained by 1-electron reduction of the corresponding triazenyl cations with K metal. These radicals reversibly oxidize back to the cations upon treatment with transition metal sources or electrophiles, and abstract H atom from xanthene to form a new N-H bond at the center N atom. Potential application of the redox couple between triazenyl cation and triazenyl radical was demonstrated as cathode active materials in Li ion batteries.

Journal of the American Chemical Society 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, COA of Formula: C10H12F6N4O6PdS2.

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

Spencer, John published the artcileMicrowave-mediated synthesis and manipulation of a 2-substituted-5-aminooxazole-4-carbonitrile library, Application of 2-Aminomalononitrile 4-methylbenzenesulfonate, the publication is Tetrahedron Letters (2012), 53(13), 1656-1659, database is CAplus.

A 2-substituted 5-aminooxazole-4-carbonitrile library has been synthesized and modified via microwave-mediated and flow chemistries. One synthesized compound, 5-(1H-pyrrol-1-yl)-4-(1H-tetrazol-5-yl)-2-(thien-2-yl)oxazole, contains three distinct heterocycles attached to the central oxazole core, highlighting the structural diversity of this approach. Three oxazoles had micromolar k_i values against cannabinoid (CB1/CB2) receptors.

Tetrahedron Letters 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 C12H13BrN2O2, Application of 2-Aminomalononitrile 4-methylbenzenesulfonate.

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

Baraldi, Pier Giovanni published the artcileAntimicrobial and antitumor activity of N-heteroimmine-1,2,3-dithiazoles and their transformation in triazolo-, imidazo-, and pyrazolopyrimidines, Related Products of nitriles-buliding-blocks, the publication is Bioorganic & Medicinal Chemistry (2001), 10(2), 449-456, database is CAplus and MEDLINE.

The reaction of Appel’s salt with o-aminonitrile heterocyclics gave the corresponding 4-chloro-5-heteroimmine-1,2,3-dithiazoles which were evaluated for their antibacterial, antifungal and antitumor activity. Although all these N-heteroimines were devoid of significant antibacterial activity, they showed significant antifungal activity. Moreover, the same derivatives represent highly versatile intermediates in heterocyclic synthesis, in fact the pyrazoleiminodithiazoles can be converted in one step into 2-cyano derivatives of the corresponding 4-methoxy-pyrazolo[3,4-d]pyrimidines by sodium methoxide in refluxing methanol. This provides a general and attractive route to 4-methoxy-6-cyanopyrazolo[3,4-d]pyrimidines from 1-substituted 5-amino pyrazoles in two simple steps. Finally, the isosteric replacement of the pyrazole ring atoms to give the imidazole[3,4-d]pyrimidine and triazole [4,5-d]pyrimidine ring systems was examined

Bioorganic & Medicinal Chemistry 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 C10H11N3O3S, Related Products of nitriles-buliding-blocks.

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

Taylor, Edward C. published the artcilePteridines. XXIX. Unequivocal route to 2,4-diamino-6-substituted pteridines, Application In Synthesis of 5098-14-6, the publication is Journal of the American Chemical Society (1973), 95(19), 6413-18, database is CAplus.

2,4-Diamino-6-substituted pteridines (I) are prepared Reaction of an α-keto-aldoxime with aminomalononitrile gives 2-amino-3-cyano-5-substituted pyrazine 1-oxides which yield 2,4-diamino-6-substituted pteridine 8-oxides upon cyclization with guanidine. 2,4-Diaminopteridines are then obtained by deoxygenation of the corresponding 8-oxides, or alternately by prior deoxygenation of these pyrazine 1-oxides, followed by cyclization with guanidine. The conversion of 2-amino-3-cyano-5-methylpyrazine 1-oxide to the corresponding 1,4-dioxide, and a number of chem. transformations of this latter intermediate, are also described.

Journal of the American Chemical Society 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 C3H8N2S, Application In Synthesis of 5098-14-6.

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