Category: nitriles-buliding-blocks

《Merging electrolysis and nickel catalysis in redox neutral cross-coupling reactions: Experiment and computation for electrochemically induced C-P and C-Se bonds formation》 was published in CCS Chemistry in 2020. These research results belong to Zhu, Chen; Yue, Huifeng; Nikolaienko, Pavlo; Rueping, Magnus. Name: 4-Bromobenzonitrile The article mentions the following:

The authors have achieved a nickel-catalyzed cross-coupling reaction via concerted paired electrolysis under mild reaction conditions. In this electrochem. transformation, the anodic oxidation of Ni(II) to Ni(III) and cathodic reduction of Ni(I) to Ni(0) occurred simultaneously, resulting in an economical and sustainable cross-coupling protocol. Moreover, mechanistic investigations were performed utilizing experiments and d. functional theory (DFT) calculations for different C-heteroatom bond formations to reveal the catalytic cycle in more detail. In the experiment, the researchers used 4-Bromobenzonitrile(cas: 623-00-7Name: 4-Bromobenzonitrile)

4-Bromobenzonitrile(cas: 623-00-7) is classified as organic nitriles, which are commonly use solvents and are reacted further for various applications such as manufacture of polymers and intermediates for pharmaceuticals and other organic chemicals,Name: 4-Bromobenzonitrile It can also be used as an aryl halide test compound in developing greener reaction conditions for Suzuki cross-coupling between aryl halides and phenyl boronic acid.

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

The author of 《Efficient cyanation of aryl halides with K4[Fe(CN)6] catalyzed by encapsulated palladium nanoparticles in biguanidine-chitosan matrix as core-shell recyclable heterogeneous nanocatalyst》 were Veisi, Hojat. And the article was published in Polyhedron in 2019. SDS of cas: 623-00-7 The author mentioned the following in the article:

Palladium nanoparticles encapsulated in biguanidine-functionalized chitosan matrix (Pd@CS-biguanidine) was applied as a reusable and core-shell nanocatalyst for cyanation of aryl iodides and bromides with K4[Fe(CN)6] as the cyanating agent. The nitriles were generated in good to excellent yield and the catalyst can be recycled and reapplied up to seven times with no significant change in its catalytic performance. The experimental process involved the reaction of 4-Bromobenzonitrile(cas: 623-00-7SDS of cas: 623-00-7)

4-Bromobenzonitrile(cas: 623-00-7) has been used in the synthesis of 4-iodobenzonitrile via photo-induced aromatic Finkelstein iodination reaction.SDS of cas: 623-00-7 It can also be used as an aryl halide test compound in developing greener reaction conditions for Suzuki cross-coupling between aryl halides and phenyl boronic acid.

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

The author of 《Nickel-Catalyzed Electrochemical Phosphorylation of Aryl Bromides》 were Bai, Ya; Liu, Nian; Wang, Shutao; Wang, Siyu; Ning, Shulin; Shi, Lingling; Cui, Lili; Zhang, Zhuoqi; Xiang, Jinbao. And the article was published in Organic Letters in 2019. Formula: C7H4BrN The author mentioned the following in the article:

A nickel-catalyzed electrochem. cross-coupling reaction of aryl bromides with dialkyl phosphites, Et phenylphosphinate, and diphenylphosphine oxide has been developed. This reaction utilizes a simple undivided cell with inexpensive carbon electrodes to synthesize aryl phosphonates, aryl phosphinates, and arylphosphine oxides at room temperature This protocol provides a mild and efficient route for the construction of C-P bond in moderate to high yields with broad substrate scope. In the experiment, the researchers used many compounds, for example, 4-Bromobenzonitrile(cas: 623-00-7Formula: C7H4BrN)

4-Bromobenzonitrile(cas: 623-00-7) has been used in the synthesis of 4-iodobenzonitrile via photo-induced aromatic Finkelstein iodination reaction.Formula: C7H4BrN It can also be used as an aryl halide test compound in developing greener reaction conditions for Suzuki cross-coupling between aryl halides and phenyl boronic acid.

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

In 2019,Synthesis included an article by Greve, Eric; Porter, Jacob D.; Dockendorff, Chris. Computed Properties of C8H6BrN. The article was titled 《DFT-Assisted Design and Evaluation of Bifunctional Amine/Pyridine-Oxazoline Metal Catalysts for Additions of Ketones to Unactivated Alkenes and Alkynes》. The information in the text is summarized as follows:

Bifunctional catalyst systems for the direct addition of ketones to unactivated alkenes/alkynes were designed and modeled by d. functional theory (DFT). The designed catalysts possess bidentate ligands suitable for binding of pi-acidic Group 10 metals capable of activating alkenes/alkynes, and a tethered organocatalyst amine to activate the ketone via formation of a nucleophilic enamine intermediate. The structures of the designed catalysts before and after C-C bond formation were optimized using DFT, and reaction steps involving Group 10 metals were predicted to be significantly exergonic. A novel oxazoline precatalyst with a tethered amine separated by a meta-substituted benzene spacer was synthesized via a 10-step sequence that includes a key regioselective epoxide ring-opening step. It was combined with Group 10 metal salts, including cationic Pd(II) and Pt(II), and screened for the direct addition of ketones to several alkenes and an internal alkyne. 1H NMR studies suggest that catalyst-catalyst interactions with this system via amine-metal coordination may preclude the desired addition reactions. The catalyst design approach disclosed here, and the promising calculations obtained with square planar Group 10 metals, light a path for the discovery of novel bifunctional catalysts for C-C bond formation. In addition to this study using 2-(3-Bromophenyl)acetonitrile, there are many other studies that have used 2-(3-Bromophenyl)acetonitrile(cas: 31938-07-5Computed Properties of C8H6BrN) was used in this study.

According to other reports, 2-(3-Bromophenyl)acetonitrile(cas: 31938-07-5) is used in the preparation of diarylpyrimidines (DAPYs) as HIV-1 non-nucleoside reverse transcriptase inhibitors.Computed Properties of C8H6BrN

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

《Thieme Chemistry Journals Awardees – Where Are They Now? Rhodium-Catalyzed Synthesis of Unsymmetric Di(heteroaryl) Ethers Using Heteroaryl Exchange Reaction》 was written by Tanii, Saori; Arisawa, Mieko; Tougo, Takaya; Horiuchi, Kiyofumi; Yamaguchi, Masahiko. SDS of cas: 99902-72-4 And the article was included in Synlett on August 31 ,2017. The article conveys some information:

Unsym. di(heteroaryl) ethers were synthesized by the rhodium-catalyzed heteroaryl exchange reaction of heteroaryl aryl ethers and heteroaryl esters at equilibrium [e.g., 2-phenoxybenzothiazole + 3-pyridyl benzoate → 2-(3-pyridyloxy)benzothiazole + Ph benzoate]. Diverse unsym. di(heteroaryl) ethers containing five- and six-membered heteroarenes were obtained. Di(heteroaryl) ethers can be synthesized starting from diaryl ethers, because heteroaryl aryl ethers are obtained by the heteroaryl exchange reaction of diaryl ethers. In the experiment, the researchers used many compounds, for example, 6-Phenoxynicotinonitrile(cas: 99902-72-4SDS of cas: 99902-72-4)

6-Phenoxynicotinonitrile(cas: 99902-72-4) belongs to nitriles. Nitriles are found in many useful compounds. Nitrile rubber is also widely used as automotive and other seals since it is resistant to fuels and oils. Organic compounds containing multiple nitrile groups are known as cyanocarbons.SDS of cas: 99902-72-4

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

In 2019,Tetrahedron included an article by Uchida, Ko; Togo, Hideo. Computed Properties of C7H4BrN. The article was titled 《Transformation of aromatic bromides into aromatic nitriles with n-BuLi, pivalonitrile and iodine under metal cyanide-free conditions》. The information in the text is summarized as follows:

Various aromatic nitriles ArCN [Ar = Ph, 4-BrC6H4, 5-ethyl-2-furyl, etc.] were obtained in good yields by the treatment of aryl bromides with n-butyllithium and then pivalonitrile, followed by the treatment with mol. iodine at 70 °C, without metal cyanides under transition-metal-free conditions. The present reaction proceeded through the radical β-elimination of imino-nitrogen-centered radicals formed from the reactions of imines and N-iodoimines under warming conditions. The results came from multiple reactions, including the reaction of 4-Bromobenzonitrile(cas: 623-00-7Computed Properties of C7H4BrN)

4-Bromobenzonitrile(cas: 623-00-7) is classified as organic nitriles, which are commonly use solvents and are reacted further for various applications such as manufacture of polymers and intermediates for pharmaceuticals and other organic chemicals,Computed Properties of C7H4BrN It can also be used as an aryl halide test compound in developing greener reaction conditions for Suzuki cross-coupling between aryl halides and phenyl boronic acid.

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

The author of 《Nickel-Catalyzed Hydrophosphonylation and Hydrogenation of Aromatic Nitriles Assisted by Lewis Acid》 were Islas, Rosa E.; Garcia, Juventino J.. And the article was published in ChemCatChem in 2019. Reference of 4-Fluorobenzonitrile The author mentioned the following in the article:

In this paper, we describe the catalytic hydrophosphonylation of several aromatic nitriles used to synthesize α-aminophosphonates (α-APs) using com. available trialkyl phosphites (P(OR)3, R=Et, iPr, Bu,) and simple and inexpensive nickel chloride (NiCl2.6H2O) as the catalytic precursor. The use of triethylborane (Et3B) as a Lewis acid (LA) was mandatory in order to successfully perform H-phosphite moiety incorporation at the CN bond of non-activated benzonitriles (BN) derivatives Interestingly, when a highly activated BN such as 2,3,4,5,6-pentafluorobenzonitrile (BN-g) was employed, it was possible to perform the reaction in the absence of an LA using milder reaction conditions. Also, we found that using HP(O)(OiPr)2 as a starting material afforded the aminobisphosphonate derivative with better selectivity than using the method involving P(OiPr)3 as the initial reagent. Remarkably, when using HP(O)(OiPr)2 with an excess of Et3B, the reaction’s selectivity completely changed to yield N-benzyl- benzylimine (BBI) and 2,4,5-triphenylimidazole. In the part of experimental materials, we found many familiar compounds, such as 4-Fluorobenzonitrile(cas: 1194-02-1Reference of 4-Fluorobenzonitrile)

4-Fluorobenzonitrile(cas: 1194-02-1) is used as chemical intermediate, solvent for perfumes and pharmaceuticals, stabilizer for chlorinated solvents, HPLC analysis, catalyst and component of transition-metal complex catalysts.Reference of 4-Fluorobenzonitrile

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

The author of 《Monophosphine Ligands Promote Pd-Catalyzed C-S Cross-Coupling Reactions at Room Temperature with Soluble Bases》 were Xu, Jessica; Liu, Richard Y.; Yeung, Charles S.; Buchwald, Stephen L.. And the article was published in ACS Catalysis in 2019. Safety of 2-(3-Bromophenyl)acetonitrile The author mentioned the following in the article:

The Pd-catalyzed cross-coupling of thiols with aromatic electrophiles is a reliable method for the synthesis of aryl thioethers, which are important compounds for pharmaceutical and agricultural applications. Since thiols and thiolates strongly bind late transition metals, previous research has focused on catalysts supported by chelating, bisphosphine ligands, which were considered less likely to be displaced during the course of the reaction. We show that, by using monophosphine ligands instead, more effective catalysis can be achieved. Notably, compared to previous methods, this increased reactivity allows for the use of much lower reaction temperature, soluble bases, and base-sensitive substrates. In contrast to conventional wisdom, our mechanistic data suggest that the extent of displacement of phosphine ligands by thiols is, first, not correlated with the ligand bulk or thiol nucleophilicity and, second, not predictive of the effectiveness of a given ligand in combination with palladium. In addition to this study using 2-(3-Bromophenyl)acetonitrile, there are many other studies that have used 2-(3-Bromophenyl)acetonitrile(cas: 31938-07-5Safety of 2-(3-Bromophenyl)acetonitrile) was used in this study.

2-(3-Bromophenyl)acetonitrile(cas: 31938-07-5) has been used in the synthesis of 2-(1-cyano-1-(3-bromophenyl))methylidene-3-phenylthiazolidine-4,5-dione or a series of aminoethylbiphenyls, novel 5-HT7 receptor ligands.Safety of 2-(3-Bromophenyl)acetonitrile

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

In 2022,Suzuka, Toshimasa; Niimi, Ryoko; Uozumi, Yasuhiro published an article in Synlett. The title of the article was 《Cyanide-Free Cyanation of Aryl Iodides with Nitromethane by Using an Amphiphilic Polymer-Supported Palladium Catalyst》.Synthetic Route of C7H4BrN The author mentioned the following in the article:

A cyanide-free aromatic cyanation was developed that used nitromethane as a cyanide source in water with an amphiphilic polystyrene-poly(ethylene glycol) resin-supported palladium catalyst and an alkyl halide (1-iodobutane). The cyanation proceeded through the palladium-catalyzed cross-coupling of an aryl halide with nitromethane, followed by transformation of the resultant (nitromethyl)arene intermediate into a nitrile by 1-iodobutane. In the experimental materials used by the author, we found 2-Bromobenzonitrile(cas: 2042-37-7Synthetic Route of C7H4BrN)

2-Bromobenzonitrile(cas: 2042-37-7) belongs to a group of ortho-substituted bromobenzenes that have varying hepatotoxicity effects in the presence of rat liver microsomes in vitro. 2-Bromobenzonitrile is also used as a starting material to synthesize novel benzothiophene derivatives that were found to exhibit antibacterial and antifungal activity.Synthetic Route of C7H4BrN

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts

Wang, Yinan; Chen, Hui; Sheng, Ruilong; Fu, Zhe; Fan, Junting; Wu, Wenhui; Tu, Qidong; Guo, Ruihua published an article in 2021. The article was titled 《Synthesis and bioactivities of marine pyran-isoindolone derivatives as potential antithrombotic agents》, and you may find the article in Marine Drugs.Name: 4-Cyanobenzyl bromide The information in the text is summarized as follows:

2,5-Bis-[8-(4,8-dimethyl-nona-3,7-dienyl)-5,7-dihydroxy-8-methyl-3-keto-1,2,7,8-teraahydro-6H-pyran[a]isoindol-2-yl]-pentanoic acid (FGFC1) is a marine pyran-isoindolone derivative isolated from a rare marine microorganism Stachybotrys longispora FG216, which showed moderate antithrombotic (fibrinolytic) activity. To further enhance its antithrombotic effect, a series of new FGFC1 derivatives I (R = CH3, Et, Pr, etc.) were synthesized via chem. modification at C-2 and C-2″” phenol groups moieties and C-1″” carboxyl group. Their fibrinolytic activities in vitro were evaluated. Among the derivatives, I (R = CH3, Et, Pr, 4-CNC6H4CH2 and 4-BrC6H4CH2) showed significant fibrinolytic activities with EC50 of 59.7, 87.1, 66.6, 82.8, and 42.3μM, resp., via enhancement of urokinase activity. Notably, derivative I (R = 4-BrC6H4CH2) presented the most remarkable fibrinolytic activity (2.72-fold than that of FGFC1). Furthermore, the cytotoxicity of derivative I (R = 4-BrC6H4CH2) was tested as well as expression of Fas/Apo-1 and IL-1 on HeLa cells. The results showed that, compared to FGFC1, derivative I (R = 4-BrC6H4CH2) possessed moderate cytotoxicity and apoptotic effect on HeLa cells (statistical significance p > 0.1), making (R = 4-BrC6H4CH2) a potential antithrombotic agent towards clin. application. In the part of experimental materials, we found many familiar compounds, such as 4-Cyanobenzyl bromide(cas: 17201-43-3Name: 4-Cyanobenzyl bromide)

4-Cyanobenzyl bromide(cas: 17201-43-3) is an important intermediate for pharmaceutical production. It can be used for the synthesis of a series of piperidine-linked aromatic diimidazolines, which have been synthesized as conformationally restricted congeners of the anti-Pneumocystis carinii (PCP) drug, Pentamidine.Name: 4-Cyanobenzyl bromide

Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts