21789-36-6

Usage

Synthesis Reference(s)

The Journal of Organic Chemistry, 38, p. 566, 1973 DOI: 10.1021/jo00943a034

InChI:InChI=1/C9H9N/c1-7-3-4-9(6-10)8(2)5-7/h3-5H,1-2H3

Upstream product

• 3862-12-2 phosphoric acid tris-(2,4-dimethyl-phenyl ester) 
• 151-50-8 potassium cyanide 
• 28042-78-6 2,4-Dimethylbenzaldehyd-azin 
• 108-38-3 m-xylene 
• 545-06-2 trichloroacetonitrile 
• 95-68-1 2,4-Xylidine 
• 544-92-3 copper(I) cyanide 
• 4214-28-2 1-iodo-2,4-dimethylbenzene 
• 79068-54-5 4-(2,4-Dimethylphenyl)-1,3,2-oxathiazolylium-5-olat 
• 762-42-5 dimethyl acetylenedicarboxylate 
• 123413-30-9 2,4-dimethylbenzotrichloride 
• 611-01-8 2,4-dimethyl-benzoic acid 
• 92114-96-0 mercury fulminate 
• 39842-01-8 2,4-dimethylphenylisothiocyanate 

Downstream Products

• 22627-03-8 2,4-dimethyl-benzophenone-imine 
• 39053-46-8 2,4-dimethyl-3-nitrobenzonitrile 
• 625112-44-9 2,4-dimethyl-5-nitrobenzonitrile 
• 73258-94-3 2,4-dimethyl benzamide 
• 73831-13-7 4-cyano-3-methylbenzoic acid 
• 94-98-4 2,4-dimethylbenzylamine 
• 611-01-8 2,4-dimethyl-benzoic acid 
• 845-02-3 2,4-Dimethyl-3'-trifluormethyl-benzophenon 
• 89-74-7 2,4-dimethylacetophenone. 
• 18039-03-7 2,4-dimethyl-N-methylbenzamide 
• 52400-13-2 N'-hydroxy-2,4-dimethylbenzenecarboximidamide 
• 96906-97-7 C₁₃H₁₅N₅S 
• 100430-84-0 2-amino-2',4,4',6-tetramethylbenzophenone 
• 100430-85-1 4-(2,4-dimethylphenyl)-2,5,7-trimethylquinazoline 

Relevant academic research and scientific papers

Dehydrogenation of Primary Alkyl Azides to Nitriles Catalyzed by Pincer Iridium/Ruthenium Complexes

Pincer metal complexes exhibit superior catalytic activity in the dehydrogenation of plain alkanes, but find limited application in the dehydrogenation of functionalized organic molecules. Starting from easily accessible primary alkyl azides, here we report an efficient dehydrogenation of azides to nitriles using pincer iridium or ruthenium complexes as the catalysts. This method offers a route to cyanide-free preparation of nitriles without carbon chain elongation and without the use of strong oxidants. Both benzyl and linear aliphatic azides can be dehydrogenated with tert-butylethylene as the hydrogen acceptor to afford nitriles in moderate to high yields. Various functional groups can be tolerated, and the H?C?C?H bond dehydrogenation does not occur for linear alkyl azide substrates. Furthermore, the pincer Ir catalytic system was found to catalyze the direct azide dehydrogenation without the use of a sacrificial hydrogen acceptor.

A Transition-Metal-Free One-Pot Cascade Process for Transformation of Primary Alcohols (RCH2OH) to Nitriles (RCN) Mediated by SO2F2

A new transition-metal-free one-pot cascade process for the direct conversion of alcohols to nitriles was developed without introducing an “additional carbon atom”. This protocol allows transformations of readily available, inexpensive, and abundant alcohols to highly valuable nitriles.

Pd(II)-immobilized on a nanoporous triazine-based covalent imine framework for facile cyanation of haloarenes with K4Fe(CN)6

A porous covalent organic framework incorporated with both imine and triazine functionalities (TPA-TCIF) was synthesized by Schiff-base condensation of 2,4,6-tris(4-aminophenyl)triazine and tris(4-formylphenyl)amine under the solvothermal condition of a 1-butanol:1,2-dichlorobenzene mixture. The resulting TPA-TCIF was a highly ordered crystalline network with surface area of 2938 m2 g?1, which was among the highest reported imine-based porous covalent organic frameworks. TPA-TCIF was also stable in water and other organic solvents. Pd(II) was immobilized into TPA-TCIF network and the resultant Pd/TPA-TCIF was tested as a catalyst for the additive-free cyanation of haloarenes with non-toxic K4[Fe(CN)6]. The catalyst showed excellent catalytic activity, and both electron-donating / -withdrawing groups attached to the para- and meta-positions of bromoarenes produced the respective nitriles with good to excellent yields. The catalyst could be reused up to five times without noticeable loss of activity or catalyst poisoning by cyanide ions during the reaction.

Dual Ligand-Enabled Nondirected C-H Cyanation of Arenes

Aromatic nitriles are key structural units in organic chemistry and, therefore, highly attractive targets for C-H activation. Herein, the development of an arene-limited, nondirected C-H cyanation based on the use of two cooperatively acting commercially available ligands is reported. The reaction enables the cyanation of arenes by C-H activation in the absence of directing groups and is therefore complementary to established approaches.

Nickel-catalyzed cyanation of aryl halides and triflates using acetonitrile: Via C-CN bond cleavage assisted by 1,4-bis(trimethylsilyl)-2,3,5,6-tetramethyl-1,4-dihydropyrazine

We developed a non-toxic cyanation reaction of various aryl halides and triflates in acetonitrile using a catalyst system of [Ni(MeCN)6](BF4)2, 1,10-phenanthroline, and 1,4-bis(trimethylsilyl)-2,3,5,6-tetramethyl-1,4-dihydropyrazine (Si-Me4-DHP). Si-Me4-DHP was found to function as a reductant for generating nickel(0) species and a silylation reagent to achieve the catalytic cyanation via C-CN bond cleavage.

Ligand-Promoted Non-Directed C?H Cyanation of Arenes

This article reports the first example of a 2-pyridone accelerated non-directed C?H cyanation with an arene as the limiting reagent. This protocol is compatible with a broad scope of arenes, including advanced intermediates, drug molecules, and natural products. A kinetic isotope experiment (kH/kD=4.40) indicates that the C?H bond cleavage is the rate-limiting step. Also, the reaction is readily scalable, further showcasing the synthetic utility of this method.

Electrochemical C-H cyanation of electron-rich (Hetero)arenes

A straightforward method for the electrochemical C-H cyanation of arenes and heteroarenes that proceeds at room temperature in MeOH, with NaCN as the reagent in a simple, open, undivided electrochemical cell is reported. The platinum electrodes are passivated by ad-sorbed cyanide, which allows conversion of an exceptionally broad range of electron-rich substrates all the way down to dialkyl arenes. The cyanide electrolyte can be replenished with HCN, opening opportunities for salt-free industrial C-H cyanation.

Cyaniding method for preparing nitrile compound

The invention provides a cyaniding method for preparing a nitrile compound. Organic halide or pseudohalide, CO2 and NH3 which are low in price and are easily obtained and a reducing agent react, a selective cyaniding reaction is conducted in the presence of a transition metal catalyst, and the target product namely organic the nitrile compound is obtained. According to the cyaniding method for preparing the nitrile compound, a new reaction route is used, through a CO2 and NH3 reaction of metal catalysis, dehalogenation cyaniding or quasi halide cyaniding of halide or pseudohalide is directly achieved through a one-pot method, the problem is solved that a traditional cyanation reaction needs equivalent toxic cyanide, a new direct and convenient method for preparing isotope-labeled nitrile compounds is provided at the same time, and the method can be applied to medicine, tracing, biology and medicine research and development.

Catalytic Cyanation Using CO2 and NH3

Li and co-workers describe the catalytic cyanation of organic halides with CO2 and NH3. In the presence of Cu2O/DABCO as the catalyst, a variety of aromatic bromides and iodides were transformed to the desired nitrile products with broad functional-group tolerance. Both 13C- and/or 15N-labeled nitriles were obtained conveniently with appropriately isotope-labeled CO2 and NH3. Construction of functionalized chemical compounds from small molecules in a highly selective and efficient manner is crucial for sustainable development. The chemical-based manufacturing sector of the future should aim to produce chemicals from very simple and abundant resources, just as nature uses CO2 and N2 to generate sugars, amino acids, and so forth. In practice, however, the utilization of CO2 for the generation of industrial products, such as drugs and related intermediates, still remains a major challenge. Here, we describe the facile cyanide-free production of high-value nitriles with CO2 and NH3 as the sole sources of carbon and nitrogen, respectively. This practical and catalytic methodology provides a unique strategy for the utilization of small molecules for sustainable and cost-effective applications. Selective cyanation of aryl halides was achieved with CO2 and NH3 as the only sources of carbon and nitrogen, respectively. In the presence of Cu catalysts under low pressure (3 atm), a variety of aromatic iodides and bromides were transformed to the desired nitrile products without the use of toxic metal cyanides. Notably, olefins, esters, amides, alcohols, and amino groups were tolerated. Mechanistic studies suggest that Cu(III)-aryl insertion by isocyanate intermediates is involved. [13C,15N]-labeled nitriles were conveniently accessible from the respective isotope-labeled CO2 and NH3 via this methodology.

Nickel-Catalyzed Cyanation of Aryl Chlorides and Triflates Using Butyronitrile: Merging Retro-hydrocyanation with Cross-Coupling

We describe a nickel-catalyzed cyanation reaction of aryl (pseudo)halides that employs butyronitrile as a cyanating reagent instead of highly toxic cyanide salts. A dual catalytic cycle merging retro-hydrocyanation and cross-coupling enables the conversion of a broad array of aryl chlorides and aryl/vinyl triflates into their corresponding nitriles. This new reaction provides a strategically distinct approach to the safe preparation of aryl cyanides, which are essential compounds in agrochemistry and medicinal chemistry.