4528-39-6

Usage

Preparation

In a 1-L round-bottomed flask, fitted with an efficient reflux condenser, were placed 2-ethylhexaneamide 1455 (286 g, 2 mol), dry benzene (300 mL), and thionyl chloride (357 g, 218 mL, 3 mol). The flask was placed in a water bath, which was quickly heated to 75–80 C° and maintained at that temperature for 4.5 h. The reaction mixture was then transferred to a 1.5-L beaker and cooled in an ice bath. A mixture of crushed ice (100 g) and water (100 mL) was added to decompose the excess thionyl chloride. Cold 50% aq. potassium hydroxide solution was then added in small portions with stirring until the mixture was alkaline to litmus. The basified mixture was then transferred to a separatory funnel, and the layers were separated. The aqueous portion was extracted with benzene (100 mL). The benzene solutions were combined and washed with 1% sodium carbonate solution (150 mL) and water (2 × 150 mL). The mixture was distilled from a modified Claisen flask, the bulk of the solvent being removed at atmospheric pressure. The yield of nitrile 1456 was 215–236 g (86–94%); bp 118–120 C°/100 mmHg.

InChI:InChI=1/C8H15N/c1-3-5-6-8(4-2)7-9/h8H,3-6H2,1-2H3

Upstream product

• 4164-92-5 (-)(R)-heptane-carboxylic acid-(3)-amide 
• 109-74-0 propyl cyanide 
• 109-69-3 n-Butyl chloride 
• 4164-92-5 2-ethyl-hexanamide 
• 109-65-9 1-bromo-butane 
• 542-69-8 1-iodo-butane 
• 628-73-9 hexanenitrile 
• 74-85-1 ethene 
• 59346-59-7 2-ethyl-hexanal-dimethylhydrazone 
• 58955-90-1 iso‐octyl azide 
• 60-29-7 diethyl ether 
• 34612-83-4 2-ethyl-hexanal oxime 
• 10026-13-8 phosphorus pentachloride 
• 149-57-5 2-Ethylhexanoic acid 

Downstream Products

• 7512-65-4 2-ethyl-2-chloro-hexanoic acid amide 
• 16493-80-4 4-ethyloctanoic acid 

Relevant academic research and scientific papers

Synthesis, characterization, catalytic and biological application of half-sandwich ruthenium complexes bearing hemilabile (κ2-: C, S)-thioether-functionalised NHC ligands

A series of cationic Ru(ii)(η6-p-cymene) complexes with thioether-functionalised N-heterocyclic carbene ligands have been prepared and fully characterized. Steric and electronic influence of the R thioether substituent on the coordination of the sulfur atom was investigated. The molecular structure of three of them has been determined by means of X-ray diffractrometry and confirmed the bidentate (κ2-C,S) coordination mode of the ligand. Interestingly, only a single diastereomer, as an enantiomeric couple, was observed in the solid state for complexes 1c, 1i and 1j. DFT calculations established a low energy inversion barrier between the two diastereomers through a sulfur pyramidal inversion pathway with R donating group while a dissociative/associative mechanism is more likely with R substituents that contain electron withdrawing group, thus suggesting that the only species observed by the 1H-NMR correspond to an average resonance position of a fluxional mixtures of isomers. All these complexes were found to catalyse the oxydant-free double dehydrogenation of primary amine into nitrile. Ru complex bearing NHC-functionalised S-tBu group was further investigated in a wide range of amines and was found more selective for alkyl amine substrates than for benzylamine derivatives. Finally, preliminary results of the biological effects on various human cancer cells of four selected Ru complexes are reported.

Direct Synthesis of Nitriles from Carboxylic Acids Using Indium-Catalyzed Transnitrilation: Mechanistic and Kinetic Study

Aliphatic and aromatic carboxylic acids can be quantitatively converted to the corresponding nitriles in the presence of catalysts using acetonitrile both as a solvent and reactant at 200 °C. This transformation is based on the acid-nitrile exchange (i.e., transnitrilation) and uses a nontoxic and water resistant catalyst, indium trichloride (InCl3). The mechanism of the transnitrilation was investigated both experimentally and computationally and compared to the previously proposed mechanism. In contrast to the usually assumed formation of amide as an intermediate, transnitrilation is an equilibrium reaction and proceeds via an equilibrated Mumm reaction with the formation of an imide as an intermediate. A simple and reversible mechanism was proposed for this reaction, which was validated by kinetics measurement and by density functional theory calculations of the reaction intermediates and reaction mechanisms.

OXIDATIVE CONVERSION OF ALIPHATIC ALDEHYDES TO NITRILES USING OXOAMMONIUM SALT

The present invention relates to an oxidative transformation method of aliphatic benzaldehydes to nitriles using NH_4OAc through oxoammonium salts. By using stoichiometric amounts of oxoammonium salts to establish optimal reaction conditions associated with the oxidative conversion of aliphatic benzaldehydes to nitriles, high yields of nitrile can be selectively obtained, and the oxoammonium salts used can be oxidized and reused in a simple method.COPYRIGHT KIPO 2020

Easy Ruthenium-Catalysed Oxidation of Primary Amines to Nitriles under Oxidant-Free Conditions

A dehydrogenation of primary amine to give the corresponding nitrile under oxidant- and base-free conditions catalysed by simple [Ru(p-cym)Cl2]2 with no extra ligand is reported. The system is highly selective for alkyl amines, whereas benzylamine derivatives gave the nitrile product together with the imine in a ratio ranging from 14:1 to 4:1 depending on the substrate. Preliminary mechanistic investigations have been performed to identify the key factors that govern the selectivity.

Oxoammonium salt-mediated oxidative nitriles synthesis from aldehydes with ammonium acetate

An efficient and scalable route for the synthesis of nitriles was developed by oxoammonium salt (4-acetamido-2,2,6,6-tetramethylpiperidine-1-oxoammonium tetrafluoroborate) mediated oxidative conversion of aldehydes with NH4OAc. A variety of aliphatic aldehydes as well as benzaldehydes were converted into the corresponding nitriles in high yields. The nitroxyl radical which is the reduced species of the used oxoammonium salt was recovered by simple acid-base extraction for the recycling.

Ligand controlled switchable selectivity in ruthenium catalyzed aerobic oxidation of primary amines

A ligand controlled catalytic system for the aerobic oxidation of 1° amines to nitriles and imines has been developed where the varying π-acidic feature of BIAN versus phen in the frameworks of ruthenium catalysts facilitates switchable selectivity.

Synthesis of nitriles from aerobic oxidation of amines catalyzed by ruthenium supported on activated carbon

Nitriles were synthesized from the aerobic oxidation of amines over commercially available catalysts, which were activated carbon-supported ruthenium catalysts (Ru/AC). The 5%Ru/AC catalyst can tolerate a wide range of substrates, such as aromatic, aliphatic, and heterocyclic amines, and afford the target nitriles in good-to-excellent yields. The 5%Ru/AC catalyst was easily recovered and no ruthenium leaking took place in the catalytic run.

Metal-Free Oxidation of Primary Amines to Nitriles through Coupled Catalytic Cycles

Synergism among several intertwined catalytic cycles allows for selective, room temperature oxidation of primary amines to the corresponding nitriles in 85-98 % isolated yield. This metal-free, scalable, operationally simple method employs a catalytic quantity of 4-acetamido-TEMPO (ACT; TEMPO=2,2,6,6-tetramethylpiperidine N-oxide) radical and the inexpensive, environmentally benign triple salt oxone as the terminal oxidant under mild conditions. Simple filtration of the reaction mixture through silica gel affords pure nitrile products.

Simple Copper Catalysts for the Aerobic Oxidation of Amines: Selectivity Control by the Counterion

We describe the use of simple copper-salt catalysts in the selective aerobic oxidation of amines to nitriles or imines. These catalysts are marked by their exceptional efficiency, operate at ambient temperature and pressure, and allow the oxidation of amines without expensive ligands or additives. This study highlights the significant role counterions can play in controlling selectivity in catalytic aerobic oxidations.

Facile oxidation of primary amines to nitriles using an oxoammonium salt

The oxidation of primary amines using a stoichiometric quantity of 4-acetamido-2,2,6,6-tetramethylpiperidine-1-oxoammonium tetrafluoroborate (1) in CH2Cl2-pyridine solvent at room temperature or at gentle reflux affords nitriles in good yield under mild conditions. The mechanism of the oxidation, which has been investigated computationally, involves a hydride transfer from the amine to the oxygen atom of 1 as the rate-limiting step.