22554-30-9

Upstream product

• 132407-56-8 N-chloro-1-amino-1-cyclohexanecarboxylic acid 
• 7664-41-7 ammonia 
• 108-94-1 cyclohexanone 
• 13130-16-0 cyclohexanone O-phenyloxime 
• 108-91-8 cyclohexylamine 
• 19573-22-9 cyclohexyl azide 
• 108-93-0 cyclohexanol 
• 6628-00-8 N-Allylcyclohexylamin 
• 5496-10-6 1-amino-1-cyanocyclohexane 
• 67398-11-2 α-amino cyclohexylphosphonic acid 
• 4998-76-9 cyclohexylamine hydrochloride 
• 126424-21-3 N-cyclohexyl-2-azanorborn-5-ene 
• 19731-71-6 cyclohexanone-O-(phenylmethyl)oxime 
• 24731-36-0 1-trimethylsilanyloxycyclohexanecarbonitrile 

Downstream Products

• 28294-78-2 (CO)5Cr(C₆H₁₀NH) 
• 14001-37-7 N-acetyl-3,4,5,6-tetrahydroaniline 

Relevant academic research and scientific papers

Kinetics and mechanism of decomposition of N-chloroamino acids. II: Conformationally restricted models

The kinetics of decomposition of the following conformationally restricted N-chloro-α-amino acids were studied: 1-amino-1-cyclopentanecarboxylic acid (2), 1-amino-1-cyclohexanecarboxylic acid (4), 2-amino-2-norbornanecarboxylic acid (6), and 2-amino-2-benzonorbornanecarboxylic acid (8). The first-order rate constants obtained were 0.520, 5.197, 0.198, and 0.078, respectively, which correlated with the ring strain in the structurally related cyclic ketones cyclopentanone, cyclohexanone, norborane-2-one, and benzonorbornane-2-one. The data are supportive of a concerted mechanism for the decomposition reaction involving an imine-like transition state.

Preparation method of cyclohexanone oxime

The invention relates to a preparation method of cyclohexanone oxime. The method comprises the following steps: carrying out partial oxidation reaction on cyclohexylamine and molecular oxygen under the action of a catalyst to obtain an oxidation reaction product consisting of cyclohexanone oxime, a byproduct and possibly unconverted cyclohexylamine; and then treating the oxidation reaction product in one of the following modes: (i) carrying out hydrogenation amination reaction with H2 and NH3 at the same time or carrying out hydrogenation and amination reaction in sequence under the action of a catalyst without separation or after part or all of water in the oxidation reaction product is separated, and then carrying out separation to obtain cyclohexanone oxime; and (ii) carrying out hydrogenation reaction with H2 under the action of a catalyst without separation or after part or all of water is separated out, and then carrying out separation to obtain the cyclohexanone oxime. The method disclosed by the invention has the characteristics of short process flow, small occupied area and investment, low material consumption and energy consumption (low cost), simplicity and convenience in operation, environment friendliness and the like.

Ambient-Temperature Synthesis of Primary Amines via Reductive Amination of Carbonyl Compounds

Efficient synthesis of primary amines via low-temperature reductive amination of carbonyl compounds using NH3 and H2 as the nitrogen and hydrogen resources is highly desired and challenging in the chemistry community. Herein, we employed naturally occurring phytic acid as a renewable precursor to fabricate titanium phosphate (TiP)-supported Ru nanocatalysts with different reduction degrees of RuO2 (Ru/TiP-x, x represents the reduction temperature) by combining ball milling and molten-salt processes. Very interestingly, the obtained Ru/TiP-100 had good catalytic performance for the reductive amination of carbonyl compounds at ambient temperature, resulting from the synergistic cooperation of the support (TiP) and the Ru/RuO2 with a suitable proportion of Ru0 (52%). Various carbonyl compounds could be efficiently converted into the corresponding primary amines with high yields. More importantly, the conversion of other substrates with reducible groups could also be achieved at ambient temperature. Detailed investigations indicated that the partially reduced Ru and the support (TiP) were indispensable. The high activity and selectivity of Ru/TiP-100 catalyst originates from the relatively high acidity and the suitable electron density of metallic Ru0.

Synthesis of: N -unsubstituted cycloalkylimines containing a 4 to 8-membered ring

Primary cycloalkylimines with a 4 to 8-membered ring were synthesized by dehydrocyanation of the corresponding α-aminonitriles on solid potassium hydroxide via a vacuum gas-solid reaction. Imine-enamine tautomerism has been demonstrated at room temperature for the most kinetically stable derivatives.

Amide: Versus amine ligand paradigm in the direct amination of alcohols with Ru-PNP complexes

The catalytic activity of a series of Ru-PNP pincer ligand complexes was studied in the direct amination of alcohols with ammonia. It turned out that all complexes of PNP ligands bearing a secondary amine showed no activity in this hydrogen-shuttling reaction sequence, while all complexes of homologous ligands bearing a tertiary amine gave active catalysts. Further comparative studies on catalysts bearing an acridine-based PNP pincer ligand and a PNP ligand of the Xantphos family provided valuable mechanistic insight that led to the design of a highly active catalyst. It appears that in the group of ligands studied here only ligands that do not form stable Ru-amido complexes are active alcohol amination catalysts.

A remarkable solvent effect on reductive amination of ketones

We report the first systematic study of solvent effect on reductive amination of ketones with ammonia and dihydrogen (H2) over Ru/C, Rh/C, Pd/C and Pt/C catalysts. Protic (water, methanol, ethanol and isopropanol), aprotic polar (dioxane and tetrahydrofuran) and aprotic apolar (cyclohexane and toluene) solvents were investigated. Reaction kinetic model was built to reveal solvent-dependent reaction pathway and solvent-related rate constant for individual steps. Primary amine is produced via two distinct routes, i.e., hydrogenation of imine and hydrogenolysis of Schiff base adduct. These two routes co-exist in organic solvents, while the preference of which route to take heavily depends on the nature of the solvent. In contrast, the formation of imine and Schiff base are not favored in water, resulting in high selectivity towards alcohol. Methanol is identified as the best solvent for reductive amination of ketones, attributed to the highest rates for imine and Schiff base formation compared to other solvents, as well as high hydrogenation activity.

Reactivity of aminophosphonic acids. Oxidative dephosphonylation of 1-aminoalkylphosphonic acids by aqueous halogens

The reactions of 1-aminoalkylphosphonic acids with bromine-water, chlorine-water and iodine-water were investigated. The formation of phosphoric(v) acid, as a result of a halogen-promoted cleavage of the Cα-P bond, accompanied by nitrogen release, was observed. The dephosphonylation of 1-aminoalkylphosphonic acids was found to occur quantitatively. In the reactions of 1-aminoalkylphosphonic acids with other halogen-water reagents investigated by 31P NMR, scission of the Cα-P bond was also observed, the reaction rates being comparable for bromine and chlorine, but much slower for iodine.

CATALYTIC PREPARATION OF ENAMIDES FROM ALKYL AZIDES AND ACYL DONORS

The present invention relates to a method to synthesize an enamide compound by generating imine which does not have a substituent group bonded to the nitrogen from an organic azide compound and conducting a reaction of the same with acyl doner. By using t

Exploiting the Nucleophilicity of N-H Imines: Synthesis of Enamides from Alkyl Azides and Acid Anhydrides

The nucleophilicity of N-unsubstituted imines, which were generated from alkyl azides by a ruthenium-catalyzed reaction, was investigated in the reaction with acid anhydrides. The initial products were N-acylimines, which isomerized to the corresponding e

Mechanistic study on the ruthenium-catalyzed direct amination of alcohols

The Ru-catalyzed direct amination of alcohols with ammonia was investigated for the RuHCl(CO)(PPh3)3/Xantphos system in order to gain mechanistic insight. For several Ru(II) precursor complexes the influence of different additives on catalytic performance was investigated. NMR studies revealed that the reaction of RuHCl(CO)(PPh3)3/Xantphos with the alcohol in the presence of a strong base initially formed an inactive dihydrido Ru species. However, by addition of a ketone, the dihydride was (re)activated, where the corresponding imine is the actual activator, formed by immediate condensation of the ketone with ammonia. In the absence of a base, added ketone significantly enhanced catalyst activity. Catalytically inactive RuCl2(PPh3)3 could be activated by base, demonstrating that also complexes without the CO ligand give active catalysts. On the basis of these observations a mechanism was proposed, closely related to known transfer hydrogenation mechanisms.