9012-16-2

Upstream product

• 128-08-5 N-Bromosuccinimide 
• 100-64-1 cyclohexanone-oxime 
• 124-04-9 Adipic acid 
• 1191-25-9 6-Hydroxyhexanoic acid 
• 2432-74-8 1-amino-5-cyanopentane 
• 2780-89-4 methyl 6-aminohexanoate hydrochloride 
• 2304-58-7 5-cyanovaleramide 
• 5299-60-5 6-hydroxy-hexanoic acid ethyl ester 
• 371-34-6 ethyl 6-aminohexanoate 
• 4450-39-9 ethyl 5-cyanovalerate 
• 4547-52-8 6-hydroxycaproamide 
• 1589-61-3 cyclohexanone semicarbazone 
• 3719-52-6 (1-nitrocyclohexyl)methanol 
• 79-24-3 Nitroethane 

Downstream Products

• 4641-56-9 1-(2-Hydroxy-2-phenylethyl)perhydro-2-azepinon 
• 109510-44-3 2-(2-oxo-hexahydro-azepine-1-carbonyl)-benzoic acid methyl ester 
• 109811-09-8 N⁶-butyryl-DL-lysine 
• 24904-53-8 (Z)-N-(2-phenylethenyl)-2-azepanone 
• 112718-30-6 6-benzoylamino-hexanoic acid anilide 
• 115012-25-4 6-aminohexanoic acid phenylamide 
• 33241-96-2 1-Benzyl-hexahydro-azepin-2-on 
• 17179-94-1 N-<(E)-2-phenylethenyl>hexahydroazepin-2-one 
• 41470-95-5 5-(3-phenyl-[1,2,4]oxadiazol-5-yl)-pentylamine 
• 93969-45-0 N-[(Z)-3-Oxo-1-(2-oxo-azepan-3-yl)-but-1-enyl]-benzamide 
• 135347-87-4 (3-Fluoro-phenyl)-piperidin-(2Z)-ylidene-amine 
• 22585-46-2 3-benzoyl-ε-caprolactam 
• 85517-53-9 N-Benzylaminomethyl-ε-caprolactam 
• 104608-38-0 (4-Benzothiazol-2-yl-benzyl)-(2-oxo-azepan-1-yl)-phosphinic acid ethyl ester 

Relevant academic research and scientific papers

PREPARATION METHOD OF CAPROLACTAM

The present disclosure discloses a method for preparing caprolactam including: (1) contacting cyclohexanone oxime with a catalyst to carry out reaction in the presence of ethanol and under the condition of gas phase Beckmann rearrangement reaction of cyclohexanone oxime; (2) separating the reaction product obtained in step (1) to produce an ethanol solution of crude caprolactam, and then separating the ethanol solution of crude caprolactam to obtain ethanol and crude caprolactam; (3) removing impurities with boiling points lower than that of caprolactam in the crude caprolactam to obtain a light component removal product; (4) mixing the light component removal product with a crystallization solvent to carry out crystallization and solid-liquid separation to obtain a crystalline crystal; (5) subjecting the crystalline crystal to a hydrogenation reaction; wherein the crystallization solvent contains 0.1-2 wt % of ethanol.

Tandem Synthesis of ?-Caprolactam from Cyclohexanone by an Acidified Metal-organic Framework

Tandem synthesis of ?-caprolactam, one of the largest scaled commercial chemicals, is highly desired from the viewpoint of cost, energy, and environment. However, relevant studies have remained largely underexplored. By using a one-pot strategy, we encapsulated phosphotungstic acid (PTA) into a chromium terephthalate metal-organic framework (MOF), MIL-101, for the efficient tandem conversion of cyclohexanone to ?-caprolactam. The highly dispersed PTA in the MOF matrix showed a high yield of ?-caprolactam through a tandem oximation-Beckmann rearrangement reaction at 100 °C for 12 h. Moreover, MIL-101-PTA was recycled three times, with only a slight loss in their catalytic performance. To the best of our knowledge, this represents the first report using acidified MOF for a tandem oximation-Beckmann rearrangement reaction.

An Integrated Cofactor/Co-Product Recycling Cascade for the Biosynthesis of Nylon Monomers from Cycloalkylamines

We report a highly atom-efficient integrated cofactor/co-product recycling cascade employing cycloalkylamines as multifaceted starting materials for the synthesis of nylon building blocks. Reactions using E. coli whole cells as well as purified enzymes produced excellent conversions ranging from >80 and 95 % into desired ω-amino acids, respectively with varying substrate concentrations. The applicability of this tandem biocatalytic cascade was demonstrated to produce the corresponding lactams by employing engineered biocatalysts. For instance, ?-caprolactam, a valuable polymer building block was synthesized with 75 % conversion from 10 mM cyclohexylamine by employing whole-cell biocatalysts. This cascade could be an alternative for bio-based production of ω-amino acids and corresponding lactam compounds.

Efficient nitriding reagent and application thereof

The invention discloses an efficient nitriding reagent and application thereof, wherein the nitriding reagent comprises nitrogen oxide, an active agent, a reducing agent and an organic solvent. By applying the nitriding reagent, nitrogen-containing compounds such as amide, nitrile and the like can be produced, and the method is simple in condition, low in waste discharge amount and simple in reaction equipment.

Trifluoroacetic Acid Hydroxylamine System as Organocatalyst Reagent in a One-Pot Salt Free Process for the Synthesis of Caprolactam and Amides of Industrial Interest

In this work we studied the reactivity of the Trifluoroacetic acid hydroxylamine system in the one step salt free synthesis of amides from ketones. A particular regards was paid to the caprolactam synthesis because of its industrial relevance. Synthesis, reactivity and characterization of the hydroxylamine trifluoroacetate is given. Fast oximation reaction of several ketones was gained at room temperature (1?h of reaction quantitative conversion for several ketones). In the same reactor, by raising the temperature at 383?K, the Beckmann rearrangement of the so obtained oximes is easily accomplished in the presence of three equivalent of TFA. The possibility of obtaining the trifluoroacetate of the hydroxylamine with a modified nitric acid hydrogenation reactions was verified, too. Reuse of solvent and trifluoroacetic acid is easily achieved by distillation. Graphical abstract: Salt free one-pot caprolactam and amides process catalyzed by CF3COOH, in the presence of NH2OH TFA as the oximation agent.[Figure not available: see fulltext.].

Ethyl 2-Cyano-2-(2-nitrobenzenesulfonyloxyimino) Acetate (ortho-NosylOXY)-Mediated Double Beckmann Rearrangement of Ketoximes under Microwave Irradiation: A Mechanistic Perception

A method for Beckmann rearrangement using ethyl 2-cyano-2-(2-nitrobenzenesulfonyloxyimino) acetate (o-NosylOXY) under microwave irradiation is reported. Ketoximes (19 examples) are converted to the corresponding amides/lactams with 69–97% yields in ～10 minutes without any Lewis acid or co-catalyst. This is an example of halogen-free organocatalytic Beckmann rearrangement. Nuclear magnetic resonance (NMR)- and high-resolution mass spectrometry (HRMS)-based detailed mechanistic investigation suggest that o-NosylOXY acts as an initiator. Such initiators are reported before based on density functional theory (DFT) calculations. However, we report here the HRMS signatures of two transient intermediates, the nitrilium ion and the nitrilium ion's dimeric species. Rigorous NMR-based investigation of the reaction mechanism is performed. Our results indicate that the reported Beckmann rearrangement proceeds via two consecutive rearrangements. (Figure presented.).

Rapid and Mild Lactamization Using Highly Electrophilic Triphosgene in a Microflow Reactor

Lactams are cyclic amides that are indispensable as drugs and as drug candidates. Conventional lactamization includes acid-mediated and coupling-agent-mediated approaches that suffer from narrow substrate scope, much waste, and/or high cost. Inexpensive, less-wasteful approaches mediated by highly electrophilic reagents are attractive, but there is an imminent risk of side reactions. Herein, a methods using highly electrophilic triphosgene in a microflow reactor that accomplishes rapid (0.5–10 s), mild, inexpensive, and less-wasteful lactamization are described. Methods A and B, which use N-methylmorpholine and N-methylimidazole, respectively, were developed. Various lactams and a cyclic peptide containing acid- and/or heat-labile functional groups were synthesized in good to high yields without the need for tedious purification. Undesired reactions were successfully suppressed, and the risk of handling triphosgene was minimized by the use of microflow technology.

Direct Deamination of Primary Amines via Isodiazene Intermediates

We report here a reaction that selectively deaminates primary amines and anilines under mild conditions and with remarkable functional group tolerance including a range of pharmaceutical compounds, amino acids, amino sugars, and natural products. An anomeric amide reagent is uniquely capable of facilitating the reaction through the intermediacy of an unprecedented monosubstituted isodiazene intermediate. In addition to dramatically simplifying deamination compared to existing protocols, our approach enables strategic applications of iminium and amine-directed chemistries as traceless methods. Mechanistic and computational studies support the intermedicacy of a primary isodiazene which exhibits an unexpected divergence from previously studied secondary isodiazenes, leading to cage-escaping, free radical species that engage in a chain, hydrogen-atom transfer process involving aliphatic and diazenyl radical intermediates.

Selective Carbon-Carbon Bond Amination with Redox-Active Aminating Reagents: A Direct Approach to Anilines?

Amines are among the most fundamental motifs in chemical synthesis, and the introduction of amine building blocks via selective C—C bond cleavage allows the construction of nitrogen compounds from simple hydrocarbons through direct skeleton modification. Herein, we report a novel method for the preparation of anilines from alkylarenes via Schmidt-type rearrangement using redox-active amination reagents, which are easily prepared from hydroxylamine. Primary amines and secondary amines were prepared from corresponding alkylarenes or benzyl alcohols under mild conditions. Good compatibility and valuable applications of the transformation were also displayed.

PROCESS FOR THE PRODUCTION OF EPSILON CAPROLACTAM FROM 6- AMINOCAPROIC ACID

The present invention refers to a new process for the production of epsilon caprolactam (CPL) from 6-aminocaproic acid (6-ACA) which can be obtained either from traditional petro chemical processes or which can be obtained from biochemical processes. With the proposed process the reaction time for conversion of 6-aminocaproic acid to the Nylon 6 monomer is shorter and significant energy savings are possible which is advantageous for industrial scale production. The conversion of 6-aminocaproic acid to the Nylon 6 monomer runs at atmospheric pressure and in the final product epsilon caprolactam with no oligomers formation of significance is obtained.