91132-81-9

Upstream product

• 4055-00-9 6-phenyl-3,4-dihydropyran-2-one 
• 10413-00-0 5-oxo-5-phenylpentanenitrile 
• 36603-28-8 5-phenylpentanitrile 
• 1198-34-1 2-Phenylcyclopentanone 
• 83849-01-8 2-phenylcyclopentan-1-one oxime 
• 108-86-1 bromobenzene 
• 120-92-3 cyclopentanone 
• 583027-32-1 5-oxo-5-phenyl-pentanoic acid 2,4-dimethoxy-benzylamide 
• 1501-05-9 5-oxo-5-phenylvaleric acid 
• 1121-89-7 piperidine-2,6-dione 
• 591-51-5 phenyllithium 
• 1501-04-8 Methyl 4-benzoylbutanoate 

Downstream Products

• 104850-13-7 5-phenyl-5-semicarbazono-valeronitrile 
• 18214-22-7 5-(2,4-dinitro-phenylhydrazono)-5-phenyl-valeronitrile 
• 19006-82-7 2-hydroxy-6-phenylpyridine 
• 169601-97-2 4-(3,6-dihydro-4-hydroxy-6-oxo-2-phenyl-2H-pyran-2-yl)butyramide 
• 34502-63-1 6-Phenyl-1,2,3,4-tetrahydropyridin-2-on 
• 10413-00-0 5-oxo-5-phenylpentanenitrile 

Relevant academic research and scientific papers

Photoinduced C—C Bond Cleavage and Oxidation of Cycloketoxime Esters

A novel structural reorganization of cycloketoxime esters beyond the traditional Beckmann rearrangement process has been established to build cyano-containing ketones in the presence of photocatalyst. This novel transformation is remarkable with selective C—C bond cleavage and an oxidation process enabled by DMSO used as the solvent, oxidant, and oxygen source avoiding acid, base and toxic cyanide salts as the cyano source. Further applications in late-stage modification of complex and chiral molecules have also been reported.

Enhanced structural variety of nonplanar N-oxyl radical catalysts and their application to the aerobic oxidation of benzylic C-H bonds

The design and synthesis of structurally variable, nonplanar N-oxyl radical catalysts and their application to the aerobic oxidation, etherification, and acetoamidation of benzylic C-H bonds are described. The catalytic oxidation of C-H bonds represents a powerful tool to synthesize oxygenated functional molecules from simple hydrocarbons in a straightforward way. Electron-deficient N-oxyl radical catalysts, such as phthalimidoyl N-oxyl (PINO) radical, generated from N-hydroxyphthalimide (1), have attracted much attention because of their applications in the oxidation of C-H bonds with high bond dissociation energy (BDE). However, a few sites in 1 are available for structural modifications and improvements of the catalytic performance. By replacing one carbonyl group in 1 with a trifluoromethyl (CF3)-substituted sp3-carbon, we generated an additional tunable site and a nonplanar backbone, while retaining the desirable electron-withdrawing properties and increasing the lipophilicity with respect to 1. We synthesized a variety of N-hydroxy pre catalysts containing such a CF3 moiety, and investigated their utility in the aerobic oxidation of benzylic C-H bonds. Precatalysts with electron-withdrawing substituents, such as trifluoroethoxy and the acetophenone moieties, afforded higher yields than a corresponding methoxy-substituted analogue. The introduction of substituents at the aromatic ring was also effective, as evident from the performance of 7-CF3 and 4,5,6,7-tetrafluoro precatalysts. Especially the combination of trifluoroethoxy- and 4,5,6,7-tetrafluoro substitution afforded a superior performance. These catalyst systems exhibited high functional group tolerance during the aerobic oxidation of C-H bonds, and benzylic etherification and Ritter-type reactions could be carried out at room temperature when a selected precatalyst and N-bromosuccinimide (NBS) were used.

Selective N-debenzylation of amides with p-TsOH

N-Benzylamides were debenzylated efficiently with 4 equiv. of p-TsOH in refluxing toluene. Good to quantitative yields of the desired primary amides were obtained within 2-4 h from a wide variety of N-2,4-dimethoxybenzylamides. N-4-Methoxylbenzyl amides and N-benzylamides were also debenzylated cleanly. In the case of N-2,4-dimethoxylbenzylamides, selective N-debenzylation was possible in the presence of N-Fmoc, N-t-BOC or N-trityl-protection. Protected amino acid amides survived these conditions without any detectable epimerization.

Efficient and scaleable methods for ω-functionalized nonanoic acids: Development of a novel process for azelaic and 9-aminononanoic acids (nylon-6,9 and nylon-9 precursors)

A new, convergent synthesis and process of the title open-chain C-9 compounds, valuable monomers for preparation of polyamides with specific properties, are discussed. Starting from relatively inexpensive raw materials, for example, cyclohexanone and activated C-3 olefins, the method provides polymer grade co-functionalized nonanoic acids. An improved protocol for cyanoethylation or carbalkoxyethylation of cyclohexanone in the presence of a catalytic amount of primary or secondary amines gave 3-(2-oxo-cyclohexane) propanecarboxylic acid derivatives 1 in high yield. Cyclohexaneperoxycarboxylic acid (CHPCA) is introduced as highly efficient reagent in Baeyer-Villiger rearrangement of 1. Pyrolysis of 2 (EWG = CN) afforded under optimized conditions 3 in high yield and regioisomeric purity, otherwise a mixture of three unsaturated isomeric ω-cyano nonenoic acids is obtained. Partial hydrogenation of unsaturated acids 3 allowed isolation of saturated long-chain difunctionalized acids 4. Hydrolysis of 4 led to 1,9-nonanedicarboxylic acid (azelaic acid) 5, whereas its hydrogenation at elevated pressure gave 9-aminononanoic acid 6. Alternatively, a practical four-step syntehsis of 5 via isolable 7-substituted oxepan-2-one (EWG = COOMe) 2 has been designed and experimentated. The versatile position of 3-(2-oxo-cyclohexane) propanecarboxylic acid derivatives 1 as raw materials for Fine Chemicals is also discussed.

6-Phenyl-6-alkylamido-5,6-dihydro-2H-pyran-2-ones: Novel HIV protease inhibitors

Publications from our laboratories have recently described a series of 3-thioaryl substituted-4-hydroxy-pyrones as HIV protease inhibitors. The current work examines the analogues 5,6-dihydro-2H-pyran-2-ones with 6,6-substitutions focusing on the use of 1

Ring-chain Tautomerism in Some 2-Piperidinone Derivatives

The course of reactions between some imides and phenyllithium has been examined and structures of the products together with observed tautomerization are discussed.