10341-75-0Relevant articles and documents
Intramolecular Amido Transfer Leading to Structurally Diverse Nitrogen-Containing Macrocycles
Kim, Heejeong,Chang, Sukbok
, p. 3344 - 3348 (2017)
Reported herein is the development of rhodium-catalyzed intramolecular amido transfer as an efficient route to nitrogen-containing macrocycles starting from acetophenone ketoximes tethered with either aryl or alkyl azides. Facile generation of rhodacycles and metal imido intermediates was the key to success in this mechanistic scaffold to represent the first example of an intramolecular inner-sphere C?H amination. While substrates bearing aryl azides underwent a monomeric ring formation in high yields, a dimeric double cyclization took place exclusively with alkyl-azide-tethered ketoximes, thus affording up to 36-membered azamacrocyclic products.
Synthesis of oximes with NH2OH.HCl/DOWEX(R)50WX4 system
Setamdideh, Davood,Khezri, Behrooz,Esmaeilzadeh, Seyran
, p. 1119 - 1124 (2012)
The oximation of a variety of carbonyl compounds was efficiently carried out with DOWEX(R)50WX4/NH2OH·HCl system. The reactions were performed in ethanol to give Z-aldoximation isomers of aldehydes and E-oximaton of acetophenone derivatives in a perfect selectively. The oximation of compounds with two carbonyl groups was carried out selectively on one carbonyl moiety. Also, the oximation of aldehydes over ketones has been accomplished successfully by this system.
Novel chemoenzymatic oxidation of amines into oximes based on hydrolase-catalysed peracid formation
Méndez-Sánchez, Daniel,Lavandera, Iván,Gotor, Vicente,Gotor-Fernández, Vicente
, p. 3196 - 3201 (2017)
The efficient transformation of benzylamines into the corresponding oximes has been described by means of a chemoenzymatic process. This strategy is based on a two-step sequence developed in one-pot at 30 °C and atmospheric pressure. First, the formation of a reactive peracid intermediate occurs by means of a lipase-catalysed perhydrolysis reaction, and then this peracid acts as a chemical oxidising agent of the amines. A total of nine ketoximes were isolated in high purity after a simple extraction protocol (90-98% isolated yield), while for the eleven synthesised aldoximes a further column chromatography purification was required (71-82% isolated yield). In all cases excellent selectivities were attained, offering a practical method for amine oxidation in short reaction times (1 hour). The environmental impact of the process was analysed and compared with a recently published alternative chemical synthesis, finding for this metric a good E-factor value.
Synthesis and Beckmann rearrangement of novel (Z)-2-organylselanyl ketoximes: promising agents against grapevine anthracnose infection
Waskow, Bianca,Mano, Renata A.,Giacomini, Rafaela X.,Oliveira, Daniela H.,Schumacher, Ricardo F.,Wilhelm, Ethel A.,Luchese, Cristiane,Savegnago, Lucielli,Jacob, Raquel G.
, p. 5575 - 5580 (2016)
We present here the synthesis of novel (Z)-2-organylselanyl ketoximes by nucleophilic substitution reaction of E/Z mixtures of 2-bromo ketoximes with nucleophilic species of selenium, which were generated in situ by simple cleavage of diorganyl diselenides with NaBH4using ethanol/THF as solvent. The new 2-organylselanyl ketoximes were synthesized in moderate to good yields and with selectivity for the (Z)-configuration. The synthesized (Z)-2-arylselanylacetophenone oximes were submitted to the Beckmann rearrangement, furnishing the corresponding N-aryl-2-(selanyl)acetamides. (Z)-1-Phenyl-2-(phenylselanyl) ketoxime has antifungal activity against Sphaceloma ampelinum and a good level of antioxidant activity in vitro in DPPH, ABTS, FRAP and lipid peroxidation assays.
Oxime-Based and Catalyst-Free Dynamic Covalent Polyurethanes
Liu, Wen-Xing,Zhang, Chi,Zhang, Huan,Zhao, Ning,Yu, Zhi-Xiang,Xu, Jian
, p. 8678 - 8684 (2017)
Polyurethanes (PUs) have many applications resulting from their preeminent properties, but being commonly used toxic catalysts, and the lack of processability for PU thermosets cause limitations. Herein, we report a new class of the PU-like dynamic covalent polymers, poly(oxime-urethanes) (POUs), which are prepared from the uncatalyzed polyaddition of multifunctional oximes and hexamethylene diisocyanate (HDI) at ambient temperature. Kinetics studies reveal that almost complete polymerization (～99% conversion) can be achieved in 3 h at 30 °C in dichloromethane (DCM), the most effective among the solvents evaluated, producing linear POUs with comparable molecular weights to the catalyzed PUs. We find that the oxime-carbamate structures are reversible at about 100 °C through oxime-enabled transcarbamoylation via a thermally dissociative mechanism. The cross-linked POUs based on oxime-carbamate bonds show efficient catalyst-free healable/recyclable properties. Density functional theory (DFT) calculations suggest that the fast oxime-urethanation and the mild thermoreversible nature are mediated by the characteristic nitrone tautomer of the oxime. Given widespread urethane-containing materials, POUs are of promising potential in applications because of the excellent mechanical performances, facile preparation, and dynamic property without using catalysts.
Triphenylphosphine catalyzed Michael addition of oximes onto activated olefins
Bhuniya, Debnath,Mohan, Sankar,Narayanan, Sanju
, p. 1018 - 1024 (2003)
A new reaction condition for Michael addition of oximes onto activated olefins has been discovered using a catalytic amount of triphenylphosphine. This is a first and milder alternative to classical base (hydroxide, alkoxide) catalyzed Michael addition of oximes. Various aldoximes 1a-h and ketoximes 2a-c (Figure 1) were reacted with different Michael acceptors such as ethyl acrylate, acrylonitrile, phenyl vinyl sulfone, methyl vinyl ketone, and 1-nitrocyclohex-1-ene to obtain the corresponding Michael adducts. About 35 different examples were attempted (Table 1 and Scheme 1); except in six cases where reactions did not produce desired products, yields varied from good to excellent. Reactions without triphenylphosphine did not proceed. A plausible mechanism of catalytic action in the present reactions is proposed (Figure 2).
Lewis acid-assisted N-fluorobenzenesulfonimide-based electrophilic fluorine catalysis in Beckmann rearrangement
Xie, Fukai,Du, Chuan,Pang, Yadong,Lian, Xu,Xue, Chentao,Chen, Yanyu,Wang, Xuefei,Cheng, Maosheng,Guo, Chun,Lin, Bin,Liu, Yongxiang
, p. 5820 - 5824 (2016)
A microwave-assisted N-fluorobenzenesulfonimide (NFSI)/Lewis acid-catalyzed Beckmann rearrangement was developed. The remarkable promotion to the electrophilicity of NFSI by Lewis acids was illustrated utilizing a series of readily available oxime substrates. The action model between NFSI and Lewis acids was probed by control experiments and theoretical calculations.
(E)-Phenyl- and -heteroaryl-substituted O-benzoyl-(or acyl)oximes as lipoprotein-associated phospholipase A2 inhibitors
Jeong, Tae-Sook,Kim, Mi Jeong,Yu, Hana,Kim, Kyung Soon,Choi, Joong-Kwon,Kim, Sung-Soo,Lee, Woo Song
, p. 1525 - 1527 (2005)
A series of (E)-phenyl- and -heteroaryl-substituted O-benzoyl- (or acyl)oximes 3a-n were synthesized for evaluating their human lipoprotein-associated phospholiphase A2 (Lp-PLA2) inhibitory activities. The less lipophilic derivatives 3a-c showed the most potent in vitro inhibitory activity on human Lp-PLA2.
NH2OH.HCl/BaCl2: A convenient system for synthesis of oximes from the corresponding of organic carbonyl compounds
Talaei, Farhad,Setamdideh, Davood
, p. 1583 - 1587 (2016)
A variety of aldehydes and ketones were converted to their corresponding oximes NH2OH·HCl/BaCl2 system in reflux conditions.
A synthesis of oximes from olefins by cobalt(II) porphyrin-catalyzed reduction-nitrosation
Sugamoto, Kazuhiro,Hamasuna, Yutaka,Matsushita, Yoh-Ichi,Matsui, Takanao
, p. 1270 - 1272 (1998)
Various olefins such as styrenes, α,β-unsaturated carbonyl compounds, and α,β,γ,δ-unsaturated carbonyl compounds were directly converted to the corresponding acetophenoximes, α-hydroxyimino carbonyl compounds and γ-hydroxyimino-α,β-unsaturated carbonyl compounds in good or moderate yields by reduction-nitrosation with t-butyl nitrite and triethylsilane in the presence of cobalt(II) porphyrin as a catalyst.
