673-66-5Relevant articles and documents
Ethyl 2-Cyano-2-(2-nitrobenzenesulfonyloxyimino) Acetate (ortho-NosylOXY)-Mediated Double Beckmann Rearrangement of Ketoximes under Microwave Irradiation: A Mechanistic Perception
Dev, Dharm,Kalita, Tapasi,Mondal, Tanmay,Mandal, Bhubaneswar
, p. 1427 - 1435 (2021/01/04)
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.).
Nitromethane as a nitrogen donor in Schmidt-type formation of amides and nitriles
Jiao, Ning,Liu, Jianzhong,Qiu, Xu,Song, Song,Wei, Jialiang,Wen, Xiaojin,Zhang, Cheng,Zhang, Ziyao
supporting information, p. 281 - 285 (2020/01/28)
The Schmidt reaction has been an efficient and widely used synthetic approach to amides and nitriles since its discovery in 1923. However, its application often entails the use of volatile, potentially explosive, and highly toxic azide reagents. Here, we report a sequence whereby triflic anhydride and formic and acetic acids activate the bulk chemical nitromethane to serve as a nitrogen donor in place of azides in Schmidt-like reactions. This protocol further expands the substrate scope to alkynes and simple alkyl benzenes for the preparation of amides and nitriles.
Synthesis method 7- aminoheptanoic acid hydrochloride
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Paragraph 0033-0042, (2020/03/16)
The invention discloses a synthesis method 7 - of, aminoheptanoic acid hydrochloride, belongs to the field: organic synthesis, and the reaction solution obtained by adding the cycloheptanone to the methanol solution, and adding concentrated HCl, to obtain, aminopimelic acid hydrochloride, is more suitable for large-scale production, by adding concentrated hydrochloric acid, reflux reaction 7 - to dichloromethane cooling crystallization. for producing the heptane lactam, in simple operation, of the present invention.
A novel synthetic route of fused tricyclic framework quinoline derivatives from readily available aliphatic amino carboxylic acid substrates
Mohammed, Shireen
, p. 611 - 617 (2019/06/07)
A novel and an efficient strategy of fused tricyclic quinoline heterocycle compounds from aliphatic amino carboxylic acid substrates was studied. The protocol here is proceed over main reaction processes including: cyclization, protection, amidine formation, further cyclization and finally coupling with boronic acid substrate through Suzuki reaction. These reactions afforded the corresponding products in high yields. Furthermore, all synthesized compounds were identified by spectral data.
In Situ Conformational Fixation of the Amide Bond Enables General Access to Medium-Sized Lactams via Ring-Closing Metathesis
Hegmann, Nina,Prusko, Lea,Diesendorf, Nina,Heinrich, Markus R.
supporting information, p. 7825 - 7829 (2019/01/04)
In this work, a novel phenethylamine-derived protecting group is introduced, which is able to significantly enhance the Grubbs I-catalyzed formation of 9- to 12-membered lactams through charge-induced conformational fixation under acidic conditions. As the new approach is particularly valuable for 10- and 11-membered ring systems, for which no related precedence was available so far, the overall strategy now offers general access to medium-sized lactams via ring closing metathesis. Cleavage of the protecting group can be achieved through a mild sequence combining N-oxidation and Cope elimination or alternatively under standard hydrogenation conditions.
Establishment of an activated peroxide system for low-temperature cotton bleaching using N-[4-(triethylammoniomethyl)benzoyl]butyrolactam chloride
Xu, Changhai,Hinks, David,Sun, Chang,Wei, Qufu
, p. 71 - 77 (2015/01/09)
Cotton bleaching is traditionally carried out in strongly alkaline solution of hydrogen peroxide (H2O2) at temperatures close to the boil. Such harsh processing conditions can result in extensive water and energy consumptions as well as severe chemical damage to textiles. In this study, an activated peroxide system was established for low-temperature cotton bleaching by incorporating a bleach activator, namely N-[4-(triethylammoniomethyl)benzoyl]butyrolactam chloride (TBBC) into an aqueous H2O2 solution. Experimental results showed that the TBBC-activated peroxide system exhibited the most effective bleaching performance in a pH range of 6-8 which could be approximated by adding sodium bicarbonate (NaHCO3). The TBBC/H2O2/NaHCO3 system led to rapid bleaching of cotton at a temperature as low as 50°C. In comparison with the hot alkaline peroxide bleaching system, the TBBC/H2O2/NaHCO3 system provided cotton fabric with an equivalent degree of whiteness, higher degree of polymerization, and slightly lower water absorbency. The new activated peroxide system may provide a more environmentally benign approach to cotton bleaching.
Construction of tertiary chiral centers by Pd-catalyzed asymmetric allylic alkylation of prochiral enolate equivalents
Kita, Yusuke,Numajiri, Yoshitaka,Okamoto, Noriko,Stoltz, Brian M.
, p. 6349 - 6353 (2015/08/18)
Abstract The palladium-catalyzed decarboxylative allylic alkylation of enol carbonates derived from lactams and ketones is described. Employing these substrates with an electronically tuned Pd catalyst system trisubstituted chiral centers are produced. These stereocenters have been previously challenging to achieve using Pd complex/chiral P-N ligand systems.
A mild, copper-catalysed amide deprotection strategy: Use of tert-butyl as a protecting group
Evans, Vikki,Mahon, Mary F.,Webster, Ruth L.
supporting information, p. 7593 - 7597 (2014/12/10)
Mild methods for the deprotection of organic substrates are of fundamental importance in synthetic chemistry. A new room temperature method using a catalytic amount of Cu(OTf)2is reported. This allows use of the tert-butyl group as an amide protecting group. The methodology is also extended to Boc-deprotection.
HISTONE DEACETYLASE 6 SELECTIVE INHIBITORS FOR THE TREATMENT OF BONE DISEASE
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Page/Page column 71-72, (2013/03/26)
This invention relates to methods for treating bone disease associated with osteoclast activation using HDAC6 selective inhibitors, e.g., small molecule inhibitors such as reverse amide compounds.
Nano-sulfated titania (TiO2/SO2-4) as a new solid acid catalyst for Friedel-Crafts acylation and Beckman rearrangement in solvent-free conditions
Hosseini-Sarvari, Mona,Safary, Ensieh
experimental part, p. 463 - 473 (2012/06/16)
The present work describes a novel application of nano-sulfated titania (nano-ST) as a solid acid catalyst for Friedel-Crafts acylation and Beckmann rearrangement. A nano-ST catalyst has been synthesized and characterized using various techniques such as XRD, scanning electron morphology, transmission electron microscopy, FT-IR, measurement of the specific surface area by Brunauer-Emmett-Teller theory and thermal analysis. The influences of various reaction parameters such as reaction temperature, molar ratio of reactants, reaction time and solvent effects have been investigated. [image omitted].
