6233-04-1Relevant articles and documents
Synthesis and chemical transformations of silicon-containing derivatives of N,N-dimethylhydrazine
Kirilin,Dokuchayev,Sokova,Chernyshev
, p. 169 - 172 (1999)
Reactions of carbofunctional organosilicon compounds with N,N-dimethyl-N'-trimethylsilylhydrazine and N,N-dimethyl-N′,N′-bis(trimethylsilyl)hydrazirie were studied. The composition and structure of the reaction products were found to be dependent on the reagent nature and the reaction conditions. 1,4-Dimethylamino-2,2,5,5-tetramethyl-1,4-diaza-2,5-disilacyclohexane, a first representative of a new type of 2,5-disilapiperazines, was synthesized. A scheme of its formation was proposed.
Exceptional thermal stability and high volatility in mid to late first row transition metal complexes containing carbohydrazide ligands
Karunarathne, Mahesh C.,Knisley, Thomas J.,Tunstull, Gabriel S.,Heeg, Mary Jane,Winter, Charles H.
, p. 820 - 830 (2013)
Treatment of metal(II) halides (metal = Cu, Ni, Co, Fe, Mn, Cr) with the potassium salts of carbohydrazides L1-L6 afforded Cu(L1)2 (75%), Cu(L2)2 (51%), Cu(L3)2 (23%), Co(L1)2 (57%), Cr(L1)2 (62%), Ni(L1)2 (76%), Ni(L2)2 (62%), Ni(L3)2 (62%), Ni(L4)2 (13%), Ni(L5)2 (11%), Ni(L6)2 (29%), [Fe(L1)2]2 (28%), and [Mn(L1)2]2 (12%) as crystalline solids, where L1 = Me2NNC(tBu)O-, L2 = Me2NNC(iPr)O-, L3 = Me2NNC(Me) O-, L4 = (CH2)5NNC(tBu)O -, L5 = (CH2)5NNC(iPr)O-, and L6 = (CH2)5NNC(Me)O-. These complexes were characterized by spectral and analytical techniques, and by X-ray crystal structure determinations for Cu(L1)2, Co(L 1)2, Cr(L1)2, Ni(L1) 2, and [Fe(L1)2]2. Cu(L 1)2, Co(L1)2, Cr(L1) 2, and Ni(L1)2 exist as square planar, monomeric complexes, whereas [Fe(L1)2]2 is a dimer. A combination of sublimation studies, thermal decomposition temperature determinations, and thermogravimetric/differential thermal analysis demonstrate that the Cu, Co, and Ni complexes Cu(L1)2, Cu(L 2)2, Co(L1)2, Ni(L1) 2, and Ni(L2)2 have the lowest sublimation temperatures and highest decomposition temperatures among the series. Additionally, these compounds have higher volatilities and thermal stabilities than commonly used ALD and CVD precursors. Hence, these new complexes have excellent properties for application as ALD precursors to Cu, Co, and Ni metal films.
N-Ammonium Ylide Mediators for Electrochemical C-H Oxidation
Saito, Masato,Kawamata, Yu,Meanwell, Michael,Navratil, Rafael,Chiodi, Debora,Carlson, Ethan,Hu, Pengfei,Chen, Longrui,Udyavara, Sagar,Kingston, Cian,Tanwar, Mayank,Tyagi, Sameer,McKillican, Bruce P.,Gichinga, Moses G.,Schmidt, Michael A.,Eastgate, Martin D.,Lamberto, Massimiliano,He, Chi,Tang, Tianhua,Malapit, Christian A.,Sigman, Matthew S.,Minteer, Shelley D.,Neurock, Matthew,Baran, Phil S.
supporting information, p. 7859 - 7867 (2021/05/26)
The site-specific oxidation of strong C(sp3)-H bonds is of uncontested utility in organic synthesis. From simplifying access to metabolites and late-stage diversification of lead compounds to truncating retrosynthetic plans, there is a growing need for new reagents and methods for achieving such a transformation in both academic and industrial circles. One main drawback of current chemical reagents is the lack of diversity with regard to structure and reactivity that prevents a combinatorial approach for rapid screening to be employed. In that regard, directed evolution still holds the greatest promise for achieving complex C-H oxidations in a variety of complex settings. Herein we present a rationally designed platform that provides a step toward this challenge using N-ammonium ylides as electrochemically driven oxidants for site-specific, chemoselective C(sp3)-H oxidation. By taking a first-principles approach guided by computation, these new mediators were identified and rapidly expanded into a library using ubiquitous building blocks and trivial synthesis techniques. The ylide-based approach to C-H oxidation exhibits tunable selectivity that is often exclusive to this class of oxidants and can be applied to real-world problems in the agricultural and pharmaceutical sectors.
Direct spectroscopic evidence of hyperconjugation unveils the conformational landscape of hydrazides
Gloaguen, Eric,Brenner, Valrie,Alauddin, Mohammad,Tardivel, Benjamin,Mons, Michel,Zehnacker-Rentien, Anne,Declerck, Valrie,Aitken, David J.
supporting information, p. 13756 - 13759 (2015/04/14)
The stereochemistry of hydrazides makes them especially interesting as building blocks for molecular design. An exhaustive conformational analysis of three model hydra-zides was conducted in a conformer-selective approach by using a combination of high-level quantum chemistry calculations and vibrational spectroscopy in the gas phase and in solution. The NH stretch frequency was found to be highly sensitive to hyper conjugation, thus making it an efficient probe of the conformation of the neighboring nitrogen atom. This property greatly assisted the identification of the isomers observed experimentally in the conformer pool. A rationalization of the hydrazide conformational landscape is proposed, therefore paving the way for a better characterization of secondary structures in larger systems.
THERMALLY STABLE VOLATILE FILM PRECURSORS
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Page/Page column 38, (2010/12/17)
A precursor for the deposition of a thin film by atomic layer deposition is provided. The compound has the formula MxLy where M is a metal and L is an amidrazone-derived ligand or an amidate-derived ligand. A process of forming a thin film using the precursors is also provided.
Base Catalysed Rearrangements involving Ylide Intermediates. Part 16. The Preparation and Thermal Rearrangement of Allylammonioamidates
Chantrapromma, Kan,Ollis, W. David,Sutherland, Ian O.
, p. 1029 - 1039 (2007/10/02)
The ammonioamidates (7) and (11) undergo rearrangement (R3=CH2Ph) and competing and rearrangements (R3=allyl).The rates of the and rearrangements of the cinnamyl ammonioamidates (11a), (11b), (11d), and (11g) show similar dependence on the nature of the substituent X.The rate of the rearrangement of the reaction products (14b), (14d), and (14g) is relatively insensitive to substituent effects, suggesting that the rates of ammonioamidate rearrangements are largely controlled by conjugation between the group X and the N(-)CO system.The and rearrangements of the cinnamylammonioamidate (11d) show moderate and similar dependence upon solvent polarity suggesting that the transition state for both reactions has considerable dipolar character.The apparent intramolecularity of the and rearrangements of the cinnamylammonioamidate (11e) as estimated by isotopic mixing methods is decreased by isotopic scrambling in the ylide due to radical recombination to give ylide (11l) in addition to products (13l) and (14l).If allowance is made for this effect the rearrangement appears to be largely, or even entirely, intramolecular and the rearrangement shows intermolecularity comparable with that found for the rearrangements of analogous ammonium ylides under similar reaction conditions.
Process for preparing N,N-disubstituted acid hydrazides
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, (2008/06/13)
A process for preparing N',N'-disubstituted acid hydrazides by reacting N'-monosubstituted acid hydrazides with aldehydes in the presence of hydrogen and a hydrogenation catalyst is disclosed.
