- Intramolecular N?H???F Hydrogen Bonding Interaction in a Series of 4-Anilino-5-Fluoroquinazolines: Experimental and Theoretical Characterization of Electronic and Conformational Effects
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The 4-anilino-6,7-ethylenedioxy-5-fluoroquinazoline scaffold is presented as a novel model system for the characterization of the weak NH???F hydrogen bonding (HB) interaction. In this scaffold, the aniline NH proton is forced into close proximity with the nearby fluorine (dH,F～2.0 ?, ∠～138°), and a through-space interaction is observed by NMR spectroscopy with couplings (1hJNH,F) of 19±1 Hz. A combination of experimental (NMR spectroscopy and X-ray crystallography) and theoretical methods (DFT calculations) were used for the characterization of this weak interaction. In particular, the effects of conformational rigidity and steric compression on coupling were investigated. This scaffold was used for the direct comparison of fluoride with methoxy as HB acceptors, and the susceptibility of the NH???F interaction to changes in electron distribution and resonance was probed by preparing a series of molecules with different electron-donating or -withdrawing groups in the positions para to the NH and F. The results support the idea that fluorine can act as a weak HB acceptor, and the HB strength can be modulated through additive and linear electronic substituent effects.
- Urner, Lorenz M.,Young Lee, Ga,Treacy, Joseph W.,Turlik, Aneta,Khan, Saeed I.,Houk,Jung, Michael E.
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supporting information
(2021/12/08)
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- Preparation of aniline derivatives
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In the present invention, provided is a novel manufacturing method of aniline derivative, which is more simple and eco-friendly and takes less cost compared with an existing synthesizing aniline method, comprising a step of manufacturing chemical formula 1 by making chemical formula 2 react with chemical formula 3 under catalyst, bases and solvents wherein the manufacturing method aniline derivative is manufactured through one pot in a simple manner and accordingly easily removes the solvent with use of distillation under reduced pressure after reaction.
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Paragraph 0087-0092
(2016/10/08)
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- Synthesis and methemoglobinemia-inducing properties of analogues of para-aminopropiophenone designed as humane rodenticides
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A number of structural analogues of the known toxicant para- aminopropiophenone (PAPP) have been prepared and evaluated for their capacity to induce methemoglobinemia - with a view to their possible application as humane pest control agents. It was found that an optimal lipophilicity for the formation of methemoglobin (metHb) in vitro existed for alkyl analogues of PAPP (aminophenones 1-20; compound 6 metHb% = 74.1 ± 2). Besides lipophilicity, this structural sub-class suggested there were certain structural requirements for activity, with both branched (10-16) and cyclic (17-20) alkyl analogues exhibiting inferior in vitro metHb induction. Of the four candidates (compounds 4, 6, 13 and 23) evaluated in vivo, 4 exhibited the greatest toxicity. In parallel, aminophenone bioisosteres, including oximes 30-32, sulfoxide 33, sulfone 34 and sulfonamides 35-36, were found to be inferior metHb inducers to lead ketone 4. Closer examination of Hammett substituent constants suggests that a particular combination of the field and resonance parameters may be significant with respect to the redox mechanisms behind PAPPs metHb toxicity.
- Rennison, David,Conole, Daniel,Tingle, Malcolm D.,Yang, Junpeng,Eason, Charles T.,Brimble, Margaret A.
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supporting information
p. 6629 - 6635
(2014/01/06)
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- Palladium-catalysed transfer hydrogenation of aromatic nitro compounds - An unusual chain elongation
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Aromatic nitro compounds are reduced via transfer hydrogenation in the presence of palladium on magnesium-lanthanum mixed oxide support in ethanol yielding the corresponding amines. With several acetophenone derivatives, the reduction was accompanied by c
- Németh, János,Kiss, árpád,Hell, Zoltán
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p. 6094 - 6096
(2013/10/22)
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- One-pot conversion of phenols to anilines via Smiles rearrangement
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A convenient one-pot synthesis of phenols to anilines using 2-chloroacetamide/K2CO3/DMF system catalyzed by KI via Smiles rearrangement has been described. The synthesis of extensive amino aromatic products from phenols containing electron withdrawing group, has been performed in moderate to excellent yields to demonstrate the potentiality of this method in bio-medicinal and pharmaceutical applications.
- Xie, Yong-Sheng,Vijaykumar,Jang, Kiwan,Shin, Hong-Hyun,Zuo, Hua,Shin, Dong-Soo
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p. 5151 - 5154
(2013/09/02)
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- Palladium-catalyzed oxidative coupling of trialkylamines with aryl iodides leading to alkyl aryl ketones
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Chemical equations presented. A new, simple method for selectively synthesizing alkyl aryl ketones has been developed by palladium-catalyzed oxidative coupling of trialkylamines with aryl iodides. In the presence of PdCl2(MeCN)2, TBAB, and ZnO, a variety of aryl iodides underwent an oxidative coupling reaction with tertiary amines and water to afford the corresponding alkyl aryl ketones in moderate to excellent yields. It is noteworthy that this method is the first example of using trialkylamines as the carbonyl sources for constructing alkyl aryl ketone skeletons.
- Liu, Yan,Yao, Bo,Deng, Chen-Liang,Tang, Ri-Yuan,Zhang, Xing-Guo,Li, Jin-Heng
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supporting information; experimental part
p. 2184 - 2187
(2011/06/20)
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- Fries-type rearrangement of acylanilides in the presence of ytterbium triflate
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Ytterbium triflate has been used to catalyse the Fries-type rearrangement of various acylanilides with moderate yields when lithium perchlorate was used as co-catalyst.
- Su, Weike,Jin, Can
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p. 611 - 613
(2007/10/03)
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