637-59-2Relevant articles and documents
Nucleophilic substitution reactions of unbranched alkyl amines using triazine reagents
Kitamura, Masanori,Kitaoka, Yuki,Fujita, Hikaru,Kunishima, Munetaka
, (2022/03/02)
Since amines are present in many organic, biological, and drug molecules, a strategy of synthesizing desired compounds by nucleophilic substitution reactions of these amines is very attractive. By using triazine reagents, we have found that nucleophilic substitution reactions of unbranched alkyl amines via morpholine derivatives are feasible. This method can be performed under milder reaction conditions than those in previously reported methods.
Ni-Catalyzed Formal Cross-Electrophile Coupling of Alcohols with Aryl Halides
Lin, Quan,Ma, Guobin,Gong, Hegui
, p. 14102 - 14109 (2021/11/20)
Direct coupling of unactivated alcohols remains a challenge in current synthetic chemistry. We herein demonstrate a strategy building upon in situ halogenation/reductive coupling of alcohols with aryl halides to forge Csp2-Csp3 bonds. The combination of 2-chloro-3-ethylbenzo[d]oxazol-3-ium salt (CEBO) and TBAB as the mild bromination reagents enables rapid transformation of a wide range of alcohols to their bromide counterparts within one to 5 min in CH3CN and DMF, which is compatible with the Ni-catalyzed cross-electrophile coupling conditions in the presence of a chemical reductant. The present method is suitable for arylation of a myriad of structurally complex alcohols with no need for prepreparation of alkyl halides. More importantly, the mild and kinetically rapid bromination process has shown good selectivity in the bromination/arylation of symmetric diols and less sterically hindered hydroxyl groups in polyols, thus offering promise for selective functionalization of diols and polyols without laborious protecting/deprotecting operations. The practicality of this work is also evident in the arylation of a number of carbohydrates, drug compounds, and naturally occurring alcohols.
Iron(II) and Copper(I) Control the Total Regioselectivity in the Hydrobromination of Alkenes
Cruz, Daniel A.,Sinka, Victoria,De Armas, Pedro,Steingruber, Hugo Sebastian,Fernández, Israel,Martín, Víctor S.,Miranda, Pedro O.,Padrón, Juan I.
supporting information, p. 6105 - 6109 (2021/08/18)
A new method that allows the complete control of the regioselectivity of the hydrobromination reaction of alkenes is described. Herein, we report a radical procedure with TMSBr and oxygen as common reagents, where the formation of the anti-Markovnikov product occurs in the presence of parts per million amounts of the Cu(I) species and the formation of the Markovnikov product occurs in the presence of 30 mol % iron(II) bromide. Density functional theory calculations combined with Fukui's radical susceptibilities support the obtained results.
Boron tribromide as a reagent for anti-Markovnikov addition of HBr to cyclopropanes
Chen, Shuming,Gieuw, Matthew H.,Houk, K. N.,Ke, Zhihai,Yeung, Ying-Yeung
, p. 9426 - 9433 (2020/10/02)
Although radical formation from a trialkylborane is well documented, the analogous reaction mode is unknown for trihaloboranes. We have discovered the generation of bromine radicals from boron tribromide and simple proton sources, such as water ortert-butanol, under open-flask conditions. Cyclopropanes bearing a variety of substituents were hydro- and deuterio-brominated to furnish anti-Markovnikov products in a highly regioselective fashion. NMR mechanistic studies and DFT calculations point to a radical pathway instead of the conventional ionic mechanism expected for BBr3
Nucleophilic Substitution of Aliphatic Fluorides via Pseudohalide Intermediates
Jaiswal, Amit K.,Prasad, Pragati K.,Young, Rowan D.
supporting information, p. 6290 - 6294 (2019/04/26)
A method for aliphatic fluoride functionalization with a variety of nucleophiles has been reported. Carbon–fluoride bond cleavage is thermodynamically driven by the use of silylated pseudohalides TMS-OMs or TMS-NTf2, resulting in the formation of TMS-F and a trapped aliphatic pseudohalide intermediate. The rate of fluoride/pseudohalide exchange and the stability of this intermediate are such that little rearrangement is observed for terminal fluoride positions in linear aliphatic fluorides. The ability to convert organofluoride positions into pseudohalide groups allows facile nucleophilic attack by a wide range of nucleophiles. The late introduction of the nucleophiles also allows for a wide range of functional-group tolerance in the coupling partners. Selective alkyl fluoride mesylation is observed in the presence of other alkyl halides, allowing for orthogonal synthetic strategies.
Visible Light-Mediated Conversion of Alcohols to Bromides by a Benzothiadiazole-Containing Organic Photocatalyst
Li, Run,Gehrig, Dominik W.,Ramanan, Charusheela,Blom, Paul W. M.,Kohl, Fabien F.,Wagner, Manfred,Landfester, Katharina,Zhang, Kai A. I.
, p. 3852 - 3859 (2019/07/15)
The search for metal-free, stable and high effective photocatalysts with sufficient photo-redox potentials remains a key challenge for organic chemists. Here, we present a benzothiadiazole-containing molecular organic photocatalyst with redox potentials of ?1.30 V and +1.64 V vs. SCE. The singlet state lifetime is 13 ns. Direct conversion from aliphatic alcohols to bromides has been conducted with the designed organic photocatalyst under visible light irradiation with high efficiency and selectivity. The catalytic efficiency of the novel benzothiadiazole-based photocatalyst is comparable with the state-of-art metal and non-metal catalysts. Furthermore, advanced photophysical studies including time-resolved photoluminescence and transient absorption spectroscopy offer a powerful support for photo-induced electron transfer from photocatalyst to the reactive substrates. Lastly, no photo-bleaching effect is observed, demonstrating the high stability and recyclable of the designed organic photocatalyst. (Figure presented.).
Promotion of Appel-type reactions by N-heterocyclic carbenes
Hussein, Mohanad A.,Nguyen, Thanh Vinh
supporting information, p. 7962 - 7965 (2019/07/12)
N-Heterocyclic carbenes (NHCs) have been extensively used as a versatile class of catalysts and ligands in organocatalytic and organometallic chemistry. However, there are only a small number of synthetic applications where they act as reagents. Here we demonstrate that NHCs can be used as stoichiometric redox reagents for Appel-type halogenation reactions of alcohols. This new reactivity reveals a fresh and interesting aspect and enriches the chemistry of NHCs in an underexplored area. The potential of performing this chemical transformation at the catalytic level using an NHC-oxide derivative is also investigated.
Method for reducing residues of N-ethyl-3-phenylpropylamine in alverine
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Paragraph 0055; 0056, (2018/11/03)
The invention relates to a method for reducing residues of N-ethyl-3-phenylpropylamine in alverine, and belongs to an impurity removal method of compounds. The method comprises the following steps: dissolving an intermediate alverine crude product containing impurity N-ethyl-3-phenylpropylamine into a water-insoluble organic solvent, extracting an organic layer by using an aqueous solution with appropriate pH and discarding a water layer; drying and filtering the organic layer, decompressing and evaporating the solvent to dryness. According to the method disclosed by the invention, a clear, simple and reliable solution to the residues of the N-ethyl-3-phenylpropylamine in the intermediate alverine is provided for the first time, so that the subsequently produced crude drug citric acid alverine has higher quality and the residue amount does not exceed 0.15 percent. The method has the advantages of simplicity, feasibility, low cost, few wastes and suitability for industrial popularization.
Purifying method of N-ethyl-3-phenylpropylamine
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Paragraph 0094-0096, (2018/12/13)
The invention relates to a purifying method of N-ethyl-3-phenylpropylamine, and belongs to purifying method of compounds. A N-ethyl-3-phenylpropylamine sample with the lower purity is dissolved in a water insoluble organic solvent, the organic phase is extracted for 1-5 times by a water solution with the appropriate pH value, the aqueous phase is combined, alkali or an alkaline solution is added,the pH value is conditioned, the aqueous phase is extracted by the water insoluble organic solvent, the organic phase is combined, drying and filtration are conducted, and the solvent is dried out through decompression. The purifying method has the advantages that the purifying effect is good, the result is stable and reliable, thus the higher and higher quality requirement of the pharmacy industry for the midbody can be better satisfied, and the yield is high and can be as high as 80% or above. Production and operation are safer and more convenient, and the purifying method is suitable for large-scale production.
ANTI-FUNGAL TREATMENT
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Paragraph 00117, (2018/03/25)
Provided are compounds, methods, and pharmaceutical compositions useful for treatment of fungal infections, e.g., aspergillosis, candidiasis, cryptococcosis, histoplasmosis, and the like. For example, the pharmaceutical composition may include a pharmaceutically acceptable carrier or excipient, and a compound represented by Ar— C(=NR1)NR2— A---X— Y— Het2 and pharmaceutically acceptable salts thereof. Ar may be an optionally substituted aryl or nitrogen- containing heteroaryl. R1 and R2 may independently be H, optionally substituted C1-C6 aikyi, or optionally substituted C3-C6 cyeloalkyi. A may be a bond or an optionally substituted linking moiety comprising 1, 2, or 3 rings. Each ring in the optionally substituted linking moiety may independently be one of: aryl, cyeloalkyi, heterocycloalkyl, and heteroaryl. X may be O, S, amide, or a bond. Y may be optionally substituted C1-C10 alkyi or optionally substituted C2-C10 alkenyl. Het2 may be an optionally substituted five-membered nitrogen-containing heteroaromatic ring comprising 1, 2, or 3 ring heteroatoms.
