- Synthesis process of 2-amino-3,5-dinitrobenzonitrile
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The invention provides a synthesis process of 2-amino-3,5-dinitrobenzonitrile. The process comprises the following steps that S1, chlorobenzonitrile and sodium methoxide are dissolved in a specific solvent, a reaction is carried out in an autoclave, after the reaction is completed, the temperature is reduced to the room temperature, an acid is used for neutralizing the mixture to be neutral, and asolvent and a first intermediate 2-methoxybenzonitrile are separated from a reaction filter liquor through rectification; S2, the first intermediate 2-methoxybenzonitrile is dissolved in the solventfor a nitration reaction, the reaction endpoint is monitored through HPLC, after the reaction is completed, elutriation operation is carried out, filtration is carried out to obtain a second intermediate 2-methoxy-3,5-dinitrobenzonitrile, and a solvent and remaining 2-methoxy-3,5-dinitrobenzonitrile are separated from the filter liquor through steam distillation; S3, the second intermediate 2-methoxy-3,5-dinitrobenzonitrile is dispersed in an ammoniation solvent, the mixture is transferred into the autoclave, a certain amount of liquid ammonia is introduced for an ammoniation reaction, and after the reaction is completed, filtration is carried out to obtain the product 2-amino-3,5-dinitrobenzonitrile.
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- Electrochemically promoted nucleophilic aromatic substitution in room temperature ionic liquids - An environmentally benign way to functionalize nitroaromatic compounds
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The current manuscript shows the electrochemical studies performed to rationalize the mechanism and develop new green synthetic routes for the synthesis of substituted nitroaromatics based on the advantages of the electrochemical approach to the nucleophilic aromatic substitution reaction (such as (a) low cost and ready availability of reagents, (b) atom economy, (c) high yields, approaching 100%) and the use of Room Temperature Ionic Liquids (RTILs) as green alternative solvents to organic aprotic solvents. Four of the most popular RTILs (1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM]BF 4), 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM]PF 6), 1-butyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)-imide ([BMIM]TFSI) and 1-butyl-3-methylimidazolium acetate ([BMIM]AcO) have been chosen since they have different properties in terms of solvation effects that can increase the regioselectivity of the reaction. The nucleophiles used to study the feasibility and viability of the reaction were the classical hydride, methoxide, ketones, cyanides and amines, whereas the nitroarenes selected were 4-nitrotoluene, 1,3-dinitrobenzene, 2,4-dinitroaniline, 1,3,5-trinitrobenzene, 1,3-dinitronaphthalene, 1-chloro-2,4,6-trinitrobenzene and 2,4,6- trinitroanisole. The electrocatalysis and regioselectivity effects of using RTILs are also investigated. The article concludes by analyzing the economic cost of performing this electrosynthesis in RTILs and organic solvent electrolyte systems, which contain 0.1 M of supporting electrolyte.
- Cruz, Hugo,Gallardo, Iluminada,Guirado, Gonzalo
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experimental part
p. 2531 - 2542
(2011/10/19)
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- Direct methoxylation of nitroarenes and nitroazaarenes with alkaline methoxides via nucleophilic displacement of an aromatic hydrogen atom
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Treatment of 1,3-dinitrobenzene and 5-substituted derivatives with excess potassium or sodium methoxide in 1,3-dimethylimidazolidin-2-one (DMI) at room temperature results in the displacement of an aromatic hydrogen at the 4-position by methoxide, affording 2,4-dinitroanisole and its 6-substituted derivatives, respectively, in low to moderate yield. In contrast, an equimolar reaction under similar conditions leads to the replacement of the nitro group in preference to the ring hydrogen. The reaction does not take place with lithium methoxide as a base. Mono- and dinitronaphthalenes and nitroquinolines undergo similar displacement of a hydrogen atom at the position ortho or para to the nitro group, giving the corresponding methoxy derivatives in moderate yield. A slow addition of the nitro compound to a large excess of potassium methoxide under an oxygen atmosphere has been found to enhance the conversion and improve the product yield. On the basis of the product distribution as well as the kinetic isotope effect kH/kD = 2.1, direct displacement of a ring hydrogen atom by methoxide ion has been interpreted in terms of the rate-determining release of an ipso-hydrogen atom as a proton from the initially formed Meisenheimer adduct.
- Kawakami, Takehiko,Suzuki, Hitomi
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p. 1259 - 1264
(2007/10/03)
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- Competition between Methoxide Attack at Ring-Carbon and at the Cyano-Group of Cyanonitroanisoles. The Effects of Cations.
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Reaction of methoxide ions with the isomeric cyanodinitroanisoles results in competition between attack at ring-carbon and at the cyano-group.Kinetic and equilibrium data are reported for reaction of 4-cyano-2,6-dinitroanisole where rapid formation of the 1,1-dimethoxy adduct is followed by slower equilibration with the imido-ester solvate.The 1,1-dimethoxy adduct is strongly stabilised by association with cations; values of the association constants decrease in the order of cations, Ba(2+) > Ca(2+) > K(+) > Na(+) > Li(+).
- Castilho, Paula C. M. F.,Crampton, Michael R.,Yarwood, Jack
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p. 2801 - 2815
(2007/10/02)
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