- Highly selective catalytic nitration of 1-nitronaphthalene with NO2 to 1,5-dinitronaphthalene over solid superacid SO42?/ZrO2 promoted by molecular oxygen and acetic anhydride under mild conditions
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A simple and efficient method for liquid-phase catalytic nitration of 1-nitronaphthalene with NO2 to 1,5-dinitronaphthalene under mild conditions has been developed. The results indicated that the sulfated zirconia (SO42?/ZrO2) as solid superacid catalyst exhibits superior catalytic performance with dioxygen and acetic anhydride. 93.8% conversion of 1-nitronaphthalene and 52.8% 1,5-dinitronaphthalene selectivity were achieved. Furthermore, the physicochemical properties of SO42?/ZrO2 were determined by XRD, Py-FT-IR, BET, FT-IR, Raman spectroscopy and ICP-OES technologies. The possible nitration reaction mechanism over SO42?/ZrO2 catalyst was proposed. The present work provides an easy-to-implement, mild and eco-friendly approach for the efficient preparation of valuable 1,5-dinitronaphthalene, which has extensive industrial application prospects.
- Yan, Jiaqi,Ni, Wenjin,You, Kuiyi,Duan, Ting,Deng, Renjie,Chen, Yi,Zhao, Fangfang,Liu, Pingle,Luo, He’an
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p. 3569 - 3582
(2021/06/14)
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- One-scale basicities of diaminobenzenes and diaminonaphthalenes: from aniline to proton sponge
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Basicity constants, pKa, for a wide range of mono-protonated diaminobenzenes and diaminonaphthalenes, including dimethylamino derivatives were for the first time uniformly measured in 20% aqueous ethanol (29 compounds) and 80% aqueous dioxane (39 compounds) spanning from aniline to 1,8-bis(dimethylamino)naphthalene (‘proton sponge’). The dioxane system proved to be more versatile and because of better solubility of N-alkylated polyaminoarenes allowed to add to the same scale some superbasic bis(dialkylamino)-, tetrakis(dialkylamino)-, and hexakis(dialkylamino)naphthalenes, thus extending the scale for almost 10 pKa units, revealing possible limits of basicity changes in aromatic amines. The basicity of reference bases, pyridine and triethylamine, was also measured in these solvent systems. A group of N-alkylated compounds was found to be less basic in aqueous dioxane when compared with their NH2-analogs. This anomaly was not observed in aqueous ethanol. Other basicity trends and correlations between different basicity scales were also discussed. Copyright
- Vlasenko, Marina P.,Ozeryanskii, Valery A.
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supporting information
(2017/01/17)
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- A simple approach for preparation of dinitronaphthalene compounds from the nitration reaction of 1-nitronaphthalene with NO2 as nitration reagent
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A simple method for the preparation of dinitronaphthalene from the nitration reaction of 1-nitronaphthalene with NO2 as nitration reagent under the mild conditions has been successfully developed in this work. The results indicated that Ni(CH3COO)2·4H2O catalyst shows better catalytic performances, and the conversion of 1-nitronaphthalene is 33.10 % with 34.10, 23.56, 19.30, and 3.56 % of the selectivity to 1,5-DNN, 1,3-DNN, 1,4-DNN, and 1,8-DNN, respectively, under the optimal reaction conditions. This is a mild, environmentally benign, and economical method for the preparation of dinitronaphthalene.
- You, Kuiyi,Zhou, Zhongcang,Jian, Jian,Deng, Renjie,Liu, Pingle,Ai, Qiuhong,Luo, He'An
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p. 8307 - 8315
(2015/03/05)
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- Aromatic nitration in liquid Ag0.51K0.42Na 0.07NO3
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(Figure Presented) Aromatic molecules have a strong affinity for silver(I) and dissolve to a limited extent in Ag0.51K0.42Na 0.07NO3, a low-melting eutectic mixture of silver, potassium, and sodium nitrates. Aromatic nitration in this inorganic ionic liquid leads to products which arise from nonelectrophilic substitution pathways.
- Mascal, Mark,Yin, Lunxiang,Edwards, Ross,Jarosh, Michael
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p. 6148 - 6151
(2008/12/22)
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- Ozone-mediated nitration of naphthalene and some methyl derivatives with nitrogen dioxide. Remarkable enhancement of the 1-nitro/2-nitro isomer ratio and mechanistic implications
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Naphthalene, 1- and 2-methylnaphthalenes were smoothly nitrated with nitrogen dioxide at low temperatures in the presence of ozone to afford the corresponding nitro derivatives in high yields.For naphthalene, the 1-nitro/2-nitro isomer ratios were remarkably high, mostly ranging from 35 to 70. 1,4-Dimethylnaphthalene suffered extensive side-chain substitution under similar conditions.The enhanced regioselectivity as compared with conventional nitrations has been interpreted in terms of the electron transfer mechanism involving the nitrogen trioxide as the initial electrophile.
- Suzzuki, Hitomi,Mori, Tadashi
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p. 677 - 684
(2007/10/03)
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- Free-Radical Nitration of Naphthalene with Nitrogen Dioxide in CCl4 and Implications for Environmental Nitrations
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The nitration of naphthalene (NAP) with nitrogen dioxide in carbon tetrachloride occurs via a free-radical mechanism, involving metastable adducts of NAP and 2-4 mol of NO2 per mole of NAP.This free radical nitration system is characterized by (1) low 1-nitronaphthalene/2-nitronaphthalene (1NNAP/2NNAP) ratios and (2) the formation of unexpected dinitronaphthalene isomers, 1,3-dinitronaphthalene (1,3-diNNAP) and 2,3-dinitronaphthalene (2,3-diNNAP), at low conversions.There is strong steric repulsion of the nitro groups in the ORTEP drawing of the 2,3-diNNAP crystal structure (Figure 1).The elimination of HNO2 from a postulated tetranitrotetrahydronaphthalene intermediate is, therefore, suggested to occur under kinetic control.The nitro substituent has a small activating effect toward free-radical nitration in 2NNAP while it has no noticeable effect in 1NNAP, contrasting sharply with conventional electrophilic nitration where the nitro substituent has a very strong deactivating effect.An ionic electrophilic reaction mechanism predominates in solvents of higher polarity and is subject to efficient acid catalysis.We suggest our conditions of free-radical nitration model the gas-phase atmospheric free-radical nitration of NAP, where low 1NNAP/2NNAP ratios and 1,3-diNNAP also have been reported.Thus, free-radical reactions might be responsible for producing some of the nitro-containing polycyclic aromatic hydrocarbon mutagens that are found in the environment.
- Squadrito, Giuseppe L.,Fronczek, Frank R.,Church, Daniel F.,Pryor, William A.
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p. 548 - 552
(2007/10/02)
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