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Preparation of sub-microspherical Fe3O4@PDA-Pd NPs catalyst and application in catalytic hydroreduction reaction of halogenated aromatic nitro compounds to prepare halogenated aromatic amines

Preparation of sub-microspherical Fe3O4@PDA-Pd NPs catalyst and application in catalytic... Background: The side reactions of dehalogenation or C–N coupling tend to occur when halogenated aromatic amines are prepared by catalytic hydrogenation reduction of halogenated aromatic nitro compounds. In this paper, we prepared the sub-microspherical Fe O @PDA-Pd NPs catalyst apply it efficiently in the hydrogenation reduction 3 4 of halogenated aromatic nitro compounds to prepare the halogenated aromatic amines under atmospheric pressure. The catalyst shows a high selectivity of greater than 96% and can effectively inhibit the occurrence of the side reac- tions of dehalogenation and C–N coupling. Results: The optimum condition of the hydroreduction reaction is when tetrahydrofuran is used as solvent and the reaction happens at 50 °C for 5 h. The selectivity of the chlorinated aromatic amine and the fluorinated aromatic amine products exceed 99% and the yield exceeds 90%. Only a small amount of dehalogenated products and C–N coupling by-products were produced in the brominated aromatic compound and the iodinated aromatic compound. Conclusion: We developed a promising method for preparing the superparamagnetic and strongly magnetic Fe O @PDA core–shell sub-microsphere-supported nano-palladium catalyst for catalyzing the hydrogenation reduc- 3 4 tion of halogenated aromatic nitro compounds. The halogenated aromatic amines were efficiently and highly selec- tively prepared under atmospheric pressure, with the side reactions of dehalogenation and C–N coupling effectively inhabited simultaneously. Keywords: Catalytic hydrogenation, Dopamine, Fe O sub-microsphere nano-palladium, Halogenated aromatic, 3 4 Nano-palladium Introduction compounds. And in industry, there are several major Aniline compounds are important intermediates in ways to prepare the aniline compounds such as cata- organic synthesis and are widely used in medicines [1], lytic hydrogenation, hydrazine hydrate, active metal and additives [2], flame retardants [3], dyes and surfactants sulfide reduction. In comparison, the latter three were [4]. Reducing aromatic nitro compounds is the most gradually eliminated due to their toxicity, harmfulness important and simplest method for preparing the aniline and sewage pollution, and only the catalytic hydrogena- tion gradually prevail due to its clean reaction process [5–8]. Halogenated aromatic amines are important clas- *Correspondence: xiaaibao@zjut.edu.cn sifications of aniline compounds especially in pesticides, Zhejiang Key Laboratory of Green Pesticides and Cleaner Production Technology, Catalytic Hydrogenation Research Center, Zhejiang such as, p-chloroaniline used to prepare Monolinuron University of Technology, Hangzhou 310014, China [9], m-chloroaniline used to prepare Barban [10], and Full list of author information is available at the end of the article © The Author(s) 2019. This article is distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The Creative Commons Public Domain Dedication waiver (http://creativecommons.org/ publicdomain/zero/1.0/) applies to the data made available in this article, unless otherwise stated. Guo et al. BMC Chemistry (2019) 13:130 Page 2 of 7 3-chloro-4-methylaniline used to prepare Chlorotoluron the halogenated aromatic amine (Fig.  1). The conversion [11]. However, when the halogenated aromatic amines and selectivity of the reaction are both very high, and the are prepared by catalytic hydrogenation reduction of occurrence of the dehalogenation and C–N coupling side halogenated aromatic nitro compounds, the side reac- reactions are effectively suppressed at the same time. tions of dehalogenation [12] or C–N coupling [13] are easy to occur. Therefore, using improved highly efficient Results and discussion and selective catalytic hydrogenation to prepare the hal- The prepared Fe O @PDA-Pd NPs catalyst was charac- 3 4 ogenated aromatic amines becomes a key technique to terized by the transmission electron microscopy (TEM) prevent the dehalogenation and C–N coupling side reac- observation and magnetic testing. The TEM image tions. Recently, some useful results had been achieved by (Fig.  2) shows that the Fe O @PDA-Pd NPs catalyst pre- 3 4 using gold complexes, palladium complexes and platinum sents core–shell micro structures which are centered complexes as catalysts in this reduction reaction [14–17]. on the Fe O sub-microspheres. The dopamine layer is 3 4 Palladium is used to catalyze the hydrogenation of uniformly coated on the surface of the Fe O sub-micro- 3 4 many unsaturated compounds such as olefins [18], spheres for form the shell-like dopamine with thickness alkynes [19], nitro compounds [20], carbonyl compounds distributed in the range of 80–90  nm. The nano palla - [21] and nitriles [22], as well as to catalyze the dehalo- dium particles, with diameters ranging from 7 to 12  nm genation, debenzylation, Suzuki–Miyaura coupling, and average diameter of 9.2  nm, are dispersed on the Heck and Sonogashira reactions [23–25]. It is known dopamine shell. that nano-palladium particles (Pd NPs) supported on Figure  3 shows the magnetization curves of the F e O , 3 4 the Fe O particles can improve both the catalytic per- Fe O @PDA and the Fe O @PDA-Pd NPs sub-micro- 3 4 3 4 3 4 formance of palladium and the selectivity of the cata- spheres under room temperature (300 K). It can be seen lytic reactions; also, the separation and recycling of the that the maximum saturation magnetic field strengths catalyst is very simple [26–31]. In this paper, we prepared of the three kinds of sub-microspheres are 75, 48 and the sub-micro-spherical Fe O @PDA-Pd NPs complex 45 emu/g, respectively, and their coercivity is 0. The pres - 3 4 as a high performance catalyst. The preparation pro - ence of the PDA layer reduced the maximum satura- cedures include: first, the surface of the Fe O particles tion value of the magnetic field strength of the Fe O @ 3 4 3 4 are covered by polydopamine (PDA) layer through the PDA-Pd NPs sub-microspheres, but the F e O @PDA-Pd 3 4 dopamine autoagglutination to form the Fe O @PDA NPs sub-microspheres still have superparamagnetic and 3 4 core–shell structures. Then the amino group of the sub- strongly magnetic properties. Therefore, the Fe O @ 3 4 microspheres are combined with proton through pro- PDA-Pd NPs sub-microspheres can be easily dispersed 2− tonation with positive electricity. The PdCl ions are into and then separated from the reaction system. then dispersed on the Fe O @PDA core–shell surface by We then used the prepared Fe O @PDA-Pd NPs sub- 3 4 3 4 charge attraction. And the nano-palladium supported on microspheres as catalyst for the halogenated aromatic the sub-microspheres is further prepared by reduction amines preparation through hydrogenation of the halo- to form the Fe O @PDA-Pd NPs complex. This complex genated aromatic nitro compounds. In order to inves- 3 4 catalyst is used to catalyze the hydrogenation reduction tigate the exact role which the Fe O @PDA-Pd NPs 3 4 of a halogenated aromatic nitro compound to produce played in the catalytic hydrogenation reduction of the Fig. 1 Preparation of F e O @PDA-Pd NPs and its catalysis in hydrogenation reaction of halogenated aromatic nitro compounds 3 4 Guo et al. BMC Chemistry (2019) 13:130 Page 3 of 7 9.2 1.7 nm 6 789 10 11 12 13 Pd particle size /nm Fig. 2 TEM images of Fe O @PDA@Pd and Pd particle size 3 4 to form about 4% of N-ethyl-p-chloroaniline, the selec- Fe O 3 4 tivity of p-chloroaniline (I) is lowered. The N-ethyl- p-chloroaniline was determined by GC–MS. Then when Fe O @PDA 3 4 tetrahydrofuran is used as the reaction solvent (Table  1, Fe O @PDA-Pd NPs entry 2), the reaction rate becomes slow; but the selec- 3 4 tivity to p-chloroaniline (I) becomes higher, and the by- product of dechlorination (II) becomes rare. The reaction rate increases with increase in the reaction temperature, -20 and the conversion rate of p-nitrochlorobenzene and the -40 selectivity to p-chloroaniline (I) are both greater than -60 99% at 50 °C (Table 1, entry 3). The selectivity of p-chlo - -80 roaniline (I) with Fe O @PDA-Pd NPs as catalyst is much 3 4 higher than that with Pd/C as catalyst (Table  1, entry 4). -10000 -50000 5000 10000 Under the same conditions, about 13% of the products Field(oe) dechlorinated with the latter as catalyst. Therefore, the Fig. 3 Magnetization curves of Fe O, Fe O @PDA and Fe O @ 3 4 3 4 3 4 PDA-Pd NPs optimum condition of the hydroreduction reaction is to use tetrahydrofuran as solvent and keep the reaction at 50 °C for a reaction time of 5 h (Table 1, entry 3). The extent of the reaction under the optimal reac - halogenated aromatic nitro compounds and its effect tion conditions (Table  1, entry 3) were examined and on inhibiting the side reaction of dehalogenation, the the results are shown in Table  2. It can be seen that the reaction temperature, solvent and reaction time were Fe O @PDA-Pd NPs catalyst has high selectivity and 3 4 optimized under atmospheric pressure using p-nitrochlo- high yield for the hydroreduction of halogenated aro- robenzene as the substrate (Table  1). The results show matic nitro compounds in preparing the halogenated that when ethanol is used as the solvent, the hydrogena- aromatic amines. The halogenated aromatic amine has tion reaction rate is the fastest (Table 1, entry 1); but due a selectivity of more than 96% and a yield of over 84%. to the alkylation reaction of ethanol and p-chloroaniline In particular, the selectivity of the chlorinated aromatic M(emu/g) frequency /% Guo et al. BMC Chemistry (2019) 13:130 Page 4 of 7 Table 1 Fe O @PDA-Pd NPs-catalyzed hydroreduction reaction of p-nitrochlorobenzene 3 4 Entry Catalyst Solvent Temperature, time Conversion /% Selectivity (I) /% 1 Fe O @PDA-Pd NPs EtOH 30 °C, 4 h >99 95 3 4 2 Fe O @PDA-Pd NPs THF 30 °C, 4 h 81 98 3 4 3 Fe O @PDA-Pd NPs THF 50 °C, 5 h > 99 > 99 3 4 4 Pd/C THF 50 °C, 2.5 h > 99 84 a b c GC;  about 4% N-ethyl-p-chloroaniline in the product;  about 13% aniline in the product amine and the fluorinated aromatic amine exceeds 99%, deionized water and 25  mL * 3 ethanol, and the washed and the yield exceeds 90%. There is no C–N coupling solid was used directly in the next step. reaction in the fluorinated aromatic compounds hap - pened (Table 2, entry 8, 9, 12), and the dechlorination of General method for the preparation of the  Fe O @PDA‑Pd 3 4 chlorinated aromatic compounds (Table 2, entry 1–5, 13) NPs is rare. Only a small amount of dehalogenated products The Fe O @PDA was taken and placed under ultra- 3 4 and C–N coupling by-products was produced in the bro- sonic washing using 25  mL of deionized water, 0.1  N of minated aromatic compound (Table  2, entry 7) and the 25  mL hydrochloric acid, 25  mL of deionized water, and iodinated aromatic compound (Table 2, entry 6). 25  mL of ethanol. Approximately 40  mL of ethanol and 4  mL of deionized water were added into the mixture, Experimental which was then mechanically stirred at 10  °C. Subse- General quently, about 0.3  mL N aPdCl aqueous solution (palla- All reagents used in the experiment are commercially dium content 2.5 mg) was slowly added into the mixture available without further purification. The transmission dropwise, and then the mixture was continuously stirred electron microscopy (TEM) image was obtained on a for another 3 h. A solution containing 60 mg of ascorbic JEOL JEM-2100F field transmission electron microscope. acid and 6 mL of deionized water was slowly added into The magnetic property information of the Fe O @PDA- the mixture in 20 min. Then, the reaction was continued 3 4 Pd NPs was obtained on a Quantum Design DynaCool-9 for another 2  h. The solid and liquid were separated by vibrating sample magnetometer. And the H NMR and a magnet. The reaction product was placed under ultra - C NMR spectra were recorded on a Bruker Avance sonic washing using 25 mL of ethanol, 25 mL * 3 of deion- 400 MHz spectrometer using tetramethylsilane (TMS) as ized water and 25 mL * 3 of ethanol. The solid was stored internal standards. in 25 mL of ethanol and sealed with nitrogen (about 0.1 g The Fe O particles were prepared according to the after drying). 3 4 method specified in Ref. [32]. General procedure for the hydrogenation of halogenated General procedure for the preparation of the  Fe O @PDA aromatic nitro compounds to prepare halogenated 3 4 About 0.15  g of strong aqueous ammonia was dissolved aromatic amines 2a–m in 50  mL of deionized water. Then, 0.1  g of Fe O and Approximately 0.1  g of Fe O @PDA-Pd NPs catalyst 3 4 3 4 0.16  g of dopamine hydrochloride were added into the was used. The aforementioned solid and liquor were solution, and the mixture was placed under uniform separated using a magnet and placed under ultrasonic ultrasonic dispersion and mechanically stirred at 40  °C washing using 10  mL * 3 THF. Then, 10  mL THF and for 24  h. After the reaction is completed, the solid and 4.3  mmol halogenated aromatic nitro compounds were the liquid are separated by a magnet. The solid product added. Nitrogen and hydrogen were introduced alter- was then placed under ultrasonic washing using 25 mL * 3 natively. The magnetic stirring was carried out at 50  °C. Guo et al. BMC Chemistry (2019) 13:130 Page 5 of 7 Table 2 Fe O @PDA-Pd NPs-catalyzed hydrogenation reaction of halogenated aromatic nitro compounds 3 4 EntryReactant Target product Selectivity /% Yield/% 1 99 91 2 99 93 3 99 95 4 99 90 5 99 88 6 95 87 7 96 87 8 99 95 9 99 96 10 96 90 11 97 84 12 99 92 13 99 95 7 h Guo et al. BMC Chemistry (2019) 13:130 Page 6 of 7 Hydrogen (hydrogen balloon) was introduced into the 1H), 6.60–6.40 (m, 1H), 3.59 (s, 2H). C NMR (101 MHz, reaction at atmospheric pressure for 4–6  h. At the end CDCl ) δ 152.79 (s), 150.42 (s), 143.16 (d), 120.94 (d), of the reaction, the catalyst was separated and recovered 116.75 (m), 114.28 (d). by a magnet, and the product was separated by column chromatography (n-hexane/dichloromethane) after the 4‑Bromo‑2‑chloroaniline (2j) H NMR (400  MHz, reaction liquid was concentrated. CDCl ) δ 7.37 (d, J = 2.2 Hz, 1H), 7.15 (dd, J = 8.5, 2.2 Hz, 1H), 6.69–6.57 (m, 2H), 4.04 (s, 2H). C NMR (101 MHz, 2‑Chloroaniline (2a) H NMR (400 MHz, C DCl ) δ 7.23 CDCl ) δ 142.11 (s), 131.63 (s), 130.54 (s), 119.93 (s), 3 3 (dd, J = 8.0, 1.1 Hz, 1H), 7.05 (td, J = 8.0, 1.3 Hz, 1H), 6.74 116.87 (s), 109.36 (s). (dt, J = 8.8, 4.4 Hz, 1H), 6.68 (td, J = 7.8, 1.4 Hz, 1H), 4.02 (s, 2H). C NMR (101 MHz, CDCl ) δ 142.92 (s), 129.44 2‑Chloro‑4‑iodoaniline (2k) H NMR (400  MHz, (s), 127.66 (s), 119.31 (s), 119.05 (s), 115.90 (s). CDCl ) δ 7.53 (d, J = 2.0 Hz, 1H), 7.31 (dd, J = 8.4, 2.0 Hz, 1H), 6.52 (d, J = 8.4  Hz, 1H), 4.05 (s, 2H). C NMR 3‑Chloroaniline (2b) H NMR (400 MHz, C DCl ) δ 7.05 (101 MHz, CDCl ) δ 142.73 (s), 137.18 (s), 136.33 (s), 3 3 (dd, J = 10.4, 5.6 Hz, 1H), 6.71 (ddd, J = 7.9, 1.8, 0.7 Hz, 1H), 120.23 (s), 117.43 (s), 77.97 (s). 6.65 (t, J = 2.1 Hz, 1H), 6.53 (ddd, J = 8.1, 2.2, 0.6 Hz, 1H), 13 1 4.17–3.03 (s, 2H). C NMR (101  MHz, CDCl ) δ 147.66 2,4‑Difluoroaniline (2l) H NMR (400  MHz, CDCl ) δ (s), 134.85 (s), 130.36 (s), 118.48 (s), 114.95 (s), 113.23 (s). 6.82–6.73 (m, 1H), 6.73–6.64 (m, 2H), 3.46 (s, 2H). C NMR (101 MHz, CDCl ) δ 156.49 (d), 154.12 (d), 152.22 (d), 4‑Chloroaniline (2c) H NMR (400  MHz, C DCl ) δ 149.82 (d), 130.68 (dd), 116.88 (dd), 110.88 (dd), 103.79 (dd). 7.09 (d, J = 8.7  Hz, 2H), 6.59 (d, J = 8.7  Hz, 2H), 3.56 (s, 2H). C NMR (101 MHz, CDCl ) δ 144.99 (s), 129.14 (s), 3,4‑Dichloroaniline (2m) H NMR (400 MHz, CDCl ) δ 3 3 123.13 (s), 116.27 (s). 7.17 (d, J = 8.6 Hz, 1H), 6.75 (d, J = 2.7 Hz, 1H), 6.50 (dd, J = 8.6, 2.7  Hz, 1H), 3.72 (s, 2H). C NMR (101  MHz, 5‑Chloro‑2‑methylaniline (2d) H NMR (400  MHz, CDCl ) δ 146.02 (s), 132.67 (s), 130.73 (s), 121.08 (s), CDCl ) δ 6.94 (d, J = 8.4 Hz, 1H), 6.65 (d, J = 5.5 Hz, 2H), 116.41 (s), 114.62 (s). 3.65 (s, 2H), 2.10 (s, 3H). C NMR (101  MHz, C DCl ) δ 145.72 (s), 132.06 (s), 131.34 (s), 120.59 (s), 118.23 (s), 114.48 (s), 16.87 (s). Conclusions We developed a method for preparing superparamag- 6‑Chloro‑2‑methylaniline (2e) H NMR (400  MHz, netic and strongly magnetic Fe O @PDA core–shell 3 4 CDCl ) δ 7.12 (d, J = 8.0 Hz, 1H), 6.94 (dd, J = 7.5, 0.5 Hz, sub-microsphere-supported nano-palladium catalyst, 1H), 6.61 (t, J = 7.7 Hz, 1H), 3.97 (s, 2H), 2.18 (s, 3H). C i.e. Fe O @PDA-Pd NPs. The catalyst was character - 3 4 NMR (101  MHz, CDCl ) δ 141.18 (s), 128.72 (s), 127.07 ized and successfully catalyzed the hydrogenation (s), 123.56 (s), 119.15 (s), 118.32 (s), 17.98 (s). reduction of halogenated aromatic nitro compounds. The halogenated aromatic amines were efficiently and selectively prepared under atmospheric pressure, which 4‑Iodoaniline (2f ) H NMR (400  MHz, CDCl ) δ 7.40 could effectively inhibit the occurrence of the side reac - (d, J = 8.7  Hz, 2H), 6.46 (d, J = 8.7  Hz, 2H), 3.97–3.33 (s, tions of dehalogenation and C–N coupling. 2H). C NMR (101 MHz, CDCl ) δ 146.08 (s), 137.92 (s), 117.32 (s), 79.41 (s). Abbreviations 4‑Bromoaniline (2  g) H NMR (400  MHz, C DCl ) δ PDA: polydopamine; Pd NPs: nano-palladium particles; THF: tetrahydrofuran; TEM: the transmission electron microscopy. 7.22 (d, J = 8.7  Hz, 2H), 6.56 (d, J = 8.7  Hz, 2H), 3.70 (s, 2H). C NMR (101 MHz, CDCl ) δ 145.50 (s), 131.99 (s), Acknowledgements 116.71 (s), 110.10 (s). This work was supported by Zhejiang University of Technology and Taizhou University. 4‑Fluoroaniline (2  h) H NMR (400  MHz, C DCl ) δ Authors’ contributions 6.95–6.78 (m, 2H), 6.72–6.50 (m, 2H), 3.48 (s, 2H). C HCG, HJJ and ZYX designed the research. HCG and RHZ performed the research. HCG and ABX analyzed the data. HJJ, RHZ, ABX and ZYX contributed NMR (101  MHz, CDCl ) δ 157.60 (s), 155.26 (s), 142.43 the reagent/material/analysis tools. HCG wrote the paper. All authors read and (d), 115.80 (m). approved the final manuscript. Funding 4‑Fluoro‑3‑chloroaniline (2i) H NMR (400  MHz, This work was supported by the Zhejiang Province Public Welfare Technology CDCl ) δ 6.91 (t, J = 8.8 Hz, 1H), 6.69 (dd, J = 6.1, 2.8 Hz, Research Program (LGG19B040001), Zhejiang Natural Science Foundation Guo et al. BMC Chemistry (2019) 13:130 Page 7 of 7 (LY18B020017), and Taizhou Science and Technology Project (1801gy21). All 17. Yan XL, Duan P, Zhang FW et al (2019) Stable single-atom platinum cata- funding bodies played no role in the design of the study and collection, analy- lyst trapped in carbon onion graphitic shells for improved chemoselec- sis, and interpretation of data and in writing the manuscript. tive hydrogenation of nitroarenes. 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Preparation of sub-microspherical Fe3O4@PDA-Pd NPs catalyst and application in catalytic hydroreduction reaction of halogenated aromatic nitro compounds to prepare halogenated aromatic amines

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Springer Journals
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Copyright © 2019 by The Author(s)
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Chemistry; Chemistry/Food Science, general
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10.1186/s13065-019-0649-9
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Abstract

Background: The side reactions of dehalogenation or C–N coupling tend to occur when halogenated aromatic amines are prepared by catalytic hydrogenation reduction of halogenated aromatic nitro compounds. In this paper, we prepared the sub-microspherical Fe O @PDA-Pd NPs catalyst apply it efficiently in the hydrogenation reduction 3 4 of halogenated aromatic nitro compounds to prepare the halogenated aromatic amines under atmospheric pressure. The catalyst shows a high selectivity of greater than 96% and can effectively inhibit the occurrence of the side reac- tions of dehalogenation and C–N coupling. Results: The optimum condition of the hydroreduction reaction is when tetrahydrofuran is used as solvent and the reaction happens at 50 °C for 5 h. The selectivity of the chlorinated aromatic amine and the fluorinated aromatic amine products exceed 99% and the yield exceeds 90%. Only a small amount of dehalogenated products and C–N coupling by-products were produced in the brominated aromatic compound and the iodinated aromatic compound. Conclusion: We developed a promising method for preparing the superparamagnetic and strongly magnetic Fe O @PDA core–shell sub-microsphere-supported nano-palladium catalyst for catalyzing the hydrogenation reduc- 3 4 tion of halogenated aromatic nitro compounds. The halogenated aromatic amines were efficiently and highly selec- tively prepared under atmospheric pressure, with the side reactions of dehalogenation and C–N coupling effectively inhabited simultaneously. Keywords: Catalytic hydrogenation, Dopamine, Fe O sub-microsphere nano-palladium, Halogenated aromatic, 3 4 Nano-palladium Introduction compounds. And in industry, there are several major Aniline compounds are important intermediates in ways to prepare the aniline compounds such as cata- organic synthesis and are widely used in medicines [1], lytic hydrogenation, hydrazine hydrate, active metal and additives [2], flame retardants [3], dyes and surfactants sulfide reduction. In comparison, the latter three were [4]. Reducing aromatic nitro compounds is the most gradually eliminated due to their toxicity, harmfulness important and simplest method for preparing the aniline and sewage pollution, and only the catalytic hydrogena- tion gradually prevail due to its clean reaction process [5–8]. Halogenated aromatic amines are important clas- *Correspondence: xiaaibao@zjut.edu.cn sifications of aniline compounds especially in pesticides, Zhejiang Key Laboratory of Green Pesticides and Cleaner Production Technology, Catalytic Hydrogenation Research Center, Zhejiang such as, p-chloroaniline used to prepare Monolinuron University of Technology, Hangzhou 310014, China [9], m-chloroaniline used to prepare Barban [10], and Full list of author information is available at the end of the article © The Author(s) 2019. This article is distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The Creative Commons Public Domain Dedication waiver (http://creativecommons.org/ publicdomain/zero/1.0/) applies to the data made available in this article, unless otherwise stated. Guo et al. BMC Chemistry (2019) 13:130 Page 2 of 7 3-chloro-4-methylaniline used to prepare Chlorotoluron the halogenated aromatic amine (Fig.  1). The conversion [11]. However, when the halogenated aromatic amines and selectivity of the reaction are both very high, and the are prepared by catalytic hydrogenation reduction of occurrence of the dehalogenation and C–N coupling side halogenated aromatic nitro compounds, the side reac- reactions are effectively suppressed at the same time. tions of dehalogenation [12] or C–N coupling [13] are easy to occur. Therefore, using improved highly efficient Results and discussion and selective catalytic hydrogenation to prepare the hal- The prepared Fe O @PDA-Pd NPs catalyst was charac- 3 4 ogenated aromatic amines becomes a key technique to terized by the transmission electron microscopy (TEM) prevent the dehalogenation and C–N coupling side reac- observation and magnetic testing. The TEM image tions. Recently, some useful results had been achieved by (Fig.  2) shows that the Fe O @PDA-Pd NPs catalyst pre- 3 4 using gold complexes, palladium complexes and platinum sents core–shell micro structures which are centered complexes as catalysts in this reduction reaction [14–17]. on the Fe O sub-microspheres. The dopamine layer is 3 4 Palladium is used to catalyze the hydrogenation of uniformly coated on the surface of the Fe O sub-micro- 3 4 many unsaturated compounds such as olefins [18], spheres for form the shell-like dopamine with thickness alkynes [19], nitro compounds [20], carbonyl compounds distributed in the range of 80–90  nm. The nano palla - [21] and nitriles [22], as well as to catalyze the dehalo- dium particles, with diameters ranging from 7 to 12  nm genation, debenzylation, Suzuki–Miyaura coupling, and average diameter of 9.2  nm, are dispersed on the Heck and Sonogashira reactions [23–25]. It is known dopamine shell. that nano-palladium particles (Pd NPs) supported on Figure  3 shows the magnetization curves of the F e O , 3 4 the Fe O particles can improve both the catalytic per- Fe O @PDA and the Fe O @PDA-Pd NPs sub-micro- 3 4 3 4 3 4 formance of palladium and the selectivity of the cata- spheres under room temperature (300 K). It can be seen lytic reactions; also, the separation and recycling of the that the maximum saturation magnetic field strengths catalyst is very simple [26–31]. In this paper, we prepared of the three kinds of sub-microspheres are 75, 48 and the sub-micro-spherical Fe O @PDA-Pd NPs complex 45 emu/g, respectively, and their coercivity is 0. The pres - 3 4 as a high performance catalyst. The preparation pro - ence of the PDA layer reduced the maximum satura- cedures include: first, the surface of the Fe O particles tion value of the magnetic field strength of the Fe O @ 3 4 3 4 are covered by polydopamine (PDA) layer through the PDA-Pd NPs sub-microspheres, but the F e O @PDA-Pd 3 4 dopamine autoagglutination to form the Fe O @PDA NPs sub-microspheres still have superparamagnetic and 3 4 core–shell structures. Then the amino group of the sub- strongly magnetic properties. Therefore, the Fe O @ 3 4 microspheres are combined with proton through pro- PDA-Pd NPs sub-microspheres can be easily dispersed 2− tonation with positive electricity. The PdCl ions are into and then separated from the reaction system. then dispersed on the Fe O @PDA core–shell surface by We then used the prepared Fe O @PDA-Pd NPs sub- 3 4 3 4 charge attraction. And the nano-palladium supported on microspheres as catalyst for the halogenated aromatic the sub-microspheres is further prepared by reduction amines preparation through hydrogenation of the halo- to form the Fe O @PDA-Pd NPs complex. This complex genated aromatic nitro compounds. In order to inves- 3 4 catalyst is used to catalyze the hydrogenation reduction tigate the exact role which the Fe O @PDA-Pd NPs 3 4 of a halogenated aromatic nitro compound to produce played in the catalytic hydrogenation reduction of the Fig. 1 Preparation of F e O @PDA-Pd NPs and its catalysis in hydrogenation reaction of halogenated aromatic nitro compounds 3 4 Guo et al. BMC Chemistry (2019) 13:130 Page 3 of 7 9.2 1.7 nm 6 789 10 11 12 13 Pd particle size /nm Fig. 2 TEM images of Fe O @PDA@Pd and Pd particle size 3 4 to form about 4% of N-ethyl-p-chloroaniline, the selec- Fe O 3 4 tivity of p-chloroaniline (I) is lowered. The N-ethyl- p-chloroaniline was determined by GC–MS. Then when Fe O @PDA 3 4 tetrahydrofuran is used as the reaction solvent (Table  1, Fe O @PDA-Pd NPs entry 2), the reaction rate becomes slow; but the selec- 3 4 tivity to p-chloroaniline (I) becomes higher, and the by- product of dechlorination (II) becomes rare. The reaction rate increases with increase in the reaction temperature, -20 and the conversion rate of p-nitrochlorobenzene and the -40 selectivity to p-chloroaniline (I) are both greater than -60 99% at 50 °C (Table 1, entry 3). The selectivity of p-chlo - -80 roaniline (I) with Fe O @PDA-Pd NPs as catalyst is much 3 4 higher than that with Pd/C as catalyst (Table  1, entry 4). -10000 -50000 5000 10000 Under the same conditions, about 13% of the products Field(oe) dechlorinated with the latter as catalyst. Therefore, the Fig. 3 Magnetization curves of Fe O, Fe O @PDA and Fe O @ 3 4 3 4 3 4 PDA-Pd NPs optimum condition of the hydroreduction reaction is to use tetrahydrofuran as solvent and keep the reaction at 50 °C for a reaction time of 5 h (Table 1, entry 3). The extent of the reaction under the optimal reac - halogenated aromatic nitro compounds and its effect tion conditions (Table  1, entry 3) were examined and on inhibiting the side reaction of dehalogenation, the the results are shown in Table  2. It can be seen that the reaction temperature, solvent and reaction time were Fe O @PDA-Pd NPs catalyst has high selectivity and 3 4 optimized under atmospheric pressure using p-nitrochlo- high yield for the hydroreduction of halogenated aro- robenzene as the substrate (Table  1). The results show matic nitro compounds in preparing the halogenated that when ethanol is used as the solvent, the hydrogena- aromatic amines. The halogenated aromatic amine has tion reaction rate is the fastest (Table 1, entry 1); but due a selectivity of more than 96% and a yield of over 84%. to the alkylation reaction of ethanol and p-chloroaniline In particular, the selectivity of the chlorinated aromatic M(emu/g) frequency /% Guo et al. BMC Chemistry (2019) 13:130 Page 4 of 7 Table 1 Fe O @PDA-Pd NPs-catalyzed hydroreduction reaction of p-nitrochlorobenzene 3 4 Entry Catalyst Solvent Temperature, time Conversion /% Selectivity (I) /% 1 Fe O @PDA-Pd NPs EtOH 30 °C, 4 h >99 95 3 4 2 Fe O @PDA-Pd NPs THF 30 °C, 4 h 81 98 3 4 3 Fe O @PDA-Pd NPs THF 50 °C, 5 h > 99 > 99 3 4 4 Pd/C THF 50 °C, 2.5 h > 99 84 a b c GC;  about 4% N-ethyl-p-chloroaniline in the product;  about 13% aniline in the product amine and the fluorinated aromatic amine exceeds 99%, deionized water and 25  mL * 3 ethanol, and the washed and the yield exceeds 90%. There is no C–N coupling solid was used directly in the next step. reaction in the fluorinated aromatic compounds hap - pened (Table 2, entry 8, 9, 12), and the dechlorination of General method for the preparation of the  Fe O @PDA‑Pd 3 4 chlorinated aromatic compounds (Table 2, entry 1–5, 13) NPs is rare. Only a small amount of dehalogenated products The Fe O @PDA was taken and placed under ultra- 3 4 and C–N coupling by-products was produced in the bro- sonic washing using 25  mL of deionized water, 0.1  N of minated aromatic compound (Table  2, entry 7) and the 25  mL hydrochloric acid, 25  mL of deionized water, and iodinated aromatic compound (Table 2, entry 6). 25  mL of ethanol. Approximately 40  mL of ethanol and 4  mL of deionized water were added into the mixture, Experimental which was then mechanically stirred at 10  °C. Subse- General quently, about 0.3  mL N aPdCl aqueous solution (palla- All reagents used in the experiment are commercially dium content 2.5 mg) was slowly added into the mixture available without further purification. The transmission dropwise, and then the mixture was continuously stirred electron microscopy (TEM) image was obtained on a for another 3 h. A solution containing 60 mg of ascorbic JEOL JEM-2100F field transmission electron microscope. acid and 6 mL of deionized water was slowly added into The magnetic property information of the Fe O @PDA- the mixture in 20 min. Then, the reaction was continued 3 4 Pd NPs was obtained on a Quantum Design DynaCool-9 for another 2  h. The solid and liquid were separated by vibrating sample magnetometer. And the H NMR and a magnet. The reaction product was placed under ultra - C NMR spectra were recorded on a Bruker Avance sonic washing using 25 mL of ethanol, 25 mL * 3 of deion- 400 MHz spectrometer using tetramethylsilane (TMS) as ized water and 25 mL * 3 of ethanol. The solid was stored internal standards. in 25 mL of ethanol and sealed with nitrogen (about 0.1 g The Fe O particles were prepared according to the after drying). 3 4 method specified in Ref. [32]. General procedure for the hydrogenation of halogenated General procedure for the preparation of the  Fe O @PDA aromatic nitro compounds to prepare halogenated 3 4 About 0.15  g of strong aqueous ammonia was dissolved aromatic amines 2a–m in 50  mL of deionized water. Then, 0.1  g of Fe O and Approximately 0.1  g of Fe O @PDA-Pd NPs catalyst 3 4 3 4 0.16  g of dopamine hydrochloride were added into the was used. The aforementioned solid and liquor were solution, and the mixture was placed under uniform separated using a magnet and placed under ultrasonic ultrasonic dispersion and mechanically stirred at 40  °C washing using 10  mL * 3 THF. Then, 10  mL THF and for 24  h. After the reaction is completed, the solid and 4.3  mmol halogenated aromatic nitro compounds were the liquid are separated by a magnet. The solid product added. Nitrogen and hydrogen were introduced alter- was then placed under ultrasonic washing using 25 mL * 3 natively. The magnetic stirring was carried out at 50  °C. Guo et al. BMC Chemistry (2019) 13:130 Page 5 of 7 Table 2 Fe O @PDA-Pd NPs-catalyzed hydrogenation reaction of halogenated aromatic nitro compounds 3 4 EntryReactant Target product Selectivity /% Yield/% 1 99 91 2 99 93 3 99 95 4 99 90 5 99 88 6 95 87 7 96 87 8 99 95 9 99 96 10 96 90 11 97 84 12 99 92 13 99 95 7 h Guo et al. BMC Chemistry (2019) 13:130 Page 6 of 7 Hydrogen (hydrogen balloon) was introduced into the 1H), 6.60–6.40 (m, 1H), 3.59 (s, 2H). C NMR (101 MHz, reaction at atmospheric pressure for 4–6  h. At the end CDCl ) δ 152.79 (s), 150.42 (s), 143.16 (d), 120.94 (d), of the reaction, the catalyst was separated and recovered 116.75 (m), 114.28 (d). by a magnet, and the product was separated by column chromatography (n-hexane/dichloromethane) after the 4‑Bromo‑2‑chloroaniline (2j) H NMR (400  MHz, reaction liquid was concentrated. CDCl ) δ 7.37 (d, J = 2.2 Hz, 1H), 7.15 (dd, J = 8.5, 2.2 Hz, 1H), 6.69–6.57 (m, 2H), 4.04 (s, 2H). C NMR (101 MHz, 2‑Chloroaniline (2a) H NMR (400 MHz, C DCl ) δ 7.23 CDCl ) δ 142.11 (s), 131.63 (s), 130.54 (s), 119.93 (s), 3 3 (dd, J = 8.0, 1.1 Hz, 1H), 7.05 (td, J = 8.0, 1.3 Hz, 1H), 6.74 116.87 (s), 109.36 (s). (dt, J = 8.8, 4.4 Hz, 1H), 6.68 (td, J = 7.8, 1.4 Hz, 1H), 4.02 (s, 2H). C NMR (101 MHz, CDCl ) δ 142.92 (s), 129.44 2‑Chloro‑4‑iodoaniline (2k) H NMR (400  MHz, (s), 127.66 (s), 119.31 (s), 119.05 (s), 115.90 (s). CDCl ) δ 7.53 (d, J = 2.0 Hz, 1H), 7.31 (dd, J = 8.4, 2.0 Hz, 1H), 6.52 (d, J = 8.4  Hz, 1H), 4.05 (s, 2H). C NMR 3‑Chloroaniline (2b) H NMR (400 MHz, C DCl ) δ 7.05 (101 MHz, CDCl ) δ 142.73 (s), 137.18 (s), 136.33 (s), 3 3 (dd, J = 10.4, 5.6 Hz, 1H), 6.71 (ddd, J = 7.9, 1.8, 0.7 Hz, 1H), 120.23 (s), 117.43 (s), 77.97 (s). 6.65 (t, J = 2.1 Hz, 1H), 6.53 (ddd, J = 8.1, 2.2, 0.6 Hz, 1H), 13 1 4.17–3.03 (s, 2H). C NMR (101  MHz, CDCl ) δ 147.66 2,4‑Difluoroaniline (2l) H NMR (400  MHz, CDCl ) δ (s), 134.85 (s), 130.36 (s), 118.48 (s), 114.95 (s), 113.23 (s). 6.82–6.73 (m, 1H), 6.73–6.64 (m, 2H), 3.46 (s, 2H). C NMR (101 MHz, CDCl ) δ 156.49 (d), 154.12 (d), 152.22 (d), 4‑Chloroaniline (2c) H NMR (400  MHz, C DCl ) δ 149.82 (d), 130.68 (dd), 116.88 (dd), 110.88 (dd), 103.79 (dd). 7.09 (d, J = 8.7  Hz, 2H), 6.59 (d, J = 8.7  Hz, 2H), 3.56 (s, 2H). C NMR (101 MHz, CDCl ) δ 144.99 (s), 129.14 (s), 3,4‑Dichloroaniline (2m) H NMR (400 MHz, CDCl ) δ 3 3 123.13 (s), 116.27 (s). 7.17 (d, J = 8.6 Hz, 1H), 6.75 (d, J = 2.7 Hz, 1H), 6.50 (dd, J = 8.6, 2.7  Hz, 1H), 3.72 (s, 2H). C NMR (101  MHz, 5‑Chloro‑2‑methylaniline (2d) H NMR (400  MHz, CDCl ) δ 146.02 (s), 132.67 (s), 130.73 (s), 121.08 (s), CDCl ) δ 6.94 (d, J = 8.4 Hz, 1H), 6.65 (d, J = 5.5 Hz, 2H), 116.41 (s), 114.62 (s). 3.65 (s, 2H), 2.10 (s, 3H). C NMR (101  MHz, C DCl ) δ 145.72 (s), 132.06 (s), 131.34 (s), 120.59 (s), 118.23 (s), 114.48 (s), 16.87 (s). Conclusions We developed a method for preparing superparamag- 6‑Chloro‑2‑methylaniline (2e) H NMR (400  MHz, netic and strongly magnetic Fe O @PDA core–shell 3 4 CDCl ) δ 7.12 (d, J = 8.0 Hz, 1H), 6.94 (dd, J = 7.5, 0.5 Hz, sub-microsphere-supported nano-palladium catalyst, 1H), 6.61 (t, J = 7.7 Hz, 1H), 3.97 (s, 2H), 2.18 (s, 3H). C i.e. Fe O @PDA-Pd NPs. The catalyst was character - 3 4 NMR (101  MHz, CDCl ) δ 141.18 (s), 128.72 (s), 127.07 ized and successfully catalyzed the hydrogenation (s), 123.56 (s), 119.15 (s), 118.32 (s), 17.98 (s). reduction of halogenated aromatic nitro compounds. The halogenated aromatic amines were efficiently and selectively prepared under atmospheric pressure, which 4‑Iodoaniline (2f ) H NMR (400  MHz, CDCl ) δ 7.40 could effectively inhibit the occurrence of the side reac - (d, J = 8.7  Hz, 2H), 6.46 (d, J = 8.7  Hz, 2H), 3.97–3.33 (s, tions of dehalogenation and C–N coupling. 2H). C NMR (101 MHz, CDCl ) δ 146.08 (s), 137.92 (s), 117.32 (s), 79.41 (s). Abbreviations 4‑Bromoaniline (2  g) H NMR (400  MHz, C DCl ) δ PDA: polydopamine; Pd NPs: nano-palladium particles; THF: tetrahydrofuran; TEM: the transmission electron microscopy. 7.22 (d, J = 8.7  Hz, 2H), 6.56 (d, J = 8.7  Hz, 2H), 3.70 (s, 2H). C NMR (101 MHz, CDCl ) δ 145.50 (s), 131.99 (s), Acknowledgements 116.71 (s), 110.10 (s). This work was supported by Zhejiang University of Technology and Taizhou University. 4‑Fluoroaniline (2  h) H NMR (400  MHz, C DCl ) δ Authors’ contributions 6.95–6.78 (m, 2H), 6.72–6.50 (m, 2H), 3.48 (s, 2H). C HCG, HJJ and ZYX designed the research. HCG and RHZ performed the research. HCG and ABX analyzed the data. HJJ, RHZ, ABX and ZYX contributed NMR (101  MHz, CDCl ) δ 157.60 (s), 155.26 (s), 142.43 the reagent/material/analysis tools. HCG wrote the paper. All authors read and (d), 115.80 (m). approved the final manuscript. Funding 4‑Fluoro‑3‑chloroaniline (2i) H NMR (400  MHz, This work was supported by the Zhejiang Province Public Welfare Technology CDCl ) δ 6.91 (t, J = 8.8 Hz, 1H), 6.69 (dd, J = 6.1, 2.8 Hz, Research Program (LGG19B040001), Zhejiang Natural Science Foundation Guo et al. BMC Chemistry (2019) 13:130 Page 7 of 7 (LY18B020017), and Taizhou Science and Technology Project (1801gy21). All 17. Yan XL, Duan P, Zhang FW et al (2019) Stable single-atom platinum cata- funding bodies played no role in the design of the study and collection, analy- lyst trapped in carbon onion graphitic shells for improved chemoselec- sis, and interpretation of data and in writing the manuscript. tive hydrogenation of nitroarenes. 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