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摘要:
苯氨基甲酸甲酯(MPC)是合成二苯甲烷二异氰酸酯(MDI)的关键原料。以二氧化碳(CO2)及其等价物或衍生物作为碳源合成MPC代表了绿色和可持续的精细化学品合成方法。基于该领域研究,概述了基于CO2转化合成苯氨基甲酸甲酯的研究方法进展。合成路线包括研究较多的CO2等价物(尿素或苯基脲)醇解法,碳酸二甲酯(DMC)氨解法以及二苯基脲和DMC耦合反应法。另外,最理想的合成方法是近几年发展的苯胺、CO2和甲醇三组分“一锅”反应法,以及使用脂肪胺类原料构建氨基甲酸烷基酯类化合物,其代表了最有前景的CO2利用途径之一。详细探讨了反应机理和催化剂选择等问题。研究进展将为进一步提升绿色催化和可持续化学过程效率提供重要理论支持。
Abstract:Methyl N-phenylcarbamate (MPC) is an important intermediate for the synthesis of diphenylmethane diisocyanate (MDI), and its preparation using CO2 or its equivalents/derivatives as carbon source represents a green and sustainable manner for fine chemicals synthesis. This review will highlight the development of MPC synthetic methods from the viewpoint of chemical fixation of CO2. The contents mainly include the introduction of MPC synthesis through CO2 equivalents (urea or phenyl urea) alcoholysis, dimethyl carbonate (DMC) aminolysis, and the coupling of DMC and diphenyl urea. Furthermore, one-pot synthesis of carbamates/MPC from aliphatic amines/aniline, CO2 and alcohols is highlighted which represents one of the most promising schemes in direct CO2 utilization. What is more, the reaction mechanisms and selection of catalysts are also discussed in detail. The advances will provide important theories on further improving the efficiency of green catalysis and sustainable chemical processes.
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Key words:
- carbon dioxide /
- CO2 equivalent /
- methyl N-phenylcarbamate /
- catalysis /
- synthetic method
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Figure 2 Proposed routes to MPC via three different processes [50]
Table 1 Metal catalysts for MPC synthesis from aniline and DMC
Entry Catalyst Supporter Conditions Results Ref. t /°C p /MPa t /h conv. /% sel. /% y /% 1 Zn(OAc)2 AC 150 0.1 4 − 98 78 [31] 2 Zn(OAc)2 − 170 0.1 2 99 90 − [33] 3 Zn(OAc)2 SiO2 190 0.1 5 97.2 89.4 − [34] 4 Zn(OAc)2 − 130 0.1 3 98 − 97 [35] 5 zinc alkyl carboxylate silica 170 0.1 1 94.6 96.8 91.6 [36] 6 Zn/Al/Ce mixed oxide − 200 0.1 7 95.8 81.6 78.2 [37] 7 ZnO-TiO2 SiO2 170 0.1 7 49.9 52.3 − [38] 8 ZrO2 SiO2 170 0.1 7 79.2 80.1 − [39] 9 PbO SiO2 150 0.1 2 91.08 90.37 82.31 [40] 10 In2O3 SiO2 150 0.1 2 75.98 78.24 59.45 [40] 11 PbO SiO2 160 0.1 4 99.7 99.8 99.5 [41] 12 PbO − 170 0.1 4 81 − − [42] Note: conversion (conv.), selectivity (sel.), yield (y), (−: mark indicates no available information in the reference) -
[1] WANG S P, YAN S L, MA X B, GONG J L. Recent advances in capture of carbon dioxide using alkali-metal-based oxides[J]. Energy Environ Sci,2011,4:3805−3819. doi: 10.1039/c1ee01116b [2] DABRAL S, SCHAUB T. The use of carbon dioxide (CO2) as a building block in organic synthesis from an industrial perspective[J]. Adv Synth Catal,2019,361(2):223−246. doi: 10.1002/adsc.201801215 [3] OTTO A, GRUBE T, SCHIEBAHNA S, STOLTEN D. Closing the loop: Captured CO2 as a feedstock in the chemical industry[J]. Energy Environ Sci,2015,8(11):3283−3297. doi: 10.1039/C5EE02591E [4] SONG Q W, ZHOU Z H, HE L N. Efficient, selective and sustainable catalysis of carbon dioxide[J]. Green Chem,2017,19:3707−3728. doi: 10.1039/C7GC00199A [5] OSTAPOWICZ T G, SCHMITZ M, KRYSTOF M, KLANKERMAYER J, LEITNER W. Carbon dioxide as a C1 building block for the formation of carboxylic acids by formal catalytic hydrocarboxylation[J]. Angew Chem Int Ed,2013,52:12119−12123. doi: 10.1002/anie.201304529 [6] YANG X P. MDI production technology progress and market analysis[J]. Technol Eco Petrochem,2019,35(1):27−31. [7] YAN Z. Development status and future opportunity of isocyanates in China[J]. Chem Ind,2021,39:21−32. [8] CUI X M. Supply/demand situation and development prospect of MDI at home and abroad[J]. Chem Ind,2015,33(2-3):53−57. [9] LI S B, WANG G Y. The synthetic methods of diphenylmethane dicarbamic acid esters[J]. Chin J Synth Chem,2004,12:137−141. [10] YANG Y, LU S W. Selenium-catalyzeds reductive carbonylatio of PhNO2 in alcohol media to phenyl carbamates[J]. Chin J Catal,1999,20(3):224−226. [11] ZHOU Z Q, LI Y, HUANG J X. Synthesis of phenyl carbamate by Hofmann rearrangement[J]. J Hubei Univ (Nat Sci Ed),1998,20(4):345−347. [12] RAGAINI F. Away from phosgene: Reductive carbonylation of nitroarenes and oxidative carbonylation of amines, understanding the mechanism to improve performance[J]. Dalton Trans,2009,32:6251−6266. [13] LI H Q, HANG K L, XIE Y S, LI K X, WU R. The research process of cleaner synthesis N, N’-diphenylurea[J]. Pop Sci Technol,2015,17(196):32−35. [14] WANG J W, LI Q F, DONG W S, KANG M Q, WANG X K, PENG S Y. A new non-phosgene route for synthesis of methyl N-phenyl carbamate from phenylurea and methanol[J]. Appl Catal A: Gen,2004,261:191−197. doi: 10.1016/j.apcata.2003.11.021 [15] GUPTE S P, CHAUDHARI R V. Synthesis of methyl N-phenyl carbamate from methanol and diphenylurea[J]. Appl Catal,1988,114(2):246−258. doi: 10.1016/0021-9517(88)90028-0 [16] WANG H, CHEN K Y, CHU Y Z, LIAO C C. Process for preparing carbonate compounds: US, 5591883[P]. 1997-01-07. [17] FENG Y L, WANG J W, LI Q F, KANG M Q, WANG X K. Synthesis of methyl N-phenyl carbamate from phenyl urea and methanol over the KF/Al2O3 catalyst[J]. J Fuel Chem Technol,2013,41(12):1507−1511. [18] ZHANG L, YUAN C G, QUE G H. Synthesis of methyl N-phenyl carbamate from methanol and diphenylurea[J]. Petrochem Technol,2006,35(11):1048−1051. [19] SUN J J, YANG B L, LIN H Y. A semicontinuous process for the synthesis of methyl carbamate from urea and methanol[J]. Chem Eng Technol,2004,27(4):435−439. doi: 10.1002/ceat.200401911 [20] LI Q F, WANG J W, DONG W S, KANG M Q, WANG X K, PENG S Y. A phosgene-free process for the synthesis of methyl N-phenylcarbamate by the reaction of aniline with methyl carbamate[J]. J Mol Catal A: Chem,2004,212:99−105. doi: 10.1016/j.molcata.2003.11.002 [21] WANG P X, MA Y B, LIU S M, ZHOU F, YANG B Q, DENG Y Q. N-Substituted carbamate synthesis using urea as carbonyl source over TiO2-Cr2O3/SiO2 catalyst[J]. Green Chem,2015,17:3964−3971. doi: 10.1039/C5GC01007A [22] DOU L Y, AN H L, LI Q, WANG G R, ZHAO X Q, WANG Y J. One-step synthesis of methyl N-phenyl carbamate from aniline, urea and methanol over γ-Al2O3[J]. J Chem Eng Chin Univ,2013,27(6):1004−1011. [23] DOU L Y, ZHAO X Q, AN H L, WANG G R, WANG Y J. Reaction path of one-pot synthesis of methyl N-phenyl carbamate from aniline, urea, and methanol[J]. Ind Eng Chem Res,2013,52:4408−4413. doi: 10.1021/ie302632c [24] QIN F, LI Q F, WANG J W, FENG Y L, KANG M Q, ZHU Y L, WANG X K. Synthesis of methyl N-phenylcarbamate from aniline, urea and methanol[J]. Fine Chem,2008,25(8):825−828. [25] QIN F, LI Q F, WANG J W, FENG Y L, KANG M Q, ZHU Y L, WANG X K. One pot synthesis of methyl N-phenyl carbamate from aniline, urea and methanol[J]. Catal Lett,2008,126:419−425. doi: 10.1007/s10562-008-9647-6 [26] ZHANG M, XU Y H, WILLIAMS B L, XIAO M, WANG S J, HAN D M, SUN L Y, MENG Y Z. Catalytic materials for direct synthesis of dimethyl carbonate (DMC) from CO2[J]. J Clean Prod,2021,279:1−25. [27] CHATURVEDI D. Recent developments on the carbamation of amines[J]. Curr Org Chem,2011,15:1593−1624. doi: 10.2174/138527211795378173 [28] ONO Y. Catalysis in the production and reactions of dimethyl carbonate, an environmentally benign building block[J]. Appl Catal A: Gen,1997,155:133−166. doi: 10.1016/S0926-860X(96)00402-4 [29] FAN Y P, YANG X G, LI J G, ZHAO Y F, CUI L L, WANG G Y. Progress in the catalysts for synthesis of carbamates by ammonolysis of dimethyl carbonate[J]. Nat Gas Chem Ind,2008,33:66−70. [30] PENG X C, WANG Z M, LI H Q, XUE W, LI F, WANG Y J. Preparation of Zn(OAc)2/SiO2 catalyst with better stability prepared by solvothermal impregnation method and its application in methyl N-phenyl carbamate[J]. Chem Ind Eng Pro (China),2019,38(3):1396−1402. [31] ZHAO X Q, WANG Y J, WANG S F, YANG H J, ZHANG J Y. Synthesis of MDI from dimethyl carbonate over solid catalysts[J]. Ind Eng Chem Res,2002,41:5139−5144. doi: 10.1021/ie020084f [32] BABA T, KOBAYASHI A, KAWANAMI Y. Characteristics of methoxycarbonylation of aromatic diamine with dimethyl carbonate to dicarbamate using a zinc acetate catalyst[J]. Green Chem,2005,7(3):159−165. doi: 10.1039/b413334j [33] GE J W, CHEN L F, LI Y N, LI J, HE W J. Synthesis of methyl N-phenyl carbamate by methoxycarbonylation of aniline with dimethyl carbonate using zinc compounds as catalysts[J]. Appl Chem Ind,2016,45(11):2088−290. [34] LIU Y Z, QIU S H, YUAN Z G, SHANGGUAN M. Thermodynamic analysis for synthesizing phenyl carbamate with dimethyl carbonate and aniline on non-phosgene approach[J]. Chem Eng (China),2011,39(9):38−40. [35] LI F, WANG X, LI H Q, WANG S F, XUE W, WANG Y J. The induction period and novel active species in Zn(OAc)2 catalyzed synthesis of aromatic carbamates[J]. Catal Lett,2017,147:1478−1484. doi: 10.1007/s10562-017-2055-z [36] WANG Y, LIU B. Efficient and recyclable heterogeneous zinc alkyl carboxylate catalyst for the synthesis of N-phenyl carbamate from aniline and dimethylcarbonate[J]. Catal Sci Technol,2015,5:109−113. doi: 10.1039/C4CY01130A [37] KANG M, ZHOU H, TANG D J, CHEN X M, GUO Y, ZHAO N. Methyl N-phenyl carbamate synthesis over Zn/Al/Ce mixed oxide derived from hydrotalcite-like precursors[J]. RSC Adv,2019,9:42474−42480. doi: 10.1039/C9RA09642F [38] HONG H, LI J, GAO L Y, WANG H O, WANG Z K, YUE H S, LI F, WANG Y J. Synthesis of methyl N-phenyl carbamate over supported ZnO-TiO2 catalyst[J]. Spec Petrochem,2014,5(31):44−48. [39] LI F, JIA Y, JIA A Z, GAO L Y, WANG Y J, WANG Z M, XUE W. Fabrication and characterization of ZrO2 and ZrO2/SiO2 catalysts and their application in the synthesis of methyl N-phenyl carbamate: A study of the reaction mechanism by using in situ FT IR spectroscopy[J]. React Kinet Mech Catal,2021,132:893−906. doi: 10.1007/s11144-021-01949-2 [40] LI Q F, WANG J W, DONG W S, KANG M Q, WANG X K, PENG S Y. Synthesis of methyl N-phenyl carbamate by methoxycarbonylation of aniline with dimethyl carbonate[J]. Chin J Catal,2003,24(8):639−642. [41] KANG W K, KANG T, MA F, ZHAO Y F, CUI L L, YAO J, WANG G Y. Catalytic performance of supported PbO catalysts for synthesis of methyl N-phenyl carbamate from aniline and dimethyl carbonate[J]. Chin J Catal,2007,28(1):5−9. [42] KANG W K, YAO J, WANG G Y, HU C W, JING X P. Study of catalytic synthesis process for methyl phenyl carbamate by reaction of dimethyl carbonate with aniline[J]. J Mol Catal (China),2003,17(2):136−139. [43] SHIVARKAR A B, GUPTE S P, CHAUDHARI R V. Carbamate synthesis via transfunctionalization of substituted ureas and carbonates[J]. J Mol Catal A: Chem,2004,223:85−92. doi: 10.1016/j.molcata.2003.09.041 [44] ZHANG L, YUAN C G, SUN Z Z. The synthesis of methyl N-phenyl carbamate (MPC) from diphenylurea and dimethyl carbanate[J]. Synth Technol Appl,2006,21(1):27−29. [45] LIU H F, YE H Q, ZHOU Y H, LI H Q. Study on the catalytic synthesis of methyl N-phenyl carbamate by alcoholysis Pb catalyst[J]. Eng Sci Technol,2009,4(6):447−452. [46] GAO J J, LI H Q, ZHANG Y F, ZHANG Y. A non-phosgene route for synthesis of methyl N-phenyl carbamate derived from CO2 under mild conditions[J]. Green Chem,2007,9:572−576. doi: 10.1039/b614229j [47] TOMISHIGE K, TAMURA M, NAKAGAWA Y. CO2 conversion with alcohols and amines into carbonates, ureas, and carbamates over CeO2 catalyst in the presence and absence of 2-cyanopyridine[J]. Chem Rec,2019,19:1354−1379. doi: 10.1002/tcr.201800117 [48] ZHANG L L, YAO S J, AN H L, ZHAO X Q, WANG Y J. Thermodynamic analysis on synthesis of methyl N-phenyl carbamate from aniline, CO2 and methanol[J]. Nat Gas Chem Ind,2013,38:42−45. [49] YAO S. Synthesis of methyl N-phenyl carbamate from aniline, carbon dioxide and methanol[D]. Tianjin: Hebei University of Technology, China, 2012. [50] ZHAO B, YAO S J, AN H L, ZHAO X Q, WANG Y J. One-pot synthesis of methyl N-phenyl carbamate from aniline, carbon dioxide and methanol[J]. J Chem Technol Biotechnol,2014,89:1553−1558. [51] ZHAO X Q, YAO S J, AN H L. One-step synthesis of aniline-based formate from aniline, carbon dioxide and alcohol: CN, 102617402A[P], 2012-08-01. [52] ZHENG L Z, YANG G Q, LIU J, HU X B, ZHANG Z B. Metal-free catalysis for the one-pot synthesis of organic carbamates from amines, CO2, and alcohol at mild conditions[J]. Chem Eng J,2021,425:131452. doi: 10.1016/j.cej.2021.131452 [53] LI Y, AN H L, ZHAO X Q, WANG Y J. One-pot synthesis of methyl N-phenyl carbamate with aniline, carbon dioxide and methanol catalyzed by Cu-Fe/ZrO2-SiO2[J]. J Chem Eng Chin Univ,2015,29(5):1271−1278. [54] TAMURA M, MIURA A, HONDA M, GU Y, NAKAGAWA Y, TOMISHIGE K. Direct catalytic synthesis of N-arylcarbamates from CO2, anilines and alcohols[J]. ChemCatChem,2018,10:4821−4825. [55] TAMURA M, WAKASUGI H, SHIMIZU K, SATSUMA A. Efficient and substrate-specific hydration of nitriles to amides in water by using a CeO2 catalyst[J]. Chem Eur J,2011,17:11428−11431. doi: 10.1002/chem.201101576 [56] ABLA M, CHOI J, SAKAKURA T. Halogen-free process for the conversion of carbon dioxide to urethanes by homogeneous catalysis[J]. Chem Commun,2001,,(21):2238−2239. [57] ABLA M, CHOI J, SAKAKURA T. Nickel-catalyzed dehydrative transformation of CO2 to urethanes[J]. Green Chem,2004,6:524−525. doi: 10.1039/b408429b [58] ION A, DOORSLAER C V, PARVULESCU V, JACOBSA P, VOS D D. Green synthesis of carbamates from CO2, amines and alcohols[J]. Green Chem,2008,10:111−116. doi: 10.1039/B711197E [59] HONDA M, SONEHARA S, YASUDA H, NAKAGAWA H, TOMISHIGE K. Heterogeneous CeO2 catalyst for the one-pot synthesis of organic carbamates from amines, CO2 and alcohols[J]. Green Chem,2011,13:3406−3413. doi: 10.1039/c1gc15646b [60] GU Y, MIURA A, TAMURA M, NAKAGAWA Y, TOMISHIGE K. Highly efficient synthesis of alkyl N-arylcarbamates from CO2, anilines, and branched alcohols with a catalyst system of CeO2 and 2-cyanopyridine[J]. Chem Eng,2019,7:16795−16802.