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Molecules 2019, 24, x FOR PEER REVIEW 16 of 42 trace of water. The reaction proceeds with a sequential electrophilic attack of amine on c, elimination Molecules 2019, 24, 182 of water from M1 and reaction between M2 and amine leading to N,N′-dialkylureas. 0-65% R=Alkyl,Ph,Aryl 16 of 41 TBD (10 mol%) O 2R NH2 + CO2 100 C,15MPa,24h R N TBD a b CO2 H2O (traces) RNH2 N R +H2O HH N CO2 N N + NNNNHNN H HOOOO O N O2N NHR OCNR2RNNR NHHO RNH NH O -TBD c M1 M2 RNH NHO -H2O NHO -H2O HH in NMP. SSchchememee1155. .Biiccyclliic guanidine-cattallyzzeeduurreeaafoformrmataitoino.n. The use of metal oxides and metal salts of oxalates significantly paved the way for The use of metal oxides and metal salts of oxalates significantly paved the way for N,N’-dialkylureasynthesisinrecentyears(Table3).CeO showedhighactivityforthedirectsynthesis N,N’-dialkylurea synthesis in recent years (Table 3).2CeO2 showed high activity for the direct of s1y,3n-tdhiebsuistyoflu1r,3e-adfirboumtylCuOrea afrnodmnC-bOu2taynladmni-nbue t[y9l2a]m. iTnhee[9c2a]t.aTlyhteicastyasltyetmic swysatsemapwplaiscabplpelitcoabvlaertious 2 amvianreisousus cahmaisnelisnseuacrhpraismlianreyaarlkpyrilmamariyneaslkaynldambirnaenschaned pbriamncahryedalpkryimlamaryinaelsk(yFliagmuirnee5s).(FMigeuarnew5h).ile, secMonedanawryhailme,inessecaonnddanryilinea,mwinheicsh wanedre uannreilainctei,ve wushiincgh CewOerein Nu-nmreathctyivl-e2-puirsrionlgidinCoenOe2(NMinP), N-methyl-2-pirrolidinone (NMP), were also transformed into the corresponding ureas when were also transformed into the corresponding ureas when 2-cyanopyridine was combined with CeO2 2-cyanopyridine was combined with CeO2 in NMP. Y2(C2O4)3 and Y0.08Zr0.92O1.96 mixed oxide were independently used to catalyze carbonylation of Table 3. Metal-catalyzed carbonylation of amines and CO aliphatic primary amines with CO2. Y2(C2O4)3 provided the highest yield of N2,.N′-dialkylurea among various metal salts of oxalates (Zr(C2O4)2, Ce2(C2O4)3, Mn(C2O4), Na2(C2O4), Ni(C2O4)) [93]. 2 Catalyst Solvent T/◦C P/MPa t/h Yield/% a Ref. Y0.08Zr0.92O1.96 mixed oxide as the heterogeneous catalyst showed higher catalytic activity than CeO2 NMP 130 5 24/48 <1–86 [92] Y2(C2O4)3 [94]. The prebsence of oxygen vacancies in the mixed oxide was of great importance for NMP 150 CO2 (2)/N2 (1) 24 62.43 [93] adsorption aYn0.0d8Zarc0.t9i2vOa1t.9i6on of CO2 in thNeMcaPrbonyla16ti0on prCoOce2(s2s)./INt2s(1h)ould12b–2e4ascr4ib7.e14d–8t0o.6t0he ad[d94it]ional Y2 (C2 O4 )3 In(N(SiMe3 )2 )Cl2 ·(THF)n , pyridine - 110 0.3 3–90 - [95] b reduction potential derived from the oxygen vacancies for the reduction of CO2 to CO and/or surface Molecules 2019, 24, x FOR PEER REVIEW a17 of 42 b GC yield; 4A zeolite as dehydrant. carbonaceous species (an important intermediate). Indium-catalyzed transformations of CO2 with aliphatic and aromatic silylamines have been exploited by Stephan et al. [95]. The indium compound In(N(SiMe3)2)Cl2·(THF)n (THF = tetrahydrofuran) was able to efficiently catalyze the reaction and afford a wide range of aryl and alkyl ureas with 0.05–5 mol% catalyst loadings. Notably, the available main group metal-catalyzed transformations of CO2 were improved. Table 3. Metal-catalyzed carbonylation of amines and CO2. Catalyst Solvent T/°C P/MPa t/h Yield/%a Ref. CeO2 NMP 130 5 24/48 <1–86 [92] FigFuigruer5e.5V.aVraioriuosuusrueraesasbybyCCeOeO/2/NMPsystem..Reepprrininteteddwwitihthpepremrmissisiosinonfrofrmom[92[9]2(C] (oCpoypriygrhitg2h0t125015 NMP 150 CO2(2)/N2(1) 24 62.43 [93] NMP 160 CO2(2)/N2(1) 12–24 47.14–80.60 [94] Y2(C2O4)3 b 2 ElsEelvseievrieIrnIcn.)c..). Y0.08Zr0.92O1.96 b In(N(SiMe3)2)Cl2·(THF)n, mixed oxide were independently used to catalyze carbonylation Y (C O ) and Y 2Pol2yur4e3as conta0i.0n8ing0.9u2rea1.9l6inkages and connected by hydrogen bonds are a new kind of Zr O - 110 0.3 3–90 - ′ [95] ofpaolilpymhaetri.cIpnri2m01a6ry,gaomoidnetsowexitchellCeOnt.yiYeld(CsoOfv)arpioruosvidpoedlyuthreahsigwheerestayciheiledveodfNw,Nith-diiaflfkeryelnutrea pyridine 22243 amdoianmgivnaersiouasnmdetaClOsa2ltsboyfohxeaxlaytletrsib(Zurty(ClphOos)ph,Coneiu(Cm Oa)m,inMontr(iCazoOle),N(Pa4,4(,4C,6AOTri)z,,Ni(ACTrOiz))[=93]. 24222432422424 Y3-aZmrino-O1H-1,2m,4i-xteridazoxleid)(e1,aSschthemeehe1t6e)rIoLgceantaeloyusts[c9a6t].aIltywstashfouwnedthaitgtherccaatatlayltyitcicpearcfotirvmitayncthean 0.08 0.92 1.96 a GC yield; b 4A zeolite as dehydrant. was essentially consistent with the basicity of ILs described by Deng et al. Recently, some functional Y2(C2O4)3 [94]. The presence of oxygen vacancies in the mixed oxide was of great importance for polyureas were successfully synthesized via the polymerization of CO2 with diamines using amino adsorption and activation of CO2 in the carbonylation process. It should be ascribed to the additional triazole alkali salts i.e., MATriz as catalysts (2, Scheme 16), and M was Li, Na, K [97]. More reduction potential derived from the oxygen vacancies for the reduction of CO2 to CO and/or surface importantly, the catalysts could be reused for several times without obvious deactivation. carbonaceous species (an important intermediate). Additionally, Arai et al. found that DBU (3, Scheme 16) was the most active among multiple organic and inorganic base catalysts in addition of CO2 to 4,7,10-trioxa-1,13-tridecanediamine (TOTDDA) [98]. DBU could activate both CO2 and -NH2 group of TOTDDA, which was demonstrated by in situ high-pressure attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), resulting in a high catalytic performance (Figure 6).PDF Image | Catalytic Conversion of Carbon Dioxide through C-N Bond
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