{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,23]],"date-time":"2026-09-23T21:22:48Z","timestamp":1790198568695,"version":"4.1.0"},"reference-count":64,"publisher":"Wiley","issue":"13","license":[{"start":{"date-parts":[[2016,6,20]],"date-time":"2016-06-20T00:00:00Z","timestamp":1466380800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"name":"Ruprechts-Karls-University Heidelberg (Heidelberg University)"},{"name":"BASF"}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["ChemSusChem"],"published-print":{"date-parts":[[2016,7,7]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>A straightforward phosgene\u2010free synthesis of aromatic isocyanates and diisocyanates is disclosed. Theoretical investigations suggested that the insertion of carbon dioxide (CO<jats:sub>2<\/jats:sub>) by dialkyltin(IV) dialkoxides could be used to convert aromatic amines into aromatic mono\u2010 and dicarbamates. Here we show, that methyl phenylcarbamate (MPC) from aniline using organotin(IV) dimethoxide and CO<jats:sub>2<\/jats:sub> can be formed in high yield of up to 92\u2009%, experimentally corroborating the predictions of density functional theory (DFT) calculations. MPC was then separated from the tin oxide residues and converted into phenyl isocyanate. Furthermore, organotin(IV) alkoxides could be regenerated from the tin oxide residues and reused, paving the way for a continuous industrial process. Extension of the scope to the synthesis of diurethanes from toluene 2,4\u2010diamine and 4,4\u2032\u2010methylenedianiline could potentially allow the efficient production of industrially relevant diisocyanates.<\/jats:p>","DOI":"10.1002\/cssc.201600580","type":"journal-article","created":{"date-parts":[[2016,6,20]],"date-time":"2016-06-20T04:15:46Z","timestamp":1466396146000},"page":"1586-1590","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":35,"title":["Synthesis of Industrially Relevant Carbamates towards Isocyanates using Carbon Dioxide and Organotin(IV) Alkoxides"],"prefix":"10.1002","volume":"9","author":[{"given":"Nicolas","family":"Germain","sequence":"first","affiliation":[{"name":"Catalysis Research Laboratory (CaRLa)  Im Neuenheimer Feld 584 69120 Heidelberg Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Imke","family":"M\u00fcller","sequence":"additional","affiliation":[{"name":"BASF SE  Carl-Bosch-Str. 38 67056 Ludwigshafen Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Matthias","family":"Hanauer","sequence":"additional","affiliation":[{"name":"BASF SE  Carl-Bosch-Str. 38 67056 Ludwigshafen Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Rocco A.","family":"Paciello","sequence":"additional","affiliation":[{"name":"BASF SE  Carl-Bosch-Str. 38 67056 Ludwigshafen Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Robert","family":"Baumann","sequence":"additional","affiliation":[{"name":"BASF SE  Carl-Bosch-Str. 38 67056 Ludwigshafen Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Oliver","family":"Trapp","sequence":"additional","affiliation":[{"name":"Catalysis Research Laboratory (CaRLa)  Im Neuenheimer Feld 584 69120 Heidelberg Germany"},{"name":"Organisch-Chemisches Institut Ruprecht-Karls-Universit\u00e4t Heidelberg  69120 Heidelberg Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2332-0376","authenticated-orcid":false,"given":"Thomas","family":"Schaub","sequence":"additional","affiliation":[{"name":"Catalysis Research Laboratory (CaRLa)  Im Neuenheimer Feld 584 69120 Heidelberg Germany"},{"name":"BASF SE  Carl-Bosch-Str. 38 67056 Ludwigshafen Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2016,6,20]]},"reference":[{"key":"e_1_2_2_1_1","doi-asserted-by":"publisher","DOI":"10.1039\/c3gc40440d"},{"key":"e_1_2_2_2_1","first-page":"63","volume-title":"Ullmann's Encyclopedia of Industrial Chemistry, Vol.\u200520","author":"Six C.","year":"2003"},{"key":"e_1_2_2_3_1","unstructured":"For recent reviews on the phosgene-free preparation of polyurethanes see:"},{"key":"e_1_2_2_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.5b00355"},{"key":"e_1_2_2_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.macromol.5b00384"},{"key":"e_1_2_2_6_1","doi-asserted-by":"publisher","DOI":"10.1002\/marc.201400209"},{"key":"e_1_2_2_7_1","unstructured":"\u00a0"},{"key":"e_1_2_2_8_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(96)02513-0"},{"key":"e_1_2_2_9_2","doi-asserted-by":"publisher","DOI":"10.1039\/C39940000957"},{"key":"e_1_2_2_10_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr068357u"},{"key":"e_1_2_2_11_1","doi-asserted-by":"publisher","DOI":"10.1039\/b106201h"},{"key":"e_1_2_2_12_1","doi-asserted-by":"publisher","DOI":"10.1039\/B711197E"},{"key":"e_1_2_2_13_1","doi-asserted-by":"publisher","DOI":"10.1039\/c1gc15646b"},{"key":"e_1_2_2_14_1","doi-asserted-by":"publisher","DOI":"10.1002\/jctb.4236"},{"key":"e_1_2_2_15_1","unstructured":"\u00a0"},{"key":"e_1_2_2_16_2","unstructured":"J.Pfeffinger P.Pfab E.Str\u00f6fer DE-OS 19820114 1999;"},{"key":"e_1_2_2_17_2","unstructured":"G.Laqua U.Schoner E.Str\u00f6fer A.Otterbach DE-OS 19627552 1998;"},{"key":"e_1_2_2_18_2","unstructured":"A.Otterbach H. 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Alternatively the formation of dimethylcarbonate4followed by a tin-promoted methanol displacement and concomitant aniline addition can also be considered."},{"key":"e_1_2_2_34_1","unstructured":"\u00a0"},{"key":"e_1_2_2_35_2","doi-asserted-by":"publisher","DOI":"10.1590\/S0104-66322006000100012"},{"key":"e_1_2_2_36_2","first-page":"5175","volume":"5167","author":"Ballivet-Tkatchenko D.","year":"2006","journal-title":"Dalton Trans."},{"key":"e_1_2_2_37_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0926-860X(03)00647-1"},{"key":"e_1_2_2_38_1","unstructured":"\u00a0"},{"key":"e_1_2_2_39_2","doi-asserted-by":"publisher","DOI":"10.1055\/s-2004-829562"},{"key":"e_1_2_2_40_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3749(200110)627:10<2413::AID-ZAAC2413>3.0.CO;2-H"},{"key":"e_1_2_2_41_1","unstructured":"See the Supporting Information for details."},{"key":"e_1_2_2_42_1","unstructured":"The investigation of the next steps required a substantial amount of12which was not available after methanolysis of tin oxide. A large batch was thus prepared from dimethyltin(IV) dichloride."},{"key":"e_1_2_2_43_1","unstructured":"The procedure used allowed to elaborate on the CO2update for each solvent at room temperature. See ESI for pressure values for each experiment."},{"key":"e_1_2_2_44_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.jorganchem.2011.02.010"},{"key":"e_1_2_2_45_1","unstructured":"For some examples of carbamates cleavages see:"},{"key":"e_1_2_2_46_2","doi-asserted-by":"publisher","DOI":"10.1021\/ie302659q"},{"key":"e_1_2_2_47_2","doi-asserted-by":"publisher","DOI":"10.1007\/s10562-008-9424-6"},{"key":"e_1_2_2_48_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(02)00094-1"},{"key":"e_1_2_2_49_2","doi-asserted-by":"publisher","DOI":"10.1039\/a807287f"},{"key":"e_1_2_2_50_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo00106a044"},{"key":"e_1_2_2_51_1","unstructured":"The thermolysis of6was not optimized as a simple condenser was used for this step. Traces of diphenylcarbodiimide and aniline were detected. The conversion was not improved after a longer reaction time. Water should be excluded for this step. Further optimizations would require specific apparatus. See the Supporting Information for more details and experimental evidences."},{"key":"e_1_2_2_52_1","unstructured":"The dialkyltin(IV) alkoxides was regenerated based on the following studies:"},{"key":"e_1_2_2_53_2","unstructured":"G. A.Knudsen E. N.Suciu R. C.Michaelson US 5545600 1996;"},{"key":"e_1_2_2_54_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jorganchem.2008.01.028"},{"key":"e_1_2_2_55_1","unstructured":"Tin oxide such as1or8have been regenerated (see Ref.\u200513\u2009b) but only high boiling alcohol are described (bp>100\u2009\u00b0C). 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