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We present an efficient process that utilizes the distinct solubility profiles of ammonium carbamate species formed through waste\u2010free and reversible salt formation of primary amines and CO<jats:sub>2<\/jats:sub>. This selective ammonium carbamate crystallization (SACC) enables the purification of challenging amine mixtures. Starting from 35% initial primary amine purity, SACC achieves very high isolated yields of up to 94% and excellent purities exceeding 99%. Additionally, the separation of secondary from tertiary amines with 86% yield and 91% purity and the fractional crystallization of primary, secondary, and tertiary amines with yields ranging from 83% to 94% and purities from 90% to\u00a0&gt;\u00a099% were successfully achieved. SACC was also successfully employed in the alcohol amination with ammonia\/ammonia alkylation to isolate primary amines with high yields of up to 84% and excellent purities exceeding 99% using a homogeneous Ru\/xantphos catalyst system. The observed average metal and phosphorus losses were at a minimal level of\u00a0&lt;\u00a01\u00a0wt% of the initial amounts. Based on this high catalyst retention, the additional potential of SACC for recycling the homogeneous catalyst was demonstrated.<\/jats:p>","DOI":"10.1002\/chem.202500059","type":"journal-article","created":{"date-parts":[[2025,6,2]],"date-time":"2025-06-02T08:48:32Z","timestamp":1748854112000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":3,"title":["Selective and Waste\u2010Free Isolation of High Purity Primary Amines from Amine and Reaction Mixtures by Selective Ammonium Carbamate Crystallization"],"prefix":"10.1002","volume":"31","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-5179-1226","authenticated-orcid":false,"given":"Bernd","family":"Rienhoff","sequence":"first","affiliation":[{"name":"Department for Biochemical and Chemical Engineering, Laboratory of Industrial Chemistry TU Dortmund University  Emil\u2010Figge\u2010Stra\u00dfe 66 Dortmund 44227 Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Dilara","family":"Mede","sequence":"additional","affiliation":[{"name":"Department for Biochemical and Chemical Engineering, Laboratory of Industrial Chemistry TU Dortmund University  Emil\u2010Figge\u2010Stra\u00dfe 66 Dortmund 44227 Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Mara","family":"Sch\u00f6ler","sequence":"additional","affiliation":[{"name":"Department for Biochemical and Chemical Engineering, Laboratory of Industrial Chemistry TU Dortmund University  Emil\u2010Figge\u2010Stra\u00dfe 66 Dortmund 44227 Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8514-5326","authenticated-orcid":false,"given":"Dieter","family":"Vogt","sequence":"additional","affiliation":[{"name":"Department for Biochemical and Chemical Engineering, Laboratory of Industrial Chemistry TU Dortmund University  Emil\u2010Figge\u2010Stra\u00dfe 66 Dortmund 44227 Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Thomas","family":"Seidensticker","sequence":"additional","affiliation":[{"name":"Department for Biochemical and Chemical Engineering, Laboratory of Industrial Chemistry TU Dortmund University  Emil\u2010Figge\u2010Stra\u00dfe 66 Dortmund 44227 Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2025,6,11]]},"reference":[{"key":"e_1_2_8_1_1","doi-asserted-by":"publisher","DOI":"10.1002\/cctc.201800365"},{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0926-860X(01)00813-4"},{"key":"e_1_2_8_3_1","first-page":"1","volume-title":"Ullmann's Encyclopedia of Industrial Chemistry","author":"Roose P.","year":"2015"},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0920-5861(97)00006-0"},{"key":"e_1_2_8_5_1","doi-asserted-by":"publisher","DOI":"10.1002\/cssc.201100187"},{"key":"e_1_2_8_6_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-328X(99)00614-2"},{"key":"e_1_2_8_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja910083q"},{"key":"e_1_2_8_6_3","doi-asserted-by":"publisher","DOI":"10.1021\/ol501739g"},{"key":"e_1_2_8_6_4","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199513481"},{"key":"e_1_2_8_6_5","doi-asserted-by":"publisher","DOI":"10.1021\/jo9622946"},{"key":"e_1_2_8_6_6","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-018-06416-6"},{"key":"e_1_2_8_6_7","doi-asserted-by":"publisher","DOI":"10.1002\/cssc.201402413"},{"key":"e_1_2_8_6_8","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.3c01150"},{"key":"e_1_2_8_6_9","doi-asserted-by":"publisher","DOI":"10.1038\/s41929-018-0202-6"},{"key":"e_1_2_8_6_10","doi-asserted-by":"publisher","DOI":"10.1126\/science.aan6245"},{"key":"e_1_2_8_6_11","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201812100"},{"key":"e_1_2_8_7_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.tetlet.2009.02.129"},{"key":"e_1_2_8_8_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201002576"},{"key":"e_1_2_8_9_1","doi-asserted-by":"publisher","DOI":"10.1021\/jo960057x"},{"key":"e_1_2_8_9_2","doi-asserted-by":"publisher","DOI":"10.1002\/cssc.202000856"},{"key":"e_1_2_8_10_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja9721881"},{"key":"e_1_2_8_10_2","doi-asserted-by":"publisher","DOI":"10.1016\/0040-4039(95)00605-C"},{"key":"e_1_2_8_10_3","unstructured":"c)F.Mosa S.Azam M. 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