{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,26]],"date-time":"2025-10-26T20:53:45Z","timestamp":1761512025759,"version":"build-2065373602"},"reference-count":33,"publisher":"Wiley","issue":"1","license":[{"start":{"date-parts":[[2004,12,20]],"date-time":"2004-12-20T00:00:00Z","timestamp":1103500800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Eur J Org Chem"],"published-print":{"date-parts":[[2005,1]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The decomposition of <jats:italic>N\u2032<\/jats:italic>\u2010benzoyl\u2010<jats:italic>N<\/jats:italic>\u2010methyl\u2010<jats:italic>N<\/jats:italic>\u2010nitrosourea (BMNU) in aqueous media over the 0\u221214 pH range has been studied. In basic and neutral media (6 &lt; pH &lt; 14) the reaction proceeds through abstraction of the acidic proton of BMNU (p<jats:italic>K<jats:sub>a<\/jats:sub><\/jats:italic> = 7.8) and subsequent decomposition of the conjugate base of the thus formed nitrosourea, via an intermediate benzoyl isocyanate. Support for this mechanism is provided by the presence of <jats:italic>N<\/jats:italic>,<jats:italic>N\u2032<\/jats:italic>\u2010dibenzoylurea in the final reaction mixtures, as the result of the trapping of benzoyl isocyanate with benzamide generated from hydrolysis of the former. The hydrolysis of BMNU takes place through three competitive pathways: spontaneous decomposition of the conjugate base of BMNU, and buffer\u2010catalyzed and hydroxide ion catalyzed water addition to the carbonyl group of the deprotonated nitrosourea. <jats:italic>N\u2032<\/jats:italic>\u2010Benzoyl\u2010<jats:italic>N<\/jats:italic>,<jats:italic>N\u2032<\/jats:italic>\u2010dimethyl\u2010<jats:italic>N<\/jats:italic>\u2010nitrosourea (BDMNU), a benzoyl nitrosourea lacking the acidic proton of BMNU, is hydrolyzed in basic media by attack of hydroxide ion on the carbonyl group of the urea. In acid media (0 &lt; pH &lt; 6), BMNU gives only deamination products, differing from the reported behavior of other <jats:italic>N<\/jats:italic>\u2010nitroso compounds and of the isoster nitrosoguanidine, in which denitrosation is almost quantitative. The reaction is acid\u2010catalyzed in the 0\u22122.5 pH range and pH\u2010independent in the 3\u22125 pH range. The presence of general acid catalysis (<jats:italic>\u03b1<\/jats:italic> = 0.60), the absence of nucleophilic catalysis, and the thermodynamic activation parameters for the reaction support the mechanism proposed in the literature for the deamination of <jats:italic>N<\/jats:italic>\u2010nitrosoureas in acidic media. (\u00a9 Wiley\u2010VCH Verlag GmbH &amp; Co. KGaA, 69451 Weinheim, Germany, 2005)<\/jats:p>","DOI":"10.1002\/ejoc.200400537","type":"journal-article","created":{"date-parts":[[2004,12,20]],"date-time":"2004-12-20T07:48:18Z","timestamp":1103528898000},"page":"154-161","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":6,"title":["Decomposition of <i>N<\/i>\u2032\u2010Benzoyl\u2010<i>N<\/i>\u2010nitrosoureas in Aqueous Media"],"prefix":"10.1002","volume":"2005","author":[{"given":"Celia","family":"Faustino","sequence":"first","affiliation":[]},{"given":"Luis","family":"Garc\u00eda\u2010R\u00edo","sequence":"additional","affiliation":[]},{"given":"Jos\u00e9\u00a0Ram\u00f3n","family":"Leis","sequence":"additional","affiliation":[]},{"given":"F\u00e1tima","family":"Norberto","sequence":"additional","affiliation":[]}],"member":"311","published-online":{"date-parts":[[2004,12,20]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"\u00a0"},{"key":"e_1_2_6_2_2","unstructured":"Cancer Chemotherapy and Biotherapy(Eds.: B. A. Chabner D. L. Longo) 2nd ed. Lippincott\u2010Raven Pub. Philadelphia 1996."},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr941192h"},{"key":"e_1_2_6_4_2","unstructured":"\u00a0"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/jm00184a007"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/jm00181a018"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00230a040"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00164a046"},{"key":"e_1_2_6_9_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00259a071"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00198a064"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo01298a048"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo00339a010"},{"key":"e_1_2_6_13_2","doi-asserted-by":"publisher","DOI":"10.1248\/cpb.21.1811"},{"key":"e_1_2_6_14_2","doi-asserted-by":"publisher","DOI":"10.1002\/jps.2600540127"},{"key":"e_1_2_6_15_2","unstructured":"\u00a0"},{"key":"e_1_2_6_16_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo00950a011"},{"key":"e_1_2_6_17_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(01)85192-3"},{"key":"e_1_2_6_18_2","unstructured":"\u00a0"},{"key":"e_1_2_6_19_2","doi-asserted-by":"publisher","DOI":"10.1246\/bcsj.55.2200"},{"key":"e_1_2_6_20_2","doi-asserted-by":"publisher","DOI":"10.1039\/P29850000437"},{"key":"e_1_2_6_21_2","doi-asserted-by":"publisher","DOI":"10.1039\/P29960002235"},{"key":"e_1_2_6_22_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00953a014"},{"key":"e_1_2_6_23_2","doi-asserted-by":"publisher","DOI":"10.1039\/p29800001372"},{"key":"e_1_2_6_24_2","first-page":"597","author":"Casado J.","year":"1985","journal-title":"Bull. Soc. Chim. Fr."},{"key":"e_1_2_6_25_2","doi-asserted-by":"publisher","DOI":"10.1246\/bcsj.57.601"},{"key":"e_1_2_6_26_2","doi-asserted-by":"publisher","DOI":"10.1039\/p19840000075"},{"key":"e_1_2_6_27_2","unstructured":"T. P. Vishnyakova I. A. Golubeva E. V. Glebova Usp. Khim.1985 54 429\u2212449;Chem. Abstr.1985 103 21850n."},{"key":"e_1_2_6_28_2","doi-asserted-by":"publisher","DOI":"10.1039\/p29740001638"},{"key":"e_1_2_6_29_2","unstructured":"Amado et al.[10]discriminated between mechanisms (i) and (ii) by treating the nitroso substrate with the nucleophile HOO\u2212(pKa= 11.64) which is a much stronger nucleophile than HO\u2212but a less strong base. In our case we found that treatment of either BMNU or BDMNU in 0.05\u22120.5Mhydroperoxide solutions of pH = 10.78 (kept constant by an external carbonate buffer) were too fast to measure. This was expected for BDMNU but not for BMNU unless the latter decomposes by nucleophilic attack on the carbonyl group. However the possibility of general base catalysis by HOO\u2212cannot be excluded as for BMNU a catalytic action was exerted by other bases above pH \u2248\ufe01 9. Nucleophilic attack of HOO\u2212on the nitroso groups of both benzoyl nitrosoureas was ruled out by the non\u2010formation of the peroxynitrite ion (\u03f5302= 1670 \u00b1 50M\u22121\u00b7cm\u22121) which is stable under the experimental conditions employed."},{"key":"e_1_2_6_30_2","doi-asserted-by":"publisher","DOI":"10.1039\/P29860000117"},{"key":"e_1_2_6_31_2","doi-asserted-by":"publisher","DOI":"10.1039\/a707216c"},{"key":"e_1_2_6_32_2","doi-asserted-by":"publisher","DOI":"10.1039\/p29750000153"},{"key":"e_1_2_6_33_2","doi-asserted-by":"publisher","DOI":"10.1039\/p29890001471"}],"container-title":["European Journal of Organic Chemistry"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fejoc.200400537","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/ejoc.200400537","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,13]],"date-time":"2025-10-13T15:52:32Z","timestamp":1760370752000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/ejoc.200400537"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2004,12,20]]},"references-count":33,"journal-issue":{"issue":"1","published-print":{"date-parts":[[2005,1]]}},"alternative-id":["10.1002\/ejoc.200400537"],"URL":"https:\/\/doi.org\/10.1002\/ejoc.200400537","archive":["Portico"],"relation":{},"ISSN":["1434-193X","1099-0690"],"issn-type":[{"type":"print","value":"1434-193X"},{"type":"electronic","value":"1099-0690"}],"subject":[],"published":{"date-parts":[[2004,12,20]]},"assertion":[{"value":"2004-07-30","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2004-12-20","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}]}}