{"title":"弗勒里吗啡试验的机制","authors":"F. Sánchez-Viesca, Reina Gómez","doi":"10.34198/ejcs.11324.379384","DOIUrl":null,"url":null,"abstract":"The test under study is due to M. Fleury. He used morphine dissolved, at room temperature, in 1/20 N sulphuric acid; added some lead superoxide (lead dioxide), stirred for 8 min., let stand 4 min; the water-clear liquid was separated, and a drop of ammonia was added. A brown colour occurs immediately. These experimental data indicate not a fast reaction, but a rather complex mechanism. In this communication a reaction mechanism is provided for the first time. Protonated lead dioxide is the reactive species which on interaction with the phenol group in morphine forms a mixed ortho-plumbate. Protonation of this ester does not favor further reaction. However, reaction with a second reactive species is favourable for a push-pull seven-member reaction mechanism. Enolization of the dienone formed restores aromaticity. Protonation of the Pb=O double bond in the obtained intermediate promotes a 7-atom concerted mechanism. 2,3-Dioxomorphine is formed along with an oxide hydrate that yields water and two molecules of plumbous oxide.","PeriodicalId":507232,"journal":{"name":"Earthline Journal of Chemical Sciences","volume":" 98","pages":""},"PeriodicalIF":0.0000,"publicationDate":"2024-06-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"The mechanism of Fleury test for morphine\",\"authors\":\"F. Sánchez-Viesca, Reina Gómez\",\"doi\":\"10.34198/ejcs.11324.379384\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"The test under study is due to M. Fleury. He used morphine dissolved, at room temperature, in 1/20 N sulphuric acid; added some lead superoxide (lead dioxide), stirred for 8 min., let stand 4 min; the water-clear liquid was separated, and a drop of ammonia was added. A brown colour occurs immediately. These experimental data indicate not a fast reaction, but a rather complex mechanism. In this communication a reaction mechanism is provided for the first time. Protonated lead dioxide is the reactive species which on interaction with the phenol group in morphine forms a mixed ortho-plumbate. Protonation of this ester does not favor further reaction. However, reaction with a second reactive species is favourable for a push-pull seven-member reaction mechanism. Enolization of the dienone formed restores aromaticity. Protonation of the Pb=O double bond in the obtained intermediate promotes a 7-atom concerted mechanism. 2,3-Dioxomorphine is formed along with an oxide hydrate that yields water and two molecules of plumbous oxide.\",\"PeriodicalId\":507232,\"journal\":{\"name\":\"Earthline Journal of Chemical Sciences\",\"volume\":\" 98\",\"pages\":\"\"},\"PeriodicalIF\":0.0000,\"publicationDate\":\"2024-06-09\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Earthline Journal of Chemical Sciences\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://doi.org/10.34198/ejcs.11324.379384\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Earthline Journal of Chemical Sciences","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.34198/ejcs.11324.379384","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
The test under study is due to M. Fleury. He used morphine dissolved, at room temperature, in 1/20 N sulphuric acid; added some lead superoxide (lead dioxide), stirred for 8 min., let stand 4 min; the water-clear liquid was separated, and a drop of ammonia was added. A brown colour occurs immediately. These experimental data indicate not a fast reaction, but a rather complex mechanism. In this communication a reaction mechanism is provided for the first time. Protonated lead dioxide is the reactive species which on interaction with the phenol group in morphine forms a mixed ortho-plumbate. Protonation of this ester does not favor further reaction. However, reaction with a second reactive species is favourable for a push-pull seven-member reaction mechanism. Enolization of the dienone formed restores aromaticity. Protonation of the Pb=O double bond in the obtained intermediate promotes a 7-atom concerted mechanism. 2,3-Dioxomorphine is formed along with an oxide hydrate that yields water and two molecules of plumbous oxide.