Dirk Hollenwäger, Daniela Staudacher, Niklas Kölbl, Dominik Leitz, Valentin Bockmair, Andreas J. Kornath
{"title":"Synthesis and Structure of Methylated Acetylenic Nitriles","authors":"Dirk Hollenwäger, Daniela Staudacher, Niklas Kölbl, Dominik Leitz, Valentin Bockmair, Andreas J. Kornath","doi":"10.1021/acs.joc.4c02405","DOIUrl":null,"url":null,"abstract":"Cyanoacetylene and dicyanoacetylene react in the ternary methylation system CH<sub>3</sub>F/SbF<sub>5</sub>/SO<sub>2</sub> under the formation of its corresponding <i>N</i>-monomethylated and <i>N,N′</i>-dimethylated species, respectively. Additionally, in the case of dicyanoacetylene, an <i>N,N′</i>-dimethylated HF-addition product was obtained. The salts were characterized by low-temperature vibrational spectroscopy. In the case of [C<sub>4</sub>H<sub>4</sub>N][SbF<sub>6</sub>], [C<sub>5</sub>H<sub>3</sub>N<sub>2</sub>][SbF<sub>6</sub>]·SO<sub>2</sub>, and [C<sub>6</sub>H<sub>8</sub>N<sub>2</sub>F<sub>2</sub>][SbF<sub>6</sub>]<sub>2</sub>, single-crystal X-ray structures are reported. Surprisingly, all of the obtained salts are room-temperature stable. The experimental data are discussed, together with quantum chemical calculations at the M06-2X/aug-cc-pVTZ level of theory.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"28 1","pages":""},"PeriodicalIF":3.3000,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Organic Chemistry","FirstCategoryId":"1","ListUrlMain":"https://doi.org/10.1021/acs.joc.4c02405","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}
引用次数: 0
Abstract
Cyanoacetylene and dicyanoacetylene react in the ternary methylation system CH3F/SbF5/SO2 under the formation of its corresponding N-monomethylated and N,N′-dimethylated species, respectively. Additionally, in the case of dicyanoacetylene, an N,N′-dimethylated HF-addition product was obtained. The salts were characterized by low-temperature vibrational spectroscopy. In the case of [C4H4N][SbF6], [C5H3N2][SbF6]·SO2, and [C6H8N2F2][SbF6]2, single-crystal X-ray structures are reported. Surprisingly, all of the obtained salts are room-temperature stable. The experimental data are discussed, together with quantum chemical calculations at the M06-2X/aug-cc-pVTZ level of theory.
期刊介绍：
Journal of Organic Chemistry welcomes original contributions of fundamental research in all branches of the theory and practice of organic chemistry. In selecting manuscripts for publication, the editors place emphasis on the quality and novelty of the work, as well as the breadth of interest to the organic chemistry community.
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