䓬[註 1](tropylium ion)即环庚三烯正离子(cycloheptatrienyl cation),化学式 [C7H7]+。 1,3,5-环庚三烯發生氧化后成为6π电子芳香性环庚三烯正离子。
1891年,G·梅尔林通过环庚三烯和溴的反应,制取出一种可溶于水的溴化合物。[4]和其它溴代烃不同,这种化合物(即溴化䓬)可溶于水,不溶于多数有机溶剂。它和硝酸银溶液反应会形成溴化银沉淀,表明其中含有自由溴离子。1954年,多林(英语:William von Eggers Doering)和诺克斯通过分析溴化䓬的红外和紫外光谱,发现它不是溴代烃,而是离子化合物C
7H+
7Br−
。[5][6]类似的高氯酸䓬(C
7H+
7ClO−
4)和碘化䓬(C
7H+
7I−
)也已通过X射线衍射确认为离子化合物。[7]䓬离子的碳-碳键键长为147 pm,比苯(140 pm)长,但比乙烷(154 pm)短。
䓬正离子经常以m/z = 91的单峰出现在能裂解出苄基正离子(PhCH2+)的化合物的质谱图中,是后者的重排产物。比如甲苯的电子电离质谱图中的基峰就在 M-1 = 91,为亚稳的䓬正离子。
- ^1.01.11.21.31.41.5tropylium | ChemSpider. www.chemspider.com: Names. [30 December 2018]. (原始内容存档于2021-12-20).
tropylium
- ^International Union of Pure and Applied Chemistry. Nomenclature of Organic Chemistry: IUPAC Recommendations and Preferred Names 2013.The Royal Society of Chemistry. 2014: 1127.ISBN 978-0-85404-182-4.doi:10.1039/9781849733069.
- ^3.03.13.23.33.4Tropylium. pubchem.ncbi.nlm.nih.gov. [30 December 2018]. (原始内容存档于2020-07-25)(英语).
Chemical Names: Tropylium; Cycloheptatrienylium; Cyc-C
7H+
7; Cyclohepta-2,4,6-trienylium
- ^Merling, G. Ueber Tropin. Berichte der Deutschen Chemischen Gesellschaft. 1891,24 (2): 3108–3126.doi:10.1002/cber.189102402151.
- ^Eggers Doering, W. von; Knox, L. H. The Cycloheptatrienylium (Tropylium) Ion. J. Am. Chem. Soc. 1954,76 (12): 3203–3206.doi:10.1021/ja01641a027.
- ^Balaban, Alexandru T.; Oniciu, Daniela C.; Katritzky, Alan R. Aromaticity as a Cornerstone of Heterocyclic Chemistry. Chem. Rev. 2004,104 (5): 2777–2812.PMID 15137807.doi:10.1021/cr0306790.
- ^Kitaigorodskii, A. I.; Struchkov, Yu. T.; Khotsyanova, T. L.; Vol'pin, M. E.; Kursanov, D. N. Crystal structures of tropylium perchlorate and iodide. Bulletin of the Academy of Sciences of the USSR Division of Chemical Science. 1960,9 (1): 32–36.ISSN 0568-5230.doi:10.1007/bf01178699(英语).
- Nic, M.; Jirat, J.; Kosata, B., eds. (2006–). "molecule". IUPAC Compendium of Chemical Terminology (Online ed.). doi:10.1351/goldbook.M04002.ISBN 0-9678550-9-8.
- Tropylium tetrafluorate Organic Syntheses, Coll. Vol. 5, p.1138 (1973); Vol. 43, p.101 (1963). link
- Merling, G. (1891), Ueber Tropin. Berichte der deutschen chemischen Gesellschaft, 24: 3108–3126. doi:10.1002/cber.189102402151
- The Cycloheptatrienylium (Tropylium) Ion W. Von E.Doering, L. H. Knox J. Am. Chem. Soc., 1954, 76 (12), pp 3203–3206 doi:10.1021/ja01641a027
- Aromaticity as a Cornerstone of Heterocyclic Chemistry Alexandru T. Balaban, Daniela C. Oniciu, Alan R. Katritzky Chem. Rev., 2004, 104 (5), pp 2777–2812 doi:10.1021/cr0306790