Design, synthesis and spectral characterization of cyclotriphosphazenes including heterocyclic rings

IF 4 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure Pub Date : 2024-11-19 DOI:10.1016/j.molstruc.2024.140772

Saliha Begeç

{"title":"Design, synthesis and spectral characterization of cyclotriphosphazenes including heterocyclic rings","authors":"Saliha Begeç","doi":"10.1016/j.molstruc.2024.140772","DOIUrl":null,"url":null,"abstract":"<div><div>In this study, described the synthesis on a cyclotriphosphazene containing the spirocyclic 2,2′-dioxybiphenyl group and 2-mercapto-1-methylimidazole (methimazole) or 2-mercaptothiazoline (MTZ) moieties. These spiro(in difunctional ligands, both ends are bound to the same phosphorus) cyclotriphosphazene derivatives (6, 7a) were synthesized in two steps. In first step; mono substituted phosphazene compounds 2,4,4,6,6-pentachloro-2-(2-mercapto-1-methylimidazolyl) cyclo2λ5, 4λ5, 6λ5, triphosphazatriene; N4P3Cl5C3S2H5 (4), and 2,4,4,6,6-pentachloro-2-(2-mercapto-tiyazolinyl) cyclo2λ5, 4λ5, 6λ5, triphosphazatriene; N4P3Cl5C4S2H4 (5)] were prepared from the reaction of hexachlorocyclotriphosphazatriene (trimer, N3P3Cl6, 1), with methimazole (2) or MTZ (3) in tetrahydrofurane (THF) in the presence of metallic sodium under an argon atmosphere.</div><div>In second step; monospiro2-mercaptothiazolinyl (7a) and dispiro2-mercapto-1-methylimidazolyl sübstituted (6) phosphazene derivatives were obtained from the reactions of 4 and 5 with 2,2′-dihydroxybiphenyl (8) in acetone in the presence of potassium carbonate (K2CO3). Structural characterizations of all obtained compounds were made using by elemental analysis, FT-IR, 1H, 13C and 31P NMR spectroscopies. Compounds 5–7a are reported for the first time in this study.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1323 ","pages":"Article 140772"},"PeriodicalIF":4.0000,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Molecular Structure","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0022286024032800","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}

引用次数: 0

Abstract

In this study, described the synthesis on a cyclotriphosphazene containing the spirocyclic 2,2′-dioxybiphenyl group and 2-mercapto-1-methylimidazole (methimazole) or 2-mercaptothiazoline (MTZ) moieties. These spiro(in difunctional ligands, both ends are bound to the same phosphorus) cyclotriphosphazene derivatives (6, 7a) were synthesized in two steps. In first step; mono substituted phosphazene compounds 2,4,4,6,6-pentachloro-2-(2-mercapto-1-methylimidazolyl) cyclo2λ⁵, 4λ⁵, 6λ⁵, triphosphazatriene; N₄P₃Cl₅C₃S₂H₅ (4), and 2,4,4,6,6-pentachloro-2-(2-mercapto-tiyazolinyl) cyclo2λ⁵, 4λ⁵, 6λ⁵, triphosphazatriene; N₄P₃Cl₅C₄S₂H₄ (5)] were prepared from the reaction of hexachlorocyclotriphosphazatriene (trimer, N₃P₃Cl₆, 1), with methimazole (2) or MTZ (3) in tetrahydrofurane (THF) in the presence of metallic sodium under an argon atmosphere.

In second step; monospiro2-mercaptothiazolinyl (7a) and dispiro2-mercapto-1-methylimidazolyl sübstituted (6) phosphazene derivatives were obtained from the reactions of 4 and 5 with 2,2′-dihydroxybiphenyl (8) in acetone in the presence of potassium carbonate (K₂CO₃). Structural characterizations of all obtained compounds were made using by elemental analysis, FT-IR, ¹H, ¹³C and ³¹P NMR spectroscopies. Compounds 5–7a are reported for the first time in this study.

Abstract Image

查看原文本刊更多论文

含杂环的环三唑膦的设计、合成和光谱表征

本研究描述了一种含有螺环 2,2′-二氧联苯基团和 2-巯基-1-甲基咪唑（甲巯咪唑）或 2-巯基噻唑啉（MTZ）分子的环三唑膦的合成。这些螺（在双官能团配体中，两端与同一磷结合）环三膦唑衍生物（6、7a）分两步合成。第一步，单取代磷杂蒽化合物 2,4,4,6,6-五氯-2-（2-巯基-1-甲基咪唑基）环 2λ5、4λ5、6λ5、三磷杂蒽；N4P3Cl5C3S2H5 (4)，以及 2,4,4,6,6-五氯-2-(2-巯基-噻唑啉基)环 2λ5, 4λ5, 6λ5, 三磷杂三烯；N4P3Cl5C4S2H4（5）]是由六氯环三磷氮杂三烯（三聚体，N3P3Cl6，1）与甲巯咪唑（2）或 MTZ（3）在四氢呋喃（THF）中，在金属钠存在下，于氩气气氛中反应制备而成。第二步，在碳酸钾（K2CO3）存在下，在丙酮中将 4 和 5 与 2,2′-二羟基联苯（8）反应，得到单螺 2-巯基噻唑啉基（7a）和二螺 2-巯基-1-甲基咪唑烷基übstituted（6）磷苯衍生物。利用元素分析、傅立叶变换红外光谱、1H、13C 和 31P NMR 光谱对所有获得的化合物进行了结构表征。本研究首次报道了化合物 5-7a。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文求助全文

来源期刊

Journal of Molecular Structure 化学-物理化学

CiteScore

7.10

自引率

15.80%

发文量

2384

审稿时长

45 days

期刊介绍： The Journal of Molecular Structure is dedicated to the publication of full-length articles and review papers, providing important new structural information on all types of chemical species including: • Stable and unstable molecules in all types of environments (vapour, molecular beam, liquid, solution, liquid crystal, solid state, matrix-isolated, surface-absorbed etc.) • Chemical intermediates • Molecules in excited states • Biological molecules • Polymers. The methods used may include any combination of spectroscopic and non-spectroscopic techniques, for example: • Infrared spectroscopy (mid, far, near) • Raman spectroscopy and non-linear Raman methods (CARS, etc.) • Electronic absorption spectroscopy • Optical rotatory dispersion and circular dichroism • Fluorescence and phosphorescence techniques • Electron spectroscopies (PES, XPS), EXAFS, etc. • Microwave spectroscopy • Electron diffraction • NMR and ESR spectroscopies • Mössbauer spectroscopy • X-ray crystallography • Charge Density Analyses • Computational Studies (supplementing experimental methods) We encourage publications combining theoretical and experimental approaches. The structural insights gained by the studies should be correlated with the properties, activity and/ or reactivity of the molecule under investigation and the relevance of this molecule and its implications should be discussed.