高纯度对称 Dialkylphosphinic 酸萃取的合成
Summary
介绍了一种合成高纯度对称 dialkylphosphinic 酸萃取的协议, 以 (23-dimethylbutyl) (24, 4 ‘-2,4,4-) 膦酸为例。
Abstract
本文以 (23-dimethylbutyl) (24、4-2,4,4-) 膦酸的合成为例, 说明了一种合成高纯度对称 dialkylphosphinic 酸萃取的方法。以低毒磷酸钠为磷源, 与烯烃 A (23-二甲基-1-丁烯) 发生反应, 生成 monoalkylphosphinic 酸中间体。采用金刚烷胺除去 dialkylphosphinic 酸副产品, 因为只有 monoalkylphosphinic 酸能与金刚烷胺反应形成 amantadine∙mono-alkylphosphinic 酸盐, 而 dialkylphosphinic 酸不能与金刚烷胺反应, 因为其巨大的空间位阻。纯化后的 monoalkylphosphinic 酸与烯烃 B (丁烯) 反应产生对称 dialkylphosphinic 酸 (NSDAPA)。未 monoalkylphosphinic 酸可以通过简单的碱酸后处理去除, 通过钴盐的沉淀可以分离出其他有机杂质。(23-dimethylbutyl) (24, 4 ‘-2,4,4-) 膦酸的结构由31P 核磁共振、 1H 核磁共振、ESI 质谱和 FT IR 证实。纯度由电位滴定法测定, 结果表明纯度可超过96%。
Introduction
酸性有机磷萃取被广泛应用于传统的湿法冶金领域, 用于稀土离子的萃取和分离1,2, 有色金属 (如钴/镍3,4), 稀有金属 (如 Hf/锆5, V6,7), 锕8,等。近年来, 它们在二次资源回收和高级液体废物处理方面也引起了更多的关注9。二 (2-乙基己基) 磷酸 (D2EHPA 或 P204), 2-ethylhexylphosphoric 酸 mono-2-ethylhexyl 酯 (EHEHPA, PC 88A, 或 P507), 和 di (24, 4 ‘-2,4,4-)-膦酸 (Cyanex272), 是 dialkylphosphoric 酸的代表,alkylphosphoric 酸单烷基酯和 dialkylphosphinic 酸分别是最常用的萃取。它们的酸度按以下顺序递减: P204 和 #62; P507 和 #62; Cyanex 272。相应的萃取能力、萃取能力、剥离酸度均为 P204 和 #62; P507 和 #62; Cyanex 272, 分离性能则相反。在大多数情况下, 这三萃取是有效的。然而, 仍有一些条件, 它们不是如此有效: 在重稀土分离, 其中存在的主要问题是选择性差, 高剥离酸性 P204 和 P507, 低萃取能力, 和乳液的趋势在提取期间为 Cyanex 272。近年来, 小说萃取的发展引起了人们的广泛关注。
dialkylphosphinic 酸萃取被认为是开发新萃取的重要研究方向之一。最近的研究表明, dialkylphosphinic 酸的提取能力主要取决于烷基取代基的结构10,11。它的范围可能比 Cyanex 27212的 P507 要低得多。然而, 对新型 dialkylphosphinic 酸萃取的探索仅限于商用烯烃结构10、12、13、14、15, 16。虽然 dialkylphosphinic 酸萃取也可以通过氏反应的方法合成, 但反应条件是严格的12,17。
NSDAPA, 其中两个烷基是不同的, 打开一扇门, 探索新的萃取。它使 dialkylphosphinic 酸的结构更加多样化, 其提取和分离性能可以通过对它的烷基结构进行 fine-tuned。传统的 NSDAPA 合成方法采用 PH 值为3作为磷源, 具有毒性高、反应条件严格、不易纯化等诸多缺点。最近, 我们报告了一种新的合成 NSDAPA 的方法, 利用磷酸钠作为磷源 (参见图 1) 并成功合成了三 NSDAPAs18。这个详细的协议可以帮助新的实践者重复实验, 掌握 NSDAPA 萃取的合成方法。我们以 (23-dimethylbutyl) (24, 4 ‘-2,4,4-) 膦酸为例。在表 1中显示了烯烃 a、单 alkylphosphinic 酸中间体、烯烃 B 和相应的 NSDAPA 的名称和结构。
Protocol
Representative Results
Discussion
协议中最关键的步骤是单 alkylphosphinic 酸合成 (图 1a)。在这个反应中, 较高的产量和较少的 dialkylphosphinic 酸 by-product 是更好的。增加 NaH2PO2/烯烃 A 的摩尔比将提高产量, 抑制 dialkylphosphinic 酸 by-product 的产生。但是, 大型 NaH2PO2用量也会增加成本并引起搅拌问题。NaH2PO2/烯烃 A 的首选摩尔比为3:1。作为溶剂, 呋喃是优?…
Declarações
The authors have nothing to disclose.
Acknowledgements
这项工作得到了中国国家自然科学基金 (21301104)、中央大学基础研究基金 (FRF-TP-16-019A3) 和国家重点化学工程实验室 (SKL-ChE-14A04) 的支持。
Materials
| sodium hypophosphite hydrate | Tianjin Fuchen Chemical Reagents Factory | Molecular formula: NaH2PO2∙H2O, purity ≥99.0% | |
| 2,3-dimethyl-1-butene | Adamas Reagent Co., Ltd. | Molecular formula: C6H12, purity ≥99% | |
| diisobutylene | Shanghai Aladdin Bio-Chem Technology Co., LTD | Molecular formula: C8H16, purity 97% | |
| acetic acid | Sinopharm Chemical Reagent Co., Ltd. | Molecular formula: C2H4O2, purity ≥99.5% | |
| di-tert-butylnperoxide | Sinopharm Chemical Reagent Co., Ltd. | Molecular formula: C8H18O2, purity ≥97.0% | |
| tetrahydrofuran | Beijing Chemical Works | Molecular formula: C4H8O, purity A.R. | |
| amantadine hydrochloride | Shanghai Aladdin Bio-Chem Technology Co., LTD | Molecular formula: C10H17N∙HCl, purity 99% | |
| ethyl ether | Sinopharm Chemical Reagent Co., Ltd. | Molecular formula: C4H10O, purity ≥99.7% | |
| ethyl acetate | Xilong Chemical Co., Ltd. | Molecular formula: C4H8O2, purity ≥99.5% | |
| acetone | Beijing Chemical Works | Molecular formula: C3H6O, purity ≥99.5% | |
| sodium hydroxide | Xilong Chemical Co., Ltd. | Molecular formula: NaOH, purity ≥96.0% | |
| concentrated sulfuric acid | Sinopharm Chemical Reagent Co., Ltd. | Molecular formula: H2SO4, purity 95-98% | |
| hydrochloric acid | Beijing Chemical Works | Molecular formula: HCl, purity 36-38% | |
| sodium chloride | Sinopharm Chemical Reagent Co., Ltd. | Molecular formula: NaCl, purity ≥99.5% | |
| anhydrous magnesium sulfate | Tianjin Jinke Institute of Fine Chemical Industry | Molecular formula: MgSO4, purity ≥99.0% | |
| Cobalt(II) chloride hexahydrate | Xilong Chemical Co., Ltd. | Molecular formula: CoCl2∙6H2O, purity ≥99.0% |
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