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布朗斯台德酸性离子液体促进 N-卤代琥珀酰亚胺（NXS）与有机化合物的卤化反应。

Brønsted acidic ionic liquid accelerated halogenation of organic compounds with N-Halosuccinimides (NXS).

机构信息

Laboratory for Organic and Bioorganic Chemistry, Jožef Stefan Institute, Jamova, Ljubljana, Slovenia.

出版信息

Molecules. 2012 Dec 21;18(1):74-96. doi: 10.3390/molecules18010074.

DOI:10.3390/molecules18010074
PMID:23344189
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC6269842/
Abstract

The Brønsted-acidic ionic liquid 1-methyl-3-(4-sulfobutyl)imidazolium triflate [BMIM(SO(3)H)][OTf] was demonstrated to act efficiently as solvent and catalyst for the halogenation of activated organic compounds with N-halosuccinimides (NXS) under mild conditions with short reaction times. Methyl aryl ketones were converted into α-halo and α,α-dihaloketones, depending on the quantity of NXS used. Ketones with activated aromatic rings were selectively halogenated, however in some cases mixtures of α-halogenated ketone and ring-halogenated ketones were obtained. Activated aromatics were regioselectively ring halogenated to give mono- and dihalo-substituted products. The [BMIM(SO(3)H)][OTf] ionic liquid (IL-A) was successfully reused eight times in a representative monohalogenation reaction with no noticeable decrease in efficiency. An effective halogenation scale-up in this IL is also presented. The reactivity trend and the observed chemo- and regioselectiivities point to an ET process in these IL-promoted halofunctionalization reactions.

摘要

布朗斯特酸性离子液体 1-甲基-3-(4-磺丁基)咪唑𬭩三氟甲磺酸酯 [BMIM(SO(3)H)][OTf] 被证明在温和条件下，通过使用 N-卤代琥珀酰亚胺 (NXS) 作为溶剂和催化剂，在短反应时间内高效地用于活化有机化合物的卤化反应。根据 NXS 的用量，甲基芳基酮可以转化为α-卤代和α,α-二卤代酮。具有活化芳环的酮被选择性卤化，但在某些情况下，得到的是α-卤代酮和环卤代酮的混合物。活化的芳烃被区域选择性地环卤化，得到单卤代和二卤代取代产物。[BMIM(SO(3)H)][OTf]离子液体 (IL-A) 在具有代表性的单卤化反应中成功重复使用了八次，没有明显的效率下降。还提出了在这种 IL 中有效扩大卤化规模的方法。反应性趋势和观察到的化学和区域选择性表明，在这些 IL 促进的卤官能化反应中存在 ET 过程。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d075/6269842/7195c763ab5c/molecules-18-00074-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d075/6269842/aedff98e5d3e/molecules-18-00074-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d075/6269842/28da8133f73c/molecules-18-00074-sch001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d075/6269842/831ecf2235eb/molecules-18-00074-sch002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d075/6269842/005428c3ac14/molecules-18-00074-sch003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d075/6269842/b10ba6094006/molecules-18-00074-sch004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d075/6269842/866f14e79765/molecules-18-00074-sch005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d075/6269842/7195c763ab5c/molecules-18-00074-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d075/6269842/aedff98e5d3e/molecules-18-00074-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d075/6269842/28da8133f73c/molecules-18-00074-sch001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d075/6269842/831ecf2235eb/molecules-18-00074-sch002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d075/6269842/005428c3ac14/molecules-18-00074-sch003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d075/6269842/b10ba6094006/molecules-18-00074-sch004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d075/6269842/866f14e79765/molecules-18-00074-sch005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d075/6269842/7195c763ab5c/molecules-18-00074-g002.jpg

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