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使用等摩尔 POCl₃ 对羟基嘧啶、吡啶、吡嗪和酰胺进行大规模无溶剂氯化。

Large-scale solvent-free chlorination of hydroxy-pyrimidines, -pyridines, -pyrazines and -amides using equimolar POCl₃.

机构信息

School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai, 200237, China.

出版信息

Molecules. 2012 Apr 16;17(4):4533-44. doi: 10.3390/molecules17044533.

DOI:10.3390/molecules17044533
PMID:22508333
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC6290571/
Abstract

Chlorination with equimolar POCl₃ can be efficiently achieved not only for hydroxypyrimidines, but also for many other substrates such as 2-hydroxy-pyridines, -quinoxalines, or even -amides. The procedure is solvent-free and involves heating in a sealed reactor at high temperatures using one equivalent of pyridine as base. It is suitable for large scale (multigram) batch preparations.

摘要

用等摩尔的 POCl₃进行氯化不仅可以有效地实现羟嘧啶,还可以实现许多其他底物,如 2-羟基吡啶、-喹喔啉,甚至 -酰胺。该过程是无溶剂的,并且涉及在密封反应器中使用吡啶作为碱在高温下加热,使用一个当量。它适用于大规模(多克)批量制备。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eab9/6290571/1f4062304103/molecules-17-04533-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eab9/6290571/1742cc8acc80/molecules-17-04533-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eab9/6290571/1f4062304103/molecules-17-04533-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eab9/6290571/1742cc8acc80/molecules-17-04533-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eab9/6290571/1f4062304103/molecules-17-04533-g002.jpg

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Bromine-lithium exchange under non-cryogenic conditions: TMSCH(2)Li-LiDMAE promoted C-2 lithiation of 2,3-dibromopyridine.
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