Xiaopeng Zhang et al. / Chinese Journal of Catalysis 37 (2016) 2034–2038
2037
Se
a low cost, atom economical, one‐pot, phosgene‐free process
for the preparation of 1,4‐dihydro‐2H‐3,1‐benzoxazin‐2‐one
without the formation of any corrosive waste or carbon diox‐
ide, making this approach a particularly promising alternative
to the existing procedures.
H O
CO
2
O
2
.
H Se
2
Et N
.
COSe Et N
3
3
References
C
A
NH
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B
Scheme 2. Proposed mechanism for the synthesis of 1,4‐dihydro‐2H‐
3,1‐benzoxazin‐2‐one.
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We have developed an efficient and economical approach
for the synthesis of 1,4‐dihydro‐2H‐3,1‐benzoxazin‐2‐one from
2‐aminobenzyl alcohol. The key features of this reaction in‐
clude the use of the cheap and recyclable non‐metal selenium
as a catalyst instead of the noble metal palladium; carbon
monoxide as a carbonylation agent instead of virulent phos‐
gene or one of its derivatives; and oxygen as an oxidant. Under
these conditions, the selenium‐catalyzed carbonylation of
2‐aminobenzyl alcohol proceeded efficiently in the presence of
triethylamine to afford the desired product 1,4‐dihydro‐2H‐3,1‐
benzoxazin‐2‐one in 87% yield. Overall, this process represents
Graphical Abstract
Chin. J. Catal., 2016, 37: 2034–2038 doi: 10.1016/S1872‐2067(16)62537‐8
Selenium‐catalyzed oxidative carbonylation of 2‐aminobenzyl alcohol to give 1,4‐dihydro‐2H‐3,1‐benzoxazin‐2‐one
Xiaopeng Zhang*, Ping Wang, Xueli Niu, Zhengwei Li, Xuesen Fan, Guisheng Zhang*
Henan Normal University
O
OH
NH2
O2, Et3N
+
CO
Cat. Se
N
O
H
phase-transfer catalysis!
87% yield
one-pot phosgene-free manner!
1,4‐Dihydro‐2H‐3,1‐benzoxazin‐2‐one was prepared in 87% yield via the one‐pot selenium‐catalyzed oxidative carbonylation of
2‐aminobenzyl alcohol. The selenium catalyst was readily recovered and recycled.