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Green Chemistry
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(0.5 mL) were mixed together. The mixture was stirred at 80 °C. equivalents of bisnucleophile and CH3NO2 at 80 °C were used
Then 1b in 0.6 M DMSO (0.5 mL) was added in 5 hours via for 4d. The procedure for synthesis oDfOcI:o1m0.1p0o3u9n/Cd9sGC40e2-2h06iFs
syringe pump after which the reaction was performed for 3 similar to that of compound 3a except that the bisnucleophile
more hours. Upon completion, the mixture was diluted with was added in one pot.
water (50 mL) and extracted with ethyl acetate (20 mL × 3).
The combined organic layers were dried over Na2SO4, filtered
and concentrated by rotary evaporation. The residue was
Conflicts of interest
purified by preparative TLC (eluting solution: petroleum
ether/ethyl acetate = 10/1 (v/v)), yielding the 2H-pryrone 3a in
82% yield (49.5 mg). Similar compounds were prepared
following the standard procedure.
There are no conflicts to declare.
Acknowledgements
The authors thank the National Natural Science Foundation of
China (2171101076, 21872060) and the Fundamental Research
Funds for the Central Universities of China (2016YXZD033,
2019kfyXJJS072) for the financial support. The Cooperative
Innovation Center of Hubei Province is also acknowledged.
Synthesis of quinaldic acid in three steps
Fresh distilled furfural (2.5 mL, 30 mmol), rose bengal (20 mg),
and methanol (50 mL) were mixed in a 100 mL round bottom
flask. The orange mixture was bubbled with oxygen gas and
irradiated by a 450W Ace medium-pressure Hg lamp (quartz
filter) for 24 hours. Upon completion, the solution was
concentrated in vacuum to afford crude 1a as an orange paste.
Then dried ethanol (60 mL) and PTSA (516.6 mg, 3 mmol) were
added inside. The mixture was stirred at 60 °C. After the
reaction was completed (monitored by TLC plate), the solution
was concentrated in vacuum. The residue was purified via
vacuum distillation (110 °C at 10 Torr), yielding 1b in 72% yield
(4.37 g, 21.6 mmol). A mixture of 2a (931.3 mg, 10 mmol), TFA
(114.0 mg), I2 (25.4 mg), and DMSO (15 mL) was stirred at 80
°C. Then 1b (10 mmol in 15 mL DMSO solution) was added via
syringe pump in 5 hours after which the reaction was
performed for 3 more hours. Upon completion, the mixture
was diluted with water (150 mL) and extracted with ethyl
acetate (50 mL × 5). The combined organic layers were dried
over Na2SO4, filtered and concentrated by rotary evaporation.
The residue was purified by column chromatography (SiO2,
petroleum ether to petroleum ether/ethyl acetate = 10/1 (v/v)
gradient elution), yielding the 3a in 80% yield (1.61 g). The 3a
(1.01 g, 5 mmol) was dissolved in a mixed solution of methanol
(10.0 mL) and THF (10.0 mL). Then a solution of NaOH (0.6 g,
15 mmol, 3.0 equiv) in H2O (10 mL) was added and the mixture
was stirred for 4 h at room temperature. The solution was
then cooled to 0 °C (in an ice and water bath) and acidified
with aq. HCl (2.00 N) to pH = 5. The solution was extracted
with ethyl acetate (3 x 50 mL) and washed with brine. The
organic layer was dried over Na2SO4, filtered and evaporated
to furnish 2-quinaldic acid in 93% yield (0.81 g).
Notes and references
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