PRACTICAL SYNTHETIC PROCEDURES
Convenient Synthesis of Propiolaldehyde
1625
cm) under atmospheric pressure to afford propiolaldehyde (38.78 g,
bp 53–83 °C/760 mm Hg) containing about 12–23% of the solvent.
Redistillation led to the collection of pure propiolaldehyde;13 yield:
30.06 g (54%); bp 54–57 °C/760 mm Hg; purity: 94%. The purity
was determined by GC. Conditions: column: HP-5 (25 m × 0.32
mm); carrier: N2; injector: 250 °C; detector (FID, H2): 250 °C; flow:
50 °C for 5 min, 3 °C/min to 150 °C and hold for 5 min; tR = 1.4 min
(propiolaldehyde, 94%), tR = 5.1 min (p-xylene, 5%).
organic solvent with a high boiling point. Fortunately,
when p-xylene was used as reaction solvent instead of
DCE, 54% isolated yield of propiolaldehyde was obtained
after only simple workup procedure and distillation
(Scheme 1).
In conclusion, we have developed a practical, mild, and
convenient procedure for the synthesis of propiolaldehyde
using molecular oxygen as oxidant under atmospheric
pressure at room temperature with a higher yield.
Note: The product should be stored in a bottle with a glass-stopper,
since contaminants from a rubber stopper may be sufficient to cata-
lyze decomposition.
IR (neat): 3272, 2880, 2098, 1669, 1390, 948, 682 cm–1.
1H NMR (300 MHz, CDCl3): δ = 9.21 (s, 1 H), 3.48 (s, 1 H).
13C NMR (75.4 MHz, CDCl3): δ = 176.4, 82.6, 81.5.
MS (EI): m/z (%) = 54 (M+, 16.93), 53 (M+ – H, 100).
1H and 13C NMR spectra were recorded with an instrument operated
1
at 300 MHz for H NMR and 75 MHz for 13C NMR in CDCl3.
Chemical shifts (δ) are given in parts per million (ppm). IR spectra
were recorded on an FT IR spectrometer. Mass spectra were record-
ed in EI mode. Fe(NO3)3·9H2O, NaCl, and p-xylene were purchased
from Sinopharm Chemical Reagent Corporation; TEMPO (purity:
99%) was purchased from AstaTech Pharmaceutical Corporation;
propargyl alcohol (purity: 98%) was available from Shanghai Darui
Fine Chemical Corporation.
Acknowledgment
We greatly acknowledge the financial support from the Major State
Basic Research Development Program of China (NO.
2009CB825300) and the National Natural Science Foundation of
China (21232006).
Propiolaldehyde (1)
A three-necked 2000 mL round-bottomed flask equipped with a
thermometer and a pressure-equalizing addition funnel was fitted
with
a magnetic stirring bar. To this flask were added
Fe(NO3)3·9H2O (20.20 g, 50.0 mmol), TEMPO (4.70 g, 30.0
mmol), NaCl (2.91 g, 50 mmol), and p-xylene (1000 mL) under the
atmosphere of air at r.t. The air atmosphere was then replaced with
oxygen by an oxygen bag commonly used in hospitals (SY-42 L,
Shanghai Sanhe Medical Instrument CO., Ltd) (Figure 1). Propar-
gyl alcohol (58.0 mL, d = 0.949, 55.85 g, 1.0 mol) was injected via
a syringe and then added to the suspension through the addition fun-
nel dropwise with stirring at r.t. within ~1 h. After stirring at r.t. for
an additional 4 h (note: the reaction was exothermic, so the internal
temperature would rise up to 45 °C; care must be taken to keep the
temperature <45 °C), the reaction was complete as monitored by 1H
NMR analysis (300 MHz, CDCl3) till the signals for the starting al-
cohol (δ = 4.24, d, J = 2.4 Hz, 2 H, CH2) disappeared. The resulting
liquid layer was separated, and the residue was washed with p-xy-
lene (2 × 50 mL). The combined organic layers were dried (Na2SO4)
and filtered through a short pad of silica gel (Φ 7 cm × 1 cm). The
filtrate was transferred to a 2 L round-bottomed flask equipped with
a magnetic stirring bar and distilled through a Liebig condenser (20
Supporting Information for this article is available online at
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Figure 1 The reaction apparatus used for the aerobic oxidation of
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© Georg Thieme Verlag Stuttgart · New York
Synthesis 2013, 45, 1624–1626