The Journal of Organic Chemistry
Note
1
4
4
-Methoxybenzaldehyde. Table 2, entry 12, light yellow liquid:
EXPERIMENTAL SECTION
■
1
3
H NMR (400 MHz, CDCl ) δ 3.88 (s, 3H), 7.00 (d, J = 8.8 Hz,
H), 7.83 (d, J = 8.8 Hz, 1H), 9.88 (s, 1H); C NMR (100.6 MHz,
CDCl ) δ 55.2, 114.0, 129.6, 131.6, 164.3, 190.5.
-(4-Methoxyphenyl)ethanone. Table 2, entry 13, light yellow
solid: H NMR (400 MHz, CDCl ) δ 2.47 (s, 3H), 3.78 (s, 3H), 6.85
3
H,H
Typical Procedure for the Oxidation of Cinnamyl Alcohol.
DDQ (2.3 mg, 0.01 mmol) was dissolved in 5 mL of CH Cl and 0.5
mL of AcOH. The solution was stirred open to air at ambient
temperature, and then cinnamyl alcohol (134.1 mg, 1 mmol) was
3
13
2
H,H
2
2
3
19
1
1
3
added, followed by NaNO (6.9 mg, 0.1 mmol). The solution was
3
3
13
2
(
d, J = 8.4 Hz, 2H), 7.85 (d, J = 8.4 Hz, 2H); C NMR (100.6
H,H H,H
stirred under dioxygen atmosphere (balloon) for 2 h. The reaction
mixture was loaded directly on a small pad of silica, and the product
was eluted with dichloromethane. The solvent was concentrated in
vacuo, and the product was further purified by column chromatog-
raphy over silica gel (n-hexane/ethyl acetate, 10:1) to afford
cinnamaldehyde (121.5 mg, yield, 92%).
MHz, CDCl ) δ 26.1, 55.2, 113.5, 130.1, 130.4, 163.3, 196.6.
3
20
4
-Hydroxybenzaldehyde. Table 2, entry 15, light yellow
1
3
acicular crystal: H NMR (400 MHz, DMSO) δ 6.93 (d, J = 8.8
H,H
3
13
Hz, 1H), 7.76 (d, J = 8.8 Hz, 2H), 9.78 (s, 1H), 10.58 (s, 1H);
NMR (100.6 MHz, DMSO) δ 116.0, 128.6, 132.3, 163.5, 191.1.
-Methylbenzaldehyde. Table 2, entry 17, colorless liquid: H
NMR (400 MHz, CDCl ) δ 2.44 (s, 3H), 7.33 (d, J = 8.0 Hz, 2H),
C
H,H
1
4
1
4
3
Large-Scale Reaction Procedure for the Oxidation of
3
H,H
1
1
Cinnamyl Alcohol.
One-Gram Reaction, CH Cl /AcOH Mixture
3
13
2
2
7.77 (d, J
= 8.0 Hz, 2H), 9.96 (s, 1H); C NMR (100.6 MHz,
H,H
as Solvent. To a 100 mL, three-necked flask was added DDQ (16.9
CDCl ) δ 22.5, 130.3, 130.4, 134.8, 146.1, 192.6.
3
mg, 0.0746 mmol), 37 mL of CH Cl , and 3.7 mL of AcOH. The
21
2
2
4-Methylacetophenone. Table 2, entry 18, light yellow liquid:
solution was stirred open to air at ambient temperature, and then
cinnamyl alcohol (1 g, 7.46 mmol) was added, followed by NaNO2
25.7 mg, 0.373 mmol). The solution was stirred under dioxygen
1
H NMR (400 MHz, CDCl ) δ 2.35 (s, 3H), 2.52 (s, 3H), 7.20
3
3
3
13
(
d, J = 8.4 Hz, 2H), 7.81 (d, J = 8.4 Hz, 2H); C NMR (100.6
H,H H,H
(
MHz, CDCl ) δ 21.3, 26.2, 128.1, 128.9, 134.4, 143.6, 197.5.
3
atmosphere (balloon). The reaction was monitored by TLC. After
completion of the reaction, the reaction mixture was loaded directly on
a small pad of silica, and the product was eluted with dichloromethane.
The solvent was concentrated in vacuo, and the product was further
purified by column chromatography over silica gel (n-hexane/ethyl
acetate, 10:1) to afford cinnamaldehyde (0.886 g, yield, 90%).
AcOH as Solvent. To a 25 mL, three-necked flask was added DDQ
16.9 mg, 0.0746 mmol) and 5 mL of AcOH. The solution was stirred
open to air at ambient temperature, and then cinnamyl alcohol (1 g,
.46 mmol) was added, followed by NaNO (25.7 mg, 0.373 mmol).
22
1
9
-Fluorenone. Table 2, entry 19, yellow solid: H NMR (400
3
MHz, CDCl ) δ 7.27 (d, J = 7.2 Hz, 2H), 7.50−7.44 (m, 4H), 7.64
3
H,H
13
3
(
1
d, J
= 7.2 Hz, 2H); C NMR (100.6 MHz, CDCl ) δ 120.2,
H,H
3
24.2,128.9, 134.0, 134.5, 144.3, 193.8.
ASSOCIATED CONTENT
Supporting Information
■
*
S
(
1
13
7
2
The solution was stirred under dioxygen atmosphere (balloon). The
reaction was monitored by TLC. After completion of the reaction, the
reaction mixture was loaded directly on a small pad of silica, and the
product was eluted with dichloromethane. The solvent was con-
centrated in vacuo, and the product was further purified by column
chromatography over silica gel (n-hexane/ethyl acetate, 10:1) to afford
cinnamaldehyde (0.866 g, yield, 88%).
AUTHOR INFORMATION
■
*
ACKNOWLEDGMENTS
■
1
4
Table 2, entry 1, light yellow liquid: 1
We gratefully acknowledge financial support from the National
Natural Science Foundation of China (No. 20643006), the
Scientific Research Foundation for the Returned Overseas
Chinese Scholars, State Education Ministry and the National
Basic Research Program of China (2009CB623505). We thank
Prof. Dr. Ulrich Kortz (Jacobs University of Bremen
(Germany)) for helpful discussion on the language and the
structure of our manuscript.
Cinnamaldehyde.
H
NMR (400 MHz, CDCl ) δ 6.55−6.61 (m, 1H), 7.28−7.35 (m, 4H),
3
3
13
7
.40−7.43 (m, 2H), 9.55 (d, J = 8.0 Hz, 1H); C NMR (100.6
MHz, CDCl ) δ 128.2, 128.3,128.8, 131.0, 133.7, 152.7, 193.6.
Phenylpropiolaldehyde. Table 2, entry 4, yellow liquid: H
H,H
3
1
5
1
3
3
NMR (400 MHz, CDCl ) δ 7.36 (t, J = 7.6 Hz, 2H), 7.45 (t, J
3
H,H
H,H
3
13
=
8.0 Hz, 1H), 7.57 (d, J = 7.2 Hz, 2H), 9.38 (s, 1H); C NMR
H,H
(
100.6 MHz, CDCl ) δ 88.3, 95.1,119.2, 128.6, 131.2, 133.1, 176.8.
3
16
1
,3-Diphenyl-2-propyn-1-one. Table 2, entry 5, yellow liquid:
1
3
H NMR (400 MHz, CDCl ) δ 7.39 (t, J = 7.6 Hz, 2H), 7.51−7.43
3
H,H
REFERENCES
3
3
■
(
m, 3H), 7.60 (t, J = 7.6 Hz, 1H), 7.66 (d, J = 7.2 Hz, 2H),
H,H H,H
(
1) (a) Hudlicky, M. Oxidations in Organic Chemistry; American
Chemical Society: Washington, D.C., 1990. (b) Larock, R. C.
Comprehensive Organic Transformations; Wiley: New York, 1999.
c) Tojo, G.; Fernandez, M. Oxidations of Alcohols to Aldehydes and
Ketones; Springer: New York, 2006.
2) March, J. Advanced Organic Chemistry: Reactions, Mechanisms, and
Structure, 4th ed.; John Wiley & Sons: New York, 1992.
3) For more recent and representative examples of transition-metal-
catalyzed aerobic oxidation of alcohols, see: (a) Mallat, T.; Baiker, A.
Chem. Rev. 2004, 104, 3037−3058. (b) Iwasawa, T.; Tokunaga, M.;
Obora, Y.; Tsuji, Y. J. Am. Chem. Soc. 2004, 126, 6554−6555.
(c) Marko, I. E.; Gaautier, A.; Dumeunier, R.; Doda, K.; Philippart, F.;
Brown, S. M.; Urch, C. J. Angew. Chem., Int. Ed. 2004, 43, 1588−1591.
(d) Gligorich, K. M.; Sigman, M. S. Angew. Chem., Int. Ed. 2006, 45,
6612−6615. (e) Stahl, S. S. Angew. Chem., Int. Ed. 2004, 43, 3400−
3420. (f) Wu, L. H.; Zhang, H. Q.; Wang, Y. Adv. Synth. Catal. 2005,
347, 1356−1360. (g) Karimi, B.; Zamani, A.; Clark, J. H.
Organometallics 2005, 24, 4695−4698. (h) Liu, L. J.; Wang, F. J.;
Shi, M. Organometallics 2009, 28, 4416−4420. (i) Enache, D. I.;
Edwards, J. K.; Landon, P.; Solsona-Espriu, B.; Carley, A. F.; Herzing,
A. A.; Watanabe, M.; Kiely, C. J.; Knight, D. W.; Hutchings, G. J.
Science 2006, 311, 362−365. (j) Guan, B. T.; Xing, D.; Cai, G. X.;
9
1
.38 (s, 1H); 13C NMR (100.6 MHz, CDCl ) δ 86.8, 93.0,119.9,
3
28.5, 128.6, 129.4, 130.7, 132.9, 134.0, 136.7, 177.8.
1
5
1
1
-Phenyl-2-propyn-1-one. Table 2, entry 6, yellow solid: H
(
3
NMR (400 MHz, CDCl ) δ 3.44 (s, 1H), 7.49 (t, J = 7.6 Hz, 1H),
7
3
H,H
3
3
13
.63 (t, J = 7.2 Hz, 1H), 8.16 (d, J = 8.0 Hz, 2H); C NMR
H,H H,H
(
(
100.6 MHz, CDCl ) δ 80.2, 80.7, 128.7, 129.6, 134.5, 136.1, 177.3.
3
1
7
1
1
-Phenylhex-1-yn-3-one. Table 2, entry 8, orange liquid: H
(
3
NMR (400 MHz, CDCl ) δ 0.973 (t, J = 7.2 Hz, 3H), 1.73−1.78
3
H,H
3
(
J
m, 2H), 2.60−2.63 (m, 2H), 7.36 (d, J = 6.4 Hz, 2H), 7.41 (d,
H,H
3
3 13
= 6.0 Hz, 1H), 7.54 (d, J = 7.2 Hz, 2H); C NMR (100.6
H,H
H,H
MHz, CDCl ) δ 13.2, 17.4, 47.1, 87.6, 90.2, 119.8, 128.4, 130.4, 132.7,
3
1
87.8.
1
4
3,4-Dimethoxybenzaldehyde. Table 2, entry 10, light yellow
1
acicular crystal: H NMR (400 MHz, CDCl ) δ 3.84 (s, 3H), 3.85
3
3
3
(
(
s, 3H), 6.87 (d, J = 8.0 Hz, 2H), 7.34 (d, J = 8.4 Hz, 2H), 9.73
H,H H,H
s, 1H); 13C NMR (100.6 MHz, CDCl ) δ 55.6, 55.3, 108.6, 110.1,
3
1
26.5, 129.8, 149.3, 154.2, 190.6.
1
8
3
,4,5-Trimethoxybenzaldehyde. Table 2, entry 11, pale
1
yellow solid: H NMR (400 MHz, CDCl ) δ 3.92 (s, 6H), 3.93
3
(
s, 3H) 7.12 (s, 2H), 9.86 (s, 1H); 13C NMR (100.6 MHz, CDCl ) δ
3
56.2, 61.0, 106.7, 131.7, 153.6, 191.0.
7
93
dx.doi.org/10.1021/jo202301s | J. Org. Chem. 2012, 77, 790−794