4
964
M. Mirza-Aghayan et al. / Tetrahedron Letters 53 (2012) 4962–4965
Table 2
Oxidation of alcohols using GO
Entry
Substrate
Product13
Conditionsa
Time (h)
Yieldb (%)
1
2
3
4
5
6
7
8
9
Benzyl alcohol
Benzyl alcohol
Benzaldehyde
A
B
A
A
A
A
A
C
A
A
A
A
A
A
D
E
2
2
2
2
3
1.5
2
1
2
0.50
1.5
1.5
2
2
1
0.16
1.5
0.25
0.5
98
32 + 54
94
92
60
92
92
45
70
24
13
10
Trace
98
35
95
71
55
Benzaldehyde + dibenzyl ether
4-Chlorobenzaldehyde
3,4-Dichlorobenzaldehyde
2,4-Dichlorobenzaldehyde
4-Nitrobenzaldehyde
3-Nitrobenzaldehyde
2-Fluorobenzaldehyde
Cinnamaldehyde
4-Methoxybenzaldehyde
4-tert-Butylbenzaldehyde
Thiophene-2-carbaldehyde
Nicotinaldehyde
4-Chlorobenzyl alcohol
3,4-Dichlorobenzyl alcohol
2,4-Dichlorobenzyl alcohol
4-Nitrobenzyl alcohol
3-Nitrobenzyl alcohol
2-Fluorobenzyl alcohol
Cinnamyl alcohol
4-Methoxybenzyl alcohol
4-tert-Butylbenzyl alcohol
Thiophene-2-methanol
3-Pyridinylmethanol
Cyclohexanol
10
11
12
13
14
15
16
17
18
19
Cyclohexanone
Benzophenone
Benzhydrol
Benzhydrol
1-Indanol
1-Indanol
10
Bis(diphenylmethyl) ether
1
1
1H-indene
2-(2,3-Dihydro-1H-inden-3-yl)-1H-indene
A
F
G
11
0
12
2-(4-Biphenylyl)-2-propanol
4-(Prop-1-en-2-yl)-1,1 -biphenyl
95
a
Conditions: (A) 200 wt% GO, toluene, 80 °C, ultrasonic bath; (B) 50 wt% GO, hexane, 50 °C, ultrasonic bath; (C) 300 wt% GO, toluene, 80 °C, ultrasonic bath; (D) 200 wt% GO,
solvent-free conditions, 80 °C, ultrasonic bath; (E) 200 wt% GO, hexane, ultrasonic probe; (F) 300 wt% GO, toluene, ultrasonic probe; (G) 200 wt% GO, toluene, ultrasonic
probe.
b
Determined by GC-MS.
Table 3
3. (a) Suslick, K. S. Science 1990, 247, 1439; (b) Mason, T. J. Chem. Soc. Rev. 1997,
26, 443; (c) Cravotto, G.; Cintas, P. Chem. Soc. Rev. 2006, 35, 180; (d) Einhorn, C.;
Einhorn, J.; Luche, J. L. Synthesis 1989, 787.
4. (a) Peters, D. J. Mater. Chem. 1996, 6, 1605; (b) Suslick, K. S.; Price, G. J. Annu.
Rev. Mater. Sci. 1999, 29, 295; (c) Gedanken, A. Ultrason. Sonochem. 2004, 11, 47;
Reusability of GO for the oxidation of 4-nitrobenzyl alcohola
Entry
Run
Yieldb (%)
1
2
3
4
First
92
78
51
24
(
d) Gedanken, A. Chem. Eur. J. 2008, 14, 3840.
Second
Third
Fourth
5.
Mirza-Aghayan, M.; Boukherroub, R.; Nemati, M.; Rahimifard, M. Tetrahedron
Lett. 2012, 53, 2473.
6
7
.
.
Hummers, W. S., Jr.; Offeman, R. E. J. Am. Chem. Soc. 1958, 80, 1339.
(a) Zhou, X.; Huang, X.; Qi, X.; Wu, S.; Xue, C.; Boey, F. Y. C.; Yan, Q.; Chen, P.;
Zhang, H. J. Phys. Chem. C 2009, 113, 10842; (b) Wang, Z.; Zhou, X.; Zhang, J.;
Boey, F. Y. C.; Zhang, H. J. Phys. Chem. C 2009, 113, 14071; (c) Kovtyukhova, N. I.;
Ollivier, P. J.; Martin, B. R.; Mallouk, T. E.; Chizhik, S. A.; Buzaneva, E. V.;
Gorchinskiy, A. D. Chem. Mater. 1999, 11, 771.
a
Conditions: 200 wt% GO, toluene, 80 °C, 1.5 h, ultrasonic bath.
Determined by GC.
b
8
.
Synthesis of graphite oxide using the modified Hummers’ method:7 graphite
In conclusion, we have investigated the oxidation of aromatic,
(
8 g) was added to a mixture of 98% H
with stirring. The solution was kept at 80 °C for 6 h. The resulting preoxidized
product was washed with H O and dried. CAUTION: The preoxidized product
8 g) was added to 98% H SO (180 mL), followed by the slow addition of
KMnO (24 g) with the temperature kept at <20 °C in order to avoid
overheating and explosion. The temperature was increased to 35 °C and
maintained for 2 h. Next, H O (400 mL) was added over 15 min. Further H
1.1 L) was added to dilute the solution, and 30% H (20 mL) was injected
into the solution to quench the excess KMnO . A brown solution was obtained,
which was washed with 1:10 (37%) HCl: H O solution (2 L) in order to remove
metal ions and finally washed with H O (2 L). Dried graphite oxide was
2 4 2 2 8 2 5
SO (14 mL), K S O (4 g), and P O (4 g)
heterocyclic, and aliphatic alcohols using graphite oxide under
ultrasonic irradiation. This protocol is advantageous as the reac-
tions take place under mild conditions in short reaction times.
The yields were good to high for benzyl alcohol derivatives with
electron-withdrawing groups and moderate for those with elec-
tron-donating groups. The yields were low for heterocyclic alco-
hols, but high yields were obtained for aliphatic alcohols. In
addition, GO is a cost effective material and can be easily recovered
from the reaction mixture by a simple filtration. Further investiga-
tions using GO for other chemical transformations are currently in
progress.
2
(
2
4
4
2
2
O
(
2 2
O
4
2
2
obtained by centrifugation followed by dehydration on a rotary evaporator
under vacuum. The prepared GO was characterized using powder XRD, UV/Vis
spectroscopy, and FT-IR spectroscopy to establish its authenticity (see the
Supplementary data).
9.
Paredes, J. I.; Villar-Rodil, S.; Martinez-Alonso, A.; Tascon, J. M. D. Langmuir
2
008, 24, 10560.
Supplementary data
1
0. (a) Tarlani, A. A.; Riahi, A.; Abedini, M.; Mohammadpour Amini, M.; Muzart, J.
Appl. Catal. A 2006, 315, 150; (b) Firouzabadi, H.; Iranpoor, N.; Jafari, A. A. J. Mol.
Catal. A: Chem. 2005, 227, 97; (c) Zhu, Z.; Espenson, J. H. J. Org. Chem. 1996, 61,
3
24.
1
1. (a) Tarlani, A. A.; Riahi, A.; Abedini, M.; Mohammadpour Amini, M.; Muzart, J. J.
Mol. Catal. A: Chem. 2006, 260, 187; (b) Jovanovic, J.; Spiteller, M.; Spiteller, P. J.
Serb. Chem. Soc. 2001, 61, 753; (c) Pizzio, L. R.; Vázquez, P. G.; Cáceres, C. V.;
Blanco, M. N.; Alesso, E. N.; Erlich, M. I.; Torviso, R.; Finkielsztein, L.; Lantaño,
B.; Moltrasio, G.; Aguirre, J. Catal. Lett. 2004, 93, 67.
References and notes
1
2. Ni, Z.-J.; Mei, N.-W.; Shi, X.; Tzeng, Y.-L.; Wang, M. C.; Luh, T.-Y. J. Org. Chem.
1
2
.
.
Spiro, M. Catal. Today 1990, 7, 167.
1991, 56, 4035.
(a) Vijay Kumar, A.; Rama Rao, K. Tetrahedron Lett. 2011, 52, 5188; (b) Dreyer, D.
R.; Jia, H.-P.; Bielawski, C. W. Angew. Chem., Int. Ed. 2010, 49, 6813; (c) Dreyer,
D. R.; Bielawski, C. W. Chem. Sci. 2011, 2, 1233; (d) Jia, H.-P.; Dreyer, D. R.;
Bielawski, C. W. Tetrahedron 2011, 67, 4431; (e) Jia, H.-P.; Dreyer, D. R.;
Bielawski, C. W. Adv. Synth. Catal. 2011, 353, 528; (f) Dreyer, D. R.; Jia, H.-P.;
Todd, A. D.; Geng, J.; Bielawski, C. W. Org. Biomol. Chem. 2011, 9, 7292; (g)
Dreyer, D. R.; Jarvis, K. A.; Ferreira, P. J.; Bielawski, C. W. Polym. Chem. 2012, 3,
13. Ultrasonic irradiation was performed in an Elmasonic P ultrasonic cleaning
unit (ultrasonic bath) with a frequency of 80 kHz and an output power of 80%,
or using an ultrasonic homogenizer (Bandelin Sonopuls HD 3100) with probe
model MS 73 and 100% power.
Typical procedure for the oxidation of alcohols: To a solution of alcohol (0.1 g) in
2 mL of solvent was added the appropriate amount of GO (as indicated in Table
2). The resulting mixture was irradiated in an ultrasonic bath or with an
ultrasonic probe (methods A to G) for the time indicated in Table 2 prior to GC/
7
57; (h) Dreyer, D. R.; Jarvis, K. A.; Ferreira, P. J.; Bielawski, C. W.
Macromolecules 2011, 44, 7659.
MS analysis. The mixture was filtered through
a sintered funnel and
evaporated under reduced pressure. Purification was achieved by column