Tetrahedron 70 (2014) 2669e2673

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Tetrahedron
journal homepage: www.elsevier.com/locate/tet

Tetrabutyl ammonium bromide-mediated benzylation of phenols in

water under mild condition
Hailei Wang a, Yuping Ma b, Heng Tian a, Ajuan Yu a, *, Junbiao Chang a, Yangjie Wu a, *
a
The College of Chemistry and Molecular Engineering, Key Laboratory of Chemical Biology and Organic Chemistry of Henan, Zhengzhou University,
Zhengzhou 450052, PR China
b
China Tobacco Industrial Co. Ltd., Zhengzhou 450052, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Benzylation of phenol was successfully achieved in water under room temperature mediated by tetra-
Received 8 September 2013 butylammonium bromide (TBAB) for only 2 h affording the corresponding benzyl phenyl ether with good
Received in revised form 27 December 2013 to excellent yields. This protocol is very efcient, simple, avoiding catalysts, easy to work-up after re-
Accepted 3 January 2014
action, and especially green.
Available online 9 January 2014
2014 Elsevier Ltd. All rights reserved.

Keywords:
Benzylation
Phenols
Water
Phase transfer catalysis (PTC)

1. Introduction the water. Therefore, performing organic reactions in water may

prot by these benecial aspects. So, the concept of water mediated
Benzylation of phenol is a very important organic reaction and nucleophilic displacement reactions, as a green protocol, needs
was rst reported by McKillop using dichloromethane as a solvent more attention. In recent years, a variety of PTCs involving the
in 1974.1 Since then, a wide variety of procedures have been de- application of tetrabutyl ammonium bromide (TBAB) has been
veloped to reach this goal, including the use of crown ethers,2 successfully conducted using water or co-solvent for reaction me-
phase-transfer catalysis (PTC),3 ionic liquids,4 microwave method, dium.6 Interested in this area, in this paper we reported the use of
and so on.5 However, most of protocols suffer rigorous conditions, tetrabutyl ammonium bromide (TBAB) as the phase transfer cata-
such as the strong base and high temperature. Furthermore, many lyst for the preparation of benzyl phenyl ether in aqueous media
of the above-mentioned methods carried out in toxic, volatile, and under mild conditions.
ammable organic solvent, examples of dichloromethane, aceto-
nitrile, and 2-methyltetrahydrofuran or in high boiling point polar
2. Results and discussion
solvent, such as N,N-dimethylformamide. Thus, the development of
an efcient, safe, and environmentally friendly method of benzy-
To extend applicability of water as a green reaction media and
lation of phenol is very attractive.
for the search of facile benzylation method, we initially in-
Organic reactions in water have recently attracted great in-
vestigated on the model reaction of benzyl bromide and phenol in
terests. The substitution of organic solvent as reaction media by
pure water to optimize the reaction conditions. To our delight, an
water minimizes the environmental impact, besides lowering the
86% isolated yield of desired product was obtained with 1 equiv of
cost and decreasing operational danger. In addition to economic
tetrabutyl ammonium chloride (TBAC) as the phase transfer cata-
and human aspects, water presents many physico-chemical prop-
lyst, K3PO4 as the base at room temperature for 2 h (Table 1, entry
erties that can be useful in the reactions, such as high polarity, ion
1). Phenol underwent O-alkylation instead of extensive C-alkyl-
solvating capacity, and the ability to form hydrogen bonds to form
ation in water under our weak base conditions, which was sharp in
a structured liquid, and to aggregate apolar molecules dissolved in
contrast to the existed report.5m,n Surprisingly, the yield was dra-
matically improved up to 98% when TBAB instead of TBAC was used
as a phase transfer catalyst (Table 1, entry 2). Other inorganic bases,
* Corresponding authors. Fax: 86 371 6776 6667; e-mail addresses: yuajuan@ such as K2HPO4$3H2O, NaOH, KOH, and K2CO3 can also be used in
zzu.edu.cn (A. Yu), [email protected] (Y. Wu). this reaction instead of K3PO4 (Table 1, entries 3e6). Among all the

0040-4020/$ e see front matter 2014 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tet.2014.01.004
2670 H. Wang et al. / Tetrahedron 70 (2014) 2669e2673

Table 1 Table 2 (continued )

Optimization of reaction conditionsa
Entry Phenol Product Yieldb(%)

OH O
Br Phase transfer catalyst 6 79
+ 1f
base, H2O 3fa

1a 2a 3a
7 93
Entry Phase transfer catalyst Base t (h) Yieldb (%)
1g 3ga
1 TBAC K3PO4 2 83
2 TBAB K3PO4 2 98
3 TBAB K2HPO4$3H2O 2 73
8 98
4 TBAB NaOH 2 39
5 TBAB KOH 2 64 1h 3ha
6 TBAB K2CO3 2 90
7 TBAB K3PO4 (1.5 equiv) 2 97c
8 TBAB K3PO4 (1.2 equiv) 2 90c 9 82
9 TBAB K3PO4 (1.5 equiv) 1 89c
1i
10 d K3PO4 (1.5 equiv) 2 d 3ia
a
Unless otherwise noted, the reaction conditions were as follows: phenol
(0.5 mmol), benzyl bromide (1.2 equiv), phase transfer catalyst (1.0 equiv), base
(2.0 equiv), and water (2 mL), room temperature, air, in a sealed tube. 10 99
b
Isolated yields.
c
1j
TBAB (0.5 equiv). 3ja

bases, the K3PO4 gave the highest yield (Table 1, entry 2). An iso- 11 98
lated yield of 97% was obtained even when the quantities of TBAB 1k
3ka
and the base were decreased to 0.5 and 1.5 equiv, respectively
(Table 1, entries 7, 8). However, the yield of the reaction was de-
12 88
creased when shorten the time to 1 h (Table 1, entry 9). No ben- 1l
3la
zylation of phenol to benzyl phenyl ether was observed under the
reaction conditions in the absence of phase transfer catalyst (Table
1, entry 10).
With the optimized conditions in hand, the substrate scope of
13 90
commercially available phenols was investigated and the results
were summarized in Table 2. Generally speaking, the reaction 1m
proceeded smoothly in the presence of a variety of functional 3ma
groups including electron-donating, electron-neutral, and electron-
withdrawing, such as methyl, methoxyl, chloro, bromo, tertiary
butyl, formacyl, and cyano groups. It was noteworthy that the
14 86
sterically hindered substrates also delivered the desired product in
high yields (Table 2, entries 7e10). Especially, even for the 1,2- 1n 3na
benzenediol that bearing two hydroxyl in ortho-position could
also give the corresponding product in high yield of 90% (Table 2,
15 66
1o
3oa
Table 2
Benzylation of benzyl bromide with different phenolsa
16 76
Entry Phenol Product Yieldb(%)
1p 3pa
a
Reaction conditions: phenol (0.5 mmol), benzyl bromide (1.2 equiv), TBAB
1 97
1a (0.5 equiv), base (1.5 equiv), and water (2 mL), room temperature, 2 h, air, in a sealed
3aa tube.
b
Isolated yields.

2 74
1b
3ba entry 13). It would be specially mentioned that naphthol 1o and
heterocycle phenol 1p were both tolerated and afforded the
etherication products in moderate yields (Table 2, entries 14e16).
3 99
1c In order to make a more systematic study, different kinds of
3ca
groups on the phenyl ring in the benzyl bromide were also exam-
ined. As shown in Table 3, the reaction was not signicantly affected
4 99 by the steric effect of the phenols (Table 3, entries 6, 7, 11). For
1d
3da example, the benzylation of 1a with ortho-benzyl bromide pro-
ceeded smoothly, affording the corresponding products 3ah in al-
most quantitative yield. Also the electronic properties of the groups
5 99
1e at the aryl moiety of benzyl bromides had some effect on the re-
3ea
action. Generally, the benzyl bromides bearing electron-
 H. Wang et al. / Tetrahedron 70 (2014) 2669e2673 2671

withdrawing groups produced the corresponding products in 4. Experimental section

slightly higher yields. Benzyl bromides with electron-decient
substituents, which were more prone to undergo nucleophilic 4.1. General details
substitution reaction with phenol than the analogs with electron-
1
rich groups. H NMR, 13C NMR spectra were recorded on a Bruker DPX-400
spectrometer with CDCl3 as the solvent and TMS as an internal
Table 3 standard. IR spectra was measured using a NEXUS 470 FT-IR ap-
Benzylation of different benzyl bromide with phenola paratus. High-resolution mass spectra were ensured on a MALDI-
Entry Benzyl bromide Product Yieldb (%) FTMS. Benzyl bromide that with a substituent on the phenyl ring
was synthesized according to the reported literature.7 The other
chemicals were bought from commercial sources and used as re-
1 82 ceived unless otherwise noted. Solvents, such as ethyl acetate, pe-
2b 3ab troleum ether, and dichloromethane were used for column
chromatography and thin-layer chromatography without further
purication.
2 84
2c 3ac
4.2. General procedure for benzylation of phenols

3 76 Phenol (0.5 mmol), benzyl bromide (1.2 equiv), TBAB (0.5 equiv),
2d 3ad K3PO4 (1.5 equiv), and water (2 mL) were added to a reaction vessel.
The mixture was stirred at room temperature for 2 h under air. After
the reaction was completed, the mixture was diluted with water
4 95
2e and extracted with CH2Cl2 (15 mL3). The combined organic layer
3ae
was dried with anhydrous sodium sulfate and concentrated under
reduced pressure. The residue was puried by thin layer chroma-
5 98 tography (TLC) on silica gel GF254 (ethyl acetate/petroleum ether) to
2f 3af give the pure product.

4.2.1. Benzyl phenyl ether (3aa).5d 1H NMR (400 MHz, CDCl3):

6 83 d 7.48e7.31 (m, 7H), 7.03e6.98 (m, 3H), 5.10 (s, 2H); 13C NMR
2g 3ag (100 MHz, CDCl3) d 158.9, 137.2, 129.5, 128.6, 128.0, 127.5, 121.0,
114.9, 70.0.

7 98
4.2.2. Benzyl 4-methylphenyl ether (3ba).8 1H NMR (400 MHz,
2h 3ah CDCl3): d 7.42e7.27 (m, 5H), 7.06 (d, J8.3 Hz, 2H), 6.86 (d, J8.4 Hz,
2H), 5.01 (s, 2H), 2.27 (s, 3H); 13C NMR (100 MHz, CDCl3) d 156.8,
137.4, 130.2, 130.0, 128.6, 127.9, 127.5, 114.8, 70.2, 20.6.
8 93
2i 3ai
4.2.3. Benzyl 4-methoxyphenyl ether (3ca).5d 1H NMR (400 MHz,
CDCl3): d 7.42e7.35 (m, 4H), 7.30 (t, J7.1 Hz, 1H), 6.92e6.88 (m,
9 95 2H), 6.84e6.80 (m, 2H), 5.01 (s, 2H), 3.76 (s, 3H); 13C NMR
(100 MHz, CDCl3): d 154.0, 153.0, 137.4, 128.6, 127.9, 127.5, 115.9,
2j 3aj
114.7, 70.8, 55.8.

10 99 4.2.4. Benzyl 4-chlorophenyl ether (3da).5j 1H NMR (400 MHz,

2k 3ak CDCl3): d 7.42e7.30 (m, 5H), 7.24e7.20 (m, 2H), 6.90e6.87 (m, 2H),
5.03 (s, 2H); 13C NMR (100 MHz, CDCl3): d 157.4, 136.6, 129.4, 128.7,
128.1, 127.5, 125.9, 116.2, 70.4.
11 90
4.2.5. Benzyl 4-bromophenyl ether (3ea).5d 1H NMR (400 MHz,
2l 3al CDCl3): d 7.43e7.32 (m, 7H), 6.87e6.85 (m, 2H), 5.04 (s, 2H); 13C
a
Reaction conditions: phenol (0.5 mmol), benzyl bromide (1.2 equiv), TBAB NMR (100 MHz, CDCl3): d 157.9, 136.6, 132.3, 128.7, 128.1, 127.5,
(0.5 equiv), base (1.5 equiv), and water (2 mL), room temperature, 2 h, air, in a sealed 116.8, 113.2, 70.3.
tube.
b
Isolated yields.
4.2.6. Benzyl 4-tert-butylphenyl ether (3fa).5j 1H NMR (400 MHz,
CDCl3): d 7.49e7.34 (m, 7H), 6.97 (d, J8.7 Hz, 2H), 5.09 (s, 2H), 1.35
3. Conclusion (s, 9H); 13C NMR (100 MHz, CDCl3): d 156.7, 143.7, 137.4, 128.6, 127.9,
127.5, 126.3, 114.4, 70.1, 34.1, 31.6.
In conclusion, the present procedure using an easily available
phase transfer catalyst TBAB provides an efcient and convenient 4.2.7. Benzyl 2-methylphenyl ether (3ga).5j 1H NMR (400 MHz,
procedure for the benzylation of phenols. This method offers CDCl3): d 7.57e7.40 (m, 5H), 7.29e7.24 (m, 2H), 7.00 (t, J7.1 Hz,
marked improvements with regard to operational applicability, 2H), 5.18 (s, 2H), 2.42 (s, 3H); 13C NMR (100 MHz, CDCl3): d 157.0,
high isolated yields of products, and greenness of procedure, 137.7, 130.9, 128.6, 127.9, 127.2, 127.2, 126.9, 120.8, 111.6, 69.9, 16.6.
avoiding hazardous organic solvents and toxic catalysts, and thus, it
provides a facile and practical procedure for the preparation of 4.2.8. Benzyl 2-bromophenyl ether (3ha).5d 1H NMR (400 MHz,
benzyl phenyl ethers. CDCl3): d 7.61 (d, J7.8 Hz, 1H), 7.53 (d, J7.5 Hz, 2H),
2672 H. Wang et al. / Tetrahedron 70 (2014) 2669e2673

13
7.46e7.35 (m, 3H), 7.27 (t, J8.0 Hz, 1H), 6.97 (d, J8.2 Hz, 1H), 2H), 6.99e6.93 (m, 3H), 5.14 (s, 2H); C NMR (100 MHz, CDCl3):
6.89 (t, J7.6 Hz, 1H), 5.18 (s, 2H); 13C NMR (100 MHz, CDCl3): d 158.1, 147.6, 144.6, 129.7, 127.6, 123.8, 121.6, 114.8, 68.6.
d 155.1, 136.6, 133.5, 128.7, 128.5, 128.0, 127.1, 122.2, 114.0,
112.6, 70.8. 4.2.21. 4-(Phenoxymethyl)benzonitrile (3af).12 1H NMR (400 MHz,
CDCl3): d 7.64 (d, J8.2 Hz, 2H), 7.52 (d, J8.4 Hz, 2H), 7.30e7.26 (m,
4.2.9. Benzyl 2-methoxyphenyl ether (3ia).9 1H NMR (400 MHz, 2H), 6.99e6.92 (m, 3H), 5.10 (s, 2H); 13C NMR (100 MHz, CDCl3):
CDCl3): d 7.49 (d, J7.4 Hz, 2H), 7.40 (t, J7.3 Hz, 2H), 7.33 (t, d 158.2, 142.6, 132.4, 129.7, 127.6, 121.5, 118.7, 114.8, 111.7, 68.8.
J7.1 Hz, 1H), 6.99e6.87 (m, 4H), 5.19 (s, 2H), 3.92 (s, 3H); 13C NMR
(100 MHz, CDCl3): d 149.8, 148.3, 137.4, 128.6, 127.9, 127.4, 121.6, 4.2.22. 2-Fluorobenzyl phenyl ether (3ag). Yellow liquid; 1H NMR
120.9, 114.4, 112.1, 71.1, 56.0. (400 MHz, CDCl3): d 7.57e7.53 (m, 1H), 7.35e7.30 (m, 3H), 7.18 (t,
J7.4 Hz, 1H), 7.11 (t, J8.8 Hz, 1H), 7.04e6.99 (m, 3H), 5.16 (s, 2H);
4.2.10. Benzyl 2,4-dimethyphenyl ether (3ja).10 1H NMR (400 MHz, 13
C NMR (100 MHz, CDCl3): d 161.8, 159.3, 158.7, 129.8, 129.8, 129.7,
CDCl3): d 7.59e7.43 (m, 5H), 7.13 (s, 1H), 7.08 (d, J8.2 Hz, 1H), 6.91 129.6, 124.4, 124.4, 124.3, 121.2, 115.5, 115.3, 114.9, 63.7, 63.6. HRMS-
(d, J8.2 Hz, 1H), 5.17 (s, 2H), 2.43 (s, 3H), 2.42 (s, 3H); 13C NMR ESI (positive ESI): m/z calcd for C13H12FO (MH): 203.0867, found:
(100 MHz, CDCl3): d 155.0, 137.9, 131.8, 129.9, 128.6, 127.8, 127.3, 203.0872. IR (KBr pellet, cm1): 3064, 3041, 2926, 2882, 2854, 1620,
127.1, 127.0, 111.7, 70.2, 20.6, 16.5. 1599, 1588, 1500, 1496, 1456, 1383, 1305, 1240, 1172, 1154, 1111,
1078, 1032, 1014, 993, 943, 883, 836, 753.
4.2.11. 4-(Benzyloxy)benzonitrile (3ka).5d 1H NMR (400 MHz,
CDCl3): d 7.58 (d, J8.7 Hz, 2H), 7.42e7.35 (m, 5H), 7.02 (d, J8.8 Hz, 4.2.23. 2-Nitrobenzyl phenyl ether (3ah).13 1H NMR (400 MHz,
2H), 5.12 (s, 2H); 13C NMR (100 MHz, CDCl3): d 162.0, 135.7, 134.0, CDCl3): d 8.15 (d, J8.2 Hz, 1H), 7.91 (d, J7.8 Hz, 1H), 7.67 (t,
128.8, 128.4, 127.5, 119.2, 115.6, 104.3, 70.3. J7.5 Hz, 1H), 7.47 (t, J7.7 Hz, 1H), 7.32 (t, J8.0 Hz, 2H), 7.02e6.99
(m, 3H), 5.48 (s, 2H); 13C NMR (100 MHz, CDCl3): d 158.2, 147.0,
4.2.12. 4-(Benzyloxy)benzaldehyde (3la).11 1H NMR (400 MHz, 134.0, 133.8, 129.7, 128.6, 128.3, 125.0, 121.6, 115.0, 66.8.
CDCl3): d 9.89 (s, 1H), 7.84 (d, J8.6 Hz, 2H), 7.45e7.36 (m, 5H), 7.08
(d, J8.6 Hz, 2H), 5.15 (s, 2H); 13C NMR (100 MHz, CDCl3): d 190.8, 4.2.24. 3-Chlorobenzyl phenyl ether (3ai).14 1H NMR (400 MHz,
163.8, 136.0, 132.0, 130.2, 128.8, 128.4, 127.5, 115.2, 70.3. CDCl3): d 7.49 (s, 1H), 7.37e7.33 (m, 5H), 7.05e7.00 (m, 3H), 5.06 (s,
2H); 13C NMR (100 MHz, CDCl3): d 158.6, 139.3, 134.6, 130.0, 129.7,
4.2.13. 1,2-Di(benzyloxy)benzene (3ma).5a 1H NMR (400 MHz, 128.1, 127.5, 125.4, 121.3, 115.0, 69.1.
CDCl3): d 7.50 (d, J7.4 Hz, 4H), 7.42e7.32 (m, 6H), 7.01e6.92 (m,
4H), 5.20 (s, 4H); 13C NMR (100 MHz, CDCl3): d 149.2, 137.5, 128.5, 4.2.25. 3-Methoxybenzyl phenyl ether (3aj).15 1H NMR (400 MHz,
127.8, 127.4, 121.7, 115.4, 71.4. CDCl3): d 7.35 (t, J7.8 Hz, 3H), 7.08e7.01 (m, 5H), 6.94e6.91 (m,
1H), 5.09 (s, 2H), 3.85 (s, 3H); 13C NMR (100 MHz, CDCl3): d 160.0,
4.2.14. Benzyl a-naphthyl ether (3na).11 1H NMR (400 MHz, CDCl3): 158.9, 138.8, 129.7, 129.6, 121.1, 119.8, 115.0, 113.6, 113.0, 69.9, 55.3.
d 8.45 (d, J7.4 Hz, 1H), 7.90e7.87 (m, 1H), 7.61e7.41 (m, 9H), 6.94
(d, J7.6 Hz, 1H), 5.30 (s, 2H); 13C NMR (100 MHz, CDCl3): d 154.6, 4.2.26. 3-Nitrobenzyl phenyl ether (3ak).16 1H NMR (400 MHz,
137.3, 134.7, 128.7, 128.0, 127.6, 127.5, 126.6, 126.0, 125.9, 125.4, CDCl3): d 8.31 (s, 1H), 8.16 (dd, J8.3 Hz, J1.3 Hz, 1H), 7.77 (d,
122.3, 120.6, 105.3, 70.2. J7.8 Hz, 1H), 7.55 (t, J8.0 Hz, 1H), 7.34e7.30 (m, 2H), 7.02e6.98
(m, 3H), 5.14 (s, 2H); 13C NMR (100 MHz, CDCl3): d 158.1, 148.3,
4.2.15. Benzyl b-naphthyl ether (3oa).11 1H NMR (400 MHz, CDCl3): 139.3, 133.1, 129.6, 129.5, 122.8, 122.0, 121.4, 114.8, 68.4.
d 7.81e7.74 (m, 3H), 7.53e7.26 (m, 9H), 5.20 (s, 2H); 13C NMR
(100 MHz, CDCl3): d 156.8, 137.0, 134.6, 129.5, 129.1, 128.7, 128.1, 4.2.27. a-Naphthylmethyl phenyl ether (3al).17 1H NMR (400 MHz,
127.7, 127.6, 126.8, 126.4, 123.8, 119.1, 107.2, 70.1. CDCl3): d 8.11 (d, J7.6 Hz, 1H), 7.96e7.89 (m, 2H), 7.66e7.49 (m,
4H), 7.38 (t, J7.8 Hz, 2H), 7.13e7.04 (m, 3H), 5.53 (s, 2H); 13C NMR
4.2.16. 4-(Phenylmethoxy)quinoline (3pa).5f 1H NMR (400 MHz, (100 MHz, CDCl3): d 159.0, 133.9, 132.5, 131.7, 129.7, 129.1, 128.8,
CDCl3): d 8.42 (d, J8.0 Hz, 1H), 7.60 (d, J7.8 Hz, 1H), 7.48 (t, 126.7, 126.6, 126.0, 125.4, 123.8, 121.2, 115.0, 68.7.
J7.3 Hz, 1H), 7.31e7.26 (m, 5H), 7.10 (d, J7.1 Hz, 2H), 7.29e7.27 (m,
1H), 5.28 (s, 2H); 13C NMR (100 MHz, CDCl3): d 178.3, 143.7, 140.1, Acknowledgements
135.2, 132.2, 129.2, 128.3, 127.4, 126.9, 126.1, 123.7, 116.2, 110.3, 56.4.
We are grateful to the National Natural Science Foundation of
4.2.17. 4-Methylbenzyl phenyl ether (3ab).3d 1H NMR (400 MHz, China (21205107, 21172202, 21172200) and Postdoctoral Scholar-
CDCl3): d 7.36e7.29 (m, 4H), 7.22 (d, J7.8 Hz, 2H), 7.01e6.96 (m, ship of China (2012M511592) for nancial support of this research.
3H), 5.04 (s, 2H), 2.38 (s, 3H); 13C NMR (100 MHz, CDCl3): d 158.9,
137.8, 134.1, 129.5, 129.3, 127.7, 120.9, 114.9, 69.9, 21.3.
Supplementary data
4b 1
4.2.18. 4-Chlorobenzyl phenyl ether (3ac). H NMR (400 MHz,
CDCl3): d 7.39e7.29 (m, 6H), 6.98 (t, J8.4 Hz, 3H), 5.04 (s, 2H); 13C Supplementary data related to this article can be found at http://
NMR (100 MHz, CDCl3): d 158.6, 135.7, 133.8, 129.6, 128.8, 121.2, dx.doi.org/10.1016/j.tet.2014.01.004.
114.9, 69.2.
References and notes
4.2.19. 4-Bromobenzyl phenyl ether (3ad).3d 1H NMR (400 MHz,
1. McKillop, A.; Fiaud, J. C.; Hug, R. P. Tetrahedron 1974, 30, 1379.
CDCl3): d 7.52 (d, J8.3 Hz, 2H), 7.31 (t, J7.9 Hz, 4H), 7.01e6.97 (m,
2. (a) Banerjee, S. K.; Gupta, B. D.; Singh, K. J. Chem. Soc., Chem. Commun. 1982,
3H), 5.02 (s, 2H); 13C NMR (100 MHz, CDCl3): d 158.6, 136.2, 131.8, 815; (b) Lissel, M.; Schimidt, S.; Neumann, B. Synthesis 1986, 5, 382.
129.6, 129.1, 121.9, 121.2, 114.9, 69.2. 3. (a) Srivastava, P.; Srivastava, R. Tetrahedron Lett. 2007, 48, 4489; (b) Benaglia, M.;
Cinquini, M.; Cozzi, F.; Tocco, G. Tetrahedron Lett. 2002, 43, 3391; (c) Albanese, D.;
Benaglia, M.; Landini, D.; Maia, A.; Lupi, V.; Penso, M. Ind. Eng. Chem. Res. 2002, 41,
4.2.20. 4-Nitrobenzyl phenyl ether (3ae).3d 1H NMR (400 MHz, 4928; (d) Tamami, B.; Ghasemi, S. J. Iran. Chem. Soc. 2008, 5, 26; (e) Chen, Z. X.; Xu,
CDCl3): d 8.21 (d, J8.6 Hz, 2H), 7.58 (d, J8.6 Hz, 2H), 7.30e7.26 (m, G. Y.; Yang, G. C.; Wang, W. React. Funct. Polym. 2004, 61, 139; (f) Denmark, S. D.;
 H. Wang et al. / Tetrahedron 70 (2014) 2669e2673 2673

Weintraub, R. C.; Gould, N. D. J. Am. Chem. Soc. 2012, 134, 13415; (g) Coleman, M. 6. (a) Wang, M. L.; Vivekanand, P. A.; Yu, M. C. Bull. Chem. Soc. Jpn. 2012, 85, 976;
T.; LeBlanc, G. Org. Process Res. Dev. 2010, 14, 732. (b) Khurana, J. M.; Kumar, S. Tetrahedron Lett. 2009, 50, 4125; (c) Xiang, D. X.; Bi,
4. (a) Badri, M.; Brunet, J. J. Tetrahedron Lett. 1992, 33, 4435; (b) Mohanazadeh, F.; X. H.; Liao, P. Q.; Fang, G. C.; Wang, Z. K.; Xin, X. Q.; Dong, D. W. RSC Adv. 2013, 3,
Aghvami, M. Monatsh. Chem. 2007, 138, 47; (c) Lourenco, N. M. T.; Afonso, C. A. 386.
M. Tetrahedron 2003, 59, 789. 7. Wang, S.; Jia, X. D.; Liu, M. L.; Lu, Y.; Guo, H. Y. Bioorg. Med. Chem. Lett. 2012, 22,
5. (a) Lee, J. C.; Yuk, J. Y.; Cho, S. H. Synth. Commun. 1995, 25, 1367; (b) Godfrey, J. D.; 5971.
Mueller, R. H.; Sedergran, T. C.; Soundararajan, N.; Colandrea, V. J. Tetrahedron 8. Keglevich, G.; Ba  Gru
lint, E.; Karsai, E.; n, A.; B
alint, M.; Greiner, I. Tetrahedron
Lett. 1994, 35, 6405; (c) Taniguchi, H.; Nomura, E. Chem. Lett. 1988, 1773; (d) Lett. 2008, 49, 5039.
Zhang, M. J.; Flynn, D. L.; Hanson, P. R. J. Org. Chem. 2007, 72, 3194; (e) Taniguchi, 9. Yadav, G. D.; Bisht, P. M. Catal. Commun. 2004, 5, 259.
H.; Otsuji, Y.; Nomura, E. Bull. Chem. Soc. Jpn.1995, 68, 3563; (f) Shah, S. T. A.; Khan, 10. Elkobaisi, F. M.; Hickinbottom, W. J. J. Chem. Soc. 1959, 1873.
K. M.; Hussain, H.; Anwar, M. U.; Fecker, M.; Voelter, W. Tetrahedron 2005, 61, 11. Chakraborti, A. K.; Chankeshwara, S. V. J. Org. Chem. 2009, 74, 1367.
6652; (g) Shah, S. T. A.; Khan, K. M.; Heinrich, A. M.; Choudhary, M. I.; Voelter, W. 12. Molander, G. A.; Canturk, B. Org. Lett. 2008, 10, 2135.
Tetrahedron Lett. 2002, 43, 8603; (h) Brown Ripin, D. H.; Vetelino, M. Synlett 2003, 13. Muralidharan, S.; Nerbonne, J. M. J. Photochem. Photobiol., B 1995, 27, 123.
2353; (i) Kendall, J. T. J. Labelled Compd. Radiopharm. 2000, 43, 505; (j) Bu, X. L.; 14. Zhao, J. L.; Liu, L.; Sui, Y.; Liu, Y. L.; Wang, D.; Chen, Y. J. Org. Lett. 2006, 8, 6127.
Jing, H. W.; Wang, L.; Chang, T.; Jin, L. L.; Liang, Y. M. J. Mol. Catal. A: Chem. 2006, 15. Penn, J. H.; Lin, Z. J. Org. Chem. 1990, 55, 1554.
259, 121; (k) Gathirwa, J. W.; Maki, T. Tetrahedron 2012, 68, 370; (l) Alauddin, M. 16. Razadeh, K.; Yates, K. J. Org. Chem. 1986, 51, 2777.
M.; Miller, J. M. Can. J. Chem. 1984, 62, 263; (m) Kornblum, N.; Berrigan, P. J.; 17. Blessley, G.; Holden, P.; Walker, M.; Brown, J. M.; Gouverneur, V. Org. Lett. 2012,
Lenoble, W. J. Am. Chem. Soc. 1963, 85, 1141; (n) Kornblum, N.; Seltzer, R.; Hab- 11, 2754.
ereld, P. J. Am. Chem. Soc. 1963, 85, 1148.