Facile synthesis of 2,2′-dialkylated 4,4′-oxybiphenols

Article abstract of DOI:10.1080/00397910500408225

2,2′-Alkyl-disubstituted 4,4′-oxybiphenols (4) were prepared in good yields through esterification of 4,4′-oxybiphenol (1), AlCl ₃-promoted Fries rearrangement, and AlCl₃/NaBH ₄-promoted reduction reaction. Copyright Taylo

Full text of DOI:10.1080/00397910500408225

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Facile Synthesis of 2,2′‐Dialkylated
4,4′‐Oxybiphenols
Katsuya Maeyama a , Yasushi Fujiwara a , Makiya Nishimuro b , Yasuhiko
Yoshida b & Noriyuki Yonezawa a
a Department of Organic and Polymer Materials Chemistry , Graduate
School, Tokyo University of Agriculture and Technology , Tokyo, Japan
b Department of Applied Chemistry, Faculty of Engineering, , Toyo
University , Kawagoe, Satima, Japan
Published online: 16 Aug 2006.
To cite this article: Katsuya Maeyama , Yasushi Fujiwara , Makiya Nishimuro , Yasuhiko Yoshida & Noriyuki
Yonezawa (2006) Facile Synthesis of 2,2′‐Dialkylated 4,4′‐Oxybiphenols, Synthetic Communications: An
International Journal for Rapid Communication of Synthetic Organic Chemistry, 36:5, 603-609
To link to this article: http://dx.doi.org/10.1080/00397910500408225
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Synthetic Communicationsw, 36: 603–609, 2006
Copyright # Taylor & Francis Group, LLC
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910500408225
Facile Synthesis of 2,20-Dialkylated
4,40-Oxybiphenols
Katsuya Maeyama and Yasushi Fujiwara
Department of Organic and Polymer Materials Chemistry,
Graduate School, Tokyo University of Agriculture and Technology,
Tokyo, Japan
Makiya Nishimuro and Yasuhiko Yoshida
Department of Applied Chemistry, Faculty of Engineering,
Toyo University, Kawagoe, Satima, Japan
Noriyuki Yonezawa
Department of Organic and Polymer Materials Chemistry,
Graduate School, Tokyo University of Agriculture and Technology,
Tokyo, Japan
Abstract: 2,20-Alkyl-disubstituted 4,40-oxybiphenols (4) were prepared in good yields
through esterification of 4,40-oxybiphenol (1), AlCl3-promoted Fries rearrangement,
and AlCl3/NaBH4-promoted reduction reaction.
Keywords: Dealkylation, Fries rearrangement, good solubility, 4,40-oxybiphenol
INTRODUCTION
Optically active compounds have been applied to asymmetric organic reaction
as asymmetric ligands.[1] Immobilization of these optically active compounds
onto polymer skeletons has been very attractive for recyclable asymmetric
catalysts. There have already been several reports on polymeric chiral
Received in Japan July 31, 2005
Address correspondence to Katsuya Maeyama, Department of Organic and Polymer
Materials Chemistry, Graduate School, Tokyo University of Agriculture and
Technology, Koganei, Tokyo 184-8588, Japan. E-mail: maeyama@cc.tuat.ac.jp
603

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K. Maeyama et al.
compounds containing optically active 2,20-disubstituted-1,10-binaphthylene
units.[2] We have also reported optically active aromatic polyketones
via nucleophilic aromatic substitution polymerization of optically active
6,60-bis(4-fluorobenzoyl)-2,20-dialkoxy-1,10-binaphthyl with aromatic diols
such as hydroquinone and 4,40-oxybiphenol.[3] In this report, we disclose
that 4,40-oxybiphenol is the most suitable monomer among aromatic diols
screened, probably owing to high reactivity. The resulting polyketones are
soluble to organic solvents such as chloroform. However, they are insoluble
to toluene and acetone. For application of these polyketones to polymeric
catalysts for asymmetric reactions, improvement of solubility of the poly-
ketones has been required. One of the solutions is the introduction of long-
chain alkyl substituents to polymer backbones. This motivated us to
synthesize 2,20-dialkylated 4,40-oxybiphenols.
In this article, we report the facile dialkylation of 4,40-oxybiphenol
through esterification, AlCl3-promoted Fries rearrangement,[4] and reduction
of carbonyl groups.
RESULTS AND DISCUSSION
Reactions of 4,40-oxybiphenol (1) with hexanoyl chloride, nonanoyl chloride,
and propanoyl chloride were carried out in CHCl3, giving the corresponding
diester 2. Without purification, treatment of crude 2 with AlCl3 at 1508C
yielded Fries rearrangement product 3 in a good yield without any
byproducts. When this reaction was performed in the presence of nitrobenzene
as a solvent, the yield of product 3 decreased. However, when the reaction was
performed without any solvent and at higher temperature, the reaction
proceeded smoothly. See Table 1.
Next, reduction of 2,20-diacyl-4,40-oxybiphenol was investigated. The
results are shown in Table 2.
When H2 in the presence of Pd/C was employed as a reducing agent of
acyl compound 3a, no reaction proceeded only to recover 3a. Raney nickel
[5]
was also useless. However, when a mixture of AlCl3 and NaBH4 was
used as a reducing reagent, reaction proceeded to give 2,20-dialkylated
4,40-oxybiphenol 4 in good yields.
This protocol is applicable to introduction of alkyl groups onto other
aromatic diol such as 5 as shown in Scheme 1. However, when bisphenol A
was employed instead of aromatic diol 5, dealkylation proceeded along with
Fries rearrangement, affording o-hydroxyhexanophenone.
In conclusion, we realized regioselective dialkylation of 4,40-oxybiphenol
through diesterification, Fries rearrangement, and reduction of carbonyl
groups. The novel 4,40-oxybiphenol derivatives (4) have higher solubility to
various organic solvents than 4,40-oxybiphenol (1). Polymerization of these
derivatives will formulate more soluble polymers, which are applicable as
asymmetric reaction catalysts.

Facile Synthesis of 2,20-Dialkylated 4,40-Oxybiphenols
605
Table 1. Esterification of 4,40-oxybiphenol (1) and Fries rearrangement
Yield of
2/%a
Yield of
3/%b
Run
R
1
2
3
C5H11
C8H17
C2H5
79 (2a)
98 (2b)
94 (2c)
94 (70) (3a)c
91 (3b)
99 (3c)
a4,40-Oxybiphenol (1), 10 mmol; acid chloride 30 mmol; CHCl3, 6 mL,
reflux, 1 h.
bDiester 2, 0.5 mmol; AlCl3, 1.5 mmol, neat, 1508C, 0.5 h.
cYield in parentheses is the case of 2 mL of nitrobenzene as solvent;
see text.
EXPERIMENTAL
1H and 13C NMR spectra were recorded on a JEOL JNM-AL300 (1H;
300 MHz, 13C; 75 MHz) spectrometer using Me4Si (1H, d 0.00) and CDCl3
(13C, d 77.0) as internal standards. IR spectra were recorded on a JEOL
FTIR-5300 spectrometer.
Typical Procedure for Esterification of 4,40-Oxybiphenol (1)
To a two-necked flask, a CHCl3 solution (6 mL) of 4,40-oxybiphenol (1, 2.02 g,
10 mmol) and acid chloride (30 mmol) was added. It was stirred at reflux for
1 h. After the reaction mixture was diluted with CHCl3, the organic solution
was washed water, 10% aqueous NaHCO3, and brine successively and dried
over anhydrous magnesium sulfate. After removal of solvent, a white solid
was obtained. The crude product was employed for a Fries rearrangement
reaction without any purification.

606
K. Maeyama et al.
Table 2. Reduction of 4,40-oxybiphenol derivatives 3a
Reducing
agent
Run
R
Solvent
Yield/%
1
2
3
4
5
6
C5H11 (3a)
H2, Pd/C
EtOH
AcOH
AcOH
THF
0
0
H2, Raney Ni
AlCl3, NaBH4
0
a
96 (4a)
94 (4b)
89 (4c)
C8H17 (3b)
C3H7 (3c)
aDiacyl compound 3, 2.5 mmol; AlCl3, 50 mmol; NaBH4, 50 mmol, THF,
5 mL; reflux, 3 h.
4,40-Oxybiphenolene dihexanoate (2a): IR n (KBr): 2930, 1748, 1502 cm21
.
1H NMR d (CDCl3): 0.93 (6H, t, J ¼ 6.9 Hz), 1.37–1.39 (8H, m), 1.76 (4H,
quint, J ¼ 6.9 Hz), 2.54 (4H, t, J ¼ 6.9 Hz), 6.98–7.05 (8H, m) ppm. 13C
NMR d (CDCl3): 13.9, 22.3, 24.3, 31.2, 34.3, 119.5, 122.7, 146.2, 154.6,
172.5 ppm.
4,40-Oxybiphenolene dinonanoate (2b): IR n (KBr): 2924, 1744, 1502 cm21
.
1H NMR d (CDCl3): 0.85–0.87 (10H, m), 1.18–1.27 (16H, m), 1.70 (4H,
quint, J ¼ 7.5 Hz), 2.49 (4H, t, J ¼ 7.5 Hz), 6.92–7.01 (8H, m) ppm. 13C
NMR d (CDCl3): 13.8, 22.4, 24.6, 28.8, 28.9, 29.0, 31.6, 33.9, 119.1, 122.5,
146.0, 154.3, 171.9 ppm.
Scheme 1.

Facile Synthesis of 2,20-Dialkylated 4,40-Oxybiphenols
607
4,40-Oxybiphenolene dipropanoate (2c): IR n (KBr): 2924, 1746, 1502 cm21
.
1H NMR d (CDCl3): 1.23 (6 H, t, J ¼ 7.5 Hz), 2.59 (4 H, q, J ¼ 7.5 Hz),
6.98–7.06 (8 H, m) ppm. 13C NMR d (CDCl3): 8.5, 27.0, 118.9, 122.3,
145.8, 154.1, 172.4 ppm.
Typical Procedure for Fries Rearrangement of Diester 2a–c
In a two-necked flask, diester (2, 0.5 mmol) and AlCl3 (200 mg, 1.5 mmol)
were placed. The reaction mixture was stirred at 150 8C for 30 min. To the
reaction mixture, aqueous 1.2M HCl was added and extracted with ethyl
acetate three times. The combined organic extracts were washed with water,
aqueous 10% NaHCO3, and brine successively and dried over anhydrous
magnesium sulfate. After removal of solvent, product 3 was obtained as a
brown liquid (for 3a or 3b) or pale yellow solid (for 3c).
2,20-Dihexanoyl-4,40-oxybiphenol (3a): IR n (neat): 2959, 1645, 1560,
1
1479 cm21. H NMR d (CDCl3): 0.90 (6H, t, J ¼ 6.6 Hz), 1.34–1.36 (8H,
m), 1.72 (4H, quint, J ¼ 7.5 Hz), 2.89 (4H, t, J ¼ 7.5 Hz), 6.98 (2H, d,
J ¼ 9.0 Hz), 7.15 (2H, dd, J ¼ 3.0, 9.0 Hz), 7.37 (2H, d, J ¼ 3.0 Hz) ppm.
13C NMR d (CDCl3): 13.7, 22.3, 23.9, 31.3, 38.2, 118.6, 119.2, 119.7,
127.1, 148.9, 158.5, 206.1 ppm. Anal. calcd. for C24H30O5: C, 72.33; H,
7.59. Found: C, 72.34; H, 7.72%.
2,20-Dinonanoyl-4,40-oxybiphenol (3b): IR n (neat): 2936, 1633, 1583,
1
1477 cm21. H NMR d (CDCl3): 0.85-0.88 (10H, m), 1.24–1.28 (16H, m),
1.72 (4H, quint, J ¼ 7.5 Hz), 2.88 (4H, t, J ¼ 7.5 Hz), 6.99 (2H, d,
J ¼ 9.3 Hz), 7.15 (2H, dd, J ¼ 3.0, 9.3 Hz), 7.38 (2H, d, J ¼ 3.0 Hz) ppm.
13C NMR d (CDCl3): 14.1, 22.6, 24.3, 29.1, 29.2, 29.3, 31.8, 38.4, 118.6,
119.2, 119.8, 127.2, 148.9, 158.5, 206.3 ppm. Anal. calcd. for C30H42O5: C,
74.65; H, 8.77. Found: C, 74.89; H, 8.68%.
2,20-Dipropanoyl-4,40-oxybiphenol (3c): IR n (neat): 2935, 1640, 1583,
1477 cm21
.
1HNMR d (CDCl3): 1.22 (6H, t, J ¼ 7.2 Hz), 2.94 (4H, t,
J ¼ 7.2 Hz), 6.98 (2H, d, J ¼ 9.0 Hz), 7.15 (2H, dd, J ¼ 3.0, 9.0 Hz), 7.36
(2H, d, J ¼ 3.0 Hz) ppm. 13C NMR d (CDCl3): 7.9, 31.6, 118.4, 119.1,
119.8, 127.2, 148.9, 158.3, 206.4 ppm. Anal. calcd. for C18H18O5: C, 68.78;
H, 5.77. Found: C, 68.66; H, 5.78%.
Bis(3-hexanoyl-4-hydroxyphenyl)methane (6): IR n (neat): 2957, 1642,
1
1485, 1356 cm21. H NMR d (CDCl3): 0.89 (6H, t, J ¼ 7.2 Hz), 1.33–1.37
(8H, m), 1.70 (4H, quint, J ¼ 7.5 Hz), 2.93 (4H, t, J ¼ 7.5 Hz), 4.12 (2H, s),
6.94 (2H, d, J ¼ 8.7 Hz), 7.27 (2H, dd, J ¼ 1.8, 8.7 Hz), 7.52 (2H, d,
J ¼ 1.8 Hz) ppm. 13C NMR d (CDCl3): 13.8, 22.4, 24.1, 31.4, 38.2, 39.9,
118.8, 119.1, 129.6, 130.9, 136.7, 161.1, 206.7 ppm. Anal. calcd. for
C25H32O4: C, 75.72; H, 8.14. Found: C, 75.54; H, 8.13%.

608
K. Maeyama et al.
Typical Procedure for Reduction of 2,20-Diacyl-4,40-
Oxybiphenol (3)
To a 50-mL, two-necked flask, 14 mL, of THF was added. AlCl3 powder
(7.71 g, 50 mmol) and NaBH4 powder (2.20 g, 50 mmol) were added slowly
to the solution. A THF solution (5 mL) of diacyl compound 3 (1.0 g,
2.5 mmol) was added and stirred under reflux for 3 h. After acetone was
added to the reaction mixture, the mixture was poured into ice water. The
mixture was extracted with ethyl acetate three times. The combined extracts
were washed with aqueous 1.2 M HCl, water, 10 mol% aqueous NaHCO3,
and brine successively and dried over anhydrous magnesium sulfate. After
removal of solvent, the residue was purified by column chromatograph
(hexane–ethyl acetate 7 : 1) to give the reduced product as a white solid
(for 4a), a brown liquid (for 4b), or a pale yellow liquid (for 4c).
2,20-Dihexyl-4,40-oxybiphenol (4a): IR n (neat): 2959, 1614, 1489,
1
1421 cm21. H NMR d (CDCl3): 0.85 (6H, t, J ¼ 6.5 Hz), 1.20–1.35 (12H,
m), 1.57 (4H, quint, J ¼ 7.2 Hz), 2.54 (4H, t, J ¼ 7.2 Hz), 6.66–6.69 (4H,
m), 6.77 (2H, s) ppm. 13C NMR d (CDCl3): 14.1, 22.6, 29.1, 29.5, 30.0,
31.7, 115.9, 116.6, 120.2, 130.6, 148.9, 151.3 ppm. Anal. calcd. for
C24H34O3: C, 77.80; H, 9.25. Found: C, 77.55; H,9.22%.
2,20-Dinonyl-4,40-oxybiphenol (4b): IR n (neat): 2926, 1612, 1498,
1431 cm21.1H NMR d (CDCl3): 0.86–0.88 (10H, m), 1.20–1.26 (20H, m),
1.56 (4H, quint, J ¼ 7.2 Hz), 2.55 (4H, t, J ¼ 7.2 Hz), 6.67–6.69 (4H, m),
6.77 (2H, s) ppm. 13C NMR d (CDCl3): 14.1, 22.7, 29.3, 29.4, 29.5, 29.6,
30.1 31.9, 31.7, 115.8, 116.7, 120.2, 130.1, 149.1, 151.3 ppm. Anal. calcd.
for C30H46O3: C, 79.24; H, 10.20. Found: C, 79.12; H,10.14%.
2,20-Dipropyl-4,40-oxybiphenol (4c): IR n (neat): 2852, 1503, 1468 cm21. 1H
NMR d (CDCl3): 0.89 (6H, t, J ¼ 7.2 Hz), 1.26–1.27 (4H, m), 2.54 (4H, t,
J ¼ 7.8 Hz), 6.98 (2H, d, J ¼ 9.0 Hz), 7.15 (2H, dd, J ¼ 3.0, 9.0 Hz), 7.36
(2H, d, J ¼ 3.0 Hz) ppm. 13C NMR d (CDCl3): 13.9, 22.7, 32.0, 115.9,
116.6, 120.3, 129.9, 149.1, 151.3 ppm. Anal. calcd. for C18H22O3: C, 75.49;
H, 7.74. Found: C, 75.32; H,7.74%.
Bis(3-hexyl-4-hydroxyphenyl)methane (7): IR n (neat): 2928, 1502, 1460,
1
1365 cm21. H NMR d (CDCl3): 0.85–0.86 (6H, m), 1.22–1.36 (8H, m),
1.52–1.58 (8H, m), 2.55 (4H, d, J ¼ 7.2 Hz), 3.80 (2H, s), 6.67 (2H, d,
J ¼ 8.1 Hz), 6.85 (2H, dd, J ¼ 2.4, 8.1 Hz), 6.91 (2H, d, J ¼ 2.4 Hz) ppm.
13C NMR d (CDCl3): 14.1, 22.6, 29.5, 29.8, 30.0, 31.7, 40.3, 115.1, 127.2,
128.4, 130.6, 133.8, 151.6 ppm. Anal. calcd. for C25H36O2: C, 81.47; H,
9.85. Found: C, 81.75; H, 9.77%.

Facile Synthesis of 2,20-Dialkylated 4,40-Oxybiphenols
ACKNOWLEDGMENT
609
This work was supported financially by the Asahi Glass Foundation and
the Ministry of Education, Culture, Sports, Science, and Technology of
Japan.
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