An efficient synthesis of ω-(2,2′-bipyridyl)alkyl alcohols and their acrylates

Article abstract of DOI:10.1081/SCC-120013727

ω-(2,2′-Bipyridyl)alkyl alcohols were synthesized by treatment of methyl-2,2′-bipyridine with LDA at -78°C followed by the addition of ω-bromoalkyl THP ether and hydrolysis of the resulting THP ether. Furthermore, ω-2,2′-bipyridylalkyl acrylates were obtained by the reaction of the corresponding ω-(2,2′-bipyridyl)alkyl alcohols with acryloyl chloride in good yields.

Full text of DOI:10.1081/SCC-120013727

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AN EFFICIENT SYNTHESIS OF ω-(2,2′-BIPYRIDYL)ALKYL
ALCOHOLS AND THEIR ACRYLATES
a
a
b
Katsuya Maeyama , Chieri Okumura & Noriyuki Yonezawa
a
Department of Organic and Polymer Materials Chemistry , Tokyo University of Agriculture
and Technology , Koganei, Tokyo, 184-8588, Japan
b
Department of Organic and Polymer Materials Chemistry , Tokyo University of Agriculture
and Technology , Koganei, Tokyo, 184-8588, Japan
Published online: 16 Aug 2006.
To cite this article: Katsuya Maeyama , Chieri Okumura & Noriyuki Yonezawa (2002) AN EFFICIENT SYNTHESIS OF ω-
2,2′-BIPYRIDYL)ALKYL ALCOHOLS AND THEIR ACRYLATES, Synthetic Communications: An International Journal for Rapid
(
Communication of Synthetic Organic Chemistry, 32:20, 3159-3167, DOI: 10.1081/SCC-120013727
To link to this article: http://dx.doi.org/10.1081/SCC-120013727
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SYNTHETIC COMMUNICATIONS
Vol. 32, No. 20, pp. 3159–3167, 2002
AN EFFICIENT SYNTHESIS OF
v-(2,29-BIPYRIDYL)ALKYL ALCOHOLS
AND THEIR ACRYLATES
Katsuya Maeyama, Chieri Okumura,
and Noriyuki Yonezawa*
Department of Organic and Polymer Materials
Chemistry, Tokyo University of Agriculture and
Technology, Koganei, Tokyo, 184-8588, Japan
ABSTRACT
0
o-(2,2 -Bipyridyl)alkyl alcohols were synthesized by treatment
0
ꢀ
of methyl-2,2 -bipyridine with LDA at À78 C followed by the
addition of o-bromoalkyl THP ether and hydrolysis of the
0
resulting THP ether. Furthermore, o-2,2 -bipyridylalkyl
acrylates were obtained by the reaction of the corresponding
0
o-(2,2 -bipyridyl)alkyl alcohols with acryloyl chloride in good
yields.
0
0
Key Words: o-(2,2 -Bipyridyl)alkyl alcohol; o-(2,2 -Bipyr-
idyl)alkyl acrylate; Carbon–carbon bond formation using
alkylation
0
2,2 -Bipyridine is one of the most widely used ligands for preparation
of transition metal complexes through efficient coordinating nature to
0
metals. Though a number of molecules containing plural 2,2 -bipyridines
*
Corresponding author. E-mail: yonezawa@cc.tuat.ac.jp
159
3
DOI: 10.1081/SCC-120013727
Copyright & 2002 by Marcel Dekker, Inc.
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com

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3
160
MAEYAMA, OKUMURA, AND YONEZAWA
0
Formulae 1. Structures of o-(2,2 -bipyridyl)alkyl acrylates.
0
have been reported, there are a few reports on polymers containing 2,2 -
1]
[
bipyridine units in the side chains. To our knowledge, the structures of the
reported polymers have been substantially limited to the following cases:
polymers where 2,2 -bipyridinyl units are connected with the main chains
without any tethers, through methylene tethers, or through other rigid
0
[2,3]
0
tethers.
We expected that more flexible circumstance around 2,2 -bipyr-
idyl unit would reveal anomalous functionality. With this expectation,
we planned the synthesis of o-bipyridylalkyl acrylates 1, in which the
acrylate unit is linked to the bipyridyl moiety through alkylene tethers
(
Formulae 1).
For the synthesis of target molecules 1, the construction of carbon–
carbon bond structure between bipyridyl ring and a hydroxyalkyl group is
crucial. In this paper, we would like to describe the efficient syntheses of
o-bipyridylalkyl alcohols and their acrylates.
First, we attempted to synthesize target molecule 1 according to Wittig
0
type conversion of 5-(2,2 -bipyridine)carbaldehyde by the action of
o-hydroxyalkylenetriphenylphosphorane derivatives and reduction of the
produced olefin. However, the desired carbon–carbon bond formation
was not achieved. When the phosphorane prepared from THP-protected
o-hydroxyalkyl halide was subjected to this reaction, no desired compound
was obtained. Next, we examined nucleophilic substitution reaction of THP-
0
protected o-hydroxyalkyl halide with 2,2 -bipyridylmethyl anion.
0
ꢀ
5
-Methyl-2,2 -bipyridine was treated with LDA in THF at À78 C
[
4,5]
followed by addition of 2-bromoethyl THP ether.
After consumption
of the starting material was confirmed, the reaction mixture was quenched
with water, followed by chromatographic separation on a short column
of alumina. The obtained mixture was treated with aqueous 6 M HCl
to hydrolyze the THP ether, yielding the corresponding alcohol (2a) in a
moderate yield.
This method is applicable for the preparation of the related o-bipyr-
idylalkyl alcohols where o-hydroxyalkyl group is substituted on the different
position of the bipyridyl ring and/or the tether has the different length.
We synthesized various o-bipyridylalkyl alcohol homologue and isomers
(
2b–d) (Sch. 1, Table 1). The synthesis of four o-bipyridylalkyl alcohols

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0
v-(2,2 -BIPYRIDYL)ALKYL ALCOHOLS
3161
Scheme 1. Synthesis of 3-bipyridylpropanol and 4-bipyridylbutanol.
Table 1. Synthesis of o-Bipyridylalkyl Alcohols 2
Alcohols 2
n þ 1Yield/%
3
4
(2a)
(2b)
74
49
3
4
(2c)
(2d)
70
53
Scheme 2. Synthesis of 2-bipyridylethanol.
0
(2a–d) was undertaken by the connection of 5- or 6-methyl-2,2 -bipyridine
and 2-bromoethyl or 3-bromopropyl THP ether.
[
According to Ziessel’s method, alcohol 2e and 2f, whose alkyl
6]
chain are -CH CH -, were also synthesized (Sch. 2). Methylbipyridines
2
2
ꢀ
were allowed to react with LDA at À78 C followed by treatment of para-
formaldehyde. The corresponding alcohols were obtained in rather low
yields. It is probably due to the lack of solubility of paraformaldehyde.
Utilization of trioxane in place of paraformaldehyde had no effect to raise
up the yield.

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3
162
MAEYAMA, OKUMURA, AND YONEZAWA
Scheme 3. Synthesis of o-bipyridylalkyl acrylates 1.
Table 2. Synthesis of o-Bipyridylalkyl Acrylates 1
Acrylates 1
n þ 1Yield/%
2
3
4
61
98
90
2
3
4
82
1 0
88
0
As a series of o-bipyridylalkyl alcohols (2) were obtained, we
examined the synthesis of the target molecules (1) from o-bipyridylalkyl
alcohols 2.
Conversion of o-bipyridylalkyl alcohols 2 to o-bipyridylalkyl acryl-
ates 1 was successfully achieved by treatment of o-bipyridylalkyl alcohols
2
with acrylolyl chloride without solvent. The desired six acrylates were
obtained as viscous liquids in good yields (Sch. 3). The results are summar-
ized in Table 2.
In conclusion, we established the synthetic method of o-bipyridylalkyl
acrylates.
In the near future, we will report the polymerization of these molecules
and the functionality of the polymers.
EXPERIMENTAL
1
13
H and C NMR spectra were recorded on a JEOL JNM-A500
1
13
1
(
H; 500 MHz, C; 125 MHz) spectrometer using Me Si ( H, ꢀ 0.00) and
4
CDCl3 ( C, ꢀ 77.0) as internal standards. IR spectra were recorded
1
3

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0
v-(2,2 -BIPYRIDYL)ALKYL ALCOHOLS
3163
0
[7]
on a JEOL FTIR-5300 spectrometer. 5-Methyl-2,2 -bipyridine and
were prepared according to the literatures.
0
[8]
6
2
3
-methyl-2,2 -bipyridine
-(2-Bromoethoxy)-3,4,5,6-tetrahydro-2H-pyran or 2-(3-bromopropoxy)-
,4,5,6-tetrahydro-2H-pyran was prepared by the reaction of o-bromoalkyl
alcohol and 3,4-dihydro-2H-pyran (DHP) in the presence of TsOH in
CH Cl . Diisopropylamine was distilled from CaH before use. Acryloyl
2
2
2
chloride was purchased from Aldrich Co. Ltd. and used without further
purification. Chromatographic separations were carried out on Wako
alumina (activated, about 300 mesh).
0
5-(3-Hydroxypropyl)-2,2 -bipyridine (2a): To a THF solution (10 mL)
of diisopropylamine (3.6 g, 36 mmol) was added a hexane solution of n-BuLi
ꢀ
(
20 mL, 30 mmol, 1.6 M) dropwise at À78 C and the reaction mixture was
0
stirred for 1h. To this mixture was added a THF solution of 5-methyl-2,2 -
bipyridine (5.1g, 30 mmol) and the resulting mixture was stirred for 3 h.
Then, a THF solution of 2-(2-bromoethoxy)-3,4,5,6-tetrahydro-2H-pyran
(
6.3 g, 30 mmol) was added dropwise into the reaction mixture. After the
ꢀ
mixture was stirred for 5 h at À78 C, the reaction mixture was quenched by
addition of water (10 mL). The organic materials were extracted with
chloroform (10 mL Â 3) and the combined extracts were dried over
Na SO . After removal of solvents, the residue was purified by a
2
4
short column of alumina with chloroform as an eluent. The obtained com-
pounds were treated with aqueous 6 M HCl. The mixture was stirred
overnight at r.t. The organic materials were extracted with chloroform
(
removal of solvents, the residue was purified by alumina column chromatog-
10 mL Â 3) and the combined extracts were dried over Na SO . After
2
4
0
raphy with chloroform to give 5-(3-hydroxypropyl)-2,2 -bipyridine (2a)
(
3.1g, 2.2 mmol, 74%).
IR (neat) 3356, 3007, 2939, 1591, 1462, 1059, 752, 650 cm ; H NMR
À1
1
ꢀ
(CDCl ) 1.77 (2H, tt, J ¼ 8.0, 6.4 Hz), 2.63 (2H, t, J ¼ 8.0 Hz), 3.54 (2H, t,
3
J ¼ 6.4 Hz), 7.17 (1H, ddd, J ¼ 8.0, 4.8, 1.2 Hz), 7.51 (1H, dd, J ¼ 8.0, 2.0 Hz),
7
.68 (1H, dt, J ¼ 8.0, 2.0 Hz), 8.16 (1H, d, J ¼ 8.0 Hz), 8.22 (1H, dd, J ¼ 8.0,
.2 Hz), 8.38 (1H, d, J ¼ 2.0 Hz), 8.54 (1H, dd, J ¼ 4.8, 1.2 Hz) ppm;
1
1
3
C NMR ꢀ (CDCl ) 28.8, 33.5, 61.1, 120.7, 120.8, 123.4, 136.8, 136.9, 137.5,
3
1
48.9, 149.1, 153.6, 155.9 ppm; Anal. Calcd. for C H N O; C, 72.88; H,
1
3
14
2
6.59; N, 13.07. Found: C, 73.21; H, 6.74; N, 12.83%.
Compounds 2b–d were synthesized according to the method for the
synthesis of compound 2a described above.
0
5
-(4-Hydroxybutyl)-2,2 -bipyridine (2b): IR (neat) 3364, 2937, 1589,
À1
1
1
1
(
(
460, 1066, 752 cm ; H NMR ꢀ (CDCl ) 1.60 (2H, quint, J ¼ 7.5 Hz),
3
.72 (2H, quint, J ¼ 7.5 Hz), 2.67 (2H, t, J ¼ 7.5 Hz), 2.89 (1H, s), 3.64
2H, t, J ¼ 7.5 Hz), 7.27–7.29 (1H, m), 7.62 (1H, dd, J ¼ 8.5, 2 Hz), 7.80
1H, dt, J ¼ 8.0, 1.5 Hz), 8.28 (1H, d, J ¼ 8.5 Hz), 8.34 (1H, dd, J ¼ 8.0,

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164
MAEYAMA, OKUMURA, AND YONEZAWA
1
3
1
ꢀ
.0 Hz), 8.49 (1H, d, J ¼ 2 Hz), 8.65 (1H, dt, J ¼ 4.5, 1Hz) ppm; C NMR
(CDCl ) 27.2, 32.0, 32.4, 62.1, 120.7, 120.8, 123.4, 136.8, 136.9, 137.8, 148.9,
3
149.1, 153.7, 156.0 ppm; Anal. Calcd. for C H N O; C, 73.66; H, 7.06;
N, 12.27. Found: C, 73.35; H, 7.08; N, 12.03%.
1
4
16
2
0
6
-(3-Hydroxypropyl)-2,2 -bipyridine (2c): IR (neat) 3362, 3061, 2935,
À1
1
1
581, 1458, 1049, 775, 621 cm ; H NMR ꢀ (CDCl ) 2.08 (2H, quint,
3
J ¼ 6.5 Hz), 3.06 (2H, t, J ¼ 6.5 Hz), 3.77 (2H, t, J ¼ 6.5 Hz), 7.21( 1H , d,
J ¼ 7.5 Hz), 7.29–7.32 (1H, m), 7.76 (1H, t, J ¼ 8.0 Hz), 7.83 (1H, dt, J ¼ 7.5,
1
.5 Hz), 8.23 (1H, d, J ¼ 8.0 Hz), 8.33 (1H, dd, J ¼ 8.0, 1.0 Hz), 8.68–8.69
1
3
(
1H, m) ppm; C NMR ꢀ (CDCl ) 31.2, 35.2, 62.3, 118.8, 121.1, 123.2,
3
123.7, 137.1, 137.7, 149.2, 155.4, 156.0, 160.8 ppm; Anal. Calcd. for
C H N O; C, 72.88; H, 6.59; N, 13.07. Found: C, 71.49; H, 6.07; N, 14.13%.
1
3
14
2
0
6-(4-Hydroxybutyl)-2,2 -bipyridine (2d): IR (neat) 3373, 3061, 2937,
À1 1
1
1
581, 1458, 1060, 777 cm ; H NMR ꢀ (CDCl ) 1.69 (2H, quint, J ¼ 7.5 Hz),
3
.77 (1H, brs), 1.92 (2H, tt, J ¼ 7.5, 6.5 Hz), 2.93 (2H, t, J ¼ 7.5 Hz), 3.71(2H,
dt, J ¼ 6.5, 1.5 Hz), 7.18 (1H, d, J ¼ 7.5 Hz), 7.29–7.31 (1H, m), 7.73 (1H, dt,
J ¼ 8.0, 1.0 Hz), 7.81 (1H, tt, J ¼ 7.5, 1.5 Hz), 8.19 (1H, d, J ¼ 8.0 Hz), 8.41
1
3
(
3
1
1H, dd, J ¼ 8.0, 1.0 Hz), 8.67–8.68 (1H, m) ppm; C NMR ꢀ (CDCl ) 25.7,
3
2.0, 37.6, 62.6, 118.5, 121.2, 122.9, 123.5, 136.9, 137.2, 149.1, 155.4, 156.4,
61.4 ppm; Anal. Calcd. for C H N O; C, 73.33; H, 7.06; N, 12.27. Found:
1
4
16
2
C, 73.39; H, 6.79; N, 11.98%.
0
5
-(2-Hydroxyethyl)-2,2 -bipyridine (2e): Compound 2e was synthesized
[
6]
referred to Ziessel’s method.
To a THF solution (10 mL) of diisopropylamine (0.53 g, 5.3 mmol)
was added a hexane solution of n-BuLi (3.1mL, 5.0 mmol, 1.6 M) drop-
ꢀ
wise at À78 C and the reaction mixture was stirred for 1h. A THF
0
solution (4 mL) of 5-methyl-2,2 -bipyridine (0.85 g, 5.0 mmol) was added
and stirred for 3 h. Next, a THF suspension of paraformaldehyde (0.18 g,
6
.0 mmol) was dropped into the reaction mixture. After the mixture was
ꢀ
stirred for 5 h at À78 C, it was quenched by the addition of water (10 mL).
The organic materials were extracted with chloroform (10 mL Â 3) and
the combined extracts were dried over Na SO . After removal of solvents,
2
4
the residue was purified by alumina column chromatography with chloro-
0
form as an eluent to give 5-(2-hydroxyethyl)-2,2 -bipyridine (2e) (0.54 g,
2.6 mmol, 52%).
À1
1
IR (neat) 3348, 3055, 2939, 1581, 1462, 1051, 750, 650 cm ; H NMR
ꢀ
(CDCl ) 2.91(2H, t, J ¼ 6.5 Hz), 3.90 (2H, dt, J ¼ 6.5, 1.5 Hz), 7.28–7.31
3
(
1H, m), 7.68 (1H, d, J ¼ 8.0 Hz), 7.81( 1H , tt, J ¼ 7.5, 1.5 Hz), 8.30 (1H, d,
J ¼ 8.0 Hz), 8.34 (1H, dd, J ¼ 8.0, 1.5 Hz), 8.52 (1H, s), 8.65–8.67 (1H, m)
1
3
ppm; C NMR ꢀ (CDCl ) 27.2, 32.0, 32.4, 62.1, 120.7, 120.8, 123.4, 136.8,
3
136.9, 137.8, 148.9, 149.1, 153.7, 156.0 ppm; Anal. Calcd. for C H N O; C,
12 12 2
71.97; H, 6.04; N, 13.99. Found: C, 71.94; H, 6.07; N, 14.13%.

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0
v-(2,2 -BIPYRIDYL)ALKYL ALCOHOLS
3165
0
2-(2,2 -Bipyridin-5-yl)ethyl acrylate (1a): Acryloyl chloride (0.21mL,
.1mmol) was added to 5-(2-hydroxyethyl)-2,2 -bipyridine (2a) (0.96 g,
0
7
4.7 mmol) neatly. The reaction mixture was stirred overnight at r.t.
The reaction was quenched by the addition of water and neutralized with
aqueous 6 M NaOH. The organic materials were extracted with chloroform
(
removal of solvents, the residue was purified by alumina column chromatog-
10 mL Â 3) and the combined extracts were dried over Na SO . After
2
4
0
raphy with chloroform as an eluent to give 2-(2,2 -bipyridin-5-yl)ethyl
acrylate (1a) (1.1 g, 2.9 mmol, 61%).
À1
1
IR (neat) 3061, 1726, 1581, 1460, 1429, 773 cm ; H NMR ꢀ (CDCl )
3
2
.94 (2H, t, J ¼ 6.5 Hz), 4.32 (2H, t, J ¼ 6.5 Hz), 5.78 (1H, d, J ¼ 10.5 Hz), 6.06
(
7
1H, dd, J ¼ 17.5, 10.5 Hz), 6.35 (1H, d, J ¼ 17.5 Hz), 7.24 (1H, t, J ¼ 7.5 Hz),
.65 (1H, d, J ¼ 8.0 Hz), 7.75 (1H, t, J ¼ 7.5 Hz), 8.31(1H, d, J ¼ 7.5 Hz), 8.33
1
3
(
1H, d, J ¼ 7.5 Hz), 8.52 (1H, s), 8.62 (1H, d, J ¼ 4.5 Hz) ppm; C NMR ꢀ
(
CDCl ) 32.0, 64.1, 120.7, 120.8, 123.5, 128.0, 130.9, 133.4, 136.8, 137.2,
3
149.0, 149.5, 154.6, 155.9, 165.8 ppm; Anal. Calcd. for C H N O ; C,
15 14 2 2
7
0.85; H, 5.55; N, 11.02. Found: C, 70.87; H, 5.67; N, 11.03%.
Acrylates 1b–f were also synthesized according to above method.
0
3
-(2,2 -Bipyridin-5-yl)propyl acrylate (1b): IR (neat) 3051, 1724, 1589,
À1
1
1
460, 1057, 750 cm ; H NMR ꢀ (CDCl ) 2.05 (2H, tt, J ¼ 7.5, 6.5 Hz), 2.77
3
(
2H, t, J ¼ 7.5 Hz), 4.21(2H, t, J ¼ 6.5 Hz), 5.83 (1H, dd, J ¼ 10.5, 1.5 Hz),
.14 (1H, dd, J ¼ 17.0, 10.5 Hz), 6.41 (1H, dd, J ¼ 17.5, 1.5 Hz), 7.26–7.29
1H, m), 7.64 (1H, dd, J ¼ 8.5, 1.5 Hz), 7.79 (1H, dd, J ¼ 8.0, 1.5 Hz),
6
(
8
8
1
1
.33 (1H, d, J ¼ 8.0 Hz), 8.37 (1H, dd, J ¼ 8.5, 1.5 Hz), 8.53 (1H, s),
1
3
.66–8.67 (1H, m) ppm; C NMR ꢀ (CDCl ) 29.0, 29.6, 63.3, 120.6,
3
20.6, 123.3, 128.1, 130.6, 136.5, 136.6, 136.7, 148.9, 149.1, 154.0, 155.9,
65.9 ppm; Anal. Calcd. for C H N O ; C, 71.62; H, 5.97; N, 10.44.
1
6
16
2
2
Found: C, 71.93; H, 5.77; N, 10.33%.
0
4
-(2,2 -Bipyridin-5-yl)butyl acrylate (1c): IR (neat) 3005, 2943, 1722,
À1
1
1
273, 1195, 810 cm ; H NMR ꢀ (CDCl ) 1.74–1.85 (4H, m), 2.73 (2H, t,
3
J ¼ 7.0 Hz), 4.20 (2H, t, J ¼ 6.0 Hz), 5.83 (1H, dd, J ¼ 10.5, 1.5 Hz), 6.12
1H, dd, J ¼ 17.0, 10.5 Hz), 6.40 (1H, dd, J ¼ 17.0, 1.5 Hz), 7.30 (1H, ddd,
J ¼ 7.5, 5.0, 1.0 Hz), 7.65 (1H, dd, J ¼ 8.0, 2.0 Hz), 7.81( 1H , dt, J ¼ 7.5,
.0 Hz), 8.32 (1H, d, J ¼ 8.0 Hz), 8.37 (1H, dt, J ¼ 7.5, 1.0 Hz), 8.52 (1H,
(
2
1
3
d, J ¼ 2.0 Hz), 8.67 (1H, ddd, J ¼ 5.0, 2.0, 1.0 Hz) ppm; C NMR ꢀ (CDCl )
3
2
1
7
7.4, 28.1, 32.3, 64.1, 120.8, 120.8, 123.4, 128.4, 130.7, 136.8, 136.9, 137.4,
49.1, 149.2, 154.1, 156.1, 166.2 ppm; Anal. Calcd. for C H N O ; C,
2.32; H, 6.43; N, 9.92. Found: C, 72.10; H, 6.43; N, 9.95%.
1
7
18
2
2
0
2
-(2,2 -Bipyridin-6-yl)ethyl acrylate (1d): IR (neat) 3061, 2961, 1724,
À1 1
1
581, 1273, 1188, 810 cm ; H NMR ꢀ (CDCl ) 3.24 (2H, t, J ¼ 7.0 Hz), 4.67
3
(
1
2H, t, J ¼ 7.0 Hz), 5.79 (1H, tt, J ¼ 10.5, 1.5 Hz), 6.10 (1H, ddd, J ¼ 17.5,
0.5, 1.5 Hz), 6.37 (1H, dt, J ¼ 17.5, 1.5 Hz), 7.21 (1H, d, J ¼ 8.0 Hz),

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3
166
MAEYAMA, OKUMURA, AND YONEZAWA
7
1
.29–7.32 (1H, m), 7.74 (1H, dt, J ¼ 8.0, 2.0 Hz), 7.81( H1 , dt,
J ¼ 8.0,
.5 Hz), 8.26 (1H, d, J ¼ 8.0 Hz), 8.45 (1H, dd, J ¼ 8.0, 1.0 Hz), 8.66–8.68
1
3
(
1H, m) ppm; C NMR ꢀ (CDCl ) 37.2, 63.7, 118.8, 121.2, 123.4, 123.6,
3
128.4, 130.7, 136.8, 137.2, 149.0 155.7, 156.2, 157.3, 166.2 ppm; Anal. Calcd.
for C H N O ; C, 70.85; H, 5.55; N, 11.02. Found: C, 70.67; H, 5.65;
N, 10.87%.
1
5
14
2
2
0
3
-(2,2 -Bipyridin-6-yl)propyl acrylate (1e): IR (neat) 3061, 2959, 1726,
À1
1
1
579, 1273, 1194, 810 cm
;
H NMR ꢀ (CDCl ) 2.25 (2H, quint,
3
J ¼ 7.0 Hz), 2.97 (2H, t, J ¼ 7.0 Hz), 4.29 (2H, t, J ¼ 7.0 Hz), 5.82 (1H, dt,
J ¼ 10.5, 1.5 Hz), 6.13 (1H, dq, J ¼ 17.0, 10.5 Hz), 6.40 (1H, dt, J ¼ 17.5,
1
2
.5 Hz), 7.17 (1H, d, J ¼ 8.0 Hz), 7.27–7.31 (1H, m), 7.73 (1H, dt, J ¼ 8.0,
.0 Hz), 7.81( 1H , dt, J ¼ 8.0, 1.5 Hz), 8.22 (1H, d, J ¼ 8.0 Hz), 8.44 (1H, dd,
1
3
J ¼ 8.0, 1.0 Hz), 8.66–8.68 (1H, m) ppm; C NMR ꢀ (CDCl ) 28.2, 34.5,
3
6
1
4.1, 118.5, 121.2, 122.8, 123.6, 128.5, 130.6, 136.9, 137.2, 149.0, 155.6,
58.4, 160.2, 166.3 ppm; Anal. Calcd. for C H N O ; C, 71.62; H, 5.97;
1
6
16
2
2
N, 10.44. Found: C, 71.32; H, 6.11; N, 10.14%.
0
4
-(2,2 -Bipyridin-5-yl)butyl acrylate (1f): IR (neat) 2951, 1724, 1579,
1
À1
1
273, 1195, 989, 810 cm ; H NMR ꢀ (CDCl ) 1.77–1.85 (2H, m), 1.90–1.96
3
(
2H, m), 2.92 (2H, t, J ¼ 7.0 Hz), 4.23 (2H, t, J ¼ 6.5 Hz), 5.81( 1H , dd,
J ¼ 10.5, 1.5 Hz), 6.12 (1H, dd, J ¼ 17.0, 10.5 Hz), 6.40 (1H, dd, J ¼ 17.0,
1
7
1
1
1
9
.5 Hz), 7.17 (1H, d, J ¼ 7.5 Hz), 7.26–7.31 (1H, m), 7.72 (1H, t, J ¼ 7.5 Hz),
.81( 1H , dt, J ¼ 8.0, 2.0 Hz), 8.21( 1H , d, J ¼ 7.5 Hz), 8.44 (1H, dt, J ¼ 8.0,
1
3
.0 Hz), 8.67–8.68 (1H, m) ppm; C NMR ꢀ (CDCl ) 25.8, 28.2, 37.6, 64.4,
3
18.4, 121.2, 122.7, 123.5, 128.6, 130.6, 136.8, 137.1, 149.0, 155.5, 156.6,
61.0, 166.3 ppm; Anal. Calcd. for C H N O ; C, 72.32; H, 6.43; N,
.92. Found: C, 72.10; H, 6.45; N, 9.69%.
1
7
18
2
2
ACKNOWLEDGMENTS
This work was supported by Mitsubishi Chemical Corporation Fund
and the Ministry of Education, Culture, Sports, Science, and Technology
of Japan.
REFERENCES
1. Kaes, C.; Katz, A.; Hosseini, M.W. Chem. Rev. 2000, 100, 3553.
2. Lewis, A.L.; Miller, J.D. J. Mater. Chem. 1993, 3, 897.
3. (a) Pitt, C.G.; Bao, Y.; Seltzman, H.H. J. Polym. Sci. Polym. Lett. 1986,
24, 13; (b) Cars, R.J.; Neckers, D.C. Inorg. Chem. 1978, 17, 2345.

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2002 Marcel Dekker, Inc. All rights reserved. This material may not be used or reproduced in any form without the express written permission of Marcel Dekker, Inc.
0
v-(2,2 -BIPYRIDYL)ALKYL ALCOHOLS
3167
0
4
. As the example for alkylation of 2,2 -bipyridylmethyl anion derivative,
see: Albrecht, M.; Riether, C. Chem. Ber. 1996, 129, 829.
0
0
5
. As the example for alkylations of 5,5 -dimethyl-2,2 -bipyridine employ-
ing ethylene oxide or I(CH ) OTHP, see: Lindner, E.; Veigel, R.;
2
3
Ortner, K.; Nachtigal, C.; Steimann, M. Eur. J. Inorg. Chem. 2000,
, 959.
5
6
7
8
. Ziessel et al. reported the synthesis of alcohol 2f. See: Ziessel, R.;
Toupet, L.; Chardon-Noblat, S.; Deronizer, A.; Matt, D. J. Chem.
Soc., Dalton Trans. 1997, 3777.
. (a) Polin, J.; Schmohel, E.; Balzani, V. Synthesis 1998, 321; (b) Huang,
T.L. J. Can. Chem. Soc. 1981, 59, 1689; (c) Kro
953, 59, 605.
. Kauffmann, T.; Ko
¨
hnke, F. Angew. Chem.
1
¨
nig, J.; Waltermann, A. Chem. Ber. 1976, 109, 3864.
Received in Japan July 25, 2001

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