An efficient route to biscardanol derivatives and cardanol-based porphyrins via olefin metathesis

Article abstract of DOI:10.1016/j.jorganchem.2006.07.020

Ru-catalyzed olefin metathesis has been successfully applied to the synthesis of biscardanol derivatives and cardanol-based porphyrins. Using Hoveyda-Grubbs catalyst (C627), the reactions were performed with various cardanol derivatives (2, 5, 7, and 9) to make novel biscardanol derivatives. With the use of the second-generation Grubbs catalyst (C848) and Ti(OⁱPr)₄, the ring-closing metathesis of cardanol-based porphyrin 11 was carried out to afford cyclic cardanol-based porphyrin derivative 12.

Full text of DOI:10.1016/j.jorganchem.2006.07.020

Journal of Organometallic Chemistry 691 (2006) 5383–5390
www.elsevier.com/locate/jorganchem
An efficient route to biscardanol derivatives and
cardanol-based porphyrins via olefin metathesis
a
b
b
b
Ying-Cen Guo , Giuseppe Mele , Francesca Martina , Eleonora Margapoti ,
b,
a,
*
Giuseppe Vasapollo *, Wen-Jing Xiao
a
Key Laboratory of Pesticide and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University,
52 Luoyu Road, Wuhan, Hubei 430079, China
1
Dipartimento di Ingegneria dell’Innovazione, University of Lecce, via Arnesano, 73100 Lecce, Italy
b
Received 1 July 2006; received in revised form 16 July 2006; accepted 16 July 2006
Available online 1 August 2006
Abstract
Ru-catalyzed olefin metathesis has been successfully applied to the synthesis of biscardanol derivatives and cardanol-based porphyrins.
Using Hoveyda–Grubbs catalyst (C627), the reactions were performed with various cardanol derivatives (2, 5, 7, and 9) to make novel
i
biscardanol derivatives. With the use of the second-generation Grubbs catalyst (C848) and Ti(O Pr)
anol-based porphyrin 11 was carried out to afford cyclic cardanol-based porphyrin derivative 12.
Ó 2006 Elsevier B.V. All rights reserved.
4
, the ring-closing metathesis of card-
Keywords: Cardanol; Olefin metathesis; Porphyrins
1
. Introduction
aimed at boarding the scope of olefin metathesis [4], we
became interested in devising a practical and concise
route to novel compounds that possessed interesting
structures or physical properties or potential applications,
from inexpensive starting materials and/or renewable
resources.
Cardanol is a unique natural source for unsaturated
long-chain phenols. It is a cheap and renewable material,
obtained by vacuum distillation of cashew nut shell liquid
(CNSL) [5]. Interest in cardanol derivatives has grown over
the last few years due to their potential use in resins, fric-
tion lining materials, surface coatings, and organic synthe-
sis [6]. More recent work has focused on molecular hybrid
systems, in which cardanol is involved [7]. Furthermore,
other molecular hybrid systems such as porphyrin-contain-
ing rotaxanes [8], ‘‘magic’’ ring rotaxanes and catenanes
Olefin metathesis reactions have become powerful tools
to achieve molecular complexity in an elegant way [1].
Since the development of well-defined single component
molybdenum and ruthenium carbene catalysts, the olefin
metathesis has already commercially utilized in the
processing of fine chemicals. For instance, with the use
of Grubbs ruthenium-based catalyst olefin metathesis
enables vegetable oils to be efficiently processed into com-
pounds that can serve as renewable sources of petroleum
product alternatives [2]. The solvent-free cross-metathesis
of 1-hexene with hexenyl acetate represents another exam-
ple of the use of metathesis to generate the precursor of a
pheromone of the peach twig borer moth [3]. Encouraged
by these studies and as a part of our research program
[
9], and align conjugated polymers [10] have received much
attention because of their unique molecular structures.
Accordingly, we design biscardanol derivatives and carda-
nol-based porphyrins for their large size, extended p-system
and possible metal ion binding ability. Herein we report the
*
Corresponding authors. Tel./fax: +39 0832 325 004 (G. Vasapollo),
+86 27 67862041 (W.-J. Xiao).
E-mail addresses: giuseppe.vasapollo@unile.it (G. Vasapollo),
wxiao@mail.ccnu.edu.cn (W.-J. Xiao).
0
022-328X/$ - see front matter Ó 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2006.07.020

5384
Y.-C. Guo et al. / Journal of Organometallic Chemistry 691 (2006) 5383–5390
synthesis of these compounds by using olefin metathesis
protocols.
Mes
N
N Mes
Ru
PCy3
Ru
Cl
Cl
Cl
Cl
2
. Results and discussion
PCy3
O
Cardanol, the main component of CNSL, is a mixture of
-n-pentadecyl phenol, 3-(pentadeca-8-enyl) phenol (85%),
-(pentadeca-8,11-dienyl) phenol, and 3-(pentadeca-
,11,14-trienyl) phenol (Fig. 1). In this work cardanol is
C801
3
3
8
C627
referred to the monoolefinic component.
PCy3
Ru
Mes
N
N Mes
Ph
Ru
Actually, cardanol is rather difficult to purify, and it has
to be run on a few columns to get the monoolefinic compo-
nent. Thus, we converted it to compound 2 via the reaction
with 1,2-dibromoethane in the presence of KOH at 70 °C
Cl
Cl
Cl
Ph
PCy3
Cl
PCy3
C823
C848
(
Eq. (1)), which is much easier to separate from others,
Scheme 1. Ruthenium catalysts investigated.
for further study.
Br
OH
O
KOH
Br
+
alyst for the formation of 3 in 60% isolated yield (entry 1
in Table 1). Other Grubbs catalysts, such as C823 (entry 2
in Table 1) and C801 (entry 3 in Table 1), were less effec-
tive for this transformation. Thus, C627 was chosen as
the catalyst for other optimizations. Increasing the cata-
lyst loading from 2 to 5 mol% did not change the reaction
efficiency (entry 6 in Table 1), while decreasing the cata-
lyst loading from 2 to 1 mol% reduced the yield of the
product 3 (entry 5 in Table 1). We ran the reaction in dif-
ferent solvents (1,2-dichloroethane, chloroform, and chlo-
robenzene) at higher temperature; however, the efficiency
of the reaction did not improve (entries 7–9 in Table 1).
The conversion of the substrate 2 could not reach 100%
in all cases, which should attribute to the reaction’s
reversibility [11]. In order to improve the conversion, we
tried to remove the second product 4 by bubbling N2
inside the reaction mixture at 132 °C in chlorobenzene;
however, the starting material 2 was recovered in 90–
Br
o
7
0 C
0%
ð1Þ
R
R
7
1
2
(
R=C15H29
)
Metathesis catalysts (Scheme 1) were initially screened
in the homo-cross-metathesis (HCM) reaction of cardanol
derivative 2 (Eq. (2)). For convenience, these catalysts are
identified by their molecular weights.
Br
O
Ru-catalyst
solvent
C15H29
2
ð2Þ
Br Br
O
O
C H
6 13
+
C H
6
13
7
6
95% yield after 64 h and the catalyst decomposition was
3
4
observed (entry 8 in Table 1). We did not rigorously
examine the effect of the concentration of the substrate
on the reaction; however, we found that the reaction gave
poor yields when the concentration reduced to 0.1 and
The catalyst screening indicated that the HCM reaction
of 2 did work in the presence of Ru-based catalysts at
0 °C in dichloromethane (Table 1); however, small vari-
4
ations in Ru carbene catalysts (C627, C823, C801,
C848) resulted in varying yields of the product. Among
the catalysts examined, Hoveyda–Grubbs second genera-
tion catalyst (C627) and Grubbs second generation cata-
lyst (C848) exhibited good catalytic activities to afford
the HCM product 3 (entries 1 and 4 in Table 1). In par-
ticular, the use of 2 mol% C627 was the most effective cat-
0
.5 mol/L.
The optimized conditions were then successfully
employed in the synthesis of novel biscardanol derivatives.
The HCM reactions of cardanol and its derivatives were per-
formed using 2 mol% C627 in dichloromethane at 40 °C for
45–87 h, and the results are summarized in Table 2.
As can be seen from Table 2, the HCM reaction reac-
tions of cardanol and three of its derivatives worked very
well under the optimized conditions. The reaction afforded
the corresponding biscardanol derivatives in moderate iso-
lated yields. All products were formed as a mixture of E-
and Z-isomers, in which E-isomers were dominant.
Porphyrins and metalloporphyrins are important mate-
rials which can be used as gas sensors, photocatalysts,
and so on [12]. However, porphyrin and its derivative do
not have good solubility in organic solvents. We believe
R =
OH
(C15H31
)
)
)
)
(
C15H29
R
(C15
H
27
cardanol
(
C15H25
Fig. 1. The structure and composition of cardanol.

Y.-C. Guo et al. / Journal of Organometallic Chemistry 691 (2006) 5383–5390
5385
Table 1
a
Ru-catalyzed HCM reaction of 2
b
c
Entry
Catalyst
Solvent
Temperature (°C)
Time (h)
Conversion (%)
Yield (%)
1
2
3
4
5
6
7
8
9
a
C627 (2 mol%)
C823 (2 mol%)
C801 (2 mol%)
C848 (2 mol%)
C627 (1 mol%)
C627 (5 mol%)
C627 (2 mol%)
C627 (2 mol%)
C627 (2 mol%)
CH
CH
CH
CH
CH
CH
CHCL
PhCl
DCE
2
2
2
2
2
2
Cl
Cl
Cl
Cl
Cl
Cl
2
2
2
2
2
2
40
40
40
40
40
40
60
132
80
64
64
64
64
64
48
64
64
64
86
47
30
54
74
84
57
5
60
32
16
44
41
60
44
0
3
d
50
40
Reaction conditions: substrate 2 (1.67 mol/L), catalyst (1–5 mol% to 2), Ch
Calculated on the base of the amount of recovered substrate.
Isolated yields.
2 2 2
Cl (1.2 mL), N atmosphere.
b
c
d
1
,2-Dichloroethane.
Table 2
a
The synthesis of biscardanol derivatives via olefine methathesis
b
Entry
1
Substrate
Product
Time (h)
64
Yield (%)
Br
Br Br
60
O
O
O
5
7
7
6
2
3
2
3
OH
72
45
56
OH
OH
5
7
7
6
5
6
O
O
OR RO
42
O
O
CHO
5
7
7
6
7
8
R = 4-formylphenyl
CN
4
CN
CN
87
65
CN
CN
NC
O
O
O
5
7
7
6
9
1
0
a
Reaction conditions: substrate (2.0 mmol), catalyst C627 (2 mol% based on the substrate), dichloromethane (1.2 mL), 40 °C.
Isolated yields.
b
that the long chain of the cardanol should improve the sol-
(DDQ) at room temperature for 64 h afforded cardanol-
based porphyrin 11 in 14% overall yield.
ubility of porphyrins and metalloporphyrins. Thus, the
cardanol-based porphyrin was designed and obtained suc-
cessfully by reaction of cardanol derivative 7 with pyrrole,
as shown in Scheme 2.
Subsequently, ring-closing metathesis (RCM) of 11 was
tested in order to get more complex porphyrins. Treatment
of 11 with C848 under dilute conditions did not give the
corresponding RCM product. We believe that the strong
coordination function of porphyrins plays a crucial role
in this RCM reaction and the coordination between the
porphyrins and a ruthenium species may turn down the
Cardanol derivative 7 reacted with pyrrole in the presence
of catalytic amounts of BF Æ OEt at room temperature for
3
2
3
0 h using chloroform as the solvent. The subsequent oxida-
tion in situ with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone

5386
Y.-C. Guo et al. / Journal of Organometallic Chemistry 691 (2006) 5383–5390
C15H29
C15H29
O
O
O
O
N
N
O
O
1
) BF OEt / CHCl
3
NH
HN
3
2
+
NH
2
) Et N; 3)DDQ
3
O
5
7
7
O
11
O
O
O
C15H29
C15H29
Scheme 2. The synthesis of cardanol-based porphyin 11.
expected RCM reaction of 11 [13]. According to our previ-
ing from a cheap and renewable starting material
through a home-cross-metathesis and ring-closing metath-
esis reactions using Grubbs’ catalysts. This methodology
provides a versatile approach for the efficient synthesis of
various molecular hybrid systems. Further studies will be
focused on the synthesis of structurally more complex por-
phyrin derivatives and examine their physical and chemical
properties.
ous finding [4], we may be able to resolve this problem by
i
adding certain amount of Ti(OPr ) to the reaction system
4
[
14]. Thus, in the solution of porphyrin 11 in dichlorometh-
i
ane, Ti(OPr ) and the Grubbs’ catalyst C848 were added
4
and the solution then refluxed for 64 h. As expected, the
reaction occurred and the RCM product were formed in
2
2% isolated yield (Eq. (3)).
4. Experimental
4.1. General
O
O
O
O
All the starting materials were purchased from Aldrich
O
O
O
O
O
O
O
O
O
O
O
Chemical Co and used as received. Stabilcardo, a distilled
technical grade cardanol provided by Oltremare S.P.A.
(Bologna, Italy), has been used as a base compound in
this study. Silica gel (Merck) was used in the chromato-
graphic separations. Solvents were dried and distilled
under an atmosphere of dry nitrogen. Melting points
were taken on an electro thermal apparatus. FT-IR spec-
tra were recorded on a JASCO FT-IR 660 Plus spectrom-
eter. UV–Vis spectra were recorded on a Cary 100 scan
N
NH HN
N
C848 (10 mol%)
N
NH HN
N
ð3Þ
i
Ti(OPr ) (100 mol%)
4
0
.025 M in CH Cl , 40 oC
2
2
O
2
2%
1
1
12
1
13
UV–Vis spectrophotometer. H and C NMR spectra
were recorded on a Bruker Avance 400 at room temper-
ature and chemical shifts are reported relative to
tetramethylsilane.
NMR and MS spectra of 12 was consistent with the pro-
1
posed structure. Indeed, H NMR spectrum of 13 shows
the disappearing of the signal corresponding to methyl
group at 0.9 ppm. LC–MS data also confirmed the pro-
posed structures. The mass spectrum of 12 exhibits a signal
Mass spectrum was recorded by using a LC mass spec-
trometer 1100 Series (Agilent) equipped with an Electro-
spray (ESI) interface. Ions were extracted via a heated
capillary to a skimmer lens arrangement at reduced pres-
sure and transferred by an octapole to the main analytical
quadrupole assembly. The instrumental conditions were as
follow: drying gas (nitrogen) 7 L/min, nebulizer pressure
60 psi, drying gas temperature 300 °C, capillary voltage
4000 V, mass range 500–3000 amu.
+
at m/z 1602 [M + H] and 801 (Fig. 2).
3
. Conclusion
We have presented a novel procedure to synthesize bis-
cardanol derivatives and cardanol-based porphyrins start-

Y.-C. Guo et al. / Journal of Organometallic Chemistry 691 (2006) 5383–5390
5387
*MSD1 SPC, time=5.991 of MARTINA\PORTI004.D API-ES, Pos, Scan, Frag: Var
Norm.
00
Max: 5713
1
8
0
0
0
0
6
4
2
0
500
1000
1500
2000
2500
m/z
Fig. 2. Mass spectrum of 12.
4.2. 1-(2-Bromo-ethoxy)-3-(pentadeca-8-enyl)-
benzene (2)
petroleum ether: 1/100) to afford compound 3 as a white
solid (342.5 mg, 60%). Mp 48–49 °C. FTIR (neat),
ꢀ
1
m/cm : 3010, 2922, 2851, 1602, 1584, 1485, 1463, 1377,
ꢀ
1
1
To the solution of 3-(pentadeca-8-enyl)-phenol 1 (4.00 g,
1257, 1218, 1078, 1040, 967,911 cm
;
H
NMR
1
3.25 mmol) in 1,2-dibromoethane (15 mL), potassium
(400 MHz,CDCl , ppm): d 1.26–1.30 (m, 16H), 1.63–1.66
3
hydroxide (1.15 g, 20.49 mmol) were added. The mixture
was stirred at 70 °C for 6 h. The mixture was then cooled
to room temperature and filtered to remove the by product,
NaBr. The filtration was concentrated at a reduced pressure,
and then purified by silica gel chromatography (petroleum
ether (40–60 °C) first, then diethyl ether/petroleum ether:
(m, 4H),1.95–1.96 (m, 4H), 2.57 (t, 4H, J = 8.0 Hz), 3.63
(t, 4H, J = 6.0 Hz), 4.28 (t, 4H, J = 6.0 Hz), 5.38 (t,
J = 2.8 Hz), 6.72 (d, 2H, J = 8.0 Hz), 6.74 (s, 2H), 6.80
1
3
(d, 2H, J = 7.6 Hz), 7.19 (t, 2H, J = 7.6 Hz). C NMR
(100 MHz, CDCl ,ppm): d: 29.0, 29.2, 29.3, 29.3, 29.6,
3
31.3, 32.6, 35.9, 67.7, 111.5, 115.0, 121.6, 129.2, 130.3,
+
3
/7) affording compound 2 as colourless liquid (3.77 g,
144.7, 158.1. MS (EI, 70 eV): m/z (%): 623 [M + 1] . Anal.
1
7
0%). H NMR (400 MHz, CDCl , ppm): d 0.89 (t, 3H,
Calc. for C H O Br : C, 61.76; H, 7.40. Found: C, 61.88;
3
32 46
2
2
J = 6.8 Hz), 1.25–1.39 (m, 16H), 1.58 (q, 2H, J = 7.6 Hz),
H, 7.52%.
2
2
2
.00 (q, 4H, J = 7.0 Hz), 2.57 (t, 2H, J = 7.6 Hz), 3.62 (t,
H, J = 6.3 Hz), 4.27 (t, 2H, J = 6.3 Hz), 5.33–5.39 (m,
H), 6.70 (s, 1H), 6.73 (d, 1H, J = 5.2 Hz), 6.80 (d, 1H,
0
4.4. 3,3 -(Hexadec-8-ene-1,16-diyl)diphenol (6)
1
3
J = 7.6 Hz), 7.18 (t, 1H, J = 8.0 Hz).
C
NMR
C627 (25.10 mg, 0.04 mmol) was added under N atmo-
2
(
100 MHz, CDCl , ppm): d 14.1, 22.7, 22.8, 25.6, 27.20
sphere to a solution of 1 (605.0, 2 mmol) in 1.2 mL of dichlo-
romethane with stirring, producing a light green solution
which were stirred at reflux for 72 h. The mixture was then
concentrated in vacuo to a dark brown oil. The crude mate-
rial was purified by silica gel chromatography (ethyl acetate/
3
(
CH ), 29.0, 29.2, 29.3, 29.4, 29.6, 29.7, 31.33 (CH ), 31.8,
2
2
3
1
1
7
6
6.0, 67.7, 111.6, 115.0, 121.6, 129.2, 129.8, 129.9, 144.8,
ꢀ1
58.1. FTIR (neat, t/cm ): 2925, 2854,1662, 1599, 1588,
484, 1456,1386, 1258, 1154, 1063, 947, 913, 873. MS (EI,
+
0 eV): m/z (%) 408 [M ]. Anal. Calc. for C H BrO: C,
petroleum ether: 1/100) affords compound 6 as a brown oil
2
3
37
1
7.48; H, 9.05. Found: C, 67.49; H, 9.06%.
(264.6 mg, 56%). H NMR (400 MHz, CDCl , ppm): d
3
1.26–1.30 (m, 16H), 1.57–1.60 (m, 4H), 1.95–1.96 (m, 4H),
4.3. 1,16-Bis(3-(2-bromoethoxy)phenyl)-
hexadec-8-ene (3)
2.54 (t, 4H, J = 7.8 Hz), 4.80 (s, 2H), 5.36–5.40 (m, 2H),
6.63 (d, 2H, J = 7.8 Hz), 6.65 (s, 2H), 6.75 (d, 2H,
J = 7.8 Hz), 7.13 (t, 2H, J = 7.6 Hz). CNMR (100 MHz,
1
3
C627 (25.10 mg, 0.04 mmol) was added under N atmo-
CDCl , ppm): d 29.0, 29.2, 29.3, 29.6, 31.2, 32.5, 35.8,
2
3
sphere to a stirred solution of 2 (818.0 mg, 2 mmol) in
112.5, 115.3, 120.9, 129.3, 130.3, 144.9, 155.3. FTIR (neat),
ꢀ
1
1
.2 mL of dichloromethane. The light green solution which
m/cm : 3336, 3020, 2924, 2852, 1714, 1611, 1588, 1487,
ꢀ1
were stirred at reflux for 64 h. The mixture was then con-
centrated in vacuo to a dark brown oil. The crude material
was purified by silica gel chromatography (ethyl acetate/
1455, 1262, 1220, 1154, 1073, 1000, 944, 874 cm . MS
+
(EI, 70 eV): m/z (%) = 407 [M ꢀ 1]. Anal. Calc. for
C H O : C, 82.35; H, 9.80. Found: C, 82.28; H, 9.72%.
2
8
40
2

5388
Y.-C. Guo et al. / Journal of Organometallic Chemistry 691 (2006) 5383–5390
4.5. 4-[2-(3-(Pentadeca-8-enyl)phenoxy)-ethoxy]-
benzaldehyde (7)
atmosphere to a stirred solution of 1 (9.06 g, 0.03 mol) and
4-nitrophthalonitrile (5.2 g, 0.03 mol) in dry DMSO
170 mL). The reaction mixture was stirred and after 1 day
(
To the solution of 2 (3.00 g, 7.33 mmol) in acetone
15 mL), 4-hydroxy benzaldehyde (1.33 g, 10.90 mmol)
it was filtered, added to 100 mL of water, extracted with
CH Cl and dried on anhydrous sodium sulfate. The crude
(
2
2
and anhydrous potassium carbonate (3.04 g, 22.03 mmol)
were added. The mixture was refluxing with stirring for
product of the reaction, obtained after evaporation of the
solvent, was further purified by silica gel chromatography
3
0 h and then cooled to room temperature. The mixture
(ethyl acetate/petroleum ether: 1/5) to give compound 9 as
1
was then concentrated in vacuo to a dark brown oil.
The crude material was purified by silica gel chromatogra-
phy (diethyl ether/petroleum ether: 3/7) to give compound
a yellow liquid (4.42 g, 26%). H NMR (400 MHz, CDCl ):
3
d 0.91 (t, J = 7.5 Hz, 3H), 1.37–1.27 (m, 22H), 1.64 (q,
J = 7.2 Hz, 2H), 2.04 (q, J = 7.2 Hz, 4H), 2.65 (t, 2H,
J = 7.6 Hz), 5.38–5.35 (m, 2H), 6.90 (s, 1H), 7.15 (d,
J = 7.5 Hz, 1H), 7.24 (d, J = 6.5 Hz, 1H), 7.26 (d, 1H),
1
7
as a white solid (1.32 g, 40%). H NMR (400 MHz,
CDCl , ppm): d 0.89 (t, 3H, J = 6.8 Hz), 1.26–1.39 (m,
3
1
3
1
6H), 1.57–1.60 (m, 2H), 2.00–2.02 (m, 4H), 2.58 (t, 2H,
7.28 (s, 1H), 7.38 (t, 1H), 7.73 (d, 1H). C NMR
J = 7.6 Hz), 4.36 (t, 2H, J = 7.6 Hz), 4.41 (t, 2H,
J = 7.6 Hz), 5.34–5.36 (m, 2H), 6.76–6.82 (m, 3H), 7.06
(100 MHz, CDCl ): d 14.5, 23.1, 27.6, 27.6, 29.4, 29.6, 29.7,
3
30.1, 31.6, 32.2, 109.0, 115.4, 115.9, 118.1, 120.9, 121.8,
125.7, 130.2, 130.4, 130.8, 135.8, 146.7, 153.9, 162.4. FTIR
(
2
d, 1H, J = 8.8 Hz), 7.21 (t, 1H, J = 8.0 Hz), 7.85 (d,
H, J = 8.8 Hz), 9.90 (s, 1H). C NMR (100 MHz,
1
3
ꢀ1
(neat), m/cm : 2925, 2854, 1599, 1580, 1564, 1483, 1444,
ꢀ
1
CDCl , ppm): d 14.5, 23.1, 27.6, 28.9, 29.4, 30.0, 30.1,
1310, 1280, 1248, 1166, 1138, 1087, 963, 879 cm . MS (EI,
3
+
3
1
1
1
1
1.9, 32.2, 36.4, 66.5, 67.3, 111.9, 115.1, 121.9, 129.7,
70 eV): m/z (%) = 429 [M + 1] . Anal. Calc. for
30.2, 130.38 (C@), 130.6, 132.4, 145.2, 158.9, 164.1,
C H N O: C, 81.31; H, 8.41. Found: C, 81.32; H, 8.42%.
2
9
36
2
ꢀ1
91.2. FTIR (neat), m/cm : 2925, 2853, 2737, 1696,
0
0
601, 1579, 1486, 1449, 1376, 1312, 1251, 1158, 1110,
4.8. 4,4 -(3,3 -(Hexadec-8-ene-1,16-diyl)bis(3,1-
phenylene))bis(oxy)diphthalonitrile (10)
066, 946, 913, 832. MS (EI, 70 eV): m/z (%) = 448
+
[
M ]. Anal. Calc. for C H O : C, 80.18; H, 9.35.
3
0
42
3
Found: C, 80.19; H, 9.36%.
C627 (22.80 mg, 0.036 mmol) was added under N2
atmosphere to a stirred solution of 9 (779.0 mg, 1.8 mmol)
in dichloromethane (4 mL), producing a light green solu-
tion which were stirred at reflux for 87 h. The mixture
was then concentrated in vacuo to a dark brown oil. The
crude material was purified by silica gel chromatography
0 0 0
.6. 4,4 -(2,2 -(3,3 -(Hexadec-8-ene-1,16-diyl)bis(3,1-
phenylene))bis(oxy)bis(ethane-2,1-
4
diyl))bis(oxy)dibenzaldehyde (8)
C627 (15.60 mg, 0.025 mmol) was added under N2
atmosphere to a solution of 7 (559.7 mg, 1.2 mmol) in
(methylene chloride) to afford compound 10 as a brown
1
oil (390.4 mg, 65%). H NMR (400 MHz, CDCl ): d
3
6
mL of dichloromethane, producing a light green solution
1.26–1.31 (m, 16H), 1.60–1.62 (m, 4H), 1.95–1.96 (m,
4H), 2.63 (t, 4H, J = 7.6 Hz), 5.38 (t, J = 3.8 Hz, 2H),
6.88 (s, 2H), 7.12 (d, 2H, J = 7.6 Hz), 7.25 (d, 2H,
J = 8.0 Hz), 7.36 (d, 2H, J = 8.0 Hz), 7.38 (s, 2H), 7.40
which were stirred at reflux for 45 h. The mixture was then
concentrated in vacuo to a dark brown oil. The crude
material was purified by silica gel chromatography (dichlo-
romethane) affords compound 8 as a white solid (183.9 mg,
4
1
3
(t, 2H, J = 8.4 Hz), 7.73 (d, 2H, J = 8.4 Hz). C NMR
1
2%). Mp 69–72 °C. H NMR (400 MHz, CDCl ): d 1.29–
(100 MHz, CDCl ): d 28.8, 29.0, 29.0, 29.3, 30.9, 32.3,
3
3
1
.31 (m, 16H), 1.58–1.61 (m, 4H), 1.96–2.01 (m, 4H), 2.57
35.5, 108.3, 114.8, 115.3, 117.2, 117.5, 120.2, 121.2, 126.1,
130.1, 130.1, 135.2, 145.97 (2C, Ar), 153.3, 161.7. FTIR
(
t, 4H, J = 8.0 Hz), 4.34 (t, 4H, J = 4.8 Hz), 4.41 (t, 4H,
ꢀ
1
J = 4.8 Hz), 5.38 (t, 2H, J = 3.2 Hz), 6.76 (d, 2H,
J = 8.0 Hz), 6.78 (s, 2H), 6.81 (d, 2H), 7.04 (d, 2H,
J = 8.0 Hz), 7.19 (t, 2H, J = 8.4 Hz), 7.83 (d, 2H,
J = 8.4 Hz), 9.88 (s, 2H). C NMR (100 MHz, CDCl3):
d 29.1, 29.2, 29.3, 29.6, 31.3, 32.5, 35.9, 66.0, 66.8, 111.4,
(neat), m/cm : 3019, 2923, 2851, 1599, 1580, 1563, 1483,
1444, 1421, 1310, 1289, 1249, 1219, 1087, 964, 878,
ꢀ1
+
836 cm . MS (EI, 70 eV): m/z (%) = 661 [M + 1] . Anal.
1
3
Calc. for C H N O : C, 80.00; H, 6.67. Found: C,
44
44
4
2
80.28; H, 6.72%.
1
1
14.8, 121.4, 129.2, 129.8, 130.1, 130.3, 131.9, 144.7,
58.4, 163.6, 190.7. FTIR (neat), m/cm : 2992, 2919,
ꢀ1
4.9. 5,10,15,20-Tetra-[4-(2-(3-pentadec-8-
enyl)phenoxy)ethoxy]phenylporphyrin (11)
2
1
848, 1770, 1759, 1680, 1605, 1509, 1454, 1376, 1307,
ꢀ1
275, 1246, 1167, 1065, 962, 929, 858, 837 cm . MS (EI,
+
7
0 eV): m/z (%) = 705 [M+1] . Anal. Calc. for C H O :
Aldehyde 7 (220.0 mg, 0.486 mmol) and pyrrole
4
6
56
6
C, 78.41; H, 7.95. Found: C, 78.18; H, 7.72%.
(32.6 mg, 0.486 mmol) in chloroform (60 mL) were stirred
at room temperature for 10 min and then BF Æ OEt
3
2
4
.7. 4-[3-(Pentadeca-8-enyl)-phenoxy]-phthalonitrile (9)
Finely ground anhydrous K CO (5.5 g, 0.04 mol) were
(23.0 mg, 0.162 mmol) solution was added. The reaction
mixture was stirred at room temperature for 30 h, then tri-
ethylamine (21 mg, 0.208 mmol) were added. After 30 min
DDQ was added and the reaction mixture was stirred for
2
3
added gradually (1.1 g at intervals of 0.5–1 h) under N2

Y.-C. Guo et al. / Journal of Organometallic Chemistry 691 (2006) 5383–5390
5389
6
4 h. The solvent was removed under vacuum and the
Province Science Found for Distinguished Young Scholar
(2004ABBC011), for support of this research.
crude was purified by silica gel chromatography (methylene
chloride) affording compound 11 as a brownish solid
1
(
(
135.5 mg, 14%). H NMR (400 MHz, CDCl ): d ꢀ2.76
3
References
br s, 2H), 0.86 (t, 12H, J = 7.0 Hz), 1.26–1.34 (m, 88H),
1
.65–1.67 (m, 8H), 2.02–2.04 (m, 16H), 2.64 (t, 8H,
[1] (a) For recent reviews on olefin metathesis reactions, see Y. Chauvin,
J = 7.6 Hz), 4.53 (t, 8H, J = 4.6 Hz), 4.63 (t, 8H,
J = 4.6 Hz) 5.34–5.37 (m, 8H), 6.85–6.92 (m, 12H), 7.28
Angew. Chem., Int. Ed. 45 (2006) 3741;
(
(
(
b) R.R. Schrock, Angew. Chem., Int. Ed. 45 (2006) 3748;
c) R.H. Grubbs, Angew. Chem., Int. Ed. 45 (2006) 3760;
d) R.H. Grubbs (Ed.), Handbook of Metathesis, vol. 1–3, Wiley-
(
t, 4H, J = 7.8 Hz), 7.34 (d, 8H, J = 8.8 Hz), 8.13 (d, 8H,
1
3
J = 8.2 Hz), 8.87 (s, 8H). C NMR (100 MHz, CDCl3):
d 14.5, 23.1, 27.6, 29.2, 29.3, 29.4, 29.5, 29.6, 29.6, 29.7,
VCH, Weinheim, 2003;
e) A. Furstner, Angew. Chem., Int. Ed. 39 (2000) 3012.
(
3
1
1
3
1
0.2, 31.8, 32.2, 36.5, 66.9, 67.3, 112.1, 113.3, 115.5,
[2] (a) J. Patel, S. Mujcinovic, W.R. Jackson, A.J. Robinson, A.K.
Serelis, C. Such, Green Chem. 8 (2006) 450;
19.6, 121.8, 129.7, 130.3, 130.4, 130.4, 130.6, 135.4,
ꢀ
1
(b) J.C. Mol, Green Chem. 4 (2002) 5;
35.6, 136.0, 145.2, 158.9, 159.2. FTIR (neat), m/cm
318, 3006, 2925, 2853, 1606, 1582, 1508, 1448, 1351,
262, 1175, 1108, 1067, 1015, 931, 895. UV–Vis (CH Cl ),
:
(
c) R.H.A. Bosma, F. Van Den Aardweg, J.C. Mol, J. Chem. Soc.,
Chem. Commun. (1981) 1132;
(d) Frost and Sullivan’s Industrial Bioprocessing Alert, September 9,
2005.
2
2
ꢀ
1
ꢀ1
nm, (loge/M cm ): 409, 518, 556, 593, 649. MS (ESI)
m/z: 1990 (M + H) , 995 (M + H) amu. Anal. Calc. for
C136H174N O : C, 82.01; H, 8.74; N, 2.81. Found: C,
+
2+
[3] (a) R.L. Pederson, I.M. Fellows, T.A. Ung, H. Ishihara, S.P. Hajela,
Adv. Synth. Catal. 344 (2002) 728;
4
8
(
6
(
b) R.L. Pederson, R.H. Grubbs, (TillieChem, Inc.), U.S. Patent
,219,019, 2001; Chem. Abstr. 2002, 136, 200046;
c) R.L. Pederson, R.H. Grubbs, (TillieChem, Inc.), WO 01/36368
A2, 2001; Chem. Abstr. 2001, 135, 5481;
d) A. Furstner, K. Langemann, Synthesis (1997) 792.
8
2.32; H, 8.76; N, 2.93%.
4
.10. Synthesis of compound 12
(
[
[
4] (a) Q. Yang, W.-J. Xiao, Z. Yu, Org. Lett. 7 (2005) 871;
Also see: D. Taber, Org. Chem. Hightlight, 17 October 2005.
Available from: <http://www.organic-chemistry.org/Highlights/
Compound 11 (64 mg, 0.032 mmol) was dissolved in
i
dichloromethane (20 mL). Then, 10 lL of Ti(O Pr)
4
(
1 equiv, 0.032 mmol) was added and the solution was
refluxing. After 1 h a solution of C848 (0.6 mg in
.5 mL of CH Cl , 0.02 equiv) was added and the result-
2
005/170october.shtm>;
(b) Q. Yang, X.-Y. Li, H. Wu, W.-J. Xiao, Tetrahedron Lett. 47
2006) 3893.
(
1
2
2
5] (a) J.H.P. Tyman, Synthetic and Natural Phenols, Elsevier, Amster-
dam, 1996;
ing mixture was stirred for 44 h. The progress of the reac-
tion was monitored by TLC analysis until the complete
disappearance of 11. The mixture was cooled to room
temperature and concentrated in vacuum. The crude
product was purified by silica gel chromatography (meth-
(
b) P.P. Kumar, R. Paramashivappa, P.J. Vithayathil, P.V.S. Rao,
A.S. Rao, J. Agric. Food Chem. 50 (2002) 4705.
[6] (a) A.R.R. Menon, C.K.S. Pillai, J.D. Sudha, A.G. Mathew, J. Sci.
Ind. Res. 44 (1985) 324;
(
(
b) M.C. Lubi, E.B. Thachill, Des. Monomers Polym. 3 (2000) 123;
c) F.H.A. Rodrigues, J.P.A. Feitosa, N.M.P.S. Ricardo, F.C.F. de
ylene chloride) to give product 12 as a brownish solid
1
(
(
(
15.4 mg, 22%). H NMR (400 MHz, CDCl ): d ꢀ2.73
3
Franca, J.O.B. Carioca, J. Braz. Chem. Soc. 17 (2006) 265;
d) G. Mele, R.D. Sole, G. Vasapollo, E. Garcia-Lopez, L. Palmi-
sano, S.E. Mazzetto, O.A. Attanasi, P. Filippone, Green Chem. 10
br s, 2H), 1.36–1.28 (m, 32H), 1.65 (m, 8H), 2.07–1.99
m, 8H), 2.66 (t, 8H), 4.36–4.42 (m, 8H), 4.65–4.73 (m,
(
(
(
2004) 604;
8
H), 5.42–5.38 (m, 4H), 6.97–6.84 (m, 12H), 7.30–7.33
e) Y.H. Kim, K. Won, J.M. Kwon, H.S. Jeong, S.Y. Park, E.S. An,
(
m, 4H), 7.36–7.42 (m, 8H), 8.15–8.30 (m, 8H), 8.89 (s,
B.K. Song, J. Mol. Catal. Enzym. 34 (2005) 33.
1
3
8
1
1
3
2
9
M
H).
C NMR (100 MHz, CDCl ): d 158.6, 145.3,
3
[
7] (a) G. Mele, G. Ciccarella, G. Vasapollo, E. Garc `ı a-Lopez, L.
Palmisano, M. Schiavello, Appl. Catal. B: Environ. 38 (2002) 309;
(b) O.A. Attanasi, G. Ciccarella, P. Filippone, G. Mele, J.
35.6, 135.4, 131.3, 130.6, 130.4, 130.3, 129.7, 121.9,
19.0, 114.8, 112.3, 112.7, 111.7, 67.1, 36.5, 33.6, 32.2,
0.1, 29.8, 29.5, 22.8. FTIR (neat), m/cm : 3461, 3006,
984, 2909, 1740, 1465, 1447, 1372, 1233, 1097, 1047,
38, 918, 847. UV–Vis (CH Cl ) kmax, nm, (loge/
ꢀ
1
Spadavecchia, G. Vasapollo, J. Porphyrins Phthalocyanines
7
(
(
2003) 52;
c) O.A. Attanasi, R. Del Sole, P. Filippone, R. Ianne, S.E.
2
2
Mazzetto, G. Mele, G. Vasapollo, Synlett 5 (2004) 799;
d) J.M. Bakker, S.J. Langford, M.J. Latter, K.A. Lee, C.P.
Woodward, Aust. J. Chem. 58 (2005) 757;
e) A. Maffezzoli, E. Cal o` , S. Zurlo, G. Mele, A. Tarzia, C.
ꢀ
1
ꢀ1
+
cm ): 420, 516, 552, 593, 650. MS (ESI) m/z: 1601
(
2+
(M + H) , 801 (M + H) amu. Anal. Calc. for
C108H146N O : C, 81.00; H, 9.12; N, 3.50. Found: C,
(
4
8
Stifani, Compos. Sci. Technol. 64 (2004) 839.
8
1.22; H, 9.21; N, 3.48%.
[
[
8] R.G.E. Coumans, J.A.A.W. Elemans, P. Thordarson, R.J.M. Nolte,
A.E. Rowan, Angew. Chem., Int. Ed. 42 (2003) 650.
9] (a) J.P. Sauvage, B. Mohr, R.H. Grubbs, M. Weck, Angew. Chem.,
Int. Ed. Engl. 36 (1997) 1308;
Acknowledgements
(
b) A.F.M. Kilbinger, S.J. Cantrill, A.W. Waltman, M.W. Day,
R.H. Grubbs, Angew. Chem., Int. Ed. 42 (2003) 3281;
c) E.N. Guidry, S.J. Cantrill, J.F. Stoddart, R.H. Grubbs, Org. Lett.
(2005) 2129.
We are grateful to MIUR (COFIN 2002), University of
Lecce, the National Science Foundation of China
(
7
(
200472021), the National Basic Research Program of Chi-
na (2004CCA00100), the program for new century excel-
lent talents in university (NCET-05-0672), and the Hubei
[
10] (a) R. Wakabayashi, Y. Kubo, O. Hirata, M. Takeuchi, S. Shinkai,
Chem. Commun. (2005) 5742;

5
390
Y.-C. Guo et al. / Journal of Organometallic Chemistry 691 (2006) 5383–5390
b) Y. Kubo, Y. Kitada, R. Wakabayashi, T. Kishida, M. Ayabe, K. [13] (a) A. Camara-Campos, C.A. Hunter, S. Tomas, Proc. Natl. Acad.
(
Kaneko, M. Takeuchi, S. Shinkai, Angew. Chem., Int. Ed. 45 (2006)
Sci. USA 103 (2006) 3034;
1
548;
(b) F. D’Souza, M.E. El-Khouly, S. Gadde, M.E. Zandler, A.L.
McCarty, Y. Araki, O. Ito, Tetrahedron 62 (2006) 1967, and
references cited therein.
(c) Wakabayashi, Y. Kubo, K. Kaneko, M. Takeuchi, S. Shinkai, J.
Am. Chem. Soc. 128 (2006) 8744.
[
[
11] Y.-C. Guo, W.-J. Xiao, Chin. J. Org. Chem. 11 (2005) 1334.
12] (a) I. Artand, K.B. Aziza, C. Chopard, D. Mansuy, J. Chem. Soc.,
Chem. Commun. (1991) 31;
[14] (a) A. Furstner, K. Langemann, J. Am. Chem. Soc. 119 (1997)
9130;
(b) A. Furstner, O.R. Thiel, L. Ackermann, H.-J. Schanz, S.P.
Nolan, J. Org. Chem. 65 (2000) 2207, and references cited
therein.
(
(
b) R. Saladino, V. Neri, E. Mincione, P. Filippone, Tetrahedron 58
2002) 8493.