Titanium phthalocyanines with axial phenylenevinylenes

Article abstract of DOI:10.1002/ejoc.200701197

The synthesis of soluble titanium(IV) phthalocyanines, axially substituted with phenylenevinylenes (PVs) (R_xPcTiX), is described. The reaction of peripherally tetra- and octasubstituted (phthalocyaninato)titanium oxides (R_xPcTiO) 1-3

Full text of DOI:10.1002/ejoc.200701197

FULL PAPER
DOI: 10.1002/ejoc.200701197
Titanium Phthalocyanines with Axial Phenylenevinylenes
Alexey Lyubimtsev,[a,b] Miraç N. Misir,[a] Mario Calvete,[a] and Michael Hanack*[a]
Keywords: Titanium / Phthalocyanines / Axial substitution / Phenylenvinylene
The synthesis of soluble titanium(IV) phthalocyanines, axi-
ally substituted with phenylenevinylenes (PVs) (RxPcTiX), is
described. The reaction of peripherally tetra- and octasubsti-
tuted (phthalocyaninato)titanium oxides (RxPcTiO) 1–3 with
chelating PV-diols 4a–4c leads to the formation of axially
substituted RxPcTiX 5–7. All compounds were characterized
by IR, UV/Vis, MS, and 1H NMR spectroscopy. Pcs 5–7 dis-
solved in dichloromethane are stable in the dark. The sta-
bility of solutions of 5–7 in sunlight depends on the nature of
the peripheral substituents in the Pc ring and the chain
length of the axial PV substituents.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2008)
nected to the central Ti atom in peripherally substituted Pcs
(Scheme 1).
Introduction
Pcs 5–7 containing phenylenevinylenes (PVs) as axial
substituents with different chain lengths in comparison with
those previously studied with axial catechol-substituted ti-
tanium phthalocyanines are expected to exhibit additional
favorable NLO (optical limiting) properties.[14] Pcs 5–7 are
even more important as so-called stopcock molecules in our
ongoing investigations of host–guest compounds with pho-
tonic antenna systems in channels of perhydrotriphenylene
(PHTP) or zeolite crystals loaded with axial fluorescent
chains of 5–7.[15] Stopcock molecules of this type can trans-
port energy and/or electrons from its Pc head to its tail
through the plugged channels of PHTP or zeolite.[15,16] To
prepare the host–guest compounds the PcTiX systems must
be completely soluble, for example, in dichloromethane,
which is accomplished by the peripheral substituents in the
Pc ring. In addition it was necessary to investigate whether
or not Pcs of the type 5–7 are generally stable in solution.
As we have shown previously,[14] axially substituted PcTi–
catechol compounds are stable in chloroform or dichloro-
methane in the dark. The stability of the solutions in sun-
light depends on the nature of the axial catechol. Electron-
withdrawing groups on the catechol increase the polarity of
the Ti–O bond in the PcTiX complexes, which leads to an
increase in the Ti–O bond strength and thereby to a higher
stability of the complexes.
(Phthalocyaninato)titanium(IV) oxide (PcTiO) as well as
their peripherally substituted derivatives (RxPcTiO) and
(naphthalocyaninato)titanium(IV) oxides (RxNcTiO) have
been extensively investigated for the photogeneration of
charge carriers.[1–6] Substituted soluble RxPcTiOs also show
remarkable nonlinear optical (NLO) properties,[7–12] for ex-
ample, they exhibit some of the highest values of third-
order optical susceptibility χ3 among organic chromo-
phores.[10,12] This is due to the large network of conjugated
π-electrons, which results in a high electrical polarizability
of the Pc ring, and the perpendicular dipole moment with
respect to the plane of the macrocycle that is induced by
the axial O ligand on the Ti atom in all the PcTiO deriva-
tives.[13] The presence of other axial ligands should have
additional favorable effects on the NLO properties of such
compounds. For this reason, highly soluble axially substi-
tuted titanium(IV) phthalocyanines have been synthesized
in our group and their NLO properties (e.g., optical limiting
properties) studied.[14] To prepare such compounds (tetra-
tert-butylphthalocyaninato)titanium(IV) oxide [(tBu)4-
PcTiO] was treated with chelating agents, for example, cate-
chols or dithiocatechol with oxygen or sulfur atoms as the
donor atoms, to form axially substituted (tBu)4PcTiX (X =
functionalized catechols, dithiocatechol, 2,3-dihydroxy-
naphthalene). The correlation between the electronic effects
of the various axial ligands in the (tBu)4PcTiX structures
and their NLO properties has been studied in detail.[14]
These investigations have now been extended to
RxPcTiX systems 5–7 in which phenylenevinylenes are con-
Results and Discussion
The substituted (phthalocyaninato)titanium(IV) oxides
1–3 (Scheme 1), the starting materials for the preparation
of compounds 5–7, were obtained as follows. (Tetra-tert-
butylphthalocyaninato)titanium(IV) oxide (1) (mixture of
isomers) has been synthesized by us previously.[14] To pre-
pare 2 (mixture of isomers), 4-[4-(1,1,3,3-tetramethylbutyl)-
[a] Institut für Organische Chemie, Universität Tübingen,
Auf der Morgenstelle 18, 72076 Tübingen, Germany
[b] Ivanovo State University of Chemistry and Technology,
Organic Chemistry Department,
F. Engels str. 7, 153460 Ivanovo, Russia
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A. Lyubimtsev, M. N. Misir, M. Calvete, M. Hanack
FULL PAPER
Scheme 1. Synthesis of axially PV-substituted titanium phthalocyanines 5–7; * octasubsituted Pcs.
phenoxy]phthalonitrile (10) was treated with Ti(OBu)4 in
In attempt to synthesize 4b, (E)-4-methylstilbene (13)[21]
pentanol at 155 °C. Phthalonitrile 10 was obtained in good was first transformed with NBS and AIBN into the benzyl
yield by nucleophilic substitution of the nitro group in 4- bromide 14[22] and subsequently into the phosphonium bro-
nitrophthalonitrile (8) with 4-(1,1,3,3-tetramethylbutyl)phe- mide 15 (Scheme 3).[23] The reaction of 15 with either 3,4-
nol (9) in DMF (Scheme 2).
dimethoxybenzaldehyde or piperonal led to the ethers 16[24]
The octasubstituted PcTiO 3 was obtained from 4,5- as a mixture of E/Z isomers. Compounds 16 were trans-
bis(3,5-di-tert-butylphenoxy)phthalonitrile[17] using the formed into the pure E isomers by heating in THF with
same procedure as described for the synthesis of 2. The UV/ phenyl disulfide.[19] The intended ether cleavage of 16 with,
Vis spectrum of 3 shows a Q-band maximum at 705 nm (see for example, BBr3 or AlI3 in various solvents to obtain the
Table 1).
target molecule 4b was not successful.
The axial ligand (E)-3,4-dihydroxy-4Ј-nitrostilbene (4c) was
Therefore a different route to the synthesis of 4b was
prepared by condensation of 4-nitrophenylacetic acid with used (Scheme 3). Benzyl bromide 14 was transformed by an
3,4-dihydroxybenzaldehyde.[18]
(E)-3,4-Dihydroxystilbene Arbuzov reaction[25] into diethyl (4-styrylbenzyl)phos-
(4a)[19] was prepared by Wittig reaction of benzyltri- phonate (17)[26] and further by a Horner–Emmons reac-
phenylphosphonium chloride (11)[20] with 3,4-dimethoxy- tion[27] with bis(tert-butyldimethylsilyloxy)benzaldehyde
benzaldehyde and subsequent ether cleavage with BBr3.
(18)[28] into 1,2-bis(tert-butyldimethylsilyloxy)-4-[2-(4-styryl-
Scheme 2. Synthesis of 4-[4-(1,1,3,3-tetramethylbutyl)phenoxy]phthalonitrile (10).
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Titanium Phthalocyanines with Axial Phenylenevinylenes
Scheme 3. The preparation of 4-[2-(4-styrylphenyl)vinyl]benzene-1,2-diol (4b). Reagents and conditions: (a) tBuOK, EtOH, room temp.,
5 h; (b) NBS, AIBN, CCl4, reflux, 8 h; (c) PPh3, DMF, reflux, 3.5 h; (d) tBuOK, EtOH, room temp., 5 h; (e) see text; (f) triethyl phosphite,
140 °C, 4 h; (g) i. LDA, THF, –78 to 0 °C; ii 18, 0 °C to room temp., 8 h; (h) TBAF, THF, room temp., 10 min.
phenyl)vinyl]benzene (19). The silyl groups in 19 were easily
removed with tetrabutylammonium fluoride to form 4b.[29] 1-H and 1Ј-H signals appear as two multiplets between δ =
In 4b the two double bonds have an E configuration. 9.2 and 8.4 ppm. Signals from the four protons in the 2- or
In the 1H NMR spectra of Pcs 6a and 6b (Scheme 1), the
By refluxing a mixture of substituted PcTiOs 1–3 and 3-position overlap with 16 proton signals of the peripheral
PV-diols 4a–c in chloroform the axially substituted titanium phenyl fragments 3-H and 4-H with a multiplet between δ
phthalocyanines 5–7 were obtained (Scheme 1) and purified = 7.8 and 7.2 ppm. The aliphatic protons of the peripheral
by recrystallization from methanol/chloroform (1:1). Purifi- substituents are represented by three multiplets at δ ≈
cation by column chromatography led to decomposition.
1.9 ppm for the eight protons of the secondary methylene
1
In the H NMR spectra of the tert-butyl-substituted Pcs group, a second multiplet at δ ≈ 1.5 ppm for the 24 protons
5a–c (Scheme 1), the phthalocyanine units give a resonance of the -C(CH3)2- groups, and a third multiplet at δ ≈
pattern in the aromatic region characteristic of tetrasubsti- 0.9 ppm for the 36 tert-butyl protons.
tution at the periphery of the Pc ring: Two multiplets, one
The octasubstituted phthalocyanines 7a and 7b
between δ = 9.7 and 9.2 ppm for the eight protons in the (Scheme 1) exhibit three signal groups: A singlet at δ =
1,4-positions (1-H and 1Ј-H) and one additional multiplet 9 ppm for the 1-H and 1Ј-H protons, a triplet at δ ≈ 7.2 ppm
between δ = 8.5 and 8.2 ppm for the four protons in the for the eight 5-H protons, and a doublet at δ ≈ 7.1 ppm for
2- or 3-positions (2-H). The 36 protons of the tert-butyl the 16 3-H protons.
substituents of the Pc rings resonate at δ = 1.90–1.84 ppm
as an intense and slightly broad signal due to structural (Scheme 1) of the axial ligands in Pcs 5–7 are upfield-
isomers, which leads to slightly split singlets. shifted due to the ring-current effect in the phthalocyanines.
The signals of the α-, β-, γ-, δ-, ε-, and η-protons
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A. Lyubimtsev, M. N. Misir, M. Calvete, M. Hanack
FULL PAPER
The signals of the κ-, λ-, µ-, and ν-protons are not upfield-
shifted due to the longer distance from the planar Pc ring,
the source of the ring-current effect. The peripheral Pc sub-
stituents do not influence very much the positions of the
proton signals of the axial ligands.
The characteristic Ti=O stretching vibration in the IR
spectra of Pcs 1, 2, and 3 at 972, 976, and 978 cm–1, respec-
tively, are absent in the IR spectra of the axially substituted
Pcs 5–7.
The UV/Vis maxima of the starting (phthalocyaninato)-
titanium oxides 1–3 and the axial substituted Pcs 5–7 (in
CH2Cl2) are listed in Table 1.
Table 1. Main UV/Vis absorption maxima of the Pcs 1–3 and 5–7
Figure 1. UV/Vis spectra of Pc 5a in dichloromethane: Decomposi-
tion in sunlight (starting concentration 10–4 molL–1, illumination
time 200 min).
(solvent: dichloromethane).
B [nm]
Q1.0 [nm]
Q0.0 [nm]
1
347
347
348
343
356
347
324
349
326
340
628
632
634
632
634
631
638
637
640
637
696
702
705
701
701
701
706
706
709
707
2
Conclusions
3
5a
5b
5c
6a
6b
7a
7b
To further investigate their NLO properties (optical lim-
iting) and their use as stopcock molecules in host–guest
compounds, the titanium(IV) phthalocyanines 5–7, axially
substituted with phenylenevinylenes of different chain
lengths, have been synthesized. The syntheses were carried
out by treating the (phthalocyaninato)titanium oxides 1–3,
which contain different peripheral substituents in the Pc
ring, with the chelating PV-diols 4a–4c in chloroform under
reflux. It has been shown that the stability of 5–7 dissolved
in dichloromethane in sunlight increases in the order 5 Ͻ 6
Ͻ 7 for the same axial substituents.
All the axially substituted complexes are characterized
by a small redshift of the Q-band with respect to the start-
ing Pcs 1–3, which is caused by the electron-donating ability
of the axial ligands (Table 1). Moreover, a broadening of
the Q- and B-bands is observed. The broadening and split-
ting of the Q-band in the spectra of 5–7 are caused by exci-
ton interactions between the phthalocyanine and the axial
ligand. The modification of the absorption pattern is caused
by the coupling of two distinct transition dipole mo-
ments.[30–32] Exciton coupling can also cause additional ab-
sorption bands.
Pcs 5–7 are stable in the solid state and in solution in the
dark. Semiquantitative UV/Vis measurements showed that
the stability of solutions of 5–7, for example, in dichloro-
methane, in sunlight depends on the nature of the periph-
eral substituents in the Pc ring and on the chain length of
Experimental Section
General: Unless otherwise noted, starting materials were obtained
from commercial suppliers and used without further purification.
All solvents were dried by standard methods. MgSO4 was used to
dry organic solutions during workup procedures. Analytical thin-
layer chromatography (TLC) was performed on Kieselgel F-254
percolated TLC plates. For column chromatography, silica gel 60
(230–400 mesh) was used. 1H NMR spectra were recorded with
Bruker AC 250 and 400 spectrometers. UV/Vis spectra were re-
corded in CH2Cl2 with a Lambda 25 UV/Vis spectrometer and IR
spectra with a Nicolet 380 FT-IR spectrometer. Mass spectra
the axial substituents. One example of these measurements (FAB-MS, EI, MALDI-TOF) were obtained with a Finnigan TSQ
70 MAT and a Bruker Autoflex spectrometer, and elemental analy-
ses with a Euro EA 3000 instrument.
is given in Figure 1: A solution of Pc 5a in dichloromethane
was exposed to sunlight, and the UV/Vis spectra were re-
corded at intervals of 15–20 min.
4-[4-(1,1,3,3-Tetramethylbutyl)phenoxy]phthalonitrile (10): A mix-
After 200 min, the Q-band at 700 nm had decreased by ture of 4-(1,1,3,3-tetramethylbutyl)phenol (9) (9.38 g; 45.5 mmol),
4-nitrophthalonitrile (8) (6.06 g; 35 mmol) and K2CO3 (29.4 g,
213 mmol) in DMF (125 mL) was heated at 80 °C under argon.
After 3 h, the reaction was completed, as checked by TLC (CHCl3).
The reaction mixture was cooled to room temperature, poured into
icy water (1.5 L) and stirred for about 30 min. The organic phase
was extracted with CHCl3 (6ϫ100 mL) and dried. After evapora-
tion to dryness, the green oil obtained was crystallized. The crystals
were washed with cold ethanol and dried in vacuo. Yield: 9.8 g
(84%). 1H NMR (200 MHz, CDCl3): δ = 7.72 (d, 3J = 8.4 Hz, 1
a factor of around 2.4. In the case of 5b, the Q-band de-
creased around three times faster. The B-band also de-
creased in the same manner. In all cases the Pc ring decom-
poses with the formation of the corresponding phthal-
imides.
In summary, the stability of solutions of Pcs 5–7 in
CH2Cl2 for the same axial substituents increases in the or-
der 5 Ͻ 6 Ͻ 7. Pcs 5a, 6a, and 7a with axial stilbene ligands
are more stable than Pcs 5b, 6b, and 7b with the longer
axial chain.
3
H), 7.47 (d, J = 8.8 Hz, 2 H), 7.26–7.18 (m, 2 H), 6.98 (d, 3J =
8.8 Hz, 2 H), 1.76 (s, 2 H), 1.41 (s, 6 H), 0.74 (s, 9 H) ppm. IR
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Titanium Phthalocyanines with Axial Phenylenevinylenes
(KBr): ν = 2956, 2904, 2232 (CϵN), 1591, 1562, 1505, 1486, 1310,
(1.1 g, 3 mmol, 1.0 equiv.) in THF (0.4 ) was added through a
˜
1283, 1249, 1212, 1174, 1087, 1015, 952, 878, 838, 584, 522 cm–1. syringe and the ice bath removed. The reaction mixture was stirred
MS (FAB): m/z (%) = 332.2 (72) [M]+, 261.1 (100) [M –
at room temperature overnight, diluted with CH2Cl2, and washed
twice with saturated aqueous NaHCO3 solution followed by satu-
rated aqueous NaCl solution. The organic layer was collected,
dried, filtered, and concentrated in vacuo. The obtained product
was purified by flash chromatography on silica gel using CH2Cl2/
hexane (7:3) as eluent. Yield: 1.3 g (80%). 1H NMR (250 MHz,
CDCl3): δ = 7.53–6.77 (m, 16 H), 1.00 (s, 9 H), 0.98 (s, 9 H), 0.22
(s, 6 H) 0.20 (s, 6 H) ppm. MS (EI): m/z (%) = 542.3 (49) [M]+,
485.2 (7) [M – C4H9]+, 370.1 (15), 115.1 (36), 73.2 (100).
C34H46O2Si2 (542.91): calcd. C 75.22, H 8.54; found C 75.22, H
8.57.
CH2C(CH3)3]+.
Synthesis of Peripherally Substituted (Phthalocyaninato)titani-
um(IV) Oxides 1–3. General Procedure:[14] 4-tert-Butyl-, 4-[4-
(1,1,3,3-tetramethylbutyl)phenoxy]- (10), or 4,5-bis(3,5-di-tert-bu-
tylphenoxy)phthalonitrile[17] (1 equiv.), urea (0.5 equiv.) and a few
drops of DBU were mixed in 1-pentanol and heated to 120 °C. At
that temperature, Ti(OBu)4 (0.3 equiv.) was added through a sy-
ringe, and the reaction mixtures were heated at reflux at 155 °C for
7 h. After cooling to room temperature, the mixtures were poured
into methanol, and precipitation was induced by adding some
water. The crude products were collected by centrifugation (or fil-
tration) and dried in vacuo. The mixtures of metal and metal-free
phthalocyanines were separated and purified by column
chromatography on silica gel.
4-[2-(4-Styrylphenyl)vinyl]benzene-1,2-diol (4b):
A solution of
tetrabutylammonium fluoride hydrate (TBAF·3H2O) (0.26 g;
0.81 mmol) in THF (1 mL) was added dropwise through a syringe
to
1,2-bis(tert-butyldimethylsilyloxy)-4-[2-(4-styrylphenyl)vinyl]-
benzene (19) (0.20 g; 0.37 mmol) in THF (10 mL). After 10 min,
several drops of 10% AcOH/THF were added. The solvent was
removed, the residue was washed with hexane and then H2O. After
drying in vacuo, the product was purified by flash chromatography
on silica gel using CH2Cl2/ethyl acetate as eluent. Yield: 52 mg
(45%). 1H NMR (250 MHz, [D6]DMSO): δ = 7.61–6.65 (m, 16 H)
R4PcTiO [R = OC6H4-p-CH(CH3)2CH2C(CH3)3] (2) was obtained
with 4-[4-(1,1,3,3-tetramethylbutyl)phenoxy]phthalonitrile (10);
yield 70% as the second chromatographic fraction using CH2Cl2
as eluent. H NMR (250 MHz, CDCl3): δ = 9.10–8.75 (m, 4ϫ1Ј-
H), 8.70–8.35 (m, 4ϫ1-H), 7.78–7.36 (m, 4ϫ2-H, 8ϫ3-H, 8ϫ4-
H), 1.88 (d, 8ϫCH2), 1.53 [t, 24ϫC(CH3)2], 0.91 (d, 36ϫtBu)
1
ppm. IR (KBr): ν = 3999 (OH), 3023, 1591, 1519, 1447, 1297, 1109,
˜
ppm. IR (KBr): ν = 2951, 1601, 1505, 1475, 1397, 1365, 1331, 1234,
˜
968, 961, 821, 751, 691, 537 cm–1. MS (EI): m/z (%) = 314.1 (100)
[M]+. C22H18O2·0.5H2O (323.40): C 81.71, H 5.92; found: C 81.83,
H 5.90.
1176, 1117, 1071, 1014, 976 (Ti=O), 949, 872, 750, 727 cm–1. UV/
Vis (CH2Cl2): λmax (logε) = 702 (5.27), 632 (4.59), 347 (4.86), 293
(4.70) nm. MS (MALDI-TOF): m/z = 1392.7 [M]+.
General Procedure for the Preparation of Axially Substituted
Phthalocyanines 5–7: Solutions of the substituted PcTiOs 1–3
(1 equiv.) and the diols 4a–c (2 equiv.) in chloroform were heated
at reflux for 2 h. The solvent was removed, and the crude products
were recrystallized from chloroform/methanol (1:1), filtered,
washed with small amounts of methanol to remove unreacted diols
and dried in vacuo.
Metal-free phthalocyanine R4PcH2 [R = OC6H4-p-CH(CH3)2-
CH2C(CH3)3] was eluted as the first fraction before metal phthalo-
cyanine 2 using CH2Cl2/n-hexane (5:2) as eluent. 1H NMR
(250 MHz, CDCl3): δ = 8.13–7.99 (m, 8 H), 7.61–7.33 (m, 20 H),
1.87 (d, 8 H), 1.50 (d, 24 H), 0.90 (d, 36 H), –0.50 (s, 2 H) ppm.
UV/Vis (CH2Cl2): λmax (logε) = 702 (5.18), 667 (5.13), 638 (sh),
605 (sh), 341 (4.90), 289 (4.76) nm. MS (MALDI-TOF): m/z =
1330.9 [M]+.
5a: Yield: 56%. 1H NMR (250 MHz, CDCl3): δ = 9.62–9.25 (m,
4ϫ1-H, 4ϫ1Ј-H), 8.46–8.31 (m, 4ϫ2-H), 7.10–6.86 (m, 2ϫδ-H,
2ϫε-H, 1ϫη-H), 6.06 (s, 2ϫγ-H), 5.61 (s, 1ϫβ-H), 4.66 (s,
1ϫαЈ-H), 4.36 (s, 1ϫα-H), 1.89–1.86 (m, 36ϫtBu) ppm. IR
R8PcTiO [R = OC6H4-3,5-C(CH3)2] (3) was obtained with 4,5-
bis(3,5-di-tert-butylphenoxy)phthalonitrile;[17] yield 62% as the sec-
ond chromatographic fraction using CH2Cl2 as eluent. 1H NMR
(250 MHz, CDCl3): δ = 9.18 (s, 8 H), 7.26 (t, 4J = 1.7 Hz, 8 H),
(KBr): ν = 2950, 1736, 1613, 1484, 1394, 1365, 1326, 1281, 1256,
˜
1201, 1151, 1077, 1014, 927, 831, 759, 694 cm–1. UV/Vis (CH2Cl2):
λmax (logε) = 701 (5.16), 632 (4.49), 343 (4.83), 275 (4.79) nm. MS
(MALDI-TOF): m/z = 994.4 [M]+.
7.15 (d, 4J = 1.7 Hz, 18 H), 1.33 (s, 144 H) ppm. IR (KBr): ν =
˜
2963, 1608, 1585, 1455, 1421, 1401, 1362, 1319, 1296, 1272, 1198,
1077, 1034, 978 (Ti=O), 961, 902, 706 cm–1. UV/Vis (CH2Cl2): λmax
(logε) = 705 (5.39), 672 (sh), 634 (4.59), 420 (4.53), 348 (4.84), 298
(4.76) nm. MS (MALDI-TOF): m/z = 2209.5 [M]+.
5b: Yield: 62%. 1H NMR (250 MHz, CDCl3): δ = 9.65–9.33 (m,
4ϫ1-H, 4ϫ1Ј-H), 8.47–8.31 (m, 4ϫ2-H), 7.58–6.75 (m, 2ϫδ-H,
2ϫε-H, 2ϫκ-H, 2ϫλ-H, 2ϫµ-H, 1ϫν-H), 6.10 (s, 2ϫγ-H), 5.67
(s, 1ϫβ-H), 4.74 (s, 1ϫαЈ-H), 4.44 (s, 1ϫα-H), 1.94–1.77 (m,
Diethyl (4-Styrylbenzyl)phosphonate (17): Compound 17 as pre-
pared by an Arbuzov reaction[26] with 4-(bromomethyl)stilbene (14)
36ϫtBu) ppm. IR (KBr): ν = 2952, 1600, 1503, 1472, 1395, 1367,
˜
[23]
(6.53 g, 23.9 mmol, 1 equiv.) and triethyl phosphite (4.2 mL,
1330, 1234, 1176, 1114, 1072, 1014, 949, 875, 727 cm–1. UV/Vis
(CH2Cl2): λmax (logε) = 701 (5.14), 632 (4.48), 356 (4.96), 291 (4.87)
nm. MS (MALDI-TOF): m/z = 1096.4 [M]+.
23.9 mmol, 1 equiv.) in 51% (4.03 g) yield. MS (EI): m/z (%) =
330.1 (65) [M]+, 193.2 (100), 178.2 (30). Phosphonate 17 was used
immediately due to decreasing yields of the Horner–Emmons reac-
tion after storage.
5c: Yield: 80%. 1H NMR (250 MHz, CDCl3): δ = 9.70–9.24 (m,
4ϫ1-H, 4ϫ1Ј-H), 8.54–8.27 (m, 4ϫ2-H), 7.0 (d, 3J = 8.4 Hz,
2ϫδ-H, 2ϫε-H), 6.23 (d, 3J = 16.2 Hz, 1ϫγ-H), 5.98 (d, 3J =
16.0 Hz, 1ϫγ-H), 5.64 (d, 3J = 7.5 Hz, 1ϫβ-H), 4.71 (s, 1ϫαЈ-
1,2-Bis(tert-butyldimethylsilyloxy)-4-[2-(4-styrylphenyl)vinyl]benzene
(19): All used glassware was oven-dried and cooled under N2. A
solution of diisopropylamine (1.06 mL, 7.5 mmol, 2.5 equiv.) in
THF (0.5 ) was cooled to –78 °C. nBuLi (2.64 mL, 6.6 mmol,
2.2 equiv., 2.5  in hexane) was added through a syringe. The mix-
ture was warmed to 0 °C for 30 min and recooled to –78 °C. Di-
ethyl (4-styrylbenzyl)phosphonate[27] (17) (1 g, 3 mmol, 1.0 equiv.)
as a THF solution (0.4 ) was precooled to –78 °C and transferred
to the LDA solution. The reaction flask was placed in an ice bath
at 0 °C, and 3,4-bis(tert-butyldimethylsilyloxy)benzaldehyde (18)[29]
3
H), 4.42 (d, J = 7.5 Hz, 1ϫα-H), 1.84 (s, 36ϫtBu) ppm. UV/Vis
(CH2Cl2): λmax (logε) = 701 (5.14), 632 (4.48), 356 (4.96), 291 (4.87)
nm. MS (MALDI-TOF): m/z = 1096.4 [M]+.
6a: Yield: 79%. 1H NMR (250 MHz, CDCl3): δ = 9.17–8.97 (m,
4ϫ1Ј-H), 8.77–8.51 (m, 4ϫ1-H), 8.00–7.20 (m, 4ϫ2-H, 8ϫ3-H,
8ϫ4-H), 7.16–6.86 (m, 2ϫδ-H, 2ϫε-H, 1ϫη-H), 6.15–5.85 (m,
2ϫγ-H), 5.55 (d, 3J = 7.5 Hz, 1ϫβ-H), 4.51 (s, 1ϫαЈ-H), 4.36
Eur. J. Org. Chem. 2008, 3209–3214
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
3213

A. Lyubimtsev, M. N. Misir, M. Calvete, M. Hanack
FULL PAPER
(d, 3J = 7.5 Hz, 1ϫα-H), 1.89–1.83 (m, 8ϫCH2), 1.53–1.47 [m,
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24ϫC(CH ) ], 0.93–0.86 (m, 36ϫtBu) ppm. IR (KBr): ν = 2954,
˜
3 2
[10]
2924, 1601, 1506, 1472, 1404, 1365, 1335, 1235, 1174, 1116, 1068,
1014, 952, 873, 757 cm–1. UV/Vis (CH2Cl2): λmax (logε) = 706
(5.07), 638 (4.45), 404 (4.56), 324 (4.85), 294 (4.85) nm. MS
(MALDI-TOF): m/z = 1587.2 [M]+.
[11]
[12]
6b: Yield: 63%. 1H NMR (250 MHz, CDCl3): δ = 9.18–8.80 (m,
4ϫ1Ј-H), 8.77–8.38 (m, 4ϫ1-H), 7.89–6.65 (m, 4ϫ2-H, 8ϫ3-H,
8ϫ4-H, 2ϫδ-H, 2ϫε-H, 2ϫκ-H, 2ϫλ-H, 2ϫµ-H, 1ϫν-H),
6.17–5.87 (m, 2ϫγ-H), 5.57 (d, 3J = 7.4 Hz, 1ϫβ-H), 4.54 (s,
[13]
[14]
[15]
3
1ϫαЈ-H), 4.31 (d, J = 7.4 Hz, 1ϫα-H), 1.90–1.84 (m, 8ϫCH2),
1.53–1.48 [m, 24ϫC(CH3)2], 0.94–0.86 (m, 36ϫtBu) ppm. IR
(KBr): ν = 2952, 1600, 1506, 1473, 1402, 1365, 1333, 1235, 1176,
˜
1116, 1073, 1015, 950, 827, 755 cm–1. UV/Vis (CH2Cl2): λmax (logε)
= 706 (4.99), 637 (4.38), 349 (4.90), 295 (4.83) nm. MS (MALDI-
TOF): m/z = 1689.3 [M]+.
7a: Yield: 72%. 1H NMR (250 MHz, CDCl3): δ = 9.10 (s, 8ϫ1-
4
4
[16]
H), 7.25 (t, J = 1.7 Hz, 8ϫ5-H), 7.13 (d, J = 1.7 Hz, 16ϫ3-H),
7.11–7.00 (m, 2ϫδ-H, 2ϫε-H, 1ϫη-H), 6.24–6.11 (m, 2ϫγ-H),
5.80 (d, 3J = 7.5 Hz, 1ϫβ-H), 4.89 (s, 1ϫαЈ-H), 4.59 (d, 3J =
7.5 Hz, 1ϫα-H), 1.32 (s, 144ϫtBu) ppm. IR (KBr): ν = 2964,
˜
[17]
[18]
1607, 1585, 1457, 1421, 1403, 1362, 1317, 1295, 1272, 1199, 1078,
1034, 959, 901, 705 cm–1. UV/Vis (CH2Cl2): λmax (logε) = 709
(5.16), 640 (sh), 420 (4.65), 326 (4.92), 299 (sh) nm. MS (MALDI-
TOF): m/z = 2406.0 [M]+.
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1
[19]
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M. A. Ali, K. Kondo, Y. Tsuda, Chem. Pharm. Bull. 1992, 40,
7b: Yield: 59%. H NMR (400 MHz, [D8]THF): δ = 9.20 (s, 8ϫ1-
1130–1136.
H), 7.55–7.00 (m, 8ϫ5-H, 16ϫ3-H, 2ϫδ-H, 2ϫε-H, 2ϫκ-H,
K.-H. Schweikart, M. Hanack, L. Lüer, D. Oelkrug, Eur. J.
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2ϫλ-H, 2ϫµ-H, 1ϫν-H), 6.31–6.20 (m, 2ϫγ-H), 5.73 (d, 3J =
3
8.0 Hz, 1ϫβ-H), 4.90 (s, 1ϫαЈ-H), 4.47 (d, J = 7.9 Hz, 1ϫα-H),
1.32 (s, 144ϫtBu) ppm. IR (KBr): ν = 2964, 1608, 1586, 1458,
1421, 1407, 1363, 1318, 1296, 1270, 1198, 1079, 1034, 961, 902,
706 cm–1. UV/Vis (CH2Cl2): λmax (logε) = 707 (5.17), 637 (sh), 421
(sh), 340 (4.85), 300 (4.83) nm. MS (MALDI-TOF): m/z = 2507.7
[M]+.
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Acknowledgments
This work was supported by the European Commission through
the Human Potential Program (Marie-Curie Research Training
Network NANOMATCH, Grant No. MRTN-CT-2006-035884).
We wish to thank “The Scientific and Technological Research
Council of Turkey (TUBITAK)” for supporting the scholarship of
M. N. M.
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Published Online: May 9, 2008
3214
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© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2008, 3209–3214