Synthesis and physicochemical characterization of meso-functionalized corroles: Precursors of organic-inorganic hybrid materials

Article abstract of DOI:10.1002/ejoc.200500374

Cobalt(III) corroles exhibit an infinite selectivity for the coordination of carbon monoxide towards dioxygen and dinitrogen. This peculiar property thus allows their use as sensing devices for CO detection. Here are described the syntheses and physico-ch

Full text of DOI:10.1002/ejoc.200500374

FULL PAPER
Synthesis and Physicochemical Characterization of meso-Functionalized
Corroles: Precursors of Organic–Inorganic Hybrid Materials
Jean-Michel Barbe,*[a] Gabriel Canard,[a] Stéphane Brandès,[a] and Roger Guilard*[a]
Keywords: Corroles / Porphyrinoids / Precursors / Synthetic methods / Sensors
Cobalt(III) corroles exhibit an infinite selectivity for the coor-
dination of carbon monoxide towards dioxygen and dinitro-
gen. This peculiar property thus allows their use as sensing
devices for CO detection. Here are described the syntheses
and physico-chemical characterization of meso mono-, bis-
and tris(triethoxysilyl)-functionalized corroles, precursors of
organic–inorganic materials. The corrole ring formation was
achieved in every case using the “2+1” method involving the
reaction of two equivalents of an encumbered dipyrrome-
thane with one equivalent of an aromatic aldehyde in the
presence of a catalytic amount of trifluoroacetic acid. The
functionalization of the corrole by triethoxysilyl chains was
carried out by a condensation reaction of an isocyanate, bear-
ing a triethoxysilyl termination, either on an amino or hy-
droxy group. Each final compound and intermediate were
characterized by various physico-chemical techniques such
as 1H NMR, UV/Vis, MALDI/TOF or EI mass spectrometry
and elemental analysis.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2005)
alized chains bound to the macrocycle. Mono-, di- and tri-
functionalized free-base corroles were thus synthesized in
respectable yields. We used a step-by-step approach starting
firstly by the synthesis of corroles substituted by phenyl
groups at the meso-positions bearing nitro, azidomethyl or
hydroxy terminations. Secondly, trialkoxysilyl-function-
alized arms were introduced using procedures affording
these derivatives in quantitative yields. These latter com-
pounds are indeed easily hydrolyzed and therefore difficult
to be purified.
There are two main routes for the preparation of meso-
substituted corroles. The “one-pot” method is theoretically
the simplest one to have access to A3-corroles.[10–12] How-
ever, this procedure is efficient only if the reacting aldehyde
is activated by electron withdrawing groups. The “2+1”
method leads to the formation of A3- and trans-A2B-cor-
roles.[8,9,12–15] Even if this synthetic pathway requires the use
of encumbered dipyrromethanes, in order to avoid the aci-
dolysis reaction, it is convenient for the preparation of meso
mono-, di- and tri-substituted corrole macrocycles. There-
fore, we investigated the synthesis of the targeted corrole
derivatives using the “2+1” method.
Introduction
The chemistry of corroles is now well-developed, and the
increasing number of new metallocorrole derivatives opens
the way to potential applications as it is the case for porphy-
rin analogs.[1–3] Some applications of metallocorroles in ca-
talysis,[4] as functional models of hemoproteins[5] and by us
as selective carbon monoxide sensors in the solid state have
already been developed.[6] Moreover, we recently demon-
strated, as a preliminary report, that the incorporation of
cobalt() corroles into a solid inorganic matrix not only
maintains the high selectivity towards CO, but also greatly
enhances the long-term stability of the incorporated
metallocorrole.[7]
In order to obtain such organic–inorganic hybrid
materials, we focused on the synthesis of corroles bearing a
hydrolysable trialkoxysilyl termination enabling the further
anchoring on a silica support or the direct formation of the
hybrid solid by the sol-gel process. From a synthetic point
of view, we decided to introduce such functionalized chains
on the corrole macrocycle by phenyl groups located at the
periphery of the ring. Therefore, recently reported syntheses
of meso-substituted corroles, rather than the multi-step syn-
theses of β-substituted corroles, were adapted to obtain
these derivatives.[8,9] Moreover, these former methods al-
lowed varying the number and the nature of the function-
Here we described the synthesis and physico-chemical
characterization of mono-, di- and trisubstituted corroles
bearing triethoxysilyl terminations, which are the precur-
sors of organic–inorganic hybrid materials. The description
and the characterization of these latter materials will be de-
[a] Laboratoire dЈIngénierie Moléculaire pour la Séparation et les veloped in a forthcoming paper.[16]
Applications des Gaz (LIMSAG, CNRS UMR 5633), Faculté
des Sciences, Université de Bourgogne,
Results and Discussion
Free-base corroles are generally more acidic than their
porphyrin counterparts and are easily deprotonated (one
6 boulevard Gabriel, 21100 Dijon, France
Fax: +33-3-8039-6117
E-mail: Jean-Michel.Barbe@u-bourgogne.fr
Roger.Guilard@u-bourgogne.fr
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DOI: 10.1002/ejoc.200500374
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J.-M. Barbe, G. Canard, S. Brandès, R. Guilard
FULL PAPER
proton removed) in basic solutions.[17–19] Moreover, it has the aniline group. The mono-functionalized free corrole
also been shown that their 4N cavity can be alkylated by base, described in Scheme 1, was further metalated by co-
electrophiles such as aryl halides and acyl chlorides.[19–22] balt, leading to the first inorganic–organic hybrid material
Therefore, in order to complete the functionalization of the incorporating a metallocorrole and exhibiting selective ad-
corrole by a chain bearing a trialkoxysilyl termination, it is sorption properties towards CO.[7]
necessary to use reactions involving weakly basic or weakly
In order to facilitate the anchoring of the triethoxysilyl-
electrophilic reagents. As a consequence, IPTES [(3-isocya- functionalized arm, we then moved to the synthesis of a
natopropyl)triethoxysilane], which exhibits these properties, corrole bearing a more reactive amine function. We chose
was used as vector of trialkoxysilyl groups in all the reac- a benzylamino group at the meso-position of the ring,
tions described in this manuscript.
which is known to be more nucleophilic than the aniline
one. The overall synthetic procedure leading to the expected
corrole is depicted in Scheme 2.
The bromobenzyl aldehyde was synthesized according to
the reaction reported by Wen et al.[23] The substitution of
the bromine atom by the azido group leading to 1, was car-
ried out in 65% yield by using sodium azide in the mixture
acetone/H2O, 3:1. The condensation of 1 (1 equiv.) on the
dipyrromethanes 6Ј and 7Ј (2 equiv.), respectively,[24,25] in
the presence of a catalytic amount of trifluoroacetic acid
(TFA, 0.08 equiv.), in dichloromethane as solvent, led to
the corroles 9 and 10 in 9.5 and 5.8% yields, respectively,
after cyclization and reoxidation by DDQ (2,3-dichloro-5,6-
dicyano-1,4-benzoquinone) according to reported general
conditions.[15] The subsequent reduction of the azido group
to the amino one with triphenylphosphane in THF afforded
after hydrolysis the free-base corroles 11 and 12 in 52 and
56% yields, respectively (Scheme 2). This latter reaction[26]
leads firstly to an iminophosphorane by elimination of a
dinitrogen molecule, the iminophosphorane being then hy-
drolyzed to an amine along with formation of triphenyl-
phosphane oxide.
Mono-Functionalized Corroles
In our preliminary report on the synthesis of organic–
inorganic hybrid materials obtained through the sol-gel
process, we focused on the study of a mono-functionalized
corrole. This latter precursor was prepared by the conden-
sation of IPTES on the amino group of the corrole in aceto-
nitrile in the presence of triethylamine (Scheme 1).[7]
Contrary to the reaction described in Scheme 1, the con-
densation of IPTES with the corroles 11 and 12 was fast
(12 hours) and only required a slight excess of IPTES
(1.05 equiv.). The reaction was performed in MeCN (aceto-
nitrile) finally giving the monotriethoxysilyl-functionalized
corroles 13 and 14 in very good yields (82 and 91%, respec-
tively) (Scheme 2). All corrole macrocycles (9–14) were
characterized by several physico-chemical methods and ele-
mental analyses (see Exp. Sect.). No peculiar variations
were observed on the UV/Vis spectra along the same series
of compounds, i.e. 9, 11, 13 and 10, 12, 14, since the substi-
tution reactions of the macrocycles only slightly affected
the electron density on the corrole rings. Conversely, all the
derivatives were well characterized by MALDI/TOF MS,
the molecular ion being in each case the most intense ionic
pattern in the spectrum (see Exp. Sect. for details). Simi-
1
larly, the H NMR spectra of derivatives 9 to 14 do not
exhibit significant differences with the exception of the spe-
cific functional group resonances. For example, the main
difference between spectra, on one hand of 9 and 11 and
on the other hand of 10 and 12 is the resonance of the NH2
group, which appears at ca. 1 ppm for 11 and 12. Further-
Scheme 1.
This reaction which requires an excess of IPTES more, the anchoring of the triethoxysilyl-functionalized
(3 equiv.) led to the functionalized corrole in a yield close chain is also clearly evidenced by the presence of new sig-
to 70%. The excess of IPTES was removed by crystalli- nals between 0.7 and 7 ppm relative to the
zation of the free-base corrole. The weak reactivity of the –NHCONHCH2CH2CH2Si(OEt)3 group for the spectra of
amino corrole was explained by the low nucleophilicity of 13 and 14.
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Scheme 2. i) NaN3, acetone, H2O. ii) 1: TFA, CH2Cl2; 2: DDQ. iii) PPh3, H2O, THF. iv) IPTES (1.05 equiv.), MeCN, 12 h.
Di-Functionalized Corroles
aldehyde (precursor of a dipyrromethane) substituted in 2-
and 6-positions with hindered groups, and at the 4-position
by another group allowing the further functionalization
with trialkoxysilyl chains. The retrosynthetic pathway is
given in Scheme 3.
The strategy we employed to synthesize di-functionalized
free-base corroles was again the “2+1” method involving
the reaction of an encumbered dipyrromethane with an aro-
matic aldehyde. In order to obtain such di-functionalized
corrole derivatives, it was necessary to synthesize firstly an
Consequently, as starting reagents we proposed to use 4-
hydroxy-2,6-dimethylbenzaldehyde and 2,6-dichloro-4-hy-
Scheme 3.
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Scheme 4. i) (2) 1: NEt3, THF; 2: ClCOCH2Cl. (3) 1: iPr2NEt, THF; 2: ClCOCH2Cl. (5) N-(2-bromoethyl)phthalimide, K2CO3, MeCN.
ii) pyrrole, TFA.
droxybenzaldehyde easily available by straightforward syn- dipyrromethanes 6, 7 and 8 in 52, 69 and 50% yield, respec-
theses from commercial products.[27,28] In order to avoid tively. Two equivalents of dipyrromethanes 6 and 7 were
any side reaction due to the presence of the hydroxy func- then condensed on an aromatic aldehyde bearing an elec-
tion, this latter one was protected by reaction either with tron withdrawing group such as CN using TFA as catalyst
chloracetyl chloride[29] or N-(2-bromoethyl)phthalimide[30] affording 15 and 16 in 18 and 5.5% yield, respectively
in a basic medium according to conditions given in (Scheme 5).
Scheme 4.
Basic conditions were tentatively employed for the depro-
The protected aldehydes 2, 3 and 5 were obtained in tection of the hydroxy functions but they were found to
rather good yields (50–95%). These derivatives are highly be ineffective in the present case. Indeed these conditions
reactive and soluble in pyrrole thus leading, in the presence required a subsequent protonation of the phenolate groups,
of a catalytic amount of trifluoroacetic acid (TFA), to the which was made difficult by the concomitant protonation
Scheme 5. i) 1: TFA, CH2Cl2; 2: DDQ. ii) PhCH2NH2, THF, EtOH. iii) IPTES (8 equiv.), iPr2NEt (8 equiv.), MeCN, 7 days.
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of the 4N cavity of the corrole in the acidic medium. In function. Then the treatment of the corroles 17 and 18 with
this regard, we turned towards the deprotection using an excess of IPTES in the presence of iPr2NEt led to di-
amines. The chloro ester group on corroles 15 and 16 is functionalized corroles 19 and 20 in 66 and 92% yield,
sufficiently activated to react with amines to lead to amides. respectively (Scheme 5).
Benzylamine was found to be, on one hand nucleophilic
We investigated another possibility to introduce a reactive
enough to react with the ester function and on the other amino group allowing the grafting of trialkoxysilyl chain.
hand not sufficiently basic to deprotonate the –OH and Phthalimide is a well-known precursor of –NH2 function
–NH functions. The excess of benzylamine and correspond- when linked to an aliphatic chain such as in the dipyrrome-
ing amide was easily removed by crystallization affording thane 8.[30] Two equivalents of 8 were treated with one equiv-
the compounds 17 and 18 in 76 and 85% yield, respectively alent of 4-fluorobenzaldehyde leading to the free-base cor-
(see Scheme 5). Generally, the condensation of a nucleo- role 21 in 10.7% yield under the same conditions as for the
phile on an isocyanate function is catalyzed by triethyl- synthesis of 15 and 16 (Scheme 6). The deprotection of the
amine that activates the isocyanate towards the subsequent amine group (22, 32% yield) was performed using hydrazine
attack of the nucleophile. Here the phenol groups of the hydrate in ethanol as solvent.[31] The grafting of the trieth-
corroles 17 and 18 were not nucleophilic enough to con- oxysilyl-functionalized chains was carried out using a slight
dense with the isocyanate in the presence of triethylamine. excess of IPTES in MeCN as solvent, yielding the di-func-
Diisopropylethylamine (iPr2NEt) is, in turn, less nucleo- tionalized free base 23 (84% yield) (Scheme 6).
philic than triethylamine due to the steric hindrance of the
As for mono-functionalized corroles, di-functionalized
1
substituents. Furthermore, its basicity allows the deproton- ones were characterized by elemental analysis, UV/Vis, H
ation of the phenol groups and enhances their nucleophilic NMR and MALDI/TOF mass spectrometry (see Exp. Sect.
character, which favors the reaction with the isocyanate for details).
Scheme 6. i) 1: TFA, CH2Cl2; 2: DDQ. ii) NH2NH2, H2O, EtOH. iii) IPTES (2.5 equiv.), iPr2NEt (6 equiv.), MeCN, 12 h.
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Scheme 7. i) 1: TFA, CH2Cl2; 2: DDQ. ii) PhCH2NH2, THF, EtOH. iii) IPTES (12 equiv.), iPr2NEt (6 equiv.), THF, MeCN, 7 days.
Tri-Functionalized Corroles
yield, respectively). Finally, the trifunctionalization of the
corrole ring with triethoxysilyl arms was performed using,
as for di-functionalized macrocycles, an excess of IPTES in
the presence of iPr2NEt. Again the yield of the reaction was
correct and close to 75% for both 28 and 29 derivatives.
Physico-chemical data and elemental analyses for all the
synthesized compounds are given in the Exp. Sect.
Tri-functionalized derivatives of corroles are powerful
precursors of organic–inorganic hybrid materials elaborated
through the sol-gel process since they provide more poly-
condensation directions. All our attempts towards the prep-
aration of such derivatives using the one-pot synthesis of
corroles were unsuccessful, mainly due to the low yield of
the reactions.[11] Therefore, we employed again the “2+1”
procedure starting from functionalized dipyrromethanes
and aromatic aldehyde. The overall procedure is depicted
on Scheme 7.
Conclusions
The condensation of 2 equivalents of dipyrromethanes 6
Mono-, bis- and tris(triethoxysilyl)-functionalized free-
or 7 on one equiv. of the protected aldehyde 4 led, accord- base corroles were synthesized in good yields using the so-
ing to classical conditions, to the corroles 24 and 25 in 13 called “2+1” method. In our hands, this method proved
and 2.6% yield. Despite the moderate yields of the reac- to be more efficient for the synthesis of tri-functionalized
tions, appreciable amounts (0.5 to 1 g) of these two corroles derivatives than the “one-pot” procedure.
were obtained due to the availability of dipyrromethanes 6
and 7, and aldehyde 4.
In a forthcoming paper, we will describe the metalation
reaction of these ligands by cobalt, their hydrolysis, and
According to procedure described for di-functionalized polycondensation leading to inorganic-organic hybrid mate-
corroles, the deprotection of the phenol functions was rials and their carbon monoxide selective adsorption prop-
achieved by reaction with benzylamine (26, 27 in 75, 87% erties.[16]
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MS (EI): m/z = 266 [M]+·. C9H5Cl3O3 (267.5): calcd. C 40.41, H
1.88; found C 40.61, H 2.35.
Experimental Section
General Remarks: All reagents of analytical grade were obtained
from commercial suppliers and used without further purification.
4-Bromomethylbenzaldehyde,[32] 4-hydroxy-2,6-dimethylbenzalde-
hyde,[27] 2,6-Dichloro-4-hydroxybenzaldehyde,[28] 5-(2,6-dichlo-
rophenyl)dipyrromethane (7Ј) and 5-mesityldipyrromethane (6Ј)
[24,25] were synthesized according to previously reported procedures.
All the triethoxysilyl-functionalized derivatives were synthesized
under argon. 1H NMR spectra were recorded either at 300 MHz
with a Bruker Avance 300 or at 500 MHz with a Bruker DRX-500
Avance spectrometer of the “Centre de Spectrométrie Moléculaire
de lЈUniversité de Bourgogne” of the FR 2604. Chemical shifts
are expressed in ppm relative to residual peaks of chloroform (δ
= 7.26 ppm), acetone (δ = 2.05 ppm) or dimethyl sulfoxide (δ =
2.50 ppm). UV/Visible spectra were recorded in solution with a
Varian Cary 50 spectrophotometer. Mass spectra were obtained
either with a Kratos Concept 32S at 70 eV (EI) and or with a
Bruker ProFLEX III spectrometer (MALDI/TOF) using dithranol
as matrix. Microanalyses were performed with a Fisons EA 1108
CHNS instrument.
4-(Chloroacetoxy)benzaldehyde (4): The same procedure as de-
scribed for 3 was used from 4-hydroxybenzaldehyde (24.42 g,
0.2 mol), triethylamine (30.9 mL, 0.22 mol, 1.1 equiv.), chloroacetyl
chloride (17.5 mL, 0.22 mol, 1.1 equiv.) and tetrahydrofuran
(400 mL). After column chromatography on silica gel with CH2Cl2/
heptane (85:15) as eluent, 4 (29.80 g, 75%) was obtained as a pale
1
yellow oil. H NMR (500 MHz, CDCl3, 303 K): δ = 4.35 (s, 2 H,
3
3
CH2), 7.32 (d, J = 8.49 Hz, 2 H, Ar-H), 7.93 (d, J = 8.49 Hz, 2
H, Ar-H), 9.99 (s, 1 H, CHO). MS (EI): m/z = 198 [M]+·. C9H7ClO3
(198.6): calcd. C 54.43, H 3.55; found C 54.36, H 3.67.
2,6-Dichloro-4-(2-phthalimidoethoxy)benzaldehyde (5): N-(2-Brom-
oethyl)phthalimide (11.87 g, 46.7 mmol, 1.05 equiv.) and 2,6-
dichloro-4-hydroxybenzaldehyde (8.5 g, 44.5 mmol) were dissolved
in a suspension of KI (0.83 g, 5 mmol) and K2CO3 (9.22 g,
69 mmol, 1.4 equiv.) in acetonitrile (250 mL). The mixture was re-
fluxed for 48 h. After cooling down to room temperature, the sol-
vent was removed under vacuum. The resulting solid was dissolved
in CH2Cl2, washed with water, and dried with MgSO4. After evapo-
ration of the solvent, the solid was chromatographed on silica gel
with CH2Cl2 giving 5 (8.05 g, 50%) as a white solid. 1H NMR
(500 MHz, CDCl3, 303 K): δ = 4.13 (t, 3J = 5.66 Hz, 2 H, CH2),
4.29 (t, 3J = 5.66 Hz, 2 H, CH2), 6.90 (s, 2 H, Ar-H), 7.73–7.76 (m,
2 H, Ar-H), 7.87–7.89 (m, 2 H, Ar-H), 10.37 (s, 1 H, CHO). MS
(EI): m/z = 363 [M]+·. C17H11Cl2NO4 (364.2): calcd. C 56.07, H
3.04, N 3.85; found C 55.96, H 3.27, N 4.02.
4-(Azidomethyl)benzaldehyde (1): 4-(Bromomethyl)benzaldehyde
(9.52 g, 47.9 mmol) and sodium azide (6.25 g, 95.7 mmol, 2 equiv.)
were dissolved in a mixture of acetone (120 mL) and distilled water
(40 mL). The solution was refluxed during 24 h. After cooling to
room temperature, the reaction mixture was extracted twice with
ether. The combined organic phases were washed with distilled
water, brine and dried with magnesium sulfate. The solvent was
evaporated under vacuum and the resulting oil was chromato-
graphed on a silica gel column using CH2Cl2/heptane (85:15) as
eluent to afford the pure aldehyde 1 (4.99 g, 65%) as a pale yellow
5-(4-Chloroacetoxy-2,6-dimethylphenyl)dipyrromethane (6): Tri-
fluoroacetic acid (590 µL, 7.9 mmol, 0.15 equiv.) was added to a
solution of 2 (12 g, 53 mmol) dissolved in freshly distilled pyrrole
(93 mL, 1.33 mol, 25 equiv.). The mixture was stirred under argon
at room temperature during 1 h and then dissolved in dichloro-
methane. The organic phase was washed with an aqueous solution
of NaOH (1.0 ⁾, dried with MgSO4 and the solvents evaporated
under vacuum. The resulting oil was chromatographed on silica gel
with CH2Cl2 as eluent, thus affording the pure dipyrromethane 6
1
oil. H NMR (500 MHz, CDCl3, 303 K): δ = 4.42 (s, 2 H, CH2),
3
3
7.45 (d, J = 8.03 Hz, 2 H, Ar-H), 7.86 (d, J = 8,03 Hz, 2 H, Ar-
H), 9.98 (s, 1 H, CHO). MS (EI): m/z = 161 [M]+·. C8H7N3O
(161.2): calcd. C 59.62, H 4.38, N 26.07; found C 59.55, H 4.30, N
24.58.
1
(9.49 g, 52%) as a white solid by precipitation in cold pentane. H
4-(Chloroacetoxy)-2,6-dimethylbenzaldehyde (2): 4-Hydroxy-2,6-di-
methylbenzaldehyde (27.21 g, 0.18 mol) and triethylamine
(30.5 mL, 0.22 mol, 1.2 equiv.) were dissolved in tetrahydrofuran
(400 mL). The mixture was stirred at room temperature for 20 min.
before chloroacetyl chloride (17.3 mL, 0.22 mol, 1.2 equiv.) was
added dropwise. The reaction mixture was then stirred at room
temperature for 1 h and the solvents evaporated. The resulting solid
was dissolved in dichloromethane and washed with water. The or-
ganic phase was dried with MgSO4 and the solvents evaporated
under vacuum. The resulting solid was chromatographed on silica
gel with CH2Cl2 as eluent giving 2 (35.60 g, 87%) as a white solid.
1H NMR (500 MHz, CDCl3, 303 K): δ = 2.61 (s, 6 H, CH3), 4.29
(s, 2 H, CH2), 6.88 (s, 2 H, Ar-H), 10.55 (s, 1 H, CHO). MS (EI):
m/z = 226 [M]+·. C11H11ClO3 (226.7): calcd. C 58.29, H 4.89; found
C 58.62, H 4.91.
NMR (300 MHz, CDCl3, 303 K): δ = 2.10 (s, 6 H, CH3), 4.29 (s,
2 H, CH2), 5.93 (s, 1 H, H-meso), 5.97 (m, 2 H, H-β), 6.17 (m, 2
H, H-β), 6.69 (m, 2 H, H-α), 6.82 (s, 2 H, Ar-H), 7.97 (br. s, 2
H, NH). MS (MALDI/TOF): m/z = 342.1 [M]+·. C19H19ClN2O2
(342.8): calcd. C 66.57, H 5.59, N 8.17; found C 66.35, H 5.66, N
8.09.
5-[2,6-Dichloro-4-(chloroacetoxy)phenyl]dipyrromethane (7): The
same procedure as described for 6 was used starting from 3
(24.84 g, 92.8 mmol), pyrrole (260 mL, 3.7 mol, 40 equiv.) and TFA
(1.03 mL, 7.9 mmol, 0.15 equiv.). After the same purification pro-
cess, 7 (24.77 g, 69%) was obtained as a white solid. 1H NMR
(500 MHz, CDCl3, 303 K): δ = 4.28 (s, 2 H, CH2), 6.06 (m, 2 H,
H-β), 6.19 (m, 2 H, H-β), 6.44 (s, 1 H, H-meso), 6.73 (m, 2 H, H-
α), 7.20 (s, 2 H, Ar-H), 8.25 (br. s, 2 H, NH). MS (MALDI/TOF):
m/z = 382.3 [M]+·. C17H13Cl3N2O2 (383.7): calcd. C 53.22, H 3.42,
N 7.30; found C 53.60, H 3.94, N 6.78.
2,6-Dichloro-4-(chloroacetoxy)benzaldehyde (3): 2,6-Dichloro-4-hy-
droxybenzaldehyde (4.87 g, 25.5 mmol) and diisopropylethylamine
(4.7 mL, 26.8 mmol, 1.05 equiv.) were dissolved in tetrahydrofuran 5-[2,6-Dichloro-4-(2-phthalimidoethoxy)phenyl]dipyrromethane (8):
(50 mL). The mixture was stirred at room temperature for 30 min The same procedure as described for 6 was used starting from 5
and chloroacetyl chloride (2.13 mL, 26.8 mmol, 1.05 equiv.) was
added dropwise. The reaction mixture was then stirred at room
temperature for 1 h and the solvents evaporated. The resulting solid
was dissolved in dichloromethane and washed with water. The or-
ganic phase was dried with MgSO4 and evaporated to afford (3)
(6.50 g, 95%) as a white solid. 1H NMR (500 MHz, CDCl3, 303 K):
(8.00 g, 22 mmol), pyrrole (60 mL, 0.88 mol, 40 equiv.) and TFA
(244 µL, 3.3 mmol, 0.15 equiv.). After the same purification pro-
cess, 8 (5.29 g, 50%) was obtained as a white solid. 1H NMR
(500 MHz, CDCl3, 303 K): δ = 4.09 (t, 3J = 5.55 Hz, 2 H, CH2),
4.20 (t, 3J = 5.55 Hz, 2 H, CH2), 6.00 (m, 2 H, H-β), 6.14–6.17 (m,
2 H, H-β), 6.34 (s, 1 H, H-meso), 6.68–6.70 (m, 2 H, H-α), 6.88 (s,
δ = 4.31 (s, 2 H, CH2), 7.28 (s, 2 H, Ar-H), 10.44 (s, 1 H, CHO). 2 H, Ar-H), 7.71–7.75 (m, 2 H, Ar-H), 7.85–7.88 (m, 2 H, Ar-
Eur. J. Org. Chem. 2005, 4601–4611
www.eurjoc.org © 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 4607

J.-M. Barbe, G. Canard, S. Brandès, R. Guilard
FULL PAPER
H), 8.21 (br. s, 2 H, NH). MS (MALDI/TOF): m/z = 478.9 [M]+·.
C25H19Cl2N3O3 (480.3): calcd. C 62.51, H 3.99, N 8.75; found C
62.30, H 4.14, N 8.84.
mol–1·L·cm–1): λmax = 407 (103.3), 426 (84.8), 567 (15.5), 604 (12.2),
638 nm (8.7). C44H41N5·CH3OH (671.9): calcd. C 80.44, H 6.75, N
10.42; found C 80.97, H 6.37, N 10.43.
10-(4-Aminomethylphenyl)-5,15-bis(2,6-dichlorophenyl)corrole (12):
The same procedure as before was used for the synthesis of 12 from
triphenylphosphane (0.29 g, 1.11 mmol, 1.3 equiv.), distilled water
(60 µL, 3.42 mmol, 4 equiv.), THF (20 mL) and corrole 10 (0.62 g,
0.86 mmol) in THF (30 mL). 12 (330 mg, 56%) was obtained as a
dark blue solid. 1H NMR (500 MHz, CDCl3, 303 K): δ = 1.05 (br.
10-(4-Azidomethylphenyl)-5,15-dimesitylcorrole (9): Compound 1
(1.62 g, 10 mmol) and 5-mesityldipyrromethane (6Ј) (5.28 g,
20 mmol, 2 equiv.) were dissolved in dichloromethane (600 mL).
The mixture was stirred at room temperature for 5 min. and TFA
(60 µL, 0.8 mmol, 0.08 equiv.) was added. After stirring at room
temperature for 5 h, the mixture was diluted with dichloromethane
(1.5 L) and a solution of DDQ (2,3-dichloro-5,6-dicyano-1,4-
benzoquinone) (4.5 g, 20 mmol, 2 equiv.) was added. The mixture
was stirred at room temperature for 30 min, concentrated under
vacuum and filtered through a silica pad. After evaporation, the
resulting solid was chromatographed twice on silica gel using
CH2Cl2 as eluent. After recrystallization in a CH2Cl2/heptane mix-
3
s, 2 H, NH2), 4.04 (s, 2 H, CH2), 7.57 (d, J = 7.80 Hz, 2 H, Ar-
3
3
H), 7.65 (d, J = 8.13 Hz, 2 H, Ar-H), 7.77 (d, J = 8.13 Hz, 4 H,
3
3
Ar-H), 8.12 (d, J = 7.80 Hz, 2 H, Ar-H), 8.40 (d, J = 4.10 Hz, 2
3
3
H, H-β), 8.51 (d, J = 4.64 Hz, 2 H, H-β), 8.58 (d, J = 4.64 Hz, 2
H, H-β), 8.99 (d, 3J = 4.10 Hz, 2 H, H-β). MS (MALDI/TOF):
m/z = 691.2 [M]+·. UV/Vis (CH2Cl2, ε×10–3, mol–1·L·cm–1): λmax
=
1
409 (88.9), 425 (72.3), 562 (12.8), 608 (8.8), 636 nm (4.9).
C38H25Cl4N5 (693.4): calcd. C 65.82, H 3.63, N 10.10; found C
65.38, H 3.39, N 10.20.
ture, 9 (0.63 g, 9.5%) was obtained as dark violet solid. H NMR
(500 MHz, CDCl3, 303 K): δ = –1.95 (br. s, 3 H, NH), 1.94 (s, 12
H, CH3), 2.61 (s, 6 H, CH3), 4.67 (s, 2 H, CH2), 7.28 (s, 4 H, Ar-
3
3
H), 7.67 (d, J = 7.89 Hz, 2 H, Ar-H), 8.19 (d, J = 7.89 Hz, 2 H,
5,15-Dimesityl-10-{4-[3-(3-triethoxysilylpropyl)ureidomethyl]-
phenyl}corrole (13): A solution of (3-isocyanatopropyl)triethoxysil-
ane, (IPTES, 0.12 g, 0.50 mmol, 1.2 equiv.) in acetonitrile (5 mL)
was added to a solution of the corrole 11 (0.27 g, 0.42 mmol) in
the same solvent (15 mL). The mixture was refluxed for 12 h. After
cooling down to room temperature, the mixture was taken with
dichloromethane (20 mL) and then evaporated under vacuum. Af-
ter recrystallization from CH2Cl2/heptane, compound 13 (0.30 g,
82%) was obtained as a dark violet solid. 1H NMR (500 MHz,
CDCl3, 303 K): δ = –1.50 (br. s, 3 H, NH), 0.71 (m, 2 H, CH2Si),
1.23 (m, 9 H, OCH2CH3), 1.72 (m, 2 H, CH2CH2Si), 1.92 (s, 12
H, Ar-CH3), 2.60 (s, 6 H, Ar-CH3), 3.29 (m, 2 H, CH2CH2CH2Si),
3.84 (m, 6 H, OCH2CH3), 4.70 (s, 2 H, Ar-CH2), 4.93 (br. s, 1 H,
3
3
Ar-H), 8.34 (d, J = 4.04 Hz, 2 H, H-β), 8.48 (d, J = 4.72 Hz, 2
3
3
H, H-β), 8.50 (d, J = 4.72 Hz, 2 H, H-β), 8.90 (d, J = 4.04 Hz, 2
H, H-β). MS (MALDI/TOF): m/z = 665.7 [M]+·. UV/Vis (CH2Cl2,
ε×10–3, mol–1·L·cm–1): λmax, = 408 (112.8), 426 (91.3), 567 (18.7),
604 (14.2), 636 nm (9.5). C44H39N7·0.5H2O (674.8): calcd. C 78.31,
H 5.97, N 14.53; found C 78.75, H 6.17, N 13.51.
10-(4-Azidomethylphenyl)-5,15-bis(2,6-dichlorophenyl)corrole (10):
The same procedure as described for the corrole 9 was used starting
from 1 (2.45 g, 15.2 mmol), 5-(2,6-dichlorophenyl)dipyrromethane
(7Ј) (8.84 g, 30.4 mmol, 2 equiv.), dichloromethane (0.91 L) and
TFA (91 µL, 3.3 mmol, 0.08 equiv.). The reaction mixture was di-
luted by the addition of CH2Cl2 (3.5 L) before the addition of
DDQ (6.8 g, 30.4 mmol, 2 equiv.) in tetrahydrofuran (200 mL). The
solution was stirred at room temperature for 30 min, concentrated
under vacuum and filtered through a silica pad. After evaporation,
the resulting solid was chromatographed on silica gel with CH2Cl2/
heptane (2:1) as eluent. After recrystallization from CH2Cl2/hep-
tane, 10 (0.63 g, 5.8%) was obtained as a dark violet solid. 1H
NMR (500 MHz, CDCl3, 303 K): δ = –2.05 (br. s, 3 H, NH), 4.68
(s, 2 H, CH2), 7.64–7.69 (m, 4 H, Ar-H), 7.75–7.78 (m, 4 H, Ar-
3
NHCO), 6.91 (br. s, 1 H, NHCO), 7.26 (s, 4 H, Ar-H), 7.64 (d, J
3
= 6.88 Hz, 2 H, Ar-H), 8.11 (d, J = 6.88 Hz, 2 H, Ar-H), 8.32 (d,
3J = 3.90 Hz, 2 H, H-β), 8.45–8.48 (m, 4 H, H-β), 8.88 (d, 3J =
3.90 Hz, 2 H, H-β). MS (MALDI/TOF): m/z = 887.2 [M]+·. UV/
Vis (CH2Cl2, ε×10–3, mol–1·L·cm–1): λmax = 408 (112.8), 426 (89.4),
568 (14.9), 605 (10.3), 637 nm (5.4). C54H62N6O4Si (887.2): calcd.
C 73.10, H 7.04, N 9.47; found C 73.20, H 6.76, N 9.54.
5,15-Bis(2,6-dichlorophenyl)-10-{4-[3-(3-triethoxysilylpropyl)-
ureidomethyl]phenyl}corrole (14): The same procedure as described
for 13 was used for the synthesis of 14, starting from 12 (0.31 g,
0.45 mmol) in acetonitrile (15 mL) and (3-isocyanatopropyl)trie-
thoxysilane (0.14 g, 0.56 mmol, 1.25 equiv.) in acetonitrile (15 mL).
Corrole 14 (0.38 g, 91%) was obtained as a dark violet solid. 1H
NMR (500 MHz, CDCl3, 303 K): δ = –2.10 (br. s, 3 H, NH), 0.72
(t, 3J = 7.98 Hz, 2 H, CH2Si), 1.23 (t, 3J = 7.00 Hz, 9 H,
OCH2CH3), 1.70–1.75 (m, 2 H, CH2CH2Si), 3.30 (m, 2 H,
3
H), 8.20 (d, J = 7.77 Hz, 2 H, Ar-H), 8.42 (br. s, 2 H, H-β), 8.54
3
3
(d, J = 4.65 Hz, 2 H, H-β), 8.58 (d, J = 4.65 Hz, 2 H, H-β), 9.01
(d, 3J = 4.00 Hz, 2 H, H-β). MS (MALDI/TOF): m/z = 717.1
[M]+·. UV/Vis (CH2Cl2, ε×10–3, mol–1·L·cm–1): λmax = 409 (136.5),
425 (107.9), 567 (19.6), 608 (12.6), 636 nm (6.2). C38H23Cl4N7
(719.4): calcd. C 63.44, H 3.22, N 13.63; found C 63.39, H 3.46, N
13.33.
10-(4-Aminomethylphenyl)-5,15-dimesitylcorrole (11): A solution of
the corrole 9 (0.60 g, 0.90 mmol) in tetrahydrofuran (30 mL) was
added dropwise to a solution of triphenylphosphane (0.48 g,
1.85 mmol, 2 equiv.) in tetrahydrofuran (20 mL). The mixture was
stirred at room temperature for 24 h before the addition of distilled
water (0.5 mL). The mixture was then refluxed during 2 h and the
solvents evaporated under vacuum. The resulting solid was chro-
matographed on basic alumina with mixtures of CH2Cl2/MeOH
(99:1, 98:2, 95:5, 90:10) as eluents. After recrystallization from
CH2Cl2/MeOH/heptane, 11 (0.30 g, 52%) was obtained as a dark
3
CH2CH2CH2Si), 3.84 (q, J = 7.00 Hz, 6 H, OCH2CH3), 4.67 (m,
3
1 H, NHCO), 4.70 (d, J = 5.75 Hz, 2 H, Ar-CH2), 4.89 (m, 1 H,
NHCO), 7.62–7.66 (m, 4 H, Ar-H), 7.76 (d, 3J = 8.21 Hz, 4 H, Ar-
3
3
H), 8.13 (d, J = 7.92 Hz, 2 H, Ar-H), 8.41 (d, J = 4.04 Hz, 2 H,
3
3
H-β), 8.51 (d, J = 4.64 Hz, 2 H, H-β), 8.56 (d, J = 4.64 Hz, 2 H,
H-β), 8.99 (d, J = 4.04 Hz, 2 H, H-β). MS (MALDI/TOF): m/z =
3
938.2 [M]+·. UV/Vis (CH2Cl2, ε×10–3, mol–1·L·cm–1): λmax = 409
(121.0), 425 (98.6), 563 (17.5), 608 (11.7), 636 nm (6.5).
C48H46Cl4N6O4Si·H2O (958.8): calcd. C 60.13, H 5.05, N 8.76;
found C 60.42, H 5.04, N 8.45.
1
blue solid. H NMR (500 MHz, CDCl3, 303 K): δ = 1.00–1.05 (br.
s, 2 H, NH2), 1.89 (s, 12 H, CH3), 2.56 (s, 6 H, CH3), 4.25 (s, 2 H,
5,15-Bis(4-chloroacetoxy-2,6-dimethylphenyl)-10-(4-cyanophenyl)-
3
CH2), 7.22 (s, 4 H, Ar-H), 7.71 (d, J = 7.65 Hz, 2 H, Ar-H), 8.13 corrole (15): The same procedure as described for the corrole 9 was
(d, 3J = 7.65 Hz, 2 H, Ar-H), 8.30 (d, 3J = 4.04 Hz, 2 H, H-β),
8.44–8.49 (m, 4 H, H-β), 8.86 (d, 3J = 4.04 Hz, 2 H, H-β). MS
used from 4-cyanobenzaldehyde (1.57 g, 12 mmol), dipyrromethane
6 (8.23 g, 24 mmol, 2 equiv.), dichloromethane (0.72 L) and TFA
(MALDI/TOF): m/z = 639.1 [M]+·. UV/Vis (CH2Cl2, ε×10–3, (72 µL, 0.96 mmol, 0.08 equiv.). The reaction mixture was diluted
4608
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Eur. J. Org. Chem. 2005, 4601–4611

meso-Functionalized Corroles: Precursors of Organic–Inorganic Hybrid Materials
FULL PAPER
by the addition of CH2Cl2 (1.5 L) and then a solution of DDQ
(5.4 g, 24 mmol, 2 equiv.) in tetrahydrofuran (500 mL). This mix-
ture was stirred at room temperature for 30 min, concentrated un-
der vacuum and filtered through a silica pad. After evaporation,
the resulting solid was chromatographed on silica gel with CH2Cl2
as eluent. After recrystallization from CH2Cl2/heptane, the corrole
15 (1.68 g, 18%) was obtained as a dark violet solid. 1H NMR
corrole 18 (0.53 g, 85%) was obtained as a dark violet solid. 1H
NMR [500 MHz, (CD3)3CO, 303 K]: δ = 7.38 (s, 4 H, Ar-H), 8.18
(d, J = 6.40 Hz, 2 H, Ar-H), 8.37 (d, J = 6.40 Hz, 2 H, Ar-H),
8.42 (br. s, 2 H, H-β), 8.50 (br. s, 2 H, H-β), 8.61 (br. s, 2 H, H-β),
9.07 (br. s, 2 H, H-β). MS (MALDI/TOF): m/z = 719.6 [M]+·. UV/
Vis (EtOAc, ε×10–3 mol–1·L·cm–1): λmax = 410 (134.0), 428 (99.4),
570 (23.8), 607 (13.8), 642 nm (3.0). C38H21Cl4N5O2·0.5EtOAc
3
3
(500 MHz, CDCl3, 303 K): δ = –2.01 (br. s, 3 H, NH), 1.95 (s, 12 (765.5): calcd. C 62.76, H 3.29, N 9.15; found C 62.81, H 3.52, N
H, CH3), 4.46 (s, 4 H, CH2), 7.26 (s, 4 H, Ar-H), 8.03 (d, 3J =
9.14.
3
8.11 Hz, 2 H, Ar-H), 8.28 (d, 3J = 8.11 Hz, 2 H, Ar-H), 8.37 (d, J
10-(4-Cyanophenyl)-5,15-bis{2,6-dimethyl-4-[(3-triethoxysilyl-
propyl)aminocarbonyloxy]phenyl}corrole (19): The corrole 17
(1.12 g, 1.75 mmol), (3-isocyanatopropyl)triethoxysilane (3.47 g,
14.0 mmol, 8 equiv.) and diisopropylethylamine (1.81 g, 14.0 mmol,
8 equiv.) were dissolved in acetonitrile (125 mL). The mixture was
refluxed for 7 days. After cooling down to room temperature, the
mixture was diluted with dichloromethane (50 mL) and the sol-
3
3
= 4.18 Hz, 2 H, H-β), 8.43 (d, J = 4.75 Hz, 2 H, H-β), 8.53 (d, J
= 4.75 Hz, 2 H, H-β), 8.95 (d, 3J = 4.18 Hz, 2 H, H-β). MS
(MALDI/TOF): m/z = 790.8 [M]+·. UV/Vis (CH2Cl2, ε × 10–3
,
mol–1·L·cm–1): λmax = 409 (141.5), 428 (115.3), 566 (23.3), 602
(13.4), 634 (5.3). C46H35Cl2N5O4 (792.7): calcd. C 69.70, H 4.45,
N 8.83; found C 69.54, H 4.43, N 8.73.
5,15-Bis(4-chloroacetoxy-2,6-dichlorophenyl)-10-(4-cyanophenyl)- vents evaporated under vacuum. The solid was twice recrystallized
corrole (16): The same procedure as described for the corrole 9
was carried out using 4-cyanobenzaldehyde (2.10 g, 16 mmol), the
dipyrromethane 7 (12.28 g, 32 mmol, 2 equiv.), dichloromethane
(0.96 L) and TFA (96 µL, 1.30 mmol, 0.08 equiv.). The reaction
mixture was diluted with CH2Cl2 (2.5 L) and a solution of DDQ
(7.2 g, 32 mmol, 2 equiv.) in tetrahydrofuran (500 mL) added. This
from CH2Cl2/heptane, filtered off and washed with pentane leading
to corrole 19 (1.314 g, 66 %) as a dark violet solid. 1H NMR
3
(500 MHz, CDCl3, 303 K): δ = –1.90 (br. s, 3 H, NH), 0.79 (t, J
3
= 7.98 Hz, 4 H, CH2Si), 1.29 (t, J = 7.06 Hz, 18 H, OCH2CH3),
1.79–1.87 (m, 4 H, CH2CH2Si), 1.93 (s, 12 H, Ar-CH3), 3.39–3.43
(m, 4 H, CH2CH2CH2Si), 3.91 (q, 3J = 7.06 Hz, 12 H, OCH2CH3),
mixture was stirred at room temperature for 30 min, concentrated 5.52–5.55 (m, 2 H, NHCO), 7.24 (s, 4 H, Ar-H), 8.02 (d, 3J =
3
under vacuum and filtered through a silica pad. After evaporation,
the resulting solid was chromatographed on silica gel using CH2Cl2
as eluent. After recrystallization from CH2Cl2/heptane, the corrole
16 (0.77 g, 5.5%) was obtained as a dark violet solid. 1H NMR
7.86 Hz, 2 H, Ar-H), 8.28 (d, 3J = 7.86 Hz, 2 H, Ar-H), 8.36 (d, J
3
3
= 3.84 Hz, 2 H, H-β), 8.40 (d, J = 4.56 Hz, 2 H, H-β), 8.54 (d, J
= 4.56 Hz, 2 H, H-β), 8.91 (d, 3J = 3.84 Hz, 2 H, H-β). MS
(MALDI/TOF): m/z = 1133.8 [M]+·. UV/Vis (CH2Cl2, ε ×10–3
,
(500 MHz, CDCl3, 303 K): δ = –2.05 (br. s, 3 H, NH), 4.47 (s, 4 mol–1·L·cm–1): λmax = 409 (107.0), 427 (82.1), 567 (16.2), 602 (11.0),
3
H, CH2), 7.66 (s, 4 H, Ar-H), 8.04 (d, J = 8.02 Hz, 2 H, Ar-H), 635 nm (5.5). C62H75N7O10Si2·H2O (1152.5): calcd. C 64.61, H
3
3
8.31 (d, J = 8.02 Hz, 2 H, Ar-H), 8.46 (d, J = 4.14 Hz, 2 H, H- 6.73, N 8.51; found C 64.77, H 7.07, N 8.73.
β), 8.51 (d, 3J = 4.58 Hz, 2 H, H-β), 8.58 (d, 3J = 4.58 Hz, 2 H, H-
5,15-Bis{2,6-dichloro-4-[(3-triethoxysilylpropyl)aminocarbonyloxy]-
β), 9.04 (d, 3J = 4.14 Hz, 2 H, H-β). MS (MALDI/TOF): m/z =
871.0 [M]+·. UV/Vis (CH2Cl2, ε×10–3, mol–1·L·cm–1): λmax = 410
(139.5), 425 (116.6), 568 (21.9), 607 (12.8), 636 nm (4.5).
C42H23Cl6N5O4·CH2Cl2 (959.3): calcd. C 53.84, H 2.63, N 7.30;
found C 53.82, H 2.84, N 7.34.
phenyl}-10-(4-cyanophenyl)corrole (20): The same procedure as de-
scribed for corrole 19 was used starting from 18 (0.46 g,
0.64 mmol), (3-isocyanatopropyl)triethoxysilane (1.26 g,
5.10 mmol, 8 equiv.), diisopropylethylamine (0.66 g, 5.10 mmol,
8 equiv.) in acetonitrile (40 mL). After purification, 20 (0.707 g,
10-(4-Cyanophenyl)-5,15-bis(4-hydroxy-2,6-dimethylphenyl)corrole 91%) was obtained as a dark violet solid. 1H NMR (500 MHz,
3
(17): The corrole 15 (1.35 g, 1.71 mmol) and benzylamine (2 mL,
18.3 mmol, 10 equiv.) were dissolved in tetrahydrofuran (200 mL)
and ethanol (200 mL). The reaction mixture was refluxed for 1 h
and the solvents evaporated under vacuum. The resulting solid was
crystallized from CH2Cl2/heptane, filtered off and then chromato-
graphed on silica gel with two different elution mixtures of CH2Cl2
and EtOAc (95:5 and 85:15). After recrystallization from CH2Cl2/
CDCl3, 303 K): δ = –2.03 (br. s, 3 H, NH), 0.78 (t, J = 7.85 Hz,
4 H, CH2Si), 1.31 (t, 3J = 6.98 Hz, 18 H, OCH2CH3), 1.82–1.86
3
(m, 4 H, CH2CH2Si), 3.42 (m, 4 H, CH2CH2CH2Si), 3.92 (q, J =
6.98 Hz, 12 H, OCH2CH3), 5.73 (m, 2 H, NHCO), 7.63 (s, 4 H,
3
3
Ar-H), 8.03 (d, J = 7.92 Hz, 2 H, Ar-H), 8.31 (d, J = 7.92 Hz, 2
3
3
H, Ar-H), 8.46 (d, J = 4.06 Hz, 2 H, H-β), 8.50 (d, J = 4.61 Hz,
2 H, H-β), 8.61 (d, J = 4.61 Hz, 2 H, H-β), 9.01 (d, J = 4.06 Hz,
3
3
heptane, the corrole 17 (0.83 g, 76%) was obtained as a dark violet 2 H, H-β). MS (MALDI/TOF): m/z 1212.9 [M]+·. UV/Vis (CH2Cl2,
1
solid. H NMR (500 MHz, CDCl3, 303 K): δ = –1.13 (br. s, 3 H,
ε×10–3, mol–1·L·cm–1): λmax = 411 (120.2), 426 (99.0), 568 (19.4),
607 (11.7), 635 nm (4.9). C58H63Cl4N7O10Si2·2 H2O (1252.2): calcd.
C 55.63, H 5.39, N 7.83; found C 55.43, H 5.64, N 8.08.
NH), 1.26 (br. s, 2 H, OH), 1.89 (s, 6 H, CH3), 6.89 (s, 4 H, Ar-
3
3
H), 8.02 (d, J = 8.24 Hz, 2 H, Ar-H), 8.29 (d, J = 8.24 Hz, 2 H,
3
3
Ar-H), 8.34 (d, J = 3.96 Hz, 2 H, H-β), 8.40 (d, J = 4.88 Hz, 2
5,15-Bis[2,6-dichloro-4-(2-phthalimidoethoxy)phenyl]-10-(4-fluoro-
phenyl)corrole (21): The same procedure as described for corrole 9
was used starting from 4-fluorobenzaldehyde (0.68 g, 5.5 mmol),
dipyrromethane 8 (5.29 g, 11 mmol, 2 equiv.), dichloromethane
(0.33 L) and TFA (33 µL, 0.44 mmol, 0.08 equiv.). The reaction
mixture was diluted by the addition of CH2Cl2 (3.3 L) and of a
solution of DDQ (2.48 g, 11 mmol, 2 equiv.) in tetrahydrofuran
(200 mL). The mixture was stirred at room temperature during
30 min, concentrated under vacuum and filtered through a silica
pad. After evaporation, the solid was chromatographed on silica
gel with CH2Cl2 as eluent. Recrystallization from CH2Cl2/heptane,
led to 21 (0.63 g, 10.7 %) as a dark violet solid. 1H NMR
3
3
H, H-β), 8.52 (d, J = 4.88 Hz, 2 H, H-β), 8.90 (d, J = 3.96 Hz, 2
H, H-β). MS (MALDI/TOF): m/z = 639.8 [M]+·. UV/Vis (CH2Cl2,
ε×10–3, mol–1·L·cm–1): λmax = 409 (162.3), 428 (125.2), 567 (36.1),
602 (27.9), 636 (19.7). C42H33N5O2·0.5H2O (648.8): calcd. C 77.76,
H 5.28, N 10.79; found C 77.37, H 5.35, N 10.60.
5,15-Bis(2,6-dichloro-4-hydroxyphenyl)-10-(4-cyanophenyl)corrole
(18): The corrole 16 (0.75 g, 0.86 mmol) and benzylamine (207 µL,
1.89 mmol, 2.2 equiv.) were dissolved in tetrahydrofuran (50 mL)
and ethanol (50 mL). The mixture was refluxed for 5 h and then
evaporated under vacuum. The resulting solid was chromato-
graphed on silica gel with CH2Cl2 and CH2Cl2/EtOAc (95:10) as
eluents. After recrystallization from CH2Cl2/EtOAc/heptane, the
3
(500 MHz, CDCl3, 303 K): δ = –2.05 (br. s, 3 H, NH), 4.28 (t, J
Eur. J. Org. Chem. 2005, 4601–4611
www.eurjoc.org
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4609

J.-M. Barbe, G. Canard, S. Brandès, R. Guilard
= 5.57 Hz, 2 H, CH2), 4.49 (t, J = 5.57 Hz, 2 H, CH2), 7.31 (s, 4 β), 8.51 (m, 4 H, H-β), 8.93 (d, 3J = 3.97 Hz, 2 H, H-β). MS
FULL PAPER
3
H, Ar-H), 7.40 (m, 2 H, Ar-H), 7.79 (m, 4 H, Ar-H), 7.95 (m, 4
(MALDI/TOF): m/z = 857.9 [M]+·. UV/Vis (CH2Cl2, ε × 10–3
,
3
H, Ar-H), 8.10 (m, 2 H, Ar-H), 8.36 (d, J = 3.95 Hz, 2 H, H-β), mol–1·L·cm–1): λmax = 407 (124.0), 426 (95.4), 566 (18.6), 603 (12.0),
8.50 (m, 4 H, H-β), 8.95 (d, 3J = 4.19 Hz, 2 H, H-β). MS (MALDI/ 635 (5.9). C47H37Cl3N4O6 (860.2): calcd. C 65.63, H 4.34, N 6.51;
TOF): m/z = 1057. 7 [M] + · . U V/ Vi s ( CH2 Cl2 , ε × 1 0– 3
,
found C 65.56, H 4.15, N 6.47.
mol–1·L·cm–1): λmax = 410 (89.1), 424 (73.4), 568 (13.0), 609 (9.8),
635 nm (5.3). C57H35Cl4FN6O6 (1060.7): calcd. C 64.54, H 3.33, N
7.92; found C 64.37, H 3.88, N 7.69.
5,15-Bis[2,6-dichloro-4-(chloroacetoxy)phenyl]-10-[4-(chloroacet-
oxy)phenyl]corrole (25): The same procedure as described for the
corrole 9 was carried out using 4-(chloroacetoxy)benzaldehyde 4
(3.24 g, 16 mmol), dipyrromethane 7 (12.50 g, 32 mmol, 2 equiv.),
dichloromethane (0.96 L) and TFA (96 µL, 1.28 mmol, 0.08 equiv.).
The reaction mixture was diluted by the addition of CH2Cl2 (2.5 L)
and a solution of DDQ (7.2 g, 32 mmol, 2 equiv.) in tetra-
hydrofuran (200 mL). This mixture was stirred at room tempera-
ture for 30 min, concentrated and filtered through a silica pad. Af-
ter evaporation, the resulting solid was chromatographed on silica
gel with CH2Cl2/heptane (85:15 and 9:1) as eluents. After
recrystallization from CH2Cl2/heptane, the corrole 25 (394 mg,
2.6%) is obtained as dark violet solid. 1H NMR (500 MHz, CDCl3,
303 K): δ = –2.07 (br. s, 3 H, NH), 4.47 (s, 4 H, CH2), 4.48 (s, 4
5,15-Bis[4-(2-aminoethoxy)-2,6-dichlorophenyl]-10-(4-fluorophenyl)-
corrole (22): Corrole 21 (0.62 g, 0.58 mmol) and hydrazine monohy-
drate (2.84 mL, 58.4 mmol, 100 equiv.) were dissolved in ethanol
(80 mL). The reaction mixture was then refluxed during one night
and the solvents evaporated. The resulting solid was dissolved in
dichloromethane, washed two times with an aqueous solution of
NaOH (5%), water, dried with MgSO4 and the solvents evaporated
to dryness. The solid was chromatographed on basic alumina with
CH2Cl2/MeOH (90:10) as eluent. Recrystallization from CH2Cl2/
heptane gave the corrole 22 (0.15 g, 32%) as a dark violet solid. 1H
NMR [500 MHz, (CD3)2SO, 303 K]: δ = 3.22 (t, 3J = 5.07 Hz, 2
H, CH2), 3.23–3.40 (br. s, 7 H, NH and NH2), 4.38 (t, 3J = 5.07 Hz,
2 H, CH2), 7.50–7.53 (m, 4 H+2 H, Ar-H), 8.09–8.12 (m, 2 H, Ar-
H), 8.18–8.23 (m, 6 H, H-β), 8.84 (d, 3J = 4.05 Hz, 2 H, H-β).
MS (MALDI/TOF): m/z = 798.2 [M]+·. UV/Vis (CH2Cl2, ε×10–3,
mol–1·L·cm–1): λmax = 410 (85.4), 425 (65.4), 570 (13.4), 609 (9.3),
639 nm (4.1). C41H31Cl4FN6O2·0.5H2O (809.6): calcd. C 60.83, H
3.98, N 10.38; found C 61.02, H 4.29, N 10.21.
3
H, CH2), 7.52 (d, J = 8.41 Hz, 2 H, Ar-H), 7.66 (s, 4 H, Ar-H),
3
3
8.21 (d, J = 8.41 Hz, 2 H, Ar-H), 8.45 (d, J = 4.18 Hz, 2 H, H-
β), 8.56 (d, 3J = 4.63 Hz, 2 H, H-β), 8.62 (d, 3J = 4.63 Hz, 2 H, H-
β), 9.03 (d, 3J = 4.18 Hz, 2 H, H-β). MS (MALDI/TOF): m/z =
938.3 [M]+·. UV/Vis (CH2Cl2, ε×10–3, mol–1·L·cm–1): λmax = 409
(130.1), 424 (104.3), 567 (19.0), 608 (12.2), 636 nm (5.8).
C43H25Cl7N4O6 (941.9): calcd. C 54.83, H 2.68, N 5.95; found C
54.54, H 2.57, N 5.95.
5,15-Bis{2,6-dichloro-4-[2-(3-triethoxysilylpropylureido)ethoxy]-
phenyl}-10-(4-fluorophenyl)corrole (23): Corrole 22 (0.13 g,
0.16 mmol) was dissolved in acetonitrile (15 mL) followed by the
addition of a solution of (3-isocyanatopropyl)triethoxysilane
(0.10 g, 0.41 mmol, 2.5 equiv.) in acetonitrile (5 mL). The mixture
was refluxed for 12 h, diluted with dichloromethane (25 mL) and
the solvents evaporated. The resulting solid was recrystallized from
CH2Cl2/heptane, yielding the corrole 23 (0.18 g, 84%) as a dark
5,15-Bis(4-hydroxy-2,6-dimethylphenyl)-10-(4-hydroxyphenyl)-
corrole (26): Corrole 24 (2.23 g, 2.6 mmol) and benzylamine (3 mL,
18.3 mmol, 10 equiv.) were dissolved in tetrahydrofuran (200 mL)
and ethanol (200 mL). The mixture was refluxed for 1 h and the
solvents evaporated under vacuum. The solid was crystallized
CH2Cl2/heptane, filtered off and then chromatographed on silica
gel with different elution mixtures of CH2Cl2 and EtOAc (9:1 and
8:2). After recrystallization from CH2Cl2/heptane, the corrole 26
(1.23 g, 75 %) was obtained as a dark violet solid. 1H NMR
[500 MHz, (CD3)2CO, 303 K]: δ = 1.90 (s, 6 H, CH3), 2.84 (br. s,
1
violet solid. H NMR (500 MHz, CDCl3, 323 K): δ = –1.90 (br. s,
3 H, NH), 0.70 (t, 3J = 7.91 Hz, 4 H, CH2Si), 1.26 (t, 3J = 6.95 Hz,
18 H, OCH2CH3), 1.68–1.73 (m, 4 H, CH2CH2Si), 3.24–3.28 (m, 4
H, CH2CH2CH2Si), 3.75 (m, 4 H, OCH2CH2NH), 3.87 (q, 3J =
6.95 Hz, 12 H, OCH2CH3), 4.30 (m, 4 H, OCH2CH2NH), 4.70 (m,
2 H, NHCO), 4.89 (m, 2 H, NHCO), 7.33 (s, 4 H, Ar-H), 7.38–7.42
3
3 H, OH), 6.97 (s, 4 H, Ar-H), 7.23 (d, J = 8.54 Hz, 2 H, Ar-H),
3
3
7.94 (d, J = 8.54 Hz, 2 H, Ar-H), 8.25 (d, J = 3.66 Hz, 2 H, H-
β), 8.44–8.48 (m, 4 H, H-β), 8.94 (d, 3J = 4.27 Hz, 2 H, H-β).
MS (MALDI/TOF): m/z = 630.2 [M]+·. UV/Vis (CH2Cl2, ε×10–3,
mol–1·L·cm–1): λmax = 404 (88.9), 425 (62.8), 567 (12.9), 605 (10.7),
636 (8.2). C41H34N4O3·0.5H2O (639.8): calcd. C 76.98, H 5.51, N
8.76; found C 76.80, H 5.87, N 8.43.
3
(m, 2 H, Ar-H), 8.10–8.13 (m, 2 H, Ar-H), 8.39 (d, J = 3.96 Hz, 2
H, H-β), 8.52–8.55 (m, 4 H, H-β), 8.96 (d, 3J = 3.96 Hz, 2 H,
H-β). MS (MALDI/TOF): m/z = 1292.7 [M]+·. UV/Vis (CH2Cl2,
ε×10–3, mol–1·L·cm–1): λmax = 409 (112.4), 424 (86.4), 569 (19.2),
609 (13.7), 639 nm (7.3). C61H73Cl4FN8O10Si2 (1295.3): calcd. C
56.56, H 5.68, N 8.65; found C 56.45, H 5.76, N 8.54.
5,15-Bis(2,6-dichloro-4-hydroxyphenyl)-10-(4-hydroxyphenyl)corrole
(27): The corrole 25 (0.35 g, 0.38 mmol) and benzylamine (135 µL,
1.23 mmol, 3.3 equiv.) were dissolved in tetrahydrofuran (30 mL)
and ethanol (30 mL). The mixture was refluxed for 6 h and the
solvents evaporated. The solid was chromatographed on silica gel
with EtOAc/heptane (1:3) as eluent. Recrystallization from EtOAc/
heptane led to the corrole 27 (0.23 g, 87%) as a dark violet solid.
1H NMR [500 MHz, (CD3)2CO, 303 K]: δ = 7.25 (br. s, 4 H, Ar-
H), 7.37 (br. s, 4 H, Ar-H), 7.97 (br. s, 2 H, H-β), 8.39 (br. s, 2 H,
H-β), 8.56 (br. s, 2 H, H-β), 9.04 (br. s, 2 H, H-β). MS (MALDI/
10-[4-(Chloroacetoxy)phenyl]-5,15-bis(4-chloroacetoxy-2,6-dimeth-
ylphenyl)corrole (24): The same procedure as described for the cor-
role 9 was carried out using 4-(chloroacetoxy)benzaldehyde (4)
(3.18 g, 16 mmol), the dipyrromethane 6 (10.96 g, 32 mmol,
2 equiv.), dichloromethane (0.96 L) and TFA (96 µL, 1.28 mmol,
0.08 equiv.). The reaction mixture was diluted by CH2Cl2 (1.92 L)
and a solution of DDQ (7.2 g, 32 mmol, 2 equiv.) in tetra-
hydrofuran (200 mL). This mixture was then stirred at room tem-
perature for 30 min, concentrated and filtered through a silica pad.
After evaporation, the resulting solid was chromatographed on sil-
ica gel with CH2Cl2/heptane (7:1 and 9:1) as eluents. Recrystalli-
zation from CH2Cl2/heptane led to the corrole 24 (1.72 g, 13%) as
TOF): m/z = 709.6 [M]+ · . UV/Vis [(CH3 )2 CO, ε × 10– 3
,
mol–1·L·cm–1]: λmax = 405 (60.5), 424 (47.5), 569 (13.2), 608 (9.3),
633 nm (9.5). C37H22Cl4N4O3·0.5 EtOAc (756.5): calcd. C 61.92, H
3.46, N 7.41; found C 61.74, H 3.62, N 7.39.
1
dark violet solid. H NMR (500 MHz, CDCl3, 303 K): δ = –1.72
5,15-Bis{2,6-dimethyl-4-[(3-triethoxysilylpropyl)aminocarbonyloxy]-
phenyl}-10-{4-[(3-triethoxysilylpropyl)aminocarbonyloxy]-
(br. s, 3 H, NH), 1.95 (s, 12 H, CH3), 4.46 (s, 4 H, CH2), 4.48 (s, 2
3
H, CH2), 7.25 (s, 4 H, Ar-H), 7.52 (d, J = 8.54 Hz, 2 H, Ar-H), phenyl}corrole (28): The corrole 26 (0.51 g, 0.80 mmol), (3-isocya-
3
3
8.18 (d, J = 8.54 Hz, 2 H, Ar-H), 8.35 (d, J = 3.97 Hz, 2 H, H- natopropyl)triethoxysilane (2.4 g, 9.7 mmol, 12 equiv.) and diiso-
4610 © 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.eurjoc.org
Eur. J. Org. Chem. 2005, 4601–4611

meso-Functionalized Corroles: Precursors of Organic–Inorganic Hybrid Materials
FULL PAPER
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(Eds.: K. M. Kadish, K. M. Smith, R. Guilard), Academic
Press, New York, 2000; vol. 2, 233–300.
[3] R. Guilard, J. M. Barbe, C. Stern, K. M. Kadish, The Porphy-
rin Handbook (Eds.: K. M. Kadish, K. M. Smith, R. Guilard),
Elsevier Science (USA), 2003; vol. 18, 303–349.
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[6] J. M. Barbe, G. Canard, S. Brandès, F. Jérôme, G. Dubois, R.
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2002, 6, 81–97.
propylethylamine (0.63 g, 4.85 mmol, 6 equiv.) were dissolved in
acetonitrile (30 mL) and tetrahydrofuran (30 mL). The mixture was
refluxed for 7 days. After cooling to room temperature, the solution
was diluted with dichloromethane (30 mL) and the solvents evapo-
rated. The resulting solid was twice recrystallized from CH2Cl2/
heptane, filtered off and washed with pentane. The corrole 28
(0.80 g, 72 %) was obtained as a dark violet solid. 1H NMR
(500 MHz, CDCl3, 303 K): δ = –1.95 (br. s, 3 H, NH), 0.79 (m, 6
H, CH2Si), 1.30 (m, 27 H, OCH2CH3), 1.82 (m, 6 H, CH2CH2Si),
1.93 (s, 12 H, Ar-CH3), 3.41 (m, 6 H, CH2CH2CH2Si), 3.90 (m, 18
H, OCH2CH3), 5.55 (m, 3 H, NHCO), 7.23 (s, 4 H, Ar-H), 7.49
3
3
(d, J = 8.21 Hz, 2 H, Ar-H), 8.12 (d, J = 8.21 Hz, 2 H, Ar-H),
3
3
8.34 (d, J = 3.95 Hz, 2 H, H-β), 8.49 (d, J = 4.69 Hz, 2 H, H-β),
3
3
8.52 (d, J = 4.69 Hz, 2 H, H-β), 8.89 (d, J = 3.95 Hz, 2 H, H-β).
MS (MALDI/TOF): m/z 1372.0 [M]+·. UV/Vis (CH2Cl2, ε×10–3,
mol–1·L·cm–1): λmax = 408 (113.2), 426 (89.3), 566 (15.1), 604 (10.1),
635 nm (5.1). C71H97N7O15Si3·H2O (1390.9): calcd. C 61.31, H
7.17, N 7.05; found C 61.52, H 7.41, N 7.31.
[10] Z. Gross, N. Galili, I. Saltsman, Angew. Chem. Int. Ed. 1999,
38, 1427–1429.
[11] R. Paolesse, A. Marini, S. Nardis, A. Froiio, F. Mandoj, D. J.
Nurco, L. Prodi, M. Montalti, K. M. Smith, J. Porphyrins
Phthalocyanines 2003, 7, 25–36.
[12] D. T. Gryko, B. Koszarna, Org. Biomol. Chem. 2003, 1, 350–
357.
5,15-Bis{2,6-dichloro-4-[(3-triethoxysilylpropyl)aminocarbonyloxy]-
phenyl}-10-{4-[(3-triethoxysilylpropyl)aminocarbonyloxy]-
phenyl}corrole (29): A solution of (3-isocyanatopropyl)triethoxysil-
ane (0.90 g, 3.64 mmol, 12 equiv.) and diisopropylethylamine
(0.24 g, 1.82 mmol, 6 equiv.) in acetonitrile (5 mL) was added to a
solution of the corrole 27 (0.22 g, 0.30 mmol) in acetonitrile (8 mL)
and tetrahydrofuran (8 mL). The reaction mixture was refluxed for
7 days. After cooling to room temperature, this mixture was diluted
with dichloromethane (30 mL) and the solvents evaporated. The
solid was twice recrystallized from CH2Cl2/heptane, filtered off and
washed with pentane leading to the corrole 29 (324 mg, 73%) as a
[13] R. Guilard, D. T. Gryko, G. Canard, J. M. Barbe, B. Koszarna,
S. Brandès, M. Tasior, Org. Lett. 2002, 4, 4491–4494.
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5669–5673.
1
dark violet solid. H NMR (500 MHz, CDCl3, 303 K): δ = –1.90
(br. s, 3 H, NH), 0.78 (m, 6 H, CH2Si), 1.30 (m, 27 H, OCH2CH3),
1.83 (m, 6 H, CH2CH2Si), 3.41 (m, 6 H, CH2CH2CH2Si), 3.90 (m,
18 H, OCH2CH3), 5.57 (m, 1 H, NHCO), 5.74 (m, 2 H, NHCO),
3
3
7.50 (d, J = 7.82 Hz, 2 H, Ar-H), 7.63 (s, 4 H, Ar-H), 8.15 (d, J
[23] L. Wen, M. Li, J. B. Schlenoff, J. Am. Chem. Soc. 1997, 119,
3
= 7.82 Hz, 2 H, Ar-H), 8.44 (d, J = 3.80 Hz, 2 H, H-β), 8.56 (d,
7726–7733.
3J = 4.47 Hz, 2 H, H-β), 8.62 (d, J = 4.47 Hz, 2 H, H-β), 8.99 (d,
3
[24] C. H. Lee, J. S. Lindsey, Tetrahedron 1994, 50, 11427–11440.
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1391–1396.
3J = 3.80 Hz, 2 H, H-β). MS (MALDI/TOF): m/z = 1451.6 [M]+·.
UV/Vis (CH2Cl2, ε×10–3, mol–1·L·cm–1): λmax = 410 (78.1), 423
(64.9), 568 (14.4), 609 (9.8), 636 nm (6.3). C67H85Cl4N7O15Si3·
3.5H2O (1517.6): calcd. C 53.03, H 6.11, N 6.46; found C 52.78, H
6.47, N 6.83.
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Acknowledgments
This work was supported by the CNRS and Air Liquide. GC grate-
fully acknowledges the “Région Bourgogne” and Air Liquide for a
financial support. The authors thank Mr M. Soustelle for his as-
sistance in the synthesis of precursors.
[32] R. Karaman, A. Blasko, O. Almarsson, R. Arasasingham,
T. C. Bruice, J. Am. Chem. Soc. 1992, 114, 4889–4898.
Received: May 25, 2005
[1] R. Paolesse, The Porphyrin Handbook (Eds.: K. M. Kadish,
K. M. Smith, R. Guilard), Academic Press, New York, 2000;
vol. 2, 201–232.
Published Online: September 12, 2005
Eur. J. Org. Chem. 2005, 4601–4611
www.eurjoc.org
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4611