Journal of Porphyrins and Phthalocyanines

J. Porphyrins Phthalocyanines 2, 455–465 (1998)

Novel and Improved Syntheses of 5,15-Diphenyl-

porphyrin and its Dipyrrolic Precursors

CHRISTIAN BRÜCKNER, JEFF J. POSAKONY, CLAIRE K. JOHNSON, ROSS W. BOYLE,† BRIAN R. JAMES and
DAVID DOLPHIN*

Department of Chemistry, University of British Columbia, Vancouver, B.C. V6T 1Z1, Canada

Received 1 August 1997

Accepted 16 September 1997

ABSTRACT: Optimized syntheses of 5,15-diphenylporphyrin (DPP, 1) and its dipyrrolic precursors are
described. A novel procedure for the synthesis of dipyrromethane (2), prepared by hydrodesulfurization of the
corresponding di-2-pyrrolylthione (8), is presented, as well as an improved method to isolate large quantities of
5-phenyldipyrromethane (4), prepared by the acid-catalysed condensation of pyrrole with benzaldehyde. These
dipyrromethanes are key reagents in two high-yield (2‡2)-type syntheses of DPP. 5-Phenyldipyrromethane
was formylated to provide 1-formyl- (11) and 1,9-diformyl-5-phenyldipyrromethane (12), and reduction of 11
provided the corresponding hydroxymethyl compound 13. These compounds (11–13), however, were much
less efficient precursors to DPP. Two polypyrrolic compounds, 1,1,2,2-dipyrrolylethane (9) and 5,10-
diphenyltripyrrane (10), potentially useful for the synthesis of porphyrinic macrocycles, were isolated as side-
products during the dipyrromethane and 5-phenyldipyrromethane syntheses. # 1998 John Wiley & Sons, Ltd.

KEYWORDS: meso-diphenylporphyrin synthesis; 5-phenyldipyrromethane; dipyrromethane; 1,1,2,2-tetra-

pyrrolylethane; 5,10-diphenyltripyrrane; 2 ‡ 2 synthesis

INTRODUCTION pended models of cytochromes [4], rod-like liquid

5,15-Diphenylporphyrin (DPP, 1) is interesting be-
cause it combines some features of 5,10,15,20-
tetraphenylporphyrin (TPP), namely the unsubstituted
b-positions and the meso-phenyl groups, with some
features of 2,3,7,8,12,13,17,18-octaethylporphyrin
(OEP), namely the unsubstituted meso-positions,
without being as difficult to prepare as the entirely
unsubstituted parent compound porphine [1].
Although DPP was first reported in 1968 by Treibs
and Häberle [2], the chemical properties unique to this
molecule are only beginning to be explored. Diphenyl-
porphyrins have been used recently in, for instance,
the synthesis of novel ethyl-linked porphyrin arrays as
models of light-harvesting antenna systems with
unique optical properties [3], dendrimerically ap-
———————
Correspondence to: D. Dolphin, Department of Chemistry, Uni-
versity of British Columbia, Vancouver, B.C. V6T 1Z1, Canada.
†Current address: Department of Biological and Chemical
Sciences, University of Essex, Wivenhoe Park, Colchester CO4
3SQ, UK.
CCC 1088–4246/98/060455–11 $17.50
# 1998 John Wiley & Sons, Ltd.
crystal porphyrins [5–7], strapped porphyrins [8],
potentially dinucleating ligands [9], the formation of a
porphyrin–cyclodextrin complex [10], the synthesis of
novel meso-diphenylbenzochlorins [11], and the
development of a bioconjugation method [12] and
development of porphyrins for non-linear optical
applications and multi-porphyrin assemblies via sub-
stitution at the meso-positions of 1 [13,14]. Whereas
the synthetic work on OEP [15, 16] and TPP [2, 17–
22] is extensive and the syntheses of these two
compounds have been optimized, there are few reports
on the synthesis of DPP [2, 23].
The highly symmetric compound TPP can be
synthesized by condensation of pyrrole with benz-
aldehyde, followed by oxidation of the intermediate
meso-tetraphenylporphyrinogen [24]. This so-called
Rothemund synthesis, in the varieties optimized by
Lindsey et al., is the route which represents the state-
of-the-art synthesis for TPP [21, 22]. The synthesis of
the less symmetric DPP requires the establishment of
two types of meso-carbons, one unsubstituted and one
bearing a phenyl group. Thus the synthesis of DPP
requires (2 ‡ 2)-type condensations in which two di-
pyrrolic compounds incorporating one type of carbon
bridge are fused together, thereby forming the other
456 C. BRÜCKNER ET AL.
Scheme 1. Selected principal pathways for the formation of 5,15-diphenylporphyrin (DPP, 1).
type of carbon bridge. The primary condensation
product is then oxidized in situ to the fully conjugated
pigment. In principle, there are many (2 ‡ 2)-type
synthetic routes to access 1. Six of them are shown in
Scheme 1.
Pathway A, the acid–catalysed condensation of di-
pyrromethane (2) with benzaldehyde (3), is the
‘classical’ synthesis for 1. This synthesis is analogous
to the Rothemund-type synthesis of TPP and is the
route used to synthesize DPP in 3% yield [2]; it was
also described in a more recent communication by
Manka and Lawrence [23]. Pathway B, the condensa-
tion of 5-phenyldipyrromethane (4) with, formally,
formaldehyde (5), is related to the method of Baldwin
et al. [25] for producing b-alkyl-substituted diphenyl-
porphyrins, which has not been described previously
for b-unsubstituted DPP. Pathways C–F differ from
the first approaches in that they involve the condensa-
tion of dipyrrolic compounds carrying the linking
carbon unit in the form of either a hydroxymethyl
group (E, F) or a formyl group (C, D). The pathways
C–F, when compared with the first two, have the
intrinsic disadvantage that they require additional
synthetic steps, and the hydroxymethyl compounds,
generally prepared by reduction of the parent carbonyl
compounds, are known to be very sensitive com-
# 1998 John Wiley & Sons, Ltd.
pounds [26–28]. Thus their pursuit would only be
economical if the overall yields of DPP based on the
common precursors 2 and 4 respectively were higher
than those obtained following routes A and B. One
related stepwise synthesis of asymmetric TPPs has
been recently published by Wallace and co-workers
[29, 30]. Pathway D, the classic MacDonald-type
synthesis of porphyrins [31], offers an additional
advantage in that it, in principle, opens up the possi-
bility to prepare in a directed way asymmetric DPPs,
i.e. DPPs which carry two differently substituted
phenyl groups.
We present here an optimized and reliable large–
scale synthesis of DPP via pathway A and a novel and
optimized synthesis along pathway B, and we report
on results found pursuing the synthesis of DPP along
routes C–E. Furthermore, we present a significantly
improved procedure for isolating multi-gram quan-
tities of 5-phenyldipyrromethane (4) reported on
recently by others [32–34]. We also present three
novel and convenient large-scale syntheses for di-
pyrromethane (2) by convenient and direct one-step
hydrodesulfurizations of dipyrrolylthione (8). Two
side-products of the dipyrromethane preparations, the
novel 1,1,2,2-tetrapyrrolylethane (9) and 5,10-di-
phenyltripyrrane (10) [32, 34, 35] are also described.
J. Porphyrins Phthalocyanines 2, 455–465 (1998)
 SYNTHESES OF 5,15-DIPHENYLPORPHYRIN AND ITS PRECURSORS 457

Scheme 2. Synthesis of dipyrromethane (2), its precursors and reaction side-product. Reaction conditions: (i) 1. EtMgBr, 2.
COCl2; (ii) 1. BH3, 2. steam distillation or 1. NH2NH2, KOH/ethylene glycol; (iii) 1. CSCl2, Et2O, 0 °C, 1 min, 2. H2O; (iv)
H2O2/KOH, MeOH; (v) EtOH, trace amine, excess Raney Ni, 1 bar H2, 25 °C, several hours 2. chromatography; (vi) 1. THF,
excess LAH, 25 °C, 12 h, 2. Glauber’s salt or 1. EtOH, KOH, excess NaBH4, D, 2. chromatography; (vii) 1. CH(OEt)3,
catalytic TFA, 25 °C, 30 min; (viii) 1. THF, 1 equiv. CO(OCCl3)2, 30 °C, 24 h, 2. MeOH.

RESULTS AND DISCUSSION tion control. As a consequence of the ease of prepara-

Synthesis of Dipyrromethane (2)
The common synthesis of dipyrromethane (2) is by
NaBH4 or Huang Minlon reduction of di-2-pyrrolyl-
ketone (7) [2, 36] with yields between 60% and 70%,
although reduction of this class of compounds is more
often achieved with diborane [37] (Scheme 2). Based
on our experience, however, these reductions are
tedious and the yields are often below 50%. Ketone 7
itself can be prepared according to an outdated
procedure directly from pyrrole (6), activated as its
Grignard salt, and phosgene [38]. Although phosgene
is being used on a large scale in industry, this highly
toxic gas is inconvenient to handle in the laboratory.
Attempts to replace phosgene by triphosgene, a
crystalline material described in 1987 by Eckert and
Foster [39], were unsatisfactory in our hands owing to
low overall yields of 7 (25%) and the relatively high
molar costs of triphosgene. Other pathways towards 7
have been described starting from pyrrole-2-carbonyl
chloride and pyrrole, also activated as its Grignard salt
[40]. The synthesis of 7, regardless of the method, is of
limited value, because an optimized synthesis of
dipyrromethane would still require reduction of 7 to
2 as the crucial step.
The sulfur congener of phosgene, thiophosgene,
used to synthesize di-2-pyrrolylthione (8) from
pyrrole, is a liquid and is easier to handle than phos-
gene. According to an efficient procedure described by
Clezy and Smythe [41], we find that di-2-pyrrolyl-
thione (8) can be prepared easily in large quantities; a
10-fold scale-up of the described procedure produced
20 g of crystalline 8 without any problems in reac-
tion of this thione, a widely used route towards 2
involves H2O2 oxidation of 8 to ketone 7 [41],
followed by borane or NaBH4 reduction as described
above. This three-step reaction sequence has an
overall yield of <35%. We believed that the method
could be shortened and the yield of 2 improved by a
direct hydrodesulfurization of thione 8.
Hydrodesulfurizations of thiones, thioethers, thio-
alcohols and compounds such as thiophenes have been
widely reported. Among the variety of reagents used
[42–46], hydrogenation over Raney Ni is a simple,
economical and versatile method [47] and is known to
desulfurize, in low to excellent yields, a great variety
of substrates containing C-S bonds [42, 43, 48].
We found that Raney Ni in the presence of H2
rapidly performed the expected hydrodesulfurization
in reasonable yields. Thus a suspension of a large
molar excess of Raney Ni in an alcoholic solution of 8
in the presence of H2 at ambient conditions, followed
by the removal of the solids by filtration, evaporation
of the solvent and either steam distillation, high–
vacuum distillation or column chromatography, pro-
duces dipyrromethane (2) as colorless crystals of
analytical purity in 45%–60% yields. The advantage
of the direct hydrodesufurization of thione 8 over
Raney Ni to prepare 2 lies in the speed, simplicity and
cost efficiency of the procedure and the high purity of
the resulting product. The reaction was successfully
scaled up to the reduction of 9 g of thione without any
loss of productivity. The disadvantages of this method
are intrinsic to the use of Raney Ni [42]: reduction is
not catalytic, and Raney Ni is unpredictably deacti-
vated on aging and is difficult to measure accurately
by weight, as it is pyrophoric and must be kept wet.

# 1998 John Wiley & Sons, Ltd. J. Porphyrins Phthalocyanines 2, 455–465 (1998)
458 C. BRÜCKNER ET AL.
Scheme 3. Synthesis of 5-phenyldipyrromethane (4) and related macrocycle precursors. Reaction conditions: (i) 1. excess
pyrrole, catalytic TFA, 2. sublimation; (ii) POCl3/DMF, 2. H2O; (iii) NaBH4.
The reaction is also ‘somewhat capricious’: rate and
yield are strongly dependent on the activity of the
Raney Ni, and varied in our hands from almost
instantaneous to requiring 12 h, with yields ranging
from 40% to >90%. Newly purchased Raney Ni slurry
in water (Aldrich) gave faster and cleaner reactions
and fair reproducibility.
At the onset of the reaction, in the absence of
sufficient H2 or in the presence of Ni2‡ ions, thione 8
forms a 2:1 complex with nickel; this and related
pigments are described in detail elsewhere [49]. A
TLC of the crude reaction mixture shows the presence
of small amounts of several pyrrolic side-products
[50], and careful chromatography after a successful
hydrodesulfurization isolated the least polar of these
side-products in the form of a tan solid. It was
identified as 1,1,2,2-tetra-2-pyrrolylethane (9), the
meso-linked dimer of 2, based on its 1H and 13C
NMR spectra which are very similar to those of
dipyrromethane 2, a mass spectrum (m/z 290,
corresponding to C18H18N4 = 2  m/z (2) ÿ 2H) and
elemental analysis. The occurrence of the dimer 9 is
good evidence for the radical nature assumed for
Raney Ni-mediated hydrodesulfurizations [42]. The
bisdipyrromethane 9, which is similar to phenyl-
bridged bisdipyrromethanes [51], looks a useful
precursor for the synthesis of directly meso-linked
porphyrin dimers.
While looking for alternatives to Raney Ni, we were
surprised to find that excess LAH in THF, or NaBH4 in
EtOH, reduces thione 8 smoothly to 2 in yields of
80%–85% after short-column chromatography of the
resulting reaction mixture. We are not aware of
hydrodesulfurization being brought about by LAH or
NaBH4. The reduction using LAH proceeds smoothly
only on relatively small scales, whereas the NaBH4
reduction is effective for up to at least 1 g of 8.
Min Wang and Bruce recently described a one-step
synthesis of 2 by the acid-catalysed condensation of
# 1998 John Wiley & Sons, Ltd.
excess pyrrole with paraformaldehyde [52] (Scheme
2). Although this represents the ideal direct route (with
an agreeable 41% yield), the work-up requires column
chromatographic separation of the product mixtures,
and the reaction has been described only for the
synthesis of 2 on a 200 mg scale. We consider that the
routes to 2 via the Raney Ni- or NaBH4-induced
hydrodesulfurization of thione 8 are better options for
large-scale synthesis.
Synthesis of 5-Phenyldipyrromethane (4)
Benzaldehyde (3) and pyrrole (6) were condensed in
neat pyrrole, catalysed by TFA, to produce 5-
phenyldipyrromethane (4) according to the procedure
of Lee and Lindsey [32] (Scheme 3) or, alternatively
and in comparable yields, in toluene catalysed by
TsOH according to a method described by Carell [33].
Other methods to synthesize 4 involve many steps [30]
or extensive column chromatography [27, 34] and are
not amenable to economical, large-scale syntheses.
Carell’s method is, in principle, useful for the
preparation of dipyrromethanes made from substituted
pyrroles, as they are not required as solvent. Both
procedures call for isolation and purification of the
product by column chromatography with a relatively
large ratio of stationary phase to compound [32]. As
this makes the synthesis of multi-gram scales of 4
time-consuming and costly, we tested several other
methods to separate the main product 4 from other
oligomers produced. When the crude or pre-purified
oil produced in this polycondensation reaction was
transferred into a sublimation apparatus and heated 4
sublimed and crystallized on the cooling finger as
colorless or white crystals of analytical purity. This
protocol enabled us to synthesize up to 15 g of
crystalline 4 per run.
TLC of the pre-purified reaction mixture indicated
the presence of the desired dipyrromethane (4) and one
J. Porphyrins Phthalocyanines 2, 455–465 (1998)
 SYNTHESES OF 5,15-DIPHENYLPORPHYRIN AND ITS PRECURSORS 459
major oligomer, identified by HR-MS (m/z 377.1881,
expected for C26H23N3: 377.1892) as the tripyrrolic
compound 10. The presence of 10 in such reaction
mixtures has been noted by others and it was pro-
visionally assigned the 5,10-diphenyltripyrromethane
structure [32, 34]. Recently, Lee and co-workers [53]
synthesized, among other related compounds, this
tripyrromethane by the acid-catalysed condensation of
2,5-bis(a-hydroxy-a-phenylmethyl)-substituted pyr-
role with pyrrole. The residue left in the bottom of
the sublimation apparatus, after all 4 had sublimed,
hardened upon cooling into a red–orange glass. This
glass, as judged by TLC, elemental analysis and 1H
NMR, contains, depending on the degree of pre-
purification, up to 95% of a compound which is
characterized unequivocally as 5,10-diphenyltripyr-
rane (10). It was obtained in 10%–20% yields and,
even when ground into a powder, is stable in the solid
form, but could not, in our hands, be further purified
without retrieving it as an unstable oil, an observation
paralleling Lee and Lindsey’s report [32]. We attribute
this to the presence of three stereoisomers and the
general acid lability of these types of compounds.
Thus reliable procedures to prepare 10 for the
synthesis of meso-phenyl-substituted macrocycles
such as porphyrins [53] and expanded porphyrins are
now available [35]. This route to tripyrrane 10 is
extraordinarily simple given that the syntheses of b-
alkyltripyrranes generally involve multi-step path-
ways [53–56]. This offsets the disadvantage of not
being able to prepare (crystalline) samples which are
100% pure.
Standard Vilsmeier–Haack formylations of 4 with
either one or two equivalents of Vilsmeier reagent
(POCl3/DMF) [36], followed by chromatographic
separation of the product mixtures, resulted in the
isolation of 1-formyl- (11) and 1,9-diformyl-5-phenyl-
dipyrromethane (12), respectively, in 50% yields.
Reduction of 11 with NaBH4 resulted in the formation
of the hydroxymethyl compound 13, which, despite its
intrinsic lability [26, 28], could be isolated and
characterized.
Synthesis of 5,15-Diphenylporphryin (1) via Route A
As noted above, the condensation of dipyrromethane
(2) with benzaldehyde (3) under acid catalysis was the
first reported method for the synthesis of DPP [2], and
Manka and Lawrence communicated such a DPP
preparation in 1989 [23]. The yield claimed in the
latter paper (92%) is extraordinarily high for any
porphyrin synthesis and could not be reproduced in
# 1998 John Wiley & Sons, Ltd.
our hands. Based on the general porphyrin-forming
conditions as described for TPP by Lindsey et al. [21]
(which is also the basis for Manka and Lawrence’s
DPP synthesis [23]), we have developed an optimized
and reliable method of synthesizing and purifying DPP
while eliminating purification by flash column chro-
matography. Accordingly, reaction of 2 and benzalde-
hyde under N2 and TFA catalysis was followed by
oxidation of the reaction mixture with chloranil
(tetrachloro-p-quinone, TCQ); treatment of the reac-
tion mixture with aqueous Na2S2O4 to reduce the
remaining TCQ, followed by removal of the tetra-
chlorohydroquinone by a wet MeOH wash, final
purification of the DPP in CH2Cl2 by filtration through
a plug of silica and alumina, subsequent evaporation
of the solvent and trituration with wet methanol,
allows for simple and fast isolation of analytically pure
DPP (25%–40%). This purification can be applied to
>500 mg of DPP per run. Oxidation of the porphyr-
inogen intermediate can also be brought about by an
Fe(II)-phthalocyanine/TCQ electron transport chain
[22], but lower yields (18%–20%) and the need for
flash column chromatography to isolate the porphyrin
are disadvantageous. The purification method
described remedies, firstly, the problem of separating
excess oxidant TCQ from the product DPP by
chromatography, as these compounds have very
similar R f-values on silica/CH2Cl2. In our experience,
chromatography alone produces DPP which is highly
contaminated with TCQ; if yields and purity of the
product are assessed by 1H NMR and weight alone,
this would imply very high yields. Secondly, owing to
the generally poor solubility of DPP, column chroma-
tographies require large amounts of solvent and are
time-consuming.
Synthesis of 5,15-Diphenylporphyrin (1) via Route B
This novel route involves the condensation of 5-
phenyldipyrromethane (4) with formaldehyde (5).
Reaction of 4 with trimethyl orthoformate under
Baldwin’s conditions (trichloroacetic acid catalysis
and air oxidation) [25], followed by chromatographic
isolation of the product, gave DPP in 30% yield.
Here chromatography was chosen for the isolation and
purification, as DPP was the only product eluting
under the conditions described, thereby minimizing
the amount of stationary phase and facilitating the
process considerably. Evaporation of the solvent
produces DPP which is partially (<5 %) protonated.
Recrystallization from basic solvent (toluene/1%
J. Porphyrins Phthalocyanines 2, 455–465 (1998)
460 C. BRÜCKNER ET AL.
pyridine) produces analytically pure DPP in overall
21% yield.
Both routes A and B produce TPP as a trace side-
product (<1%) which results from some acid-cata-
lysed dipyrromethane or porphyrinogen scrambling
[21, 30, 32, 57–60]. Another scrambling product,
formed in minute amounts along pathway A, is a
pigment which, based on its UV-vis (max: 400
(Soret), 496, 528, 568, 630 nm) and mass spectral
data (HR-MS (EI): calc. for C26H18N4: 386.15314,
found 386.15245), is almost certainly 5-phenylpor-
phyrin.
Synthesis of 5,15-Diphenylporphyrin (1) via Routes
C–E
As yet another option for the synthesis of DPP, the
acid-catalysed self-condensation of 11 (route C) and
13 (route E) and the classic MacDonald 2 ‡ 2
condensation of 4 and 12 (route D) were tested using
conditions which have been reported for similar 2 ‡ 2
syntheses [30, 31]. Firstly, the reactants were dis-
solved in toluene under N2 to which was added a
catalytic quantity of TsOH, the mixture was heated to
reflux, neutralized with pyridine and oxidized with air
(routes C–E). Secondly, the dipyrrolic precursors were
dissolved in CH2Cl2 under N2, a small quantity of
TCA dissolved in CH2Cl2 was added and the mixture
was stirred for 6 h; neutralization with pyridine and
oxidation with 2,3-dichloro-5,6-dicyano-1,4-quinone
completed the synthesis (routes C and E). In a third set
of reactions, the reactants were refluxed in propionic
acid while the mixture was exposed to air (routes C
and E). Next, the conditions outlined for route B were
applied to compounds 12 and 4 (route D). Lastly, the
classic MacDonald conditions were tried [31]: 11 was
dissolved in glacial acetic acid containing HI (route
C). Again, neutralization and air oxidation completed
the synthetic efforts. The results of all the experiments
were equally disappointing in that only little (<5%), if
any, DPP was formed.
Although the formation of porphyrins using the
MacDonald 2 ‡ 2 method frequently requires the use
of special and carefully controlled conditions unique
to a particular system, the almost complete failure to
form DPP along the pathways C–E is puzzling,
particularly as species 13 is assumed to be an inter-
mediate in the formation of DPP via route B. Wallace
et al. have reported poor to good yields (5–31%) in the
(2 ‡ 2)-type synthesis of hydroxymethyl dipyrro-
methanes to obtain TPP derivatives [30], and others
have reported yields of up to 20% for the synthesis of
# 1998 John Wiley & Sons, Ltd.
b-alkyl-substituted DPP derivatives by condensing a
hydroxymethyl dipyrromethane with an a-free di-
pyrromethane [28]. Thus it seems that the synthesis of
b-unsubstituted and bis-meso-unsubstituted DPP is
challenging perhaps because of the lability of the
pyrrolic intermediates. Our results discouraged the
investigation of the synthesis of DPP along route F,
particularly because the anticipated sensitivity of 2
would render formation of 13 via benzoylation and
reduction along known synthetic strategies difficult
[61, 62], and other perceivable pathways would be too
laborious [30, 63, 64] to be considered as efficient
methods to ultimately synthesize DPP.
CONCLUSIONS
In conclusion, we present two optimized, reliable,
high-yield and large-scale methods to prepare DPP
(Scheme 1, routes A and B), the latter being new. We
also provide novel and optimized procedures for the
large-scale synthesis of the precursors dipyrromethane
(2) and 5-phenyldipyrromethane (4). Two polypyrro-
lic side-products of the dipyrrane preparations,
1,1,2,2-tetra-2-pyrroylethane (9) and 5,10-diphenyl-
tripyrrane (10), were isolated and characterized; both
compounds have potential in the preparation of
unusual porphyrinic structures. The mono- and di-
formylation of dipyrromethane (4) to provide the
building blocks 1-formyl- (11) and 1,9-diformyl-5-
phenyldipyrromethane (12), respectively, and the
reduction of 11 to provide 1-hydroxymethyl-5-phenyl-
dipyrromethane (13), are also described. A series of
(2 ‡ 2)-type condensations of the dipyrrolic building
blocks 11–13 towards alternative DPP syntheses
(Scheme 1, routes C–E) yielded at best only traces
of the compound; because of the (acid) lability of 11–
13, these types of condensations do not provide viable
routes to DPP, in contrast with the synthesis of b-
octaalkylporphyrins.
EXPERIMENTAL
Materials and Instrumentation
Raney Ni (50% slurry in water pH > 9, Aldrich) was
used as supplied, pyrrole (Aldrich) was dried over and
distilled from KOH before use and benzaldehyde
(Aldrich) was freshly distilled before use. Where
indicated that dry, degassed CH2Cl2 was used, it was
distilled from CaH2 under N2. All other reagents and
J. Porphyrins Phthalocyanines 2, 455–465 (1998)
 SYNTHESES OF 5,15-DIPHENYLPORPHYRIN AND ITS PRECURSORS 461
solvents were used as purchased. The alumina used for
chromatography was Fisher basic, activity II/III. The
silica gel used in the flash chromatographies was
Merck Silica Gel 60, 230–400 mesh, whilst R f-values
were measured on Merck silica TLC aluminium sheets
(silica gel 60 F254). 1H and 13C NMR spectra were
recorded on a Bruker AC-200 or a Varian XL-300
instrument. UV-vis spectra were recorded on an
HP8452A photodiode array spectrophotometer
(2 nm). Elemental analyses were performed by Mr
P. Borda of the departmental microanalytical labora-
tory on a Fisons CHN/O Analyzer, model 1108. The
high- and low-resolution mass spectra were obtained
at the departmental mass spectrometry service labora-
tories (G. Eigendorf, Director) on an AEI MS902 and a
Kratos MS50, respectively.
Di(2-pyrrolyl)methane (2)
Method I. Di-2-pyrrolylthione (8) [41] (2.0 g,
11.3 mmol) was dissolved in ethanol or THF (50–
75 mL) containing conc. aqueous NH3 or Et3N
(0.5 mL) and a 50% slurry of Raney Ni in water
pH >9 (4–10 mL) was added. The flask containing the
rapidly stirred mixture was left at ambient temperature
connected to a standard pressure hydrogenation
apparatus. Alternatively, H2 was bubbled through the
solution. Hydrodesulfurization set in instantaneously
and was, depending on the activity of the Raney Ni,
completed within 20 min–12 h. In cases where TLC
revealed after several hours the presence of starting
material, more Raney Ni was added until all thione
was consumed, at which time the Raney Ni was
filtered off (CAUTION: dry Raney Ni is pyrophoric)
through a short plug of Celite1 and washed with EtOH
(or THF) until the rinsings contained no more 2. The
combined filtrates were reduced in vacuo to an oil,
taken up in CHCl3 and chromatographed on basic
alumina (activity II/III)/CH2Cl2 (4  12 cm2) or on
silica gel/CHCl3. The first fraction was collected and
evaporated to dryness to yield 0.805 g (49%) of 2 as an
off-white crystalline solid. Yields typically 40%–50%,
but sometimes 60%. M.p. 73 °C ([36]: 73 °C). 1H NMR
(200 MHz, CDCl3):  3.95 (s, 2H), 6.05 (m, 2H), 6.15
(dd, 2H), 6.60 (dd, 2H), 7.65 (br s, 2H). 13C NMR
(CDCl3):  26.4, 106.5, 108.3, 117.4, 129.1. Anal.
calc. for C9H10N2: C, 73.95; H, 6.90; N, 19.16. Found:
C, 73.96; H, 6.70; N, 19.08.
Method II. Thione 8 (200 mg, 1.14 mmol) was
dissolved in dry THF (10 mL) and, at 0 °C and under
anhydrous conditions, LAH (150 mg, 3.75 mmol) was
# 1998 John Wiley & Sons, Ltd.
added in portions to the orange solution over 2 h. The
mixture was stirred for an additional 12 h at ambient
temperature. The then yellow solution was quenched
by the addition of Glauber’s salt (Na2SO4
10H2O),
diluted with CHCl3 (10 mL) and filtered through
Celite1. The filtrates were evaporated and the oily
residue was chromatographed on a short column
(10  2 cm2 silica/CHCl3). The first colorless fraction
was collected to produce, after evaporation of the
solvent in vacuo, 130 mg (80% yield) of analytically
pure 2.
Method III. Thione 8 (1.0 g, 5.7 mmol) and KOH (0.2
g) were dissolved in 95% EtOH and NaBH4 (1.0 g,
26.5 mmol) was added. The mixture was refluxed
under N2 for 3 h or until no 8 remained as indicated by
TLC. The pale orange solution was purged with N2
while the reaction was cooled to room temperature to
help facilitate removal of sulfurous products. Acetone
(5 mL) was added and, once effervescence ceased,
several grams of basic alumina were added and the
solvent was removed. The product on alumina was
then loaded onto a basic alumina (II/III) column
(100 g, 10  3 cm2) and eluted with CH2Cl2 until the
eluate contained only traces of 2. The solvent was
removed to yield 0.695 g (84% yield) of analytically
pure 2, m.p. 74.5–75.5 °C, which had a light sulfurous
odor.
1,1,2,2-Tetrapyrrolylethane (9)
All products remaining on the chromatography
column after 2 (prepared by method I) were eluted
(5% MeOH in CH2Cl2). These fractions were
evaporated in vacuo onto a few grams of silica. This
was loaded onto a flash column and chromatographed
(gradient of 20:1 to 10:1 toluene:THF). Following
residual 2, 9 eluted as a colorless fraction. Evaporation
to dryness yielded 9 as an off-white to brown
crystalline solid in 3% yield (105 mg). M.p. 153–
155 °C (decomp.). R f = 0.78 (CHCl3). 1H NMR
(200 MHz, CDCl3):  4.80 (s, 1H), 5.88 (m, 2H),
6.09 (dd, 2H, J 4, 3 Hz), 6.75 (m, 2H), 7.6 (br s, 2H).
13
C NMR (75 MHz, CDCl3):  42.6, 107.4, 108.5,
112.2, 117.3, 131.2. LR-MS (EI, 220 °C): m/z 290
(10.0, M‡), 288 (20, M‡ ÿ 2H), 222 (12.1,
M‡ ÿ pyrrolyl), 145 (MH22‡ ÿ 4H). LR-MS (FAB):
m/z 289 (ÿH). HR-MS (FAB): calc. for C18H17N4
(ÿH): m/z 289.14532, found 289.14439. Anal. calc.
for C18H18N4: C, 74.46; H, 6.25; N, 19.29. Found: C,
74.34; H, 6.49; N, 19.15. In the solid state, 9 exhibited
noticeable darkening over the time course of several
J. Porphyrins Phthalocyanines 2, 455–465 (1998)
462 C. BRÜCKNER ET AL.
weeks, but still retained a clean 1H NMR spectrum
after several months in a tightly capped vial.
5-Phenyldipyrromethane (4) and 5,10-
Diphenyltripyrromethane (10)
Method I. (Adapted from Ref. 32). Benzaldehyde
(6.0 mL, 59 mmol) was mixed with pyrrole (150 mL,
2.16 mol) and the mixture was deoxygenated by
bubbling dry N2 through it for 15 min; TFA (0.45 mL,
5.8 mmol) was added and the mixture was stirred
under N2 for 15 min at ambient temperature. The
excess pyrrole was then evaporated in vacuo (5 Torr)
with slight heating on a rotary evaporator to yield a
dark oil. The oil was taken up in minimal CH2Cl2 and
charged onto a flash chromatography column (silica
gel, 5.5  20 cm2, CH2Cl2) to separate off the bulk of
the higher polymers from the desired compound. The
appropriate fractions were collected and reduced on a
rotary evaporator to yield a tan oil. This was trans-
ferred into a sublimation apparatus and subjected to
vacuum (0.1 Torr). A slow heating rate (0.75 °C
minÿ1) was maintained until visible sublimation set in
at 130 °C. After all sublimation ceased, 4 was collected
from the cooling finger as white to colorless crystals in
55% yield (7.2 g).
Method II. (Adapted from Ref. 33). Benzaldehyde
(12 mL, 0.118 mol) and pyrrole (52 mL, 0.745 mol)
were dissolved in toluene (750 mL). A catalytic
amount of p-toluenesulfonic acid monohydrate
(1 mL of a saturated solution in hot toluene) was
added and the mixture was refluxed under N2 for 1 h.
The mixture was then evaporated on a rotary
evaporator to produce a light brown oil, which was
subjected to the same treatment (crude chro-
matography, then sublimation) as described above to
produce 4 in 44% yield (13.8 g). Both methods
produce 4 with analytical and spectroscopic properties
identical to those described in the literature [32].
The orange to brown glassy residue in the sublima-
tion apparatus consists of, depending on the degree of
pre-purification of the raw reaction mixture during the
chromatography step, more or less pure diphenyltri-
pyrrane (10) in yields of 10%–20% (1.8–3.6 g). M.p.
75–80 °C. R f = 0.63 (CH2Cl2:CCl4 1:1). 1H NMR
(200 MHz, CD2Cl2):  5.35 (s, 2H), 5.78 (d, 2H, J
4 Hz), 5.89 (s, 2H), 6.14 (m, 2H), 6.66 (m, 2H), 7.15–
7.38 (m, 10H), 7.75 (br s, 1H), 7.88 (br s, 2H). 13C
NMR (50 MHz, CDCl3):  44.1, 107.2, 107.4, 108.4,
117.2, 127.0, 128.4, 128.6, 132.3, 132.5, 142.1. LR-
MS (EI, 150 °C): m/z 377 (45, M‡), 221 (18), 156 (14),
# 1998 John Wiley & Sons, Ltd.
145 (23), 80 (20), 67 (100). HR-MS (EI, 200 °C):
expected for C26H23N3: m/z 377.1892, found
377.1881. Anal. calc. for C26H23N3: C, 82.73; H,
6.14; N, 11.13%. Typical analysis found: C, 82.13; H,
6.03; N, 10.72%.
1-Formyl-5-phenyldipyrromethane (11)
Vilsmeier reagent was prepared by adding POCl3
(32 mmol, 3.0 mL) dropwise under N2 to DMF
(20.0 mL) at 0 °C. 5-Phenyldipyrromethane (4)
(1.00 g, 4.5 mmol) was dissolved in DMF (15.0 mL)
under N2 and the solution was cooled to 0 °C. To this
stirred solution was added dropwise Vilsmeier reagent
(3.5 mL, 1.08 equiv.) and the mixture was stirred at
0 °C for 1.5 h. Saturated aqueous sodium acetate
solution (50 mL) was carefully added and the mixture
was stirred for 4 h at room temperature. The solution
was extracted three times with ethyl acetate, the
extracts were washed with brine and H2O, dried over
Na2SO4 and evaporated in vacuo to give a brown oil.
This was purified by flash chromatography (silica:
eluent initially CH2Cl2, gradually increasing to
CH2Cl2/10% ethyl acetate) to give, after evaporation
of the solvent in vacuo, the desired product in 47%
yield (524 mg) as a light brown oil that solidified upon
standing. This was recystallized from MeOH/H2O to
give analytically pure, cream crystals. M.p. 142–
143.5 °C. R f = 0.55 (CH2Cl2/20% AcOEt). 1H NMR
(200 MHz, acetone-d6):  5.65 (s, 1H), 5.78–5.86 (m,
1H), 6.00–6.08 (m, 2H), 6.75 (dd, 1H, J 4.5, 2 Hz, 6.93
(dd, 1H, J 4, 1 Hz), 7.19–7.28 (m, 5H), 9.43 (s, 1H),
9.90 (br s, 1H), 10.98 (br s, 1H). 13C NMR (50 MHz,
acetone-d6):  44.7, 107.9, 108.3, 110.9, 118.3, 121.7,
127.5, 129.1, 129.2, 132.4, 133.6, 142.9, 144.1, 179.1.
LR-MS (EI): m/z 250 (100). Anal. calc. for
C16H14N2O: C, 76.78; H, 5.64%; N, 11.19. Found:
C, 76.59; H, 5.55; N, 11.08%.
1,9-Diformyl-5-phenyldipyrromethane (12)
This was prepared in 53% yield as a pale brown foam
using the procedure described above for 11, albeit with
2.4 equivalents of Vilsmeier reagent. Recrystallization
from MeOH/H2O gave analytically pure, pale brown
powder. M.p. 154–156 °C. R f = 0.17 (CH2Cl2/20%
AcOEt). 1H NMR (200 MHz, acetone-d6):  5.76 (s,
1H), 5.99–6.08 (m, 2H), 6.87–6.98 (m, 2H), 7.19–7.41
(m, 5H), 9.45 (s, 2H), 11.15 (br s, 2H). 13C NMR
(50 MHz, acetone-d6):  44.6, 111.1, 121.3, 127.9,
129.2, 129.3, 134.0, 141.5, 142.2, 179.1. LR-MS (EI):
m/z 278 (100). HR-MS (EI): expected for
J. Porphyrins Phthalocyanines 2, 455–465 (1998)
 SYNTHESES OF 5,15-DIPHENYLPORPHYRIN AND ITS PRECURSORS 463
C17H14N2O2: m/z 278.1056, found 278.1056. Anal.
calc. for C17H14N2O2: C, 73.37; H, 5.07; N, 10.07%.
Found: C, 73.33; H, 5.09; N, 10.02%.
1-Hydroxymethyl-5-phenyldipyrromethane (13)
1-Formyl-5-phenyldipyrromethane (11) (165 mg,
0.66 mmol) was dissolved in MeOH:CH2Cl2 (1:1,
16 mL). The solution was stirred at room temperature
and excess NaBH4 was added until the reaction was
complete by TLC. Water was added and the solution
was extracted three times with CH2Cl2. The extracts
were washed with H2O and brine and dried over
Na2SO4. The solvent was removed in vacuo to give the
alcohol as a pale brown oil. 1H NMR (200 MHz,
acetone-d6):  3.92 (br s, 1H), 4.48 (s, 2H), 5.44 (s,
1H), 5.69 (t, 1H, J 3 Hz), 5.76–5.82 (m, 1H), 5.91 (t,
1H, J 3 Hz), 6.03 (q, 1H, J 3 Hz), 6.69 (q, 1H, J 2 Hz),
7.22–7.30 (m, 5H), 9.46–9.72 (two overlapping br s,
2H). 13C NMR (50 MHz, acetone-d6):  45.0, 57.9,
106.8, 107.3, 107.4, 108.1, 117.8, 127.0, 128.9, 129.2,
132.6, 133.9, 134.2, 144.4. LR-MS (EI): m/z 252 (18,
M‡), 234 (100, M‡ÿH2O).
5,15-Diphenylporphyrin (1)
Route A. In an oven-dried, 1 L three-neck round-
bottom flask purged with N2, 2 (0.294 g, 2.0 mmol)
was dissolved in dry, degassed CH2Cl2 (500 mL). To
this solution were added benzaldehyde (215 mL,
2.12 mmol) and TFA (30–35 mL). The flask contents
were stirred in the dark for 15–17 h while N2 was
passed over the solution. Then tetrachloro-1,4-benzo-
quinone (TCQ) (1.5 g, 6.1 mmol) was added and the
solution was refluxed in air for 75 min. The reaction
mixture was then stirred with an excess of aqueous
Na2S2O4 and MeOH (100 mL) until all the TCQ was
reduced, as indicated by TLC (silica/cyclohexane:to-
luene 1:1). The organic phase was separated, the
solvent removed and the residue taken up in MeOH/
H2O (95:5) and the solution was filtered to isolate
insoluble 1: this was then washed until the solid was
free of dihydroxytetrachlorobenzene (R f = 0.4,
CH2Cl2). The filtrant was taken up in CH2Cl2
(100 mL) and filtered through a plug of alumina and
a plug of silica to provide, after evaporation of the
solvent and subsequent trituration with MeOH/H2O
(95:5), 1 in 42% yield (0.195 g) as a dark purple,
microcrystalline material. Yields were typically 25%–
40%, but on occasion reached 50%. Anal. calc. for
C32H22N4: C, 83.09; H, 4.79; N, 12.11%. Found; C,
83.06; H, 4.86; N, 11.87%.
# 1998 John Wiley & Sons, Ltd.
Route B. To a stirred solution of 5-phenyldipyrro-
methane (4) (500 mg, 2.25 mmol) and trimethyl ortho-
formate (18 mL, 0.165 mol) in CH2Cl2 (630 mL) was
added dropwise, over 15 min, a solution of trichloro-
acetic acid (8.83 g, 54 mmol) in CH2Cl2 (227 mL).
After the addition was complete, the solution was
stirred, in the dark and at room temperature, for 4 h,
before being quenched with pyridine (15.6 mL) and
stirred, again in the dark, for a further 17 h. The
solution was then purged with air for 10 min and
stirred, under ambient lighting conditions, for 4 h.
Solvent was evaporated in vacuo, first using water
aspiration, then vacuum overnight. The resulting black
solid was preadsorbed onto silica (5 g) and loaded onto
the top of a flash chromatography column (50 g). The
crude product was eluted from the column using a
mixture of CH2Cl2:hexane (7:3). Evaporation of the
eluent gave a purple solid which was triturated with
MeOH and filtered to give purple crystals (153 mg).
Recrystallization from toluene (15 mL) containing 1%
pyridine gave analytically pure 5,15-diphenylporphy-
rin in 21% yield (107 mg). UV-vis max (loge): 406
(5.59), 502 (4.24), 536 (3.72), 574 (3.73), 630
(3.20) nm. 1H NMR (300 MHz, CDCl3): ÿ3.12 (br
s, 1H), 7.80 (m, 6H), 8.27 (dd, 4H), 9.07 (d, 4H, J
4.5 Hz), 9.38 (d, 4H, J 4.5 Hz), 10.31 (s, 2H). 13C
NMR (CDCl3):  105.2, 119.1, 127.0, 127.7, 131.0,
131.6, 134.8, 141.4, 145.2, 147.2. HR-MS (EI): calc.
for C32H22N4: m/z 462.1844, found 462.1823. Anal.
calc. for C32H22N4: C, 83.09; H, 4.79; N, 12.11%.
Found: C, 82.96; H, 4.86; N, 11.96%.
Acknowledgement
This work was supported by the Natural Sciences and
Engineering Research Council of Canada (D.D.,
B.R.J.).
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