Functionalization of the "bay Region" of Perylene in Reaction with 1-Arylalk-2-yn-1-ones Catalyzed by Trifluoromethanesulfonic Acid: One-Step Approach to 1-Acyl-2-alkylbenzo[ ghi]perylenes

Article abstract of DOI:10.1021/acs.joc.8b02280

We describe a convenient method of the synthesis of 1-acyl-2-alkylbenzo[ghi]perylenes via functionalization of the "bay region" of perylene in the reaction with 1-arylalk-2-yn-1-ones catalyzed by trifluoromethanesulfonic acid. We showed that the formation

Full text of DOI:10.1021/acs.joc.8b02280

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Note
Functionalization of the “bay region” of perylene in reaction
with 1-arylalk-2-yn-1-ones catalyzed by trifluoromethanesulfonic
acid—one-step approach to 1-acyl-2-alkylbenzo[ghi]perylenes
Marta Glodek, Anna Makal, and Damian Plazuk
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.8b02280 • Publication Date (Web): 24 Oct 2018
Downloaded from http://pubs.acs.org on October 24, 2018
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Functionalization of the “bay region” of perylene in reaction with 1-arylalk-2-
yn-1-ones catalyzed by trifluoromethanesulfonic acid—one-step approach to
1-acyl-2-alkylbenzo[ghi]perylenes
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Marta Głodeka, Anna Makalb, Damian Plażuka*
aDepartment of Organic Chemistry, Faculty of Chemistry, University of Łódź, Tamka 12, 91-403
Łódź, Poland. Fax: (+48)42 6786583; Tel: (+48)42 6355616;
bUniversity of Warsaw, Biological and Chemical, Research Centre, ul. Żwirki i Wigury 101, 02-
096 Warsaw, Poland
Corresponding Author E-mail Address
damian.plazuk@chemia.uni.lodz.pl
Dedication
This work is dedicated to Professor Janusz Zakrzewski of University of Łódź on the occasion of
his 70th birthday
Table of Contents/Abstract Graphic
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ABSTRACT
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We describe a convenient method of the synthesis of 1-acyl-2-alkylbenzo[ghi]perylenes via
functionalization of the “bay region” of perylene in the reaction with 1-arylalk-2-yn-1-ones
catalyzed by trifluoromethanesulfonic acid. We showed that the formation of 1-acyl-2-
alkylbenzo[ghi]perylenes from perylene and 1-arylalk-2-yn-1-ones might occur via
spontaneously aromatization of 1-acyl-2-alkyl-2a,12a-dihydrogenbenzo[ghi]perylenes by
oxidation with dioxygen or by the hydrogen transfer to 1-arylalk-2-yn-1-ones. These compounds
are fluorescent in solution with a high Stokes shift and with a FF value of up to 0.17 (and 0.36 in
solid).
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Functionalized polycyclic aromatic hydrocarbons (PAHs) are widely used in organic
semiconductors and organic photovoltaics1. These compounds are often synthesized in the Scholl
reaction2-7 or by inter- and intramolecular Diels–Alder reactions;8 however, some other methods
including ring-closing metathesis and photocyclization are also applied.2,9 Unfortunately, many
of these reactions require multistep synthesis of starting reagents,10 or extreme reaction
conditions such as high temperature. Moreover, the Scholl reaction is difficult to control which
often results in a low yield of the desired products.7,10,11 Despite these disadvantages, the Scholl
reaction is still commonly used for the synthesis of PAHs.12-14 Recently, comprehensive reviews
in this field have been published.9,15-17
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Perylene 1, a simple example of a PAH containing “bay region”, can be readily
functionalized in an electrophilic substitution reaction leading to 3-substituted perylenes as the
primary product. In some cases, for instance, formylation of 1,18 the formation of 1-
formylperylene has also been observed with significantly lower yield than that of predominant 3-
formylperylen.
Because the “bay region” of hydrocarbons are notoriously resistant to Diels–Alder
reaction, they require harsh conditions such as very high temperature, prolonged reaction time,
and highly oxidative conditions, and the availability of dienophiles that can withstand such
reaction conditions limits its use. The functionalization of “bay regions” of hydrocarbons such as
1 and its homologs such as bisanthen 2 can be performed in the Diels–Alder cycloaddition with
dienophiles such as maleic anhydride or diethyl acetylenedicarboxylate, leading to the formation
of compounds 3-4 (Scheme 1a). For instance, 1 reacts with an excess of melted maleic anhydride
and chloranil at 202°C to produce 3 with a yield of up to 100%19 or with an excess of diethyl
acetylenedicarboxylate at 150°C to produce 1,2-diethoxycarbonylbenzo[ghi]perylene with an
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yield of 25% after 72 h. 7,14-bismesitylbisanthen 2 reacts smoothly with diethyl
acetylenedicarboxylate in toluene solution at 120°C to form a mono- (compound 4a) and di-
addition (compound 4b) products with a yield of 44 and 12%, respectively (Scheme 1b).20
Alkenes bearing EWG groups are commonly used as dienophiles in Diels–Alder reaction,21,22
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however, acetylenic ketones have been reported only as dienophiles in reaction with simple
23,24
dienes catalyzed by Lewis acids and chiral Lewis acids
cyclohexadiene derivatives.
leading to the formation of 1,4-
Scheme 1. Diels-Alder Reaction of (a) 1 with Maleic Anhydride; and (b) 2 with Diethyl
Acetylenedicarboxylate
a)
b)
R'
R'
R'
peri
3
2
O
O
O
O
R
R
R
R
R
R
1
bay
R
R
O
chloranil
no solvent
202 o
R=EtOCO
C
O
R'
R'
R'
2
4a
4b
R'=mesityl
1
3
Continuing our study of straightforward functionalization of perylene,25 we became interested in
the reaction of 1-arylalk-2-yn-1-ones with 1 catalyzed by a strong protic acid,
trifluoromethanesulfonic acid, which should allow to functionalize the “bay region” of 1 thereby
producing benzo[ghi]perylenes (Scheme 2). Herein, we describe the synthesis, mechanistic
investigation, and fluorescence properties of
a
new PAH derivative, 1-acyl-2-
alkylbenzo[ghi]perylenes 6.
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Scheme 2. Reaction of 1 with 1-arylalk-2-yn-1-ones Studied Herein
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To realize our goal, first, we performed a preliminary experiment starting from 1 and 1-
phenylbut-2-yn-1-one 7a. Our study showed that the reaction of an equimolar amount of 1 with
7a in DCM catalyzed by an equimolar amount of TfOH leads to the formation of 8a with a yield
of 39% (Scheme 3). 1D and 2D NMR spectra and MS analysis have confirmed the structure of
the product. Unfortunately, further attempts to optimize the reaction by changing the reaction
conditions or ratios of the modifying reagents failed.
Scheme 3. Reaction of 1 with 7a Catalyzed by Trifluoromethanesulfonic Acid
Next, we examined the scope of reaction of 1 with a series of 1-arylbut-2-yn-1-ones 7b-g and 9a-
c. The required 7b-g were synthesized with an yield of 45–78% in a reaction of acid chlorides
10b-g with 1-trimethylsilylpropyne catalyzed by aluminum chloride (Scheme 4), whereas
compounds 9a-c were synthesized in Friedel–Crafts acylation of corresponding arenes with but-
2-ynoic acid 11a, TFAA, and TfOH (Schemes 5 and 6) by applying known procedure.26
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Scheme 4. Synthesis of 1-arylbut-2-yn-1-ones 7a-g
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O
O
Cl
TMS
AlCl3
8
9
R
R
10a-g
7a-g
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R= (a) H, (b) 4-CF3, (c) 2-Cl, (d) 4-Me, (e) 4-OMe, (f) 3,4,5-(OMe) 3, (g) 2,4,6-F3
Scheme 5. Synthesis of 1-(pyren-1-yl)but-2-yn-1-one 9b and 1-(coronen-1-yl)but-2-yn-1-one 9c
To our surprise, acylation of 1 with 11a not only produced the expected product, 1-(perylen-3-
yl)but-2-yn-1-one 9a (56% yield) but also gave 8h (10% yield) together with 1-(perylen-3-yl)but-
2-en-1-one 12a (11% yield) (Scheme 6). These results encored us to study the reaction of 1 with
alk-2-ynoic acid, and the results have been discussed in the following sections.
Scheme 6. Reaction of 1 with 11a in the Presence of TfOH
O
O
O
(CF3CO)2O, CF3SO3
H
O
DCM
+
+
+
2h, rt
OH
1
11a
9a
8h
12a
We found that 1 reacts with 7b-g or 9a-c and TfOH under optimized conditions to yield
compounds 8b-g and 8h-j, respectively, in decent yields (Scheme 7). The structure of the
1
products have been confirmed by using H, 13C, and 2D NMR spectra. The structures of two
compounds, 8d and 8h, have also been confirmed by using X-ray crystallography (Figure S6-S7).
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In general, in all cases, 1-acyl-1-alkylbenzo[ghi]perylenes 8a-j have been isolated in similar
yields, ca. 42%; however, in two instances, 8b and 8f, the yield of the products was found to be
significantly higher, 77 and 71% yield, respectively.
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We also found that 1 does not react with 7a in refluxing xylene (24 h, with and without DDQ) or
with dimethyl acetylenedicarboxylate in the presence of TfOH. Moreover, in the reaction of 8a
with an additional amount of 7a, we did not observe the formation of any products, and only
unreacted substrates were recovered. As could be expected, phenanthrene, which is significantly
less active as dienes in Diels–Alder reaction,20,27 does not react with 7a and TfOH even after
prolonged reaction times, and only starting hydrocarbon was recovered.
Scheme 7. Reaction of 1 with 7b-g and 9a-c Catalyzed by TfOH
Unexpected formation of 8h in the reaction of 1 with 11a and TFAA catalyzed by TfOH (Scheme
6) inspired us to study the reaction of 1 with various alk-2-ynoic acids 11a-f in detail. We
expected the formation of 1-(perylen-3-yl)alk-2-yn-1-ones (compounds 9a and 14b-f) as the
primary products in addition to the formation of 1-acyl-2-alkylbenzo[ghi]perylenes (compounds
8h and 15b-f), 1-(perylen-1-yl)alk-2-yn-1-ones (compounds 13a-f), and 1-(perylen-3-yl)alk-2-en-
1-ones (compounds 12a-f) as the minor products. Indeed, most of the investigated alk-2-ynoic
acids produced a complex mixture of the expected compounds (Scheme 8). The reaction of 1
with phenylpropynoic acid 11d gave 14d with a yield of 42% as the sole isolable product. In this
reaction, we did not observe the formation of benzo[ghi]perylenes or the formation of other
products. All other alk-2-ynoic acids bearing alkyl substituent at C-3 position such as methyl
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(but-2-ynoic acid, 11a), n-propyl (hex-2-ynoic acid, 11b), n-pentyl (oct-2-ynoic acid, 11c),
benzyl (4-phenylbut-2-ynoic acid, 11e), and phenethyl group (5-phenylpent-2-ynoic acid, 11f)
gave a mixture of 1-(perylen-3-yl)alk-2-yn-1-ones (compounds 9a and 14b-c,e-f, respectively) as
the primary products and 1-(perylen-1-yl)alk-2-yn-1-ones (compounds 13a-c,e-f, respectively) as
the minor products, in addition to small amounts (10–14% yield of the isolated products) of 1-
(perylen-3-oyl)-2-alkylbenzo[ghi]perylenes (compounds 8h, 15b-c,e-f, respectively) and 1-
(perylen-3-yl)alk-2-en-1-ones (compounds 12a-c,e-f, respectively). The structure of the products
was confirmed by 1D and 2D NMR spectra and MS analysis. Moreover, structure of 9a and 14d
were also confirmed by X-ray crystallography (Figures S8-S9).
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Scheme 8. Reaction of 1 with 11a-f , TFAA and TfOH
*—inseparable mixture of 1- and 3-isomers; ND—not determined
Scheme 9. The Proposed Mechanism of the Reaction of 1 with 7 Catalyzed by TfOH
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The formation of benzo[ghi]perylenes 8 and alkenes 12 in the reaction of 1 and 7 catalyzed by
TfOH or in the reaction of 1 with but-2-ynoic acid 11a and TFAA and TfOH (in this case 7 is
formed in a reaction of 1 with 11a) can occur in stepwise mechanism (Scheme 9) or according to
Diels–Alder reaction. We hypothesized that two pathways may occurs. First, the protonation of 7
leads to the formation of allenium cation A (Pathway A) which reacts as an electrophile with 1 to
yield 2a,12a-dihydrobenzo[ghi]perylene D. In the pathway B, 1 is protonated to cation E which
reacts as an electrophile with 7 to yield D. Finally, D is aromatized in the reaction with dioxygen
(from the air) or in a hydrogen transfer to 7, which resulted in the formation of 8 and 12. The
NMR studies confirmed that 1 and 7 are protonated by TfOH and the resulted species E and A,
respectively, afforded the same products in reaction with 7 or 1, respectively. The hydrogen
transfer from D to 1-arylalk-2-yn-1-ones is in contrast to the results reported in previous studies
of Diels-Alder reaction of 1 or 2 with diethyl acetylenedicarboxylate where it was not
observed.20,28 Therefore, to prove the proposed mechanism, we performed additional experiments
using perylene-d12 16 instead of 1 and/or using TfOD instead of TfOH. We observed that reaction
of 1 with 9b catalyzed by TfOH or TfOD afforded 8i and 17 lacking deuterium atoms. The
reaction of 16 with 9b catalyzed by TfOH in DCM led to the synthesis of two isolable products:
deuterated-benzo[ghi]perylene 18 (42%) and deuterated-alkene 19 (37%) (Schemes S1-S2 and
Figure S1-S3). When TfOH was replaced by TfOD, the same products were formed from 16 and
9b. Moreover, we did not observe the exchange of proton in the solution of 1-(pyren-1-yl)but-2-
en-1-one in DCM in the presence of 1 eq of TfOD. The reaction of 16 with 11a catalyzed by
TfOH led to a separable mixture of the deuterated products: 20 (38%), 21 (17%), and 22 (18%)
and unreacted 16 (38%), which were isolated by column chromatography and identified by NMR
and MS spectroscopy (Scheme S3 and Figures S4-S5). These results confirmed that the formation
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of benzo[ghi]perylenes in the reaction of 1 with 1-arylbut-2-yn-1-ones catalyzed by TfOH might
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occur via aromatization of intermediate D by oxidation with dioxygen or by hydrogen transfer to
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1-arylbut-2-yn-1-ones which are reduced to 1-arylbut-2-en-1-ones.
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A comparison of electronic absorption spectra in DCM solution of 8a-i and 15b,c,e,f
showed that benzo[ghi]perylenes bearing benzoyl moiety (compounds 8a-g) possess very similar
spectra with the absorption maximum in the range of 390-391 nm, whereas compounds bearing
perylen-3-oyl moiety (compounds 8h and 15b,c,e,f) showed an additional broad absorption band
with the absorption maximum in the range of 467–470 nm. However, pyren-1-oyl derivative 8i
exhibits the absorption maximum of 391 nm. All of the investigated compounds were fluorescent
in dilute DCM solution and in solid state at room temperature. Benzo[ghi]perylenes bearing
benzoyl moiety 8a-g showed broad fluorescence band in the range of 400–700 nm with low
fluorescence quantum yield (up to FF=0.039 for 8d). The fluorescence lifetimes were in the range
of nanoseconds with one or two components. All of these compounds possess high Stokes shift in
the range of 3002–7227 cm−1. In comparison, benzo[ghi]perylenes bearing perylen-3-oyl,
(compounds 8h and 15b,c,e,f) showed broad fluorescence band in the range of 500–700 nm, with
significantly higher fluorescence quantum yields (FF values in the range of 0.058–0.17) and
significantly lower Stokes shift (in the range of 2229–2474 cm−1). All of the synthesized
compounds were fluorescent in solid state (Table S1, Figures S10–S23). The quantum yields of
investigated compounds in the solid state were found to be significantly higher (up to FF=0.36
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for powdered and FF=0.22 for crystals of 8d) than that in the DCM solution, with a maximum
emission wavelength in the range of 543–674 nm. In addition, compounds bearing benzoyl
moiety (compounds 8a, c-g) possess two emission bands at ca. 450–479 nm and 586–611 nm,
whereas compounds bearing perylen-3-oyl (compounds 8h and 15b,c,e,f) or pyren-1-oyl moiety
8i exhibit one, broad fluorescence band.
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We developed a convenient method of the synthesis of 1-acyl-2-alkylbenzo[ghi]perylenes
via functionalization of the “bay region” of perylene. We have found that perylene reacts
smoothly with readily available 1-arylalk-2-yn-1-ones in the presence of TfOH. We showed that
the formation of 1-acyl-2-alkylbenzo[ghi]perylenes from perylene and 1-arylalk-2-yn-1-ones
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might
involve
the
hydrogen
transfer
from
preliminarily
formed
2a,12a-
dihydrobenzo[ghi]perylenes to 1-arylalk-2-yn-1-ones. In addition, we showed that acylation of
perylene with alk-2-ynoyl trifluoroacetates (generated in situ from alk-2-ynoic acids and
trifluoroacetic anhydride) catalyzed by TfOH led to a mixture of 1-(perylen-3-yl)alk-2-yn-1-ones
and 1-(perylen-1-yl)alk-2-yn-1-ones, 1-acyl-2-alkylbenzo[ghi]perylenes, and 1-(perylen-1-yl)alk-
2-en-1-ones.
The new PAH derivatives are fluorescent in solution and in solid state with high Stokes
shift and fluorescence quantum yield (up to 0.17 and 0.36 in DCM solution and solid state,
respectively). In our opinion, the developed method of functionalization of the “bay region” of 1
might be useful in the functionalization of other PAHs containing “bay regions”.
EXPERIMENTAL SECTION
General Experimental Methods. All reagents were purchased from Sigma-Aldrich of
Fluorochem or TCI Chemicals and used as received. Solvents for column chromatography were
of HPLC grade and used as received. DCM was dried by distillation from calcium hydride under
argon atmosphere and stored over molecular sieves 4 A under argon atmosphere. Column
chromatography was performed on silica gel 60 (0.040–0.063 mm). H, C{1H} and 2D NMR
1
13
(1H-1H COSY, H-13C HSQC, H-13C HMBC, DEPT 135) spectra were recorded in CDCl3 or
1
1
CD2Cl2 on a Bruker Avance III 600 MHz (600.26 MHz for H and 150.90 MHz for 13C).
1
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Chemical shifts were referenced to the residual solvent peak d=7.26 ppm for CDCl3 and 5.32 ppm
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1
for CD2Cl2 for H and 77.0 ppm for CDCl3 and 53.84 ppm for CD2Cl2 for 13C. Spectra were
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recorded at 299 K, chemical shifts are in ppm, and coupling constants in Hz. IR spectra were
recorded on FT-IR Nexus spectrometer in KBr pellets or in a neat film. HRMS spectra were
recorder at Institute of Organic Chemistry Polish Academy of Science (Warsaw, Poland) on
magnetic sector mass spectrometer AutoSpec Premier (Waters, USA), equipped with an electron
impact (EI) ion source and the EBE double focusing geometry mass analyzer. The instrument
was controlled and recorded data were processed using MassLynx 4.1 software package (Waters,
USA). Thin layer chromatography (TLC) was performed on aluminum sheets precoated with
Merck 5735 Kieselgel 60F254. Melting points were determined for all new compounds with at
least 95% purity in capillaries with a DigiMelt MPA161 apparatus (SRS) and were uncorrected.
UV-Vis spectra were recorded on Lambda 45 UV-VIS spectrometer (PerkinElmer) at 294 K,
whereas emission spectra were recorded on Fluoromax-4 (Horiba) spectrofluorimeter equipped
with long pass filter. The fluorescence lifetimes were measured on the same spectrofluorimeter
equipped with the TCSPC accessory by using the time-domain technique. The quantum yields
were measured on the same spectrofluorimeter equipped with integrating sphere Quanta.
General procedure A - synthesis of 1-arylbut-2-yn-1-ones 7a-g
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1-phenylbut-2-yn-1-one (7a). Briefly, anhydrous aluminum chloride (300 mg, 2.25 mmol) was
added in one portion to a stirred solution of benzoyl chloride (281 mg, 232 µL, 2 mmol) and 1-
(trimethylsilyl)propyne (224.5 mg, 294 µL, 2.0 mmol) in 6 mL of anhydrous DCM. The resulting
mixture was stirred at room temperature for 2 h, and the reaction was quenched by adding 10 mL
of 1 M hydrochloric acid. The product was extracted with DCM, and the organic solution was
washed with water and brine and then dried over sodium sulfate; finally, the solvent was
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evaporated. Purified compound 7a was obtained as a yellow oil with a yield of 66% (191 mg) via
column chromatography on silica gel using DCM:cyclohexane 1:1 (v/v) as the eluent. Its NMR
spectra (in CD2Cl2) were identical with those of an authentic sample.29
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1-(4-trifluoromethylphenyl)but-2-yn-1-one (7b). This compound was synthesized according to
the General Procedure A starting from 421 mg (300 µL, 2 mmol) of 10b. Pure 7b was obtained as
a white solid with a yield of 72% (308 mg) via column chromatography on silica using
DCM:cyclohexane 3:2 (v/v) as the eluent. Its NMR spectra were identical with those of an
authentic sample.30
1-(2-chlorophenyl)but-2-yn-1-one (7c). This compound was synthesized as 2a starting from
367.5 mg (266 µL, 2 mmol) of 10c. Pure 7c was obtained as an orange oil with a yield of 60%
1
(225 mg) via column chromatography on silica using DCM:n-hexane 3:7 (v/v) as the eluent. H
NMR (CDCl3, 600.29 MHz): d = 8.01-7.99 (m, 1H, HArH), 7.45-7.41 (m, 2H, HArH), 7.35 (ddd,
J=7.9, 5.7, 2.7 Hz, 1H, HArH), 2.19 (s, 3H, CH3); 13C{1H}- NMR (CDCl3, 150.90 MHz): d =
176.9 (C=O), 135.8 (CAr), 133.3 (CAr), 133.1 (CHArH), 132.6 (CHArH), 131.4 (CHArH), 126.6
(CHArH), 93.4 (CºC), 80.3 (CºC), 4.4 (CH3); IR (neat film, cm-1) 2234 (CºC), 2212 (CºC), 1656
(C=O); HRMS (EI-EBE) m/z: [M+] Calcd for C10H7ClO 178.0185; Found 178.0179.
1-(4-methylphenyl)but-2-yn-1-one (7d). This compound was synthesized according to General
Procedure A starting from 315 mg (270 µL, 2 mmol) of 10d. Pure 7d was obtained as a yellow
oil with a yield of 60% (255 mg) via column chromatography on silica using DCM:n-hexane 7:3
(v/v) as the eluent. 1H NMR (CDCl3, 600.29 MHz): d = 8.02 (d, J=8.2 Hz, 2H, HArH), 7.26 (d,
J=7.9 Hz, 2H, HArH), 2.42 (s, 3H, CH3), 2.14 (s, 3H, CH3); 13C{1H} NMR (CDCl3, 150.90 MHz):
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(CºC), 21.7 (CH3), 4.2 (CH3); IR (neat film, cm-1) 2243 (CºC), 2202 (CºC), 1636 (C=O);
HRMS (EI-EBE) m/z: [M+] Calcd for C11H10O 158.0732; Found 158.0727.
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1-(4-methoxyphenyl)but-2-yn-1-one (7e) This compound was synthesized according to General
Procedure A starting from 340 mg (270 µL, 2.0 mmol) of 10e. Pure compound 7e was obtained
as a white foam with a yield of 78% (275 mg) via column chromatography on silica using
DCM:n-hexane 1:1 (v/v) as the eluent. Its NMR spectra were identical with those of an authentic
sample.30 1H NMR (CDCl3, 600.29 MHz): d = 8.10 (d, J=8.9 Hz, 2H, HArH ), 6.93 (d, J=8.9 Hz,
2H, HArH), 3.87 (s, 3H, OCH3), 2.13 (s, 3H, CH3).
1-(3,4,5-trimethoxyphenyl)but-2-yn-1-one (7f). This compound was synthesized according to
General Procedure A starting from 461.2 mg (2.0 mmol) of 10f. Pure compound 7f was obtained
as a white foam with a yield of 45% (209 mg) via column chromatography on silica using
DCM:n-hexane 1:1 (v/v) as the eluent. Its NMR spectra were identical with those of an authentic
sample.31 1H NMR (CDCl3, 600.29 MHz): d = 7.40 (s, 2H, HArH), 3.921 (s, 3H, OCH3), 3.916 (s,
6H, OCH3), 2.15 (s, 3H, CH3).
1-(2,4,6-trifluorophenyl)but-2-yn-1-one (7g). This compound was synthesized according to the
General Procedure A starting from 389 mg (262 µL, 2.0 mmol) of 10g. Pure compound 2g was
obtained as a yellow oil with a yield of 56% (220 mg) via column chromatography on silica using
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DCM:n-hexane 1:1 (v/v) as the eluent. H NMR (CDCl3, 600.29 MHz): d = 6.73-6.69 (m, 2H,
HArH), 2.10 (s, 3H, CH3); 13C{1H} NMR (CDCl3, 150.90 MHz): d = 170.3 (C=O), 164.5 (dt, 1JC-
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F=257, JC-F=15 Hz, CAr), 161.75 (dd, JC-F=257, JC-F=15 Hz, CAr) overlapped with 161.69 (dd,
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(neat film, cm-1) 2250 (CºC), 2209 (CºC), 1639 (C=O); HRMS (EI-EBE) m/z: [M+] Calcd for
C10H5F3O 198.0292; Found 198.0295.
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1-(pyren-1-yl)but-2-yn-1-one (9b) This compound was synthesized as previously described.26
1-(coronen-1-yl)but-2-yn-1-one (9c) This compound was synthesized by adopting the known
procedure26 starting from 300 mg (1.0 mmol) of coronene, 102 mg (1.0 mmol) of but-2-ynoic
acid, 210 mg (2.0 mmol) of TFAA, and 150 mg (1.0 mmol) of TfOH. Compound 9c was
obtained as a yellow solid with a yield of 28% (102 mg) via column chromatography on silica
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using DCM–cyclohexane as the eluent. Mp: 216-217; H NMR (CDCl3, 600.29 MHz): d = 9.72
(d, J=8.6 Hz, 1H), 9.22 (s, 1H), 8.46-8.41 (m, 5H), 8.39 (d, J=8.2 Hz, 1H), 8.28 (d, J=8.2 Hz,
1H), 8.24 (d, J=8.2 Hz, 1H), 8.21 (d, J=8.2 Hz, 1H), 2.43 (s, 3H); 13C{1H} NMR (CDCl3, 150.90
MHz): d = 180.5 (C=O), 134.4 (CHArH), 129.5 (CAr), 129.4 (CAr), 128.3 (CAr), 127.8 (CAr), 127.7
(CAr), 127.2 (CHArH), 127.0 (CHArH), 126.2 (CHArH), 126.0 (CHArH), 125.8 (CHArH), 125.7 (CAr),
125.6 (CHArH), 125.5 (CHArH), 125.4 (CAr), 125.3 (CAr), 123.6 (CHArH), 121.8 (CAr), 121.1 (CAr),
120.9 (CAr), 120.8 (CAr), 120.6 (CAr), 91.2 (CºC), 81.2 (CºC), 4.7 (CH3); IR (KBr, cm-1) 2228
(CºC), 2207 (CºC), 1635 (C=O), HRMS (EI-EBE) m/z: [M+] Calcd for C28H14O 366.1045;
Found 366.1045.
General procedure B—synthesis of 1-methyl-2-(aroyl)benzo[ghi]perylenes (compounds 8a-j)
1-methyl-2-benzoylbenzo[ghi]perylene (8a). Briefly, 89 µl (1 mmol) of TfOH was added
dropwise to a solution of 144 mg (1 mmol) of 7a and 252.3 mg (1 mmol) of 1 in 35 mL of
anhydrous DCM. A resulting solution was stirred at RT for 4 h and the reaction was quenched by
addition of 100 mL of sodium bicarbonate. The product was extracted with DCM and organic
solution was washed with brine, dried over sodium sulfate, and evaporated. Compound 8a was
obtained as a yellow solid with a yield of 39% (155 mg) via column chromatography on silica
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using the mixture of DCM:cyclohexane 3:2 (v/v) as the eluent. Mp: >260 °C; H NMR (CDCl3,
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600.29 MHz): d = d 9.03 (t, J=8.2 Hz, 2H, HArH), 8.36 (d, J=9.0 Hz, 1H, HArH), 8.22 (d, J=7.6 Hz,
1H, HArH), 8.19 (d, J=9.1 Hz, 1H, HArH), 8.15 (d, J=7.5 Hz, 1H, HArH), 8.05 (t, J=7.7 Hz, 1H,
HArH), 8.01 (t, J= 7.7 Hz, 1H, HArH), 7.98 (d, J= 9.0 Hz, 1H, HArH), 7.90 (br s, 1H, Ph), 7.88 (br s,
1H, Ph), 7.80 (d, J = 8.9 Hz, 1H, HArH), 7.60 (dt, J=7.4, 1.3 Hz, 1H, Ph), 7.45 (d, J=7.4 Hz, 1H,
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Ph), 7.43 (d, J=7.5 Hz, 1H, Ph), 2.89 (s, 3 H, CH3); C{1H} NMR (CDCl3, 150.90 MHz): d =
200.9 (C=O); 138.1 (CAr), 135.1 (CAr), 133.9 (CHPh), 132.1 (CAr), 131.7 (CAr), 130.6 (CAr), 130.2
(CAr), 130.0 (CHPh), 128.9 (CHPh), 128.6 (CAr), 128.1 (2xC, CHArH and CAr), 128.0 (CHArH),
126.8 (2xCHArH), 126.6 (CHArH), 126.4 (CHArH), 126.1 (CAr), 125.7 (CAr), 125.6 (CAr), 124.4
(CHArH and CAr), 123.3 (CHArH), 122.9 (CAr), 121.0 (2xCHArH), 17.2 (CH3); IR (KBr, cm-1) 1664
(C=O), HRMS (EI-EBE) m/z: [M+] Calcd for C30H18O 394.1358; Found 394.1352.
1-methyl-2-(4-trifluoromethylbenzoyl)benzo[ghi]perylene (8b). This compound was
synthesized according to the General Procedure B starting from 53.4 mg (0.25 mmol) of 7b, 63.1
mg (0.25 mmol) of 1, 22 µL (0.25 mmol) of TfOH and 25 mL of DCM. Chromatography on
silica using DCM:cyclohexane 3:2 (v/v) as the eluent produced 20 mg of unreacted 1 followed by
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89 mg (77% yield) of pure 8b as a yellow solid. Mp: 218-220 °C; H NMR (CDCl3, 600.29
MHz): d = 9.04 (t, J=7.3 Hz, 2H, HArH), 8.36 (d, J=9.0 Hz, 1H, HArH), 8.24 (d, J=7.6 Hz, 1H,
HArH), 8.20 (d, J=9.1 Hz, 1H, HArH), 8.16 (d, J=7.6 Hz, 1H, HArH), 8.07 (t, J=7.7 Hz, 1H, HArH),
8.03 (t, J=7.7 Hz, 1H, HArH), 7.99-7.98 (m, 3H, HPh and HArH), 7.72 (d, J=9.0 Hz, 1H, HArH), 7.71
(br s, 1H, HPh), 7.70 (br s, 1H, HPh),2.87 (s, 3H, CH3); 13C{1H} NMR (CDCl3, 150.90 MHz): d =
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199.9 (C=O), 140.6 (CAr), 135.6 (d, JC-F=32.6 Hz, CAr), 134.1 (CAr), 132.2 (CAr), 131.7 (CAr),
130.7 (CAr), 130.3 (CAr), 130.2 (CHArH), 128.7 (CAr), 128.4 (CHArH), 128.3 (CHArH), 128.0 (CAr),
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125.6 (2xCAr), 124.7 (CAr), 124.0 (CHArH), 123.2 (CHArH), 123.0 (CAr), 121.2 (2xCHArH), 17.3
(CH3); IR (KBr, cm-1) 1672 (C=O); HRMS (EI-EBE) m/z: [M+] Calcd for C31H17F3O 462.1232;
Found 462.1242.
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1-methyl-2-(2-chlorobenzoyl)benzo[ghi]perylene (8c). This compound was synthesized
according to the General Procedure B starting from 44.2 mg (0.25 mmol) of 7c, 63 mg (0.25
mmol) of 1, 22 µL (0.25 mmol) of TfOH and 25 mL of DCM. Chromatography on silica using
DCM:n-hexane 1:1 (v/v) as the eluent produced 20 mg of unreacted 1 followed by 45 mg (42%
yield) of pure 8c as a yellow solid. Mp: 214-215 °C; 1H NMR (CDCl3, 600.29 MHz): d = 8.96 (d,
J=7.8 Hz, 2H, HArH), 8.29 (d, J=9.0 Hz, 1H, HArH), 8.15 (d, J=7.6 Hz, 1H, HArH), 8.12 (d, J=7.2
Hz, 1H, HArH), 8.11 (d, J=8.9 Hz, 1H, HArH), 8.01-7.96 (m, 3H, HArH), 7.89 (d, J=8.9 Hz, 1H,
HArH), 7.57 (d, J=8.0 Hz, 1H, HPh), 7.50 (d, J=7.1 Hz, 1H, HPh), 7.43 (td, J=8.1, 1.1 Hz, 1H, HPh),
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7.16 (t, J=7.6 Hz, 1H, HPh), 2.90 (s, 3H, CH3); C{1H} NMR (CDCl3, 150.90 MHz): d = 199.3
(C=O), 137.2 (CAr), 135.7 (CAr), 133.9 (CAr), 133.3 (CHPh), 133.1 (CHPh), 132.1 (CAr), 132.0
(CHPh), 131.6 (CAr), 130.6 (CAr), 130.1 (CAr), 128.9 (CAr), 128.3 (CHArH), 128.0 (CHArH and CAr),
126.9 (CHArH), 126.8 (CHPh), 126.7 (CHArH), 126.6 (CHArH), 126.3 (CHArH), 126.1 (CAr), 125.5
(CAr), 124.6 (CAr), 124.0 (CHArH), 123.2 (CHArH), 122.9 (CAr), 121.0 (2xCHArH), 17.0 (CH3); IR
(KBr, cm-1) 1680 (C=O); HRMS (EI-EBE) m/z: [M+] Calcd for C30H17ClO 428.0968; Found
428.0971.
1-methyl-2-(4-methylbenzoyl)benzo[ghi]perylene (8d). This compound was synthesized
according to the General Procedure B starting from 42.2 mg (0.267 mmol) of 7d, 67.3 mg (0.267
mmol) of 1, 23.5 µL (0.267 mmol) of TfOH and 25 mL of DCM. Chromatography on silica using
DCM:n-hexane 3:2 (v/v) as the eluent produced 28 mg of unreacted 1 followed by 65 mg (60%
yield) of pure 8d. Crystallization from DCM:n-hexane yielded 8d as green crystals. Mp: 237-238
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°C; H NMR (CDCl3, 600.29 MHz): d = 9.04 (t, J=8.9 Hz, 2H, HArH), 8.37 (d, J=9.1 Hz, 1H,
HArH), 8.23 (d, J=7.6 Hz, 1H, HArH), 8.19 (d, J=9.0 Hz, 1H, HArH), 8.15 (d, J=7.6 Hz, 1H, HArH),
8.05 (t, J=7.7 Hz, 1H, HArH), 8.01 (t, J=7.7 Hz, 1H, HArH), 7.97 (d, J=8.9 Hz, 1H, HArH), 7.80 (d,
J=8.9 Hz, 1H, HArH), 7.78 (d, J=7.7 Hz, 2H, HPh), 7.23 (d, J=8.2 Hz, 2H, HPh), 2.88 (s, 3H, CH3),
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2.41 (s, 3H, CH3); C{1H} NMR (CDCl3, 150.90 MHz): d = 200.5 (C=O), 145.0 (CAr), 135.8
(CAr), 135.4 (CAr), 132.1 (CAr), 131.7 (CAr), 130.7 (CAr), 130.3 (CAr), 130.2 (CHArH), 129.6
(CHArH), 128.5 (CAr), 128.1 (CAr), 128.0 (2xCHArH), 126.8 (CHArH), 126.7 (CHArH), 126.6
(CHArH), 126.3 (CHArH), 126.1 (CArH), 125.7 (2xCAr), 124.5 (CHArH), 124.4 (CAr), 123.4 (CHArH),
122.9 (CAr), 121.0 (2xCHArH), 21.8 (CH3), 17.2 (CH3); IR (KBr, cm-1) 1662 (C=O); HRMS (EI-
EBE) m/z: [M+] Calcd for C31H20O 408.1514; Found 408.1505.
1-methyl-2-(4-methoxybenzoyl)benzo[ghi]perylene (8e). This compound was synthesized
according to the General Procedure B starting from 43.6 mg (0.25 mmol) of 7e, 63.1 mg (0.25
mmol) of 1, 22 µL (0.25 mmol) of TfOH, and 25 mL of DCM. Chromatography on silica using
DCM:cyclohexane 3:2 (v/v) as the eluent produced 47 mg of unreacted 1 followed by 45 mg
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(42% yield) of pure 8e as a yellow solid. Mp: 241-242 °C; H NMR (CDCl3, 600.29 MHz): d =
9.02 (t, J=8.4 Hz, 2H, HArH), 8.36 (d, J=9.1 Hz, 1H, HArH), 8.21 (d, J=7.7 Hz, 1H, HArH), 8.18 (d,
J=9.1 Hz, 1H, HArH), 8.14 (d, J=7.6 Hz, 1H, HArH), 8.04 (t, J=7.7 Hz, 1H, HArH), 8.00 (t, J=7.7 Hz,
1H, HArH), 7.97 (d, J=9.0 Hz, 1H, HArH), 7.85 (br s, 2H, HArH), 7.82 (d, J=8.9 Hz, 1H, HArH), 6.90
(d, J=8.9 Hz, 2H, HArH), 3.84 (s, 3H, CH3), 2.89 (s, 3H, CH3); C{1H} NMR (CDCl3, 150.90
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MHz): d = 199.3 (C=O), 164.3 (CAr), 135.4 (CAr), 132.4 (CAr), 132.1 (CAr), 131.7 (CAr), 131.5
(CAr), 130.6 (CAr), 130.2 (CAr), 128.5 (CAr), 128.1 (CAr), 128.0 (2xCHArH), 126.8 (CHArH), 126.7
(CHArH), 126.5 (CHArH), 126.3 (CHArH), 126.2 (CArH), 125.7 (2xCAr), 124.6 (CHArH), 124.4 (CAr),
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123.4 (CHArH), 122.9 (CAr), 121.0 (2xCHArH), 114.2 (CHArH), 55.5 (OCH3), 17.2 (CH3); IR (KBr,
cm-1) 1655 (C=O); HRMS (EI-EBE) m/z: [M+] Calcd for C31H20O2 424.1463; Found 424.1470.
1-methyl-2-(3,4,5-trimethoxybenzoyl)benzo[ghi]perylene (8f). This compound was
synthesized according to the General Procedure B starting from 58.6 mg (0.25 mmol) of 7f, 63.1
mg (0.25 mmol) of 1, 22 µL (0.25 mmol) of TfOH and 25 mL of DCM. Chromatography on
silica using gradient of DCM:cyclohexane as the eluent starting from 1:1 to 7:3 (v/v) produced 32
mg of unreacted 1 followed by 86 mg (71% yield) of pure 8f as a yellow solid. Mp: >260 °C; 1H
NMR (CDCl3, 600.29 MHz): d = 9.05 (t, J=9.4 Hz, 2H, HArH), 8.38 (d, J=9.0 Hz, 1H, HArH), 8.24
(d, J=7.6 Hz, 1H, HArH), 8.20 (d, J=9.1 Hz, 1H, HArH), 8.17 (d, J=7.6 Hz, 1H, HArH), 8.06 (t, J=7.7
Hz, 1H, HArH), 8.03 (t, J=7.7 Hz, 1H, HArH), 8.00 (d, J=8.9 Hz, 1H, HArH), 7.82 (d, J=8.9 Hz, 1H,
HArH), 7.17 (br s, 2H, HArH), 3.94 (s, 3H, OCH3), 3.69 (br s, 6H, OCH3), 2.91 (s, 3H, CH3);
13C{1H} NMR (CDCl3, 150.90 MHz): d = 199.7 (C=O), 153.4 (CAr), 143.6 (CAr), 134.9 (CAr),
133.3 (CAr), 132.1 (CAr), 131.7 (CAr), 130.7 (CAr), 130.3 (CAr), 128.7 (CAr), 128.1 (CHArH), 128.0
(CHArH), 126.8 (2xCHArH), 126.7 (CHArH), 126.4 (CHArH), 126.2 (CAr), 125.7 (CAr), 125.6 (CAr),
124.5 (CHArH), 123.4 (CHArH), 122.9 (CAr), 121.1 (2xCHArH), 107.5 (CAr), 60.9 (OCH3), 56.3
(OCH3), 17.3 (CH3); IR (KBr, cm-1) 1664 (C=O); HRMS (EI-EBE) m/z: [M+] Calcd for
C33H24O4 484.1675; Found 484.1683.
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1-methyl-2-(2,4,6-trifluorobenzoyl)benzo[ghi]perylene (8g). This compound was synthesized
according to the General Procedure B starting from 49.5 mg (0.25 mmol) of 7g, 63.1 mg (0.25
mmol) of 1, 22 µL (0.25 mmol) of TfOH and 25 mL of DCM. Chromatography on silica using
gradient starting from 3:2 to 1:1 (v/v) of DCM:n-hexane as the eluent produced 15 mg of
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unreacted 1 followed by 23 mg (20% yield) of pure 8g as a yellow solid. Mp: 226-228 °C; H
NMR (CDCl3, 600.29 MHz): d = 9.02 (d, J=7.7 Hz, 1H, HArH), 9.01 (d, J=7.7 Hz, 1H, HArH),
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8.35 (d, J=9.1 Hz, 1H, HArH), 8.20 (d, J=7.7 Hz, 1H, HArH), 8.16 (d, J=8.7 Hz, 2H, HArH), 8.04 (t,
J=7.7 Hz, 1H, HArH), 8.04 (d, J=9.1 Hz, 1H, HArH), 8.01 (t, J=7.7 Hz, 1H, HArH), 7.95 (d, J=9.0
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Hz, 1H, HArH), 6.71 (t, J=8.6 Hz, 2H, HArH), 2.97 (s, 3H, CH3); C{1H} NMR (CDCl3, 150.90
MHz): d = 193.7 (C=O), 165.0 (dt, 1JC-F=257.1, 3JC-F=15.7 Hz, CAr), 162.24 (dd, 1JC-F=259.7, 3JC-
F=15.0 Hz, CAr) overlapped with 162.18 (dd, 1JC-F=261.1, 3JC-F=15.0 Hz, CAr), 136.7 (CAr), 132.2
(CAr), 131.6 (CAr), 130.7 (CAr), 130.2 (CAr), 128.6 (CAr), 128.3 (CHArH), 128.1 (CHArH), 126.9
(CHArH), 126.8 (2xCHArH), 126.4 (CHArH), 125.7 (CAr), 125.6 (CAr), 125.4 (CAr), 124.8 (CAr),
123.4 (2xCHArH), 123.0 (CAr), 121.1 (CHArH), 121.0 (CHArH), 116.2 (brs, CAr), 101.6 (td, J=26.1,
4.6 Hz, CHArH), 16.9 (CH3); IR (KBr, cm-1) 1677 (C=O); HRMS (EI-EBE) m/z: [M+] Calcd for
C30H15F3O 448.1075; Found 448.1074.
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1-methyl-2-(perylen-3-oyl)benzo[ghi]perylene (8h). This compound was synthesized as 8a
starting from 15.9 mg (0.05 mmol) of 9a, 12.6 mg (0.05 mmol) of 1, 4.4 µL (0.05 mmol) of
TfOH, and 7.5 mL of DCM. Chromatography on silica using DCM:cyclohexane 3:2 (v/v) as the
eluent produced 8 mg (28% yield) of pure 8h as an orange solid. Due to the very low solubility of
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this compound in the available solvents, we were not able to obtain C{1H} NMR spectra. Mp:
1
>260°C; H NMR (CDCl3, 600.29 MHz): d = 9.65 (d, J=7.7 Hz, 1H, CHArH), 9.10 (d, J=7.6 Hz,
1H, CHArH), 9.07 (d, J=8.0 Hz, 1H, CHArH), 8.46 (d, J=7.7 Hz, 1H, CHArH), 8.42 (d, J=9.0 Hz,
1H, CHArH), 8.37 (d, J=7.6 Hz, 1H, CHArH), 8.27 (d, J=8.0 Hz, 1H, CHArH), 8.23 (J=9.1 Hz, 1H,
CHArH), 8.17 (d, J=7.7 Hz, 1H, CHArH), 8.13 (d, J=7.5 Hz, 1H, CHArH), 8.09 (t, J=7.8 Hz, 1H,
CHArH), 8.04 (t, J=7.7 Hz, 1H, CHArH), 8.00 (s, 2H, CHArH), 7.93 (d, J=8.2 Hz, 1H, CHArH), 7.89
(t. J=8.0 Hz, 1H, CHArH), 7.78 (d, J=7.9 Hz, 1H, CHArH), 7.76 (d, J=8.0 Hz, 1H, CHArH), 7.58 (t,
J=7.8 Hz, 2H, CHArH), 7.46 (t, J=7.8 Hz, 1H, CHArH), 2.98 (s, 3H, CH3); IR (KBr, cm-1) 1646
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(C=O); Anal. Calcd for C44H24O: 92.93; H 4.25; Found: C 93.19; H 4.25; HRMS (EI-EBE) m/z:
[M+] Calcd for C44H24O 568.1827; Found 568.1822.
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1-methyl-2-(pyren-1-oyl)benzo[ghi]perylene (8i). This compound was synthesized according to
the General Procedure B starting from 67 mg (0.25 mmol) of 7i, 63.1 mg (0.25 mmol) of 1, and
22 µL (0.25 mmol) of TfOH. Chromatography on silica using DCM:cyclohexane 3:2 (v/v) as the
eluent produced 54 mg (42% yield) of pure 8i as a yellow solid. Due to the very low solubility of
this compound in the available solvents, we were not able to obtain 13C{1H} NMR spectra of 8i.;
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Mp: >260°C; H NMR (CDCl3, 600.29 MHz): d = 9.97 (brs, 1H, HArH), 9.10 (d, J=7.7 Hz, 1H,
HArH), 9.07 (d, J=7.7 Hz, 1H, HArH), 8.50 (d, J=9.2 Hz, 1H, HArH), 8.42 (d, J=9.0 Hz, 1H, HArH),
8.41 (d, J=7.6 Hz, 1H, HArH), 8.33 (d, J=7.6 Hz, 1H, HArH), 8.27 (d, J=7.7 Hz, 1H, HArH), 8.23 (d,
J=9.0 Hz, 1H, HArH) overlapped with 8.23 (d, J=8.8 Hz, 1H, HArH), 8.15 (t, J=7.7 Hz, 1H, HArH
)
overlapped with 8.15 (d, J=7.6 Hz, 1H, HArH), 8.09 (t, J=7.8 Hz, 1H, HArH), 8.04-7.99 (m, 4H,
HArH), 7.95 (d, J=9.1 Hz, 1H, HArH), 7.90 (d, J=8.2 Hz, 1H, HArH), 2.98 (s, 3H, CH3); IR (KBr,
cm-1) 1648 (C=O); HRMS (EI-EBE) m/z: [M+] Calcd for C40H22O 518.1671; Found 518.1675.
The reaction of 25.2 mg (0.1 mmol) of 1, 53.7 mg (0.2 mmol) of 7i, and 8.8 µL (0.1
mmol) of TfOH afforded 13 mg of unreacted 1 followed by 24 mg of 8i, 23 mg of unreacted 7i,
and 10 mg of 17—in this case, chromatography was performed on silica using DCM:n-hexane
1:1 (v/v) as the eluent.
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1-(pyren-1-yl)but-2-en-1-one (17). Mp: 91-93°C; H NMR (CDCl3, 600.29 MHz): d = 8.54 (d,
J=9.2 Hz, 1H, HArH), 8.23 (d, J=7.6 Hz, 1H, HArH), 8.17 (d, J=8.0 Hz, 1H, HArH), 8.15 (t, J=8.2
Hz, 1H, HArH), 8.07 (d, J=8.8 Hz, 1H, HArH), 8.04 (t, J=7.6 Hz, 1H, HArH), 6.92-6.83 (m, 2H,
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CHvinyl), 2.01 (d, J=6.2 Hz, 3H, CH3); C{1H} (CDCl3, 150.90 MHz): d = 196.3 (C=O), 146.9
(CHvinyl), 133.7 (CAr), 133.1 (CHvinyl), 133.0 (CAr), 131.2 (CAr), 130.7 (CAr), 129.7 (CAr), 129.3
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(CAr), 129.0 (CHArH), 128.9 (CHArH), 127.2 (CHArH), 126.3 (CHArH), 126.1 (CHArH), 126.0
(CHArH), 125.8 (CHArH), 124.9, 124.7 (CHArH), 124.5 (CAr), 123.9 (CHArH), 18.6 (CH3); IR (KBr,
cm-1) 1630 (C=O); HRMS (EI-EBE) m/z: [M+] Calcd for C20H14O 270.1045; Found 270.1042.
1-methyl-2-(coronen-1-oyl)benzo[ghi]perylene (8j). This compound was synthesized according
to the General Procedure B starting from 36.6 mg (0.1 mmol) of 7j, 25.2 mg (0.1 mmol) of 1, 9
µL (0.1 mmol) of TfOH, and 15 mL of DCM. Chromatography on silica using DCM:n-hexane
3:2 (v/v) as the eluent produced 17 mg (28% yield) of pure 8j as a yellow powder.
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Due to the very low solubility of this compound in available solvents we were not able to obtain
NMR spectra. HRMS (EI-EBE) Calcd for C48H24O: 616.1827; Found 616.1830.
General procedure C—reaction of 1 with 2-alkynoic acids
Briefly, 71 µL (0.51 mmol) of TFAA was added to a solution of 0.51 mmol of 2-alkynoic acid
11a-f in 11 mL of anhydrous DCM. To the resulting solution, 126 mg (0.5 mmol) of 1 followed
by 45 µL (0.51 mmol) of TfOH were added. After 2 h of stirring at room temperature, 50 mL of
sodium bicarbonate was added and the products were extracted with DCM (5 × 30 mL). The
organic solution was washed with sodium bicarbonate, water, and brine and then dried over
sodium sulfate and evaporated. Chromatography on silica allows separating products.
Reaction with but-2-ynoic acid 11a. This reaction was performed according to the General
procedure C starting from 43.1 mg (0.51 mmol) of 11a. Chromatography on silica using
DCM:cyclohexane 3:2 (v/v) as the eluent gave 8 mg of recovered 1 followed by 30 mg (10%) of
8h, 89 mg (56%) of 9a, and 20 mg (11%) of 12a.
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1-(perylen-3-yl)but-2-yn-1-one (9a): Mp: >260°C; H NMR (CDCl3, 600.29 MHz): d = 9.18
(d, J=8.6 Hz, 1H, HArH), 8.56 (d, J=8.0 Hz, 1H, HArH), 8.32 (d, J=7.4 Hz, 1H, HArH) overlapped
with 8.32 (d, J=7.6 Hz, 1H, HArH), 8.29 (d, J=7.4 Hz, 1H, HArH), 8.26 (d, J=8.0 Hz, 1H, HArH),
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MHz): d = 179.1 (C=O), 137.2 (CAr), 135.4 (CHArH), 134.4 (CAr), 132.6 (CAr), 131.6 (CAr), 131.2
(CAr), 130.9 (CAr), 130.1 (CAr), 129.8 (CHArH), 129.1 (CHArH), 128.3 (CHArH), 128.2 (CAr), 127.0
(CHArH), 126.7 (CHArH), 126.0 (CHArH), 122.6 (CHArH), 121.5 (CHArH), 121.1 (CHArH), 118.8
(CHArH), 90.8 (CºC), 80.7 (CºC), 4.4 (CH3); IR (KBr, cm-1) 1615 (C=O); HRMS (EI-EBE) m/z:
[M+] Calcd for C24H14O 318.1045; Found 318.1044.
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1-(perylen-3-yl)but-2-en-1-one (12a). The NMR spectra were identical with those of authentic
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Reaction with hex-2-ynoic acid 11b. This reaction was performed according to the General
procedure C starting from 57 mg (58 µL, 0.51 mmol) of 11b. Chromatography on silica using
DCM:cyclohexane 1:1 (v/v) as the eluent produced 27 mg of recovered 1 followed by 43 mg
(10%) of 15b, 95 mg (55%) of a mixture of 14b and 13b, and 30 mg (17%) of 12b.
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1-(perylen-3-yl)hex-2-en-1-one (12b). Mp: 170-171 °C; H NMR (CDCl3, 600.29 MHz): d =
8.24 (d, J=6.8 Hz, 1H, HArH), 8.23 (d, J=6.7 Hz, 1H, HArH), 8.22 (d, J=7.1 Hz, 1H, HArH), 8.18 (d,
J=7.8 Hz, 1H, HArH), 8.17 (dd, J=8.4, 0.6 Hz, 1H, HArH), 7.74 (d, J=8.0 Hz, 1H, HArH), 7.71 (d,
J=8.0 Hz, 1H, HArH), 7.67 (d, J=7.8 Hz, 1H, HArH), 7.55 (dd, J=8.4, 7.6 Hz, 1H, HArH), 7.509 (t,
J=7.8 Hz, 1H, HArH), 7.508 (t, J=7.8 Hz, 1H, HArH), 6.9d (dt, J=15.7, J=6.9 Hz, 1H, COCH=CH),
6.67 (dt, J=15.7, 1.4 Hz, 1H, COCH=CH), 2.32-2.28 (m, 2H, CH2), 1.58-1.52 (m, 2H), 0.98 (t,
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J=7.4 Hz, 3H); C{1H} NMR (CDCl3, 150.90 MHz): d = 195.6 (C=O), 151.2 (CHvinyl), 136.1
(CAr), 134.6 (CAr), 134.2 (CAr), 132.2 (CAr), 131.3 (CAr), 131.0 (CHvinyl and CAr), 130.5 (CAr),
129.1 (CAr), 128.9 (CHArH), 128.4 (CAr), 128.1 (CHArH), 128.0 (CHArH), 127.7 (CHArH), 126.8
(CHArH), 126.6 (CHArH), 125.7 (CHArH), 121.4 (CHArH), 120.9 (CHArH), 120.7 (CHArH), 118.8
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(CHArH), 34.8 (CH2), 21.4 (CH2), 13.8 (CH3); IR (KBr, cm-1) 1662 (C=O); HRMS (EI-EBE) m/z:
[M+] Calcd for C26H20O 348.1514; Found 348.1510.
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9.14 (d, J=8.5 Hz, 1H, HArH), 8.49 (d, J=8.0 Hz, 1H, HArH), 8.23 (d, J=7.5 Hz, 2H, HArH), 8.20 (d,
J=7.4 Hz, 1H, HArH), 8.16 (d, J=8.0 Hz, 1H, HArH), 7.77 (d, J=8.0 Hz, 1H, HArH), 7.70 (d, J=8.0
Hz, 1H, HArH), 7.62 (dd, J=8.4, 7.7 Hz, 1H, HArH), 7.50 (t, J=7.8 Hz, 1H, HArH), 7.50 (t, J=7.7 Hz,
1H, HArH), 2.53 (t, J=7.1 Hz, 2H, CH2), 1.78-1.73 (m, 2H, CH2), 1.14 (t, J=7.4 Hz, 3H, CH3);
13C{1H} NMR (CDCl3, 150.90 MHz): d = 179.1 (C=O), 137.0 (CAr), 135.2 (CHArH), 134.3 (CAr),
132.5 (CAr), 131.6 (CAr), 131.1 (CAr), 130.8 (CAr), 130.0 (CAr), 129.7 (CHArH), 129.0 (CHArH and
CAr), 128.2 (CHArH), 128.1 (CAr), 126.9 (CHArH), 126.6 (CHArH), 126.0 (CHArH), 122.5 (CHArH),
121.3 (CHArH), 120.9 (CHArH), 118.7 (CHArH), 94.9 (CºC), 81.6 (CºC), 21.5 (CH2), 21.3 (CH2),
13.7 (CH3); IR (KBr, cm-1) 2209 (CºC), 1625 (C=O); HRMS (EI-EBE) m/z: [M+] Calcd for
C26H18O 346.1358; Found 346.1352.
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1-propyl-2-(perylen-3-oyl)benzo[ghi]perylene (15b). Mp: 224-225 °C; H NMR (CDCl3,
600.29 MHz): d = 9.58 (brs, 1H, HArH), 9.08 (d, J=8.1 Hz, 1H, HArH), 9.07 (d, J=8.1 Hz, 1H,
HArH), 8.45 (d, J=7.6 Hz, 1H, HArH), 8.39 (d, J=9.1 Hz, 1H, HArH), 8.36 (d, J=7.6 Hz, 1H, HArH),
8.25 (d, J=7.6 Hz, 1H, HArH), 8.21 (d, J=9.0 Hz, 1H, HArH), 8.16 (d, J=7.6 Hz, 1H, HArH), 8.11 (d,
J=7.6 Hz, 1H, HArH), 8.08 (t, J=7.8 Hz, 1H, HArH), 8.03 (t, J=7.7 Hz, 1H, HArH), 8.00 (s, 2H,
HArH), 7.90 (d, J=8.1 Hz, 1H, HArH), 7.89 (t, J=8.04, 1H, HArH), 7.77 (d, J=8.0 Hz, 1H, HArH), 7.75
(d, J=8.2 Hz, 1H, HArH), 7.57 (t, J=7.9 Hz, 1H, HArH), 7.56 (d, J=8.0 Hz, 1H, HArH), 7.45 (t, J=7.8
Hz, 1H, HArH), 3.42 (br s, 1H, HArH), 3.23 (br s, 1H, CH2), 1.93 (br s, 1H, CH2), 1.82 (brs, 1H,
CH2), 1.00 (t, J=7.3 Hz, 3H, CH3); 13C{1H} NMR (CDCl3, 150.90 MHz): d = 202.1 (C=O), 137.1
(CAr), 136.7 (CAr), 135.1 (CHArH), 134.4 (CAr), 133.9 (CAr), 133.3 (CAr), 132.7 (CAr), 132.1 (CAr),
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131.7 (CAr), 131.5 (CAr), 131.0 (CAr), 130.7 (CAr), 130.3 (CAr), 130.0 (CAr), 129.8 (CHArH), 129.5
(CAr), 129.4 (CHArH), 128.4 (CHArH), 128.2 (CHArH and CAr), 128.0 (CHArH), 127.7 (CAr), 127.0
(CHArH), 126.8 (CAr), 126.7 (2xCHArH), 126.6 (2xCHArH), 126.4 (2xCHArH), 125.9 (CAr), 125.7
(CAr), 124.9 (CAr), 124.8 (CHArH), 123.6 (CHArH), 123.0 (CAr), 122.5 (CHArH), 121.5 (CHArH),
121.2 (CHArH), 121.0 (2xCHArH), 118.9 (CHArH), 33.5 (CH2), 25.1 (CH2), 14.8 (CH3); IR (KBr,
cm-1) 1648 (C=O); HRMS (EI-EBE) m/z: [M+] Calcd for C46H28O 596.2140; Found 596.2150.
Reaction with oct-2-ynoic acid 11c. This reaction was performed according to the General
procedure C starting from 71.5 mg (74 µL, 0.51 mmol) of 11c. Chromatography on silica using
DCM:cyclohexane 3:2 (v/v) as the eluent produced 28 mg of recovered 1 followed by 41 mg
(13%) of 15c, 63 mg of 14c, 11 mg of a mixture of 13c and 12c, and 30 mg of pure 12c.
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1-(perylen-3-yl)oct-2-en-1-one (12c). Mp: 148-149 °C; H NMR (CDCl3, 600.29 MHz): d =
8.26-8.23 (m, 3H, HArH), 8.19 (d, J=7.8 Hz, 1H, HArH), 8.17 (d, J=8.4 Hz, 1H, HArH), 7.75 (d,
J=8.0 Hz, 1H, HArH), 7.72 (d, J=8.1 Hz, 1H, HArH), 7.67 (d, J=7.7 Hz, 1H, HArH), 7.55 (t, J=8.0
Hz, 1H, HArH), 7.52 (t, J=7.7 Hz, 1H, HArH), 7.51 (t, J=7.8 Hz, 1H, HArH), 6.92 (dt, J=15.8, 6.9
Hz, 1H, Hvinyl), 6.67 (dt, J=15.6, 1.2 Hz, 1H, Hvinyl), 2.33-2.30 (m, 2H, CH2), 1.52-1.51 (m, 2H,
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CH2), 1.35-1.34 (m, 4H, CH2), 0.92-0.90 (m, 3H, CH3); C{1H} NMR (CDCl3, 150.90 MHz): d
= 195.7 (C=O), 151.5 (CHvinyl), 136.2 (CAr), 134.6 (CAr), 134.2 (CAr), 132.2 (CAr), 131.4 (CAr),
131.0 (CAr), 130.9 (CHvinyl), 130.5 (CAr), 129.2 (CAr), 128.9 (CHArH), 128.5 (CAr), 128.1 (CHArH),
128.0 (CHArH), 127.7 (CHArH), 126.8 (CHArH), 126.6 (CHArH), 125.7 (CHArH), 121.4 (CHArH),
120.9 (CHArH), 120.7 (CHArH), 118.8 (CHArH), 32.8 (CH2), 31.4 (CH2), 27.8 (CH2), 22.4 (CH2),
13.9 (CH3); IR (KBr, cm-1) 1661 (C=O); HRMS (EI-EBE) m/z: [M+] Calcd for C28H24O
376.1827; Found 376.1824.
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1-(perylen-3-yl)oct-2-yn-1-one (14c). Mp: 138-141 °C; H NMR (CDCl3, 600.29 MHz): d =
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J=7.4 Hz, 1H, HArH), 8.17 (d, J=8.0 Hz, 1H, HArH), 7.77 (d, J=8.0 Hz, 1H, HArH), 7.71 (d, J=8.0
Hz, 1H, HArH), 7.62 (dd, J=8.4, 7.7 Hz, 1H, HArH), 7.51 (t, J=7.8 Hz, 1H, HArH), 7.50 (t, J=7.8 Hz,
1H, HArH), 2.54 (t, J=7.2 Hz, 2H, CH2), 1.75-1.70 (m, 2H, CH2), 1.53-1.48 (m, 2H, CH2), 1.43-
1.39 (m, 2H, CH2), 0.97 (t, J=7.3 Hz, 3H, CH3); 13C{1H} NMR (CDCl3, 150.90 MHz): d = 179.2
(C=O), 137.0 (CAr), 135.2 (CHArH), 134.3 (CAr), 132.5 (CAr), 131.7 (CAr), 131.1 (CAr), 130.9
(CAr), 130.0 (CAr), 129.7 (CHArH), 129.0 (CHArH and CAr), 128.2 (CHArH), 128.1 (CAr), 126.9
(CHArH), 126.6 (CHArH), 126.0 (CHArH), 122.5 (CHArH), 121.3 (CHArH), 120.9 (CHArH), 118.7
(CHArH), 95.2 (CºC), 81.4 (CºC), 31.2 (CH2), 27.6 (CH2), 22.2 (CH2), 19.3 (CH2), 13.9 (CH3);
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IR (KBr, cm-1) 2211 (CºC), 1626 (C=O); HRMS (EI-EBE) m/z: [M+] Calcd for C28H22O
374.1671; Found 374.1664.
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1-pentyl-2-(perylen-3-oyl)benzo[ghi]perylene (15c). Mp: 182-183 °C; H NMR (CDCl3,
600.29 MHz): d = 9.58 (brs, 1H, HArH), 9.08-9.05 (m, 2H, HArH), 8.44 (d, J=7.6 Hz, 1H, HArH),
8.39 (d, J=9.1 Hz, 1H, HArH), 8.35 (d, J=7.2 Hz, 1H, HArH), 8.25 (d, J=7.6 Hz, 1H, HArH), 8.21 (d,
J=9.1 Hz, 1H, HArH), 8.15 (dd, J=7.6, 0.8 Hz, 1H, HArH), 8.10 (d, J=7.4 Hz, 1H, HArH), 8.08 (t,
J=7.8 Hz, 1H, HArH), 8.02 (t, J=7.7 Hz, 1H, HArH), 8.00 (s, 2H, HArH), 7.89 (d, J=8.2 Hz, 1H,
HArH), 7.88 (t, J=7.9 Hz, 1H, HArH), 7.77 (d, J=7.9 Hz, 1H, HArH), 7.74 (d, J=8.2 Hz, 1H, HArH),
7.57 (t, J=7.9 Hz, 1H, HArH), 7.56 (d, J=8.1 Hz, 1H, HArH), 7.45 (t, J=7.8 Hz, 1H, HArH), 3.41 (brs,
1H, CH2), 3.24 (brs, 1H, CH2), 1.91 (brs, 1H, CH2), 1.75 (brs, 1H, CH2), 1.37 (brs, 2H, CH2),
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1.28-1.25 (m, 2H, CH2), 0.79 (t, J=7.3 Hz, 3H, CH3); C{1H} NMR (CDCl3, 150.90 MHz): d =
202.1 (C=O), 137.1 (CAr), 136.6 (CAr), 135.1 (CHArH), 134.4 (CAr), 134.1 (CAr), 133.2 (CAr),
132.7 (CAr), 132.1 (CAr), 131.7 (CAr), 131.4 (CAr), 131.0 (CAr), 130.7 (CAr), 130.3 (CAr), 130.0
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(CAr), 129.7 (CHArH), 129.5 (CHArH), 129.4 (CHArH), 128.3 (CHArH), 128.2 (CHArH and CAr),
128.0 (CHArH), 127.6 (CArH), 127.0 (CHArH), 126.8 (CHArH), 126.7 (CHArH), 126.6 (2xCHArH and
CAr), 126.4 (CHArH), 125.9 (CAr), 125.7 (CAr), 124.9 (CAr), 124.8 (CHArH), 123.6 (CHArH), 123.0
(CAr), 122.5 (CHArH), 121.5 (CHArH), 121.2 (CHArH), 121.0 (2xCHArH), 118.9 (CHArH), 32.5
(CH2), 31.4 (2xCH2), 22.3 (CH2), 13.9 (CH3); IR (KBr, cm-1) 1648 (C=O); HRMS (EI-EBE) m/z:
[M+] Calcd for C48H32O 624.2453; Found 624.2458.
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Reaction with phenylpropynoic acid 11d. This reaction was performed according to the
General procedure C starting from 146 mg of phenylpropynoic acid. Chromatography on silica
using DCM as the eluent produced 20 mg of recovered 1 followed by158 mg (42%) of 14d.
3-(phenylpropynoyl)perylene (14d). Mp: 248-249 °C; 1H NMR (CDCl3, 600.29 MHz): d = 9.23
(d, J=8.5 Hz, 1H, HArH), 8.65 (d, J=8.0 Hz, 1H, HArH), 8.32 (d, J=7.4 Hz, 1H, HArH), 8.29 (d,
J=7.4 Hz, 1H, HArH), 8.28 (d, J=8.0 Hz, 1H, HArH), 7.75 (d, J=8.0 Hz, 1H, HArH), 7.73-7.69 (m,
3H, HArH), 7.57-7.54 (m, 2H, HArH), 7.51-7.48 (m, 1H, HArH), 7.46-7.43 (m, 2H, HArH);
13C{1H}NMR (CDCl3, 150.90 MHz): d = 178.8 (C=O), 137.5 (CAr), 135.4 (CHArH), 134.4 (CAr),
132.9 (CHArH), 132.6 (CAr), 131.7 (CAr), 131.2 (CAr), 130.9 (CAr), 130.5 (CHArH), 130.0 (CHArH and
CAr), 129.2 (CHArH), 129.1 (CAr), 128.7 (CHArH), 128.4 (CHArH), 128.2 (CAr), 127.0 (CHArH),
126.7 (CHArH), 126.0 (CHArH), 122.7 (CHArH), 121.5 (CHArH), 121.1 (CHArH), 120.6 (CAr), 118.9
(CHArH), 91.6 (CºC), 88.7 (CºC); IR (KBr, cm-1) 2198 (CºC) 1613 (C=O); HRMS (EI-EBE)
m/z: [M+] Calcd for C29H16O 380.1201; found 380.1198.
Reaction with 4-phenylbut-2-ynoic acid 11e. This reaction was performed according to the
General procedure C starting from 81.7 mg (0.51 mmol) of 11e. Chromatography on silica using
DCM:cyclohexane 1:1 (v/v) as the eluent produced 35 mg of recovered 1 followed by 46 mg
(14%) of 15e, 24 mg of 14e, 33 mg of 13e, and 30 mg of 12e.
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Due to the very low solubility of 15e in available solvents, we were not able to obtain C NMR
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in available solvents, we were not able to obtain NMR spectra of 12e. Mp. 151-154 °C; HRMS
(EI-EBE) m/z: [M+] Calcd for C30H20O 396. 1514; Found 396.1512.
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1-(perylen-1-yl)-4-phenylbut-2-yn-1-one (13e). Mp: 147-148 °C; H NMR (CDCl3, 600.29
MHz): d = 8.36 (d, J=7.4 Hz, 1H, HArH), 8.32 (d, J=7.4 Hz, 1H, HArH), 7.85 (d, J=8.0 Hz, 1H,
HArH), 7.79 (t, J=7.9 Hz, 2H, HArH), 7.76 (d, J=8.5 Hz, 1H, HArH) overlapped with 7.76 (d, J=7.3
Hz, 1H, HArH), 7.71 (d, J=8.4 Hz, 1H, HArH), 7.65 (t, J=7.7 Hz, 1H, HArH), 7.65 (t, J=7.7 Hz, 1H,
HArH), 7.49 (t, J=7.7 Hz, 1H, HArH), 7.05 (t, J=7.4 Hz, 1H, HArH), 6.91 (t, J=7.7 Hz, 2H, HArH),
6.70 (d, J=7.5 Hz, 2H, HArH), 3.45 (s, 2H, CH2); 13C{1H} NMR (CDCl3, 150.90 MHz): d = 183.1
(C=O), 136.4 (CAr), 135.1 (CAr), 134.0 (CAr), 133.9 (CAr), 133.0 (CAr), 132.1 (CHArH), 131.7
(CAr), 130.5 (CAr), 129.8 (CHArH), 129.2 (CAr), 128.9 (CAr), 128.6 (CAr), 128.3 (CHArH), 128.2
(CHArH), 128.0 (CHArH), 127.6 (CHArH), 127.2 (2x CHArH), 127.1 (CHArH), 126.7 (2x CHArH),
126.1 (CHArH), 121.3 (CHArH), 121.2 (CHArH), 88.0 (CºC), 83.5 (CºC), 25.1 (CH2); IR (KBr, cm-
1) 2212 (CºC), 1625 (C=O); HRMS (EI-EBE) m/z: [M+] Calcd for C30H18O 394.1358; Found
394.1371.
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1-(perylen-3-yl)-4-phenylbut-2-yn-1-one (14e). Mp: 174-178 °C; H NMR (CDCl3, 600.29
MHz): d = 9.16 (d, J=8.5 Hz, 1H, HArH), 8.51 (d, J=8.0 Hz, 1H, HArH), 8.26-8.22 (m, 2H, HArH),
8.15 (d, J=8.1 Hz, 1H, HArH), 7.77 (d, J=8.0 Hz, 1H, HArH), 7.71 (d, J=8.0 Hz, 1H, HArH), 7.63
(dd, J=8.5, 7.6 Hz, 1H, HArH), 7.51 (t, J=7.8 Hz, 2H, HArH), 7.45 (d, J=7.2 Hz, 2H, HArH), 7.40 (t,
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J=7.7 Hz, 2H, HArH), 7.32 (t, J=7.3 Hz, 1H, HArH), 3.96 (s, 2H, CH2); C{1H} NMR (CDCl3,
150.90 MHz): d = 178.8 (C=O), 137.3 (CAr), 135.5 (, CHArH), 134.8 (CAr), 134.3 (CAr), 132.5
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(CAr), 131.4 (CAr), 131.1 (CAr), 130.8 (CAr), 129.9 (CAr), 129.8 (CHArH), 129.1 (CHArH), 129.0
(CAr), 128.9 (CHArH), 128.3 (CHArH), 128.1 (CHArH and CAr), 127.2 (CHArH), 126.9 (CHArH),
126.6 (CHArH), 125.9 (CHArH), 122.6 (CHArH), 121.4 (CHArH), 121.0 (CHArH), 118.8 (CHArH), 91.7
(CºC), 82.9 (CºC), 25.7 (CH2); IR (KBr, cm-1) 2213 (CºC), 1625 (C=O); HRMS (EI-EBE) m/z:
[M+] Calcd for C30H18O 394.1358; Found 394.1367.
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1-benzyl-2-(perylen-3-oyl)benzo[ghi]perylene (15e). Mp: 245-246 °C; H NMR (CDCl3,
600.29 MHz): d = 9.54 (brs, 1H, HArH), 9.10 (d, J=7.6 Hz, 1H, HArH), 9.09 (d, J=7.9 Hz, 1H,
HArH), 8.42 (d, J=7.8 Hz, 1H, HArH), 8.34 (d, J=7.7 Hz, 1H, HArH), 8.30 (d, J=9.0 Hz, 1H, HArH),
8.21 (d, J=7.6 Hz, 1H, HArH), 8.19 (d, J=7.7 Hz, 1H, HArH), 8.10-8.02 (m, 6H, HArH), 7.82 (t,
J=8.1 Hz, 1H, HArH), 7.79 (d, J=8.3 Hz, 1H, HArH), 7.78 (d, J=8.0 Hz, 1H, HArH), 7.75 (d, J=8.2
Hz, 1H, HArH), 7.57 (t, J=7.9 Hz, 1H, HArH), 7.52 (d, J=8.0 Hz, 1H, HArH), 7.46 (d, J=7.8 Hz, 1H,
HArH), 7.13-7.08 (m, 4H, HArH), 7.04 (t, J=6.7 Hz, 1H, HArH), 4.80 (s, 2H, CH2); IR (KBr, cm-1)
1648 (C=O); HRMS (EI-EBE) m/z: [M+] Calcd for C50H28O 644.2140; Found 644.2147.
Reaction with 4-phenylpent-2-ynoic acid 11f. This reaction was performed according to the
General procedure C starting from 88.8 mg (0.51 mmol) of 11f. Chromatography on silica using
DCM:cyclohexane 1:1 (v/v) as the eluent produced 13 mg of recovered 1 followed by 32 mg
(10%) of 15f and 70 mg of a mixture of 13f and 14f and 12 mg of 12f. Small amounts of
analytically pure samples of 14f were obtained by repeated column chromatography of a mixture
of 13f and 14f on silica.
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1-(perylen-3-yl)-5-phenylpent-2-en-1-one (12f). Mp: 187-188 °C; H NMR (CDCl3, 600.29
MHz): d = 8.25-8.22 (m, 3H, HArH), 8.16 (d, J=7.8 Hz, 1H, HArH), 8.14 (dd, J=8.5, 0.7 Hz, 1H,
HArH), 7.75 (d, J=8.0 Hz, 1H, HArH), 7.72 (d, J=8.0 Hz, 1H, HArH), 7.60 (d, J=7.7 Hz, 1H, HArH),
7.54 (dd, J=8.3, 7.6 Hz, 1H, HArH), 7.52 (t, J=7.8 Hz, 1H, HArH), 7.51 (t, J=7.7 Hz, 1H, HArH),
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