Tandem Friedel-Crafts annulation to novel perylene analogues

Article abstract of DOI:10.1021/jo800558c

(Chemical Equation Presented) Novel dialkyloxy- and dihydroxyoctahydroperylenes are regioselectively available via a new tandem Friedel-Crafts alkylation of tetrahydronaphthalene precursors followed by oxidative aromatization. Heating of 5-alkyloxy-1-tetralol with p-toluenesulfonic acid in sulfolane gave the corresponding octahydroperylenes in moderate yields. Studies with Lewis acids and tetralin-1,5-diol in acetonitrile at room temperature provided the 4,10-dihydroxy analogue cleanly, albeit in reduced yields. Examples of these new series of perylene analogues were partially oxidized to the corresponding contiguously aromatic, anthracene core products or fully aromatized to 3,9-dialkyloxyperylenes in good yields.

Full text of DOI:10.1021/jo800558c

SCHEME 1. Tandem Friedel-Crafts Annulation Approach
Tandem Friedel-Crafts Annulation to Novel
Perylene Analogues1
Mark A. Penick, Mathew P. D. Mahindaratne,
Robert D. Gutierrez, Terrill D. Smith, Edward R. T. Tiekink,
and George R. Negrete*
mercially available perylene diimides10 and their derivatives11
are widely employed in these studies.12 Alkyloxy-substituted
perylenes13 are attractive targets since they are expected to
stabilize perylene radical cation intermediates, resulting in
improved photoacceptor properties. Here we describe a regi-
oselective synthesis of 3,9-dialkyloxyperylene (1: Scheme 1)
based on a new tandem Friedel-Crafts alkylation of tetrahy-
dronaphthols.
Department of Chemistry, UniVersity of Texas at San
Antonio, One UTSA Circle, San Antonio, Texas 78249
george.negrete@utsa.edu
ReceiVed March 14, 2008
Tandem reactions are important processes in organic chem-
istry because of their pragmatic value and aesthetic appeal.14
Those that involve a Friedel-Crafts reaction in prelude to a
second transformation have been reported;15 however, domino
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therein.
Novel dialkyloxy- and dihydroxyoctahydroperylenes are
regioselectively available via a new tandem Friedel-Crafts
alkylation of tetrahydronaphthalene precursors followed by
oxidative aromatization. Heating of 5-alkyloxy-1-tetralol with
p-toluenesulfonic acid in sulfolane gave the corresponding
octahydroperylenes in moderate yields. Studies with Lewis
acids and tetralin-1,5-diol in acetonitrile at room temperature
provided the 4,10-dihydroxy analogue cleanly, albeit in
reduced yields. Examples of these new series of perylene
analogues were partially oxidized to the corresponding
contiguously aromatic, anthracene core products or fully
aromatized to 3,9-dialkyloxyperylenes in good yields.
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displays,6 molecular electronics,7 and solid-state lighting.8 In
some photovoltaic materials, perylene photoemission initiates
an electron cascade that results in an electric current.9 Com-
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see: (c) Takahashi, M.; Morimoto, H.; Miyake, K.; Yamashita, M.; Kawai, H.;
Sei, Y.; Yamaguchi, K. Chem. Commun. 2006, 3084–3086, and references cited
therein.
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6378 J. Org. Chem. 2008, 73, 6378–6381
10.1021/jo800558c CCC: $40.75 2008 American Chemical Society
Published on Web 07/16/2008

SCHEME 2. Products from Tandem Friedel-Crafts
tioned above, use of 2a with benzene resulted in formation of
olefin 3a only, with no evidence of product 4a (entry 1).
Reaction in refluxing chlorobenzene gave 4a in modest yield
and good selectivity (see entry 2; 9:1 ratio of 4a to 5a), though
at higher temperature. Use of nitrobenzene as solvent at 150
°C gave no evidence of product. A similar result was obtained
in sulfolane at 132 °C where the starting material and products
were destroyed after 22 h of heating giving only a black solution
containing traces of 4a and 5a (entry 3). In an identical reaction
monitored by TLC 2a gave 4a and 5a in 40% yield and in 1:2
ratio within 2 h (entry 4). Upon employment of the n-octyloxy
analogue (2b), prepared via alkylation of the commercially
available 1,5-diol (2c), the reaction gave a poor result, as
Alkylation of Tetrahydronaphthols
SCHEME 3. Mechanism of Redox Conversions to 5 and 6
1
determined by H NMR spectroscopy (entry 5). At reduced
temperature (95 °C), however, reaction of 2b in sulfolane gave
4b and 5b (ratio of 83:17) in 55% total yield within 26 h (entry
6). In addition, it was observed that at a higher mole percent of
catalyst used, the formation of 4b and 5b dominated over 3b
(entries 6-8). These reactions were also improved upon use of
inert atmosphere, in that less 5b was formed (cf. entry 6 versus
entries 9 and 10).
A sample with a high percentage of 4b (entry 10) was
recrystallized in toluene and subjected to single-crystal X-ray
diffraction analysis.18 The monomer exhibits antiannulation
coupling at the dibenzylic positions (C-6b and C-12b; Scheme
2) and extended octyloxy chains.18a
Friedel-Crafts reactions are unknown. Recognizing that the
perylene skeleton consists of peri-annulated naphthalenes
(Scheme 1), we considered a novel route to the perylene core
via sequential Friedel-Crafts alkylations. The starting com-
pounds, 5-methoxy- and 5-n-octyloxy-1,2,3,4-tetrahydro-1-
naphthols (2a, R ) CH3, and 2b, R ) n-C8H17, respectively),
are accessible from commercially available 5-methoxy-1-
tetralone and 1,2,3,4-tetrahydronaphth-1,5-diol (2c, R ) H),
respectively. Domino Friedel-Crafts alkylations would result
in an annulated, partially hydrogenated dialkyloxyperylene
skeleton (4; Scheme 2) that can be oxidized to fully aromatic
perylene 1. Here we describe results on the implementation of
such an approach.
Oxidation of the mixture of 4a and 5a (entry 2; Table 1) to
3,9-dimethoxyperylene (1a, R ) CH3, Scheme 4) occurred upon
treatment with 10% Pd/C/cyclododecene.19 The solid product
was insoluble in CHCl3 and DMSO but was sparingly soluble
in THF. The oxidation product was identified by mass spec-
1
trometry (m/z 312) and H and 2D COSY NMR spectra, but
Upon heating in acidic condition (10 mol % TsOH, C6H6,
70 °C, 6 h), 2a (R ) Me) generated corresponding olefin 3a
initially,16 but under more vigorous conditions (100 mol %
TsOH, C6H5Cl, 132 °C, 22 h) a greenish-yellow crystalline
precipitate was obtained, which was isolated by filtration (33%
poor solubility precluded the collection of 13C NMR data. The
poor solubility of this compound contrasts sharply with its
precursors 4a and 5a, both of which were readily dissolVed in
CDCl3, and is likely a consequence of strong stacking associations.
To afford increased perylene solubility, 4b (R ) n-C8H17)
was prepared from 2b with use of the TsOH/sulfolane system
under N2 (entries 9-12; Table 1). Although the reaction time
was as much as 25 h, the optimized reaction condition (3.6
mmol; entry 10) allowed near exclusive formation of 4b (97%
of the isolated mixture) in satisfactory yield (63%; entry 10).
When the reaction was further scaled up to 27 mmol the
products were isolated in the same ratio (93:7) with slightly
reduced yield (56%; entry 12) compared to 1 mmol scale (entry
9). As anticipated,17b 3b also formed the product mixture of 4b
and 5b (70:30 ratio) in 40% yield under the same conditions.
The mixture was subsequently aromatized19 to produce 1b in
90% yield (R ) n-C8H17; Scheme 4), which was soluble in a
wide range of organic solvents as anticipated. Spectroscopic
analysis including NMR, FT-IR, UV, and MS confirmed the
formation of novel 4b and its oxidized form 3,9-dioctyloxyper-
ylene (1b).
mass yield).17 The initial analysis of the solid by H and 13C
1
NMR was consistent with a mixture of octahydroperylene 4a
(90% of the mixture), a self-condensate of 2a, and a small
amount of fluorescent bluish green 5a (<10%; Scheme 2). Mass
spectrometry data supported the assignments of both structures.
Product 4a was eventually isolated and fully characterized (vida
infra).
The isolation of 5-methoxy-1,2,3,4-tetrahydronaphthalene (6a,
R ) Me) from the filtrate suggested the involvement of 2a or
3a in the oxidation of 4a to 5a. It is likely that the benzylic
cation derived under acidic conditions from 2a or 3a abstracts
a hydride from 4a to initiate its conversion to 5a (Scheme 3).
Thus, this oxidation occurs upon concomitant reduction of 2a
(or 3a) to 6a. In accord with this suggestion, oxidation of 4a
under hydride abstraction conditions (excess Ph3CCl and
lutidine, sulfolane, 120-165 °C, N2) generated a mixture rich
in 5a (4a to 5a ratio was shown to be 26:74), which began to
precipitate upon cooling below 110 °C.
Tandem Friedel-Crafts reactions of 1,5-diol 2c with TsOH
in sulfolane produced intractable mixtures. On the other hand,
saturated solutions of 2c in CH3CN (0.3 M) and Lewis acids
(0.015 equiv of Sc(OTf)3 or Hf(OTf)4, or 0.30 equiv of
La(OTf)3)20 at ambient temperature gave modest yields of diol
Several experiments were conducted to improve the modest
tandem Friedel-Crafts annulation yields (Table 1). As men-
(16) The acid catalyzed elimination of 2 to 3 occurs under mild conditions
compared to the tandem Friedel-Crafts alkylations. Thus, it is possible that this
reaction proceeds via the intermediacy of 3.
(17) For detailed study of p-toluenesulfonic acid as Friedel-Crafts catalyst
see: (a) Mahindaratne, M. P. D.; Wimalasena, K. J. Org. Chem. 1998, 63, 2858–
2866. (b) Mahindaratne, M. P. D. Ph.D. Dissertation, Wichita State University,
Wichita, KS, 2000.
(18) (a) For all crystallographic data of 4b see the Supporting Information,
pp 13-24: (a) Crystal structure of 4b (page 13). (b) Molecular packing of the
unit cell of 4b (page 13).
(19) Neumann, R.; Lissel, M. J. Org. Chem. 1989, 54, 4607–4610, and
references cited therein.
J. Org. Chem. Vol. 73, No. 16, 2008 6379

TABLE 1. Preparation of Octahydroperylene Derivativesa
product(s)b c
,
entry
subst./mol% TsOH
solvent /temp (°C)/time (h)
3
4
5
isolated yieldd
1
2
3
4
5
6
7
8
2a/10
C6H6/70/6
99
0
0
9
tr
-
5
35
58
1
0
90
33
0
2a/100
2a/100
2a/100
2b/100
2b/100
2b/50
C6H5Cl/132/22
sulfolane/132/12.5
sulfolane/132/2.0e
sulfolane/132/12.5
sulfolane/95/25
sulfolane/95/25
sulfolane/95/26
sulfolane/95/22g
sulfolane/95/25g,h
sulfolane/95/25g,h
sulfolane/95/22g,i
CH3CN/25/24g
<1
0
tr
f
f
f
-
-
40 (34:66)
0
tr
9
12
4
11
10
10
tr
55 (83:17)
55 (83:17)
29 (80:20)
59 (93:7)
63 (97:3)
58 (97:3)
56 (93:7)
29(<99:1)
2b/20
9
2b/100
2b/100
2b/50
6
53
10
f
f
f
10
11
12
13
-
-
-
6
33
1
f
f
f
2b/100
-
-
-
-
-
-
2c/1.5j
f
f
f
a All reactions were performed in 0.5 M (1 mmol scale) in air unless otherwise noted. b Starting material 2a (R ) CH3; entries 1-4), 2b (R )
n-C8H17; entries 5-12), or 2c (R ) H; entry 13) not detected in TLC (5% EtOAc/hexanes) after indicated reaction time. c Ratio of crude mixture
determined by 1H NMR after workup. d Combined yield of the mixture of 4 and 5 (ratio in parentheses). e Reaction performed in 2.0 mmol scale.
f NMR ratios not determined. g Reaction performed under N2. h Reaction performed in 3.6 mmol scale. i Reaction performed on 27 mmol scale.
j Reaction performed in 0.3 M solution with Hf(OTf)4 as the catalyst.
SCHEME 4. Synthetic Route to Prepare
3,9-Dialkyloxyperylenes
mmol) in DMF (100 mL) under N2 was added K2CO3 (8.93 g, 65
mmol) and 1-bromooctane (11 mL, 63 mmol). The mixture was
heated to 55-60 °C for 4 days while being monitored by TLC
(silica gel, 5% ethyl acetate/hexanes). More K2CO3 (1.62 g, 11.7
mmol) and 1-bromooctane (1.4 mL, 8 mmol) were added and
heating was continued for another day. The product was extractively
isolated and purified by crystallization (hexanes) to give 22.5 g of
1
4c (19%, 29%, and 27% isolated yields, respectively) along with
complex mixtures of unidentified byproducts. The precipitation
of 4c from these reaction mixtures allowed its facile isolation
without chromatography. Solvent (ether, acetone, THF, EtOAc,
CH3NO2) or temperature variation (0-70 °C), or changes in
the addition protocol did not improve these results. It is
noteworthy that the availability of phenolic 4c (R ) H) enables
access to diverse perylene analogues.
In summary, domino Friedel-Crafts alkylation/self-conden-
sation of tetrahydronaphthol analogues generated partially
hydrogenated dialkyloxyperylene frameworks, which were
readily oxidized to anthracenyl and perylenyl products. The self-
condensation can be performed under relatively mild conditions
with easily accessible substrates. Additional investigations on
the photophysical and photochemical properties of these novel
alkyloxyperylenes are ongoing and will be reported in due
course.
2b as a white solid (74% yield), mp 54-56 °C. H NMR: δ 7.16
(t, 1H, J ) 8.2 Hz), 7.04 (d, 1H, J ) 8.2 Hz), 6.73 (d, 1H, J ) 8.2
Hz), 4.80-4.73 (m, 1H), 3.98-3.91 (m, 2H), 2.84-2.72 (m, 1H),
2.62-2.48 (m, 1H), 2.03-1.69 (m, 6H), 1.63 (d, 1H, J ) 3.9 Hz),
1.54-1.40 (m, 2H), 1.40-1.18 (m, 8H), 0.94-0.82 (m, 3H). 13C
NMR: δ 14.1 (q), 18.0 (t), 22.6 (t), 23.0 (t), 26.2 (t), 29.2 (t), 29.3
(t), 31.7 (t), 31.8 (t), 67.8 (t), 69.1 (d), 109.4 (d) 120.2 (d), 126.1
(s), 126.2 (d), 140.0 (s), 156.4 (s). MS (m/z): 276 (M+, 22), 258
(M+ - H2O, 45), 146 (M+ - H2O - C8H16, 100), 145 (M+
-
H2O - C8H17, 63). IR (cm-1): 3361, 2919, 2852, 1582, 1459, 1308,
1245, 1077, 1039, 1016, 783, 691. Exact mass analysis calcd for
C18H29O2 (MH+) 277.2168, found 277.2165.
General Preparation of Octahydroperylene 4. Aryl ether
alcohol 2 (10.0 mmol) and p-toluenesulfonic acid monohydrate
(1.95 g, 10.3 mmol) in sulfolane (20 mL) under N2 were heated
(at 132 °C for 2a and at 95 °C for 2b) for an appropriate time (2.0
h for 2a and 22 h for 2b) with stirring. The reaction mixture was
allowed to cool to room temperature and the resultant precipitate
was separated by filtration. The solid was further purified by
crystallization (EtOAc/CH2Cl2) to obtain 4 (with a detectable
amount of 5) as a greenish yellow solid in both cases.
Experimental Section
5-Methoxy-1,2,3,4-tetrahydro-1-naphthol (2a).21 Prepared from
5-methoxy-1-tetralone as a white solid in 74% yield, mp 69-72
°C (lit.21a mp 74-79). 1H NMR (300 MHz):21b δ 7.19 (t, 1H, J )
8 Hz), 7.06 (d, 1H, J ) 8 Hz), 6.76 (d, 1H, J ) 8 Hz), 4.82-4.72
(m, 1H), 3.82 (s, 3H), 2.82-2.69 (m, 1H), 2.61-2.47 (m, 1H),
2.01-1.71 (m, 4H), 1.69 (d, 1H, J ) 6 Hz). 13C NMR:21b δ 18.0
(t), 22.9 (t), 31.7 (t), 55.3 (q), 68.1 (d), 108.6 (d) 120.5 (d), 126.0
(s), 126.5 (d), 140.0 (s), 157.0 (s). IR (cm-1): 3326, 2935, 1580,
1466, 1427, 1312, 1248, 1042, 1015, 788, 729.
4,10-Dimethoxy-1,2,3,6b,7,8,9,12b-octahydroperylene (4a). Pre-
pared from 2a in 37% yield (90:10 ratio of 4a:5a) as a greenish
yellow solid, mp 249-252 °C dec. H NMR: δ 7.26 (d, 2H, J )
1
8.3 Hz), 6.84 (d, 2H, J ) 8.3 Hz), 3.85 (s, 6H), 3.76-3.70 (m,
2H), 3.10 (ddd, 2H, J ) 5.1, 7.1, 16.1 Hz), 2.58-2.47 (m, 4H),
2.05 (ddq, 2H, J ) 5.1, 13.2, 8.1 Hz), 1.74 (dddt, 2H, J ) 3.9, 7.1,
13.4, 8.5 Hz), 1.51 (tt, 2H, J ) 8.5, 12.4 Hz). 13C NMR: δ 20.8
(t), 21.0 (t), 29.8 (t), 36.0 (d), 55.6 (q), 108.6 (d), 124.6 (d), 126.2
(s), 127.9 (s), 136.8 (s), 154.4 (s). MS (m/z): 320 (M+, 95), 319
(M+ - H, 70), 289 (M+ - H - 2CH3 and M+ - OCH3, 100). IR
(cm-1): 2929, 2859, 2835, 1602, 1487, 1463, 1346, 1259, 1081,
1002, 800, 753. Calcd for C22H25O2 (MH+) 321.1855, found
321.1853.
5-(1-Octyloxy)-1,2,3,4-tetrahydro-1-naphthol (2b). To a flask
containing 1,2,3,4-tetrahydronaphthal-1,5-diol (2c; 10.00 g, 61
(20) Noji, M.; Ohno, T.; Fuji, K.; Futaba, N.; Tajima, H.; Ishii, K. J. Org.
Chem. 2003, 68, 9340–9347.
4,10-Bis(1-octyloxy)-1,2,3,6b,7,8,9,12b-octahydroperylene (4b).
(21) (a) Banerjee, A. K.; Poon, P. S.; Laya, M. S.; Azocar, J. A.; Russ, J.
Gen. Chem 2003, 73, 1815–1820. (b) Bichlmaier, I.; Siiskonen, A.; Finel, M.;
Yli-Kauhaluoma, J. J. Med. Chem. 2006, 49, 1818–1827.
Prepared from 2b in 60% yield (98:2 ratio of 4b:5b) as a greenish
1
yellow solid, mp 125-127 °C. H NMR: δ 7.23 (d, J ) 9.0 Hz),
6380 J. Org. Chem. Vol. 73, No. 16, 2008

6.81 (d, J ) 9.0 Hz), 4.01-3.92 (m, 4H), 3.75-3.69 (m, 2H),
3.16-3.08 (m, 2H), 2.58-2.46 (m, 4H), 2.09-1.99 (m, 2H),
1.84-1.69 (m, 6H), 1.56-1.43 (m, 6H), 1.40-1.24 (m, 16H),
0.92-0.86 (m, 6H). 13C NMR: δ 14.1 (q), 20.9 (t), 21.1 (t), 22.7
(t), 26.2 (t), 29.3 (t), 29.4 (t), 29.5 (t), 29.8 (t), 31.8 (t), 36.0 (d),
68.3 (t), 109.7 (d), 124.5 (d), 126.5 (s), 127.8 (s), 136.8 (s), 153.9
(s). MS (m/z): 516 (M+, 50), 387 (M+ - C8H17O, 100), 275 (M+
- C8H17O - C8H16, 50). IR (cm-1): 2940, 2917, 2848, 1604, 1581,
1465, 1395, 1344, 1261, 1081, 999, 795, 754. Calcd for C36H53O2
(MH+) 517.4046, found 517.4042. Single-crystal X-ray analysis
3008, 2962, 2839, 1581, 1501, 1385, 1248, 1138, 1109, 1038, 823,
762, 684. Calcd for C22H23O2 (MH+) 319.1698, found 319.1695.
3,9-Dimethoxyperylene (1a). A mixture of 4a and 5a (350 mg,
1.1 mmol), 10% Pd/C (38 mg), and cyclododecene (0.65 mL, 3.5
mmol) in mesitylene (10 mL) was heated at 150-155 °C overnight
under N2. Product 1a was isolated as a golden solid after workup
1
(257 mg, 75%), mp >300 °C. H NMR (THF-d8): δ 4.02 (s, 6H),
6.94 (d, 2H, J ) 8.3 Hz), 7.40 (dd, 2H, J ) 7.6, 8.3 Hz), 7.97 (dd,
2H, J ) 1.0, 8.3 Hz), 8.16 (dd, 2H, J ) 1.0, 7.4 Hz), 8.17 (d, 2H,
J ) 8.3 Hz). IR (cm-1): 1583, 1503, 1386, 1250, 1040, 825, 805,
764. MS (m/z): 312 (M+, 100), 297 (M+ - Me, 96), 282 (M+
-
j
at 223(2) K: triclinic crystal system (space group P1) with unit
2Me, 40). Calcd for C22H16O2 (M+) 312.1150, found 312.1147.
3,9-Bis(1-octyloxy)perylene (1b). A mixture of 4b and 5b (461
mg, 0.89 mmol), 5% Pd/C (53 mg), and cyclododecene (0.86 mL,
4.46 mmol) in mesitylene (13.5 mL) was refluxed under N2 for
5 h. Product 1b was isolated as a bright yellow solid after workup
(410 mg, 90%), mp 219-220 °C. 1H NMR: δ 0.95-0.85 (m, 6H),
1.46-1.21 (m, 16H), 1.64-1.50 (m, 4H), 6.84 (d, 2H, J ) 8.6
Hz), 7.44 (t, 2H, J ) 7.7 Hz), 8.12-8.01 (m, 6H). Due to its low
cell dimensions a ) 4.608(2) Å, b ) 9.424(4) Å, c ) 17.933(7)
Å, R ) 90.869(5)°, ꢀ ) 95.234(10)°, γ ) 103.709(9)°, V )
752.8(6) Å3, Z ) 1, and Dx ) 1.140 g/cm3.
4,10-Dihydroxy-1,2,3,6b,7,8,9,12b-octahydroperylene (4c). A
mixture of 1,5-dihydroxy-1,2,3,4-tetrahydronaphthalene (2c; 166
mg, 1.01 mmol) and hafnium(IV) trifluoromethanesulfonate (12 mg,
0.015 mmol) in acetonitrile (3 mL) was stirred at room temperature
for 30 h. Precipitated solid was separated by centrifugation, washed
once with fresh acetonitrile (2 mL), and again with acetonitrile/
methanol (1:1; 2 mL) to obtain 4c in 29% yield as a white solid,
solubility at room temperature, it was necessary to acquire the 13
C
NMR spectrum of 1b at 47 °C. Additional peaks beyond the 18
expected were seen, which suggest the formation of isomeric
π-stacked dimers. 13C NMR: δ 14.0, 22.7, 26.3, 29.27, 29.38, 29.43,
31.9, 68.4, 77.1, 105.84, 105.87, 119.5 (br), 120.3 (br), 120.6 (br),
124.1, 125.9 (br), 126.0 (br), 126.8, 129.4, 131.6, 154.8. UV
(hexanes, nm): 457, 428, 404. IR (cm-1): 3062, 2924, 2582, 1582,
1503, 1467, 1380, 1252. MS (APCI): m/z 508 (M+). Elemental
Anal. Calcd for C36H44O2: C, 84.99; H, 8.72. Found: C, 85.12; H,
8.81.
1
mp >300 °C dec. H NMR (DMSO-d6): δ 8.98 (s, 2H), 7.06 (d,
2H, J ) 8.3 Hz), 6.72 (d, 2H, J ) 8.8 Hz), 3.60-3.54 (m, 2H),
2.94 (ddd, 2H, J ) 4.9, 6.8, 15.6 Hz), 2.47 (ddt, 2H, J ) 12.2, 8.3,
4.4 Hz), 2.38 (dt, 2H, J ) 15.6, 8.3 Hz), 1.97 (dtt, 2H, J ) 4.9,
8.3, 10.2 Hz), 1.63-1.53 (m, 2H), 1.26 (tt, 2H, J ) 8.3, 12.2 Hz).
13C NMR (DMSO-d6): δ 20.5 (t), 20.7 (t), 29.7 (t), 35.3 (d), 113.0
(d), 123.4 (s), 124.4 (d), 125.7 (s), 136.3 (s), 151.7 (s). MS (m/z):
292 (M+, 11), 275 (M+ - H2O, 4), 263 (M+ - CH3O, 8), 91
(C7H7+, 100). IR (cm-1): 3261, 2946, 2863, 1591, 1456, 1373, 1299,
1243, 948, 803, 606. Calcd for C20H21O2 (MH+) 293.1536, found
293.1545.
Acknowledgment. Preliminary findings were supported by
grants from The Welch Foundation (No. 96-086) and the
NIGMS (S06 GM08194). R.G. was supported by funds from
the NIGMS (MARC-U*STAR GM 07717). We gratefully
acknowledge Mr. Justin King, Mr. Ahmed Khan (Minu), and
Dr. Fred Lakner for technical contributions.
4,10-Dimethoxy-1,2,3,7,8,9-hexahydroperylene (5a). A mixture
of 4a and 5a (40 mg; ∼5:1 ratio) was heated with 2,6-lutidine (9
equiv), chlorotriphenylmethane (8 equiv), and p-toluenesulfonic acid
(0.66 equiv) in sulfolane at 120-165 °C for 5 h. Upon cooling, a
5a-rich mixture (∼74% of 5a) crystallized. The crystals were
separated by filtration in 77% yield as a golden solid, mp >260 °C
Supporting Information Available: Proton and 13C NMR
spectra of new compounds and crystallographic data for 4b.
This material is available free of charge via the Internet at
http://pubs.acs.org.
1
dec. H NMR: δ 8.09 (d, J ) 9.3 Hz), 7.35 (d, J ) 9.6 Hz), 3.98
(s, 6H), 3.50 (t, J ) 6.3 Hz), 3.13 (t, J ) 6.3 Hz), 2.16 (quintet, J
) 6.3 Hz). 13C NMR: δ 22.4 (t), 23.6 (t), 26.9 (t), 56.9 (q), 114.7
(d), 120.7 (s), 122.7 (d), 125.5 (s), 127.2 (s), 128.6 (s), 150.5 (s).
MS (m/z): 318 (M+, 100), 303 (M+ - Me, 55). IR (cm-1): 3066,
JO800558C
J. Org. Chem. Vol. 73, No. 16, 2008 6381