The Journal of Organic Chemistry
ARTICLE
In hydrocarbon solvents, the BPI fluorophores exhibit spectral
characteristics of two closely spaced excited states (S1 and S2),
separated by only 562 cmꢀ1. The vibrational assignments are
tabulated from the electronic spectra and their alternating nature
suggest that a two-state system is operative. Further low tem-
perature fluorescence experiments are being conducted to ana-
lyze the nature of the observed phenomena; the results will be
presented in future work.
solution was refluxed overnight at 175οC, and then allowed to reach
room temperature. A 230-mL portion of methanol was added and the
red precipitate collected. The solid was boiled out in 1:1 methanol/water
and collected by filtration to afford a 0.86 g of product. Mp.: >320οC
Due to very low solubility no NMR data could be collected. FT-IR:
2925 cmꢀ1(w), 2855(w), 1752 (w), 1696 (s), 1353 (m), 1309 (w), 1189
(w), 1050 (m), 1027 (m), 826 (s). Anal.: C27H17NO2 Calcd., C (83.70),
H (4.42), N (3.62), O (8.26); Found, C (83.12), H (4.48), N (3.56), O
(8.84).
2-(Nonan-5-yl)-1H-peryleno[1,12-efg]isoindole-1,3(2H)-
dione (3b). A 1.73-g portion, 5.00 mmol, of (1) was added to a solution
of (2b) (1.33 g, 9.35 mmol) in DMA (100 mL) and refluxed overnight.
The solution was allowed to cool to room temperature and methanol
(230 mL) was added to complete the crystallization. The obtained solid
was dissolved in hot 4:1 toluene/hexane and purified by column
chromatography (silica, toluene/hexane, Rf = 0.55), and finally boiled
out in 200 mL methanol, leaving (3b) as an orange powder (2.09 g,
89%). Mp.: 226ꢀ228οC 1H NMR (400 MHz, CDCl3): δ9.30 (d, J = 9.2
Hz, 2H), 9.09 (d, 7.8 Hz, 2H), 8.27 (d, 7.8 Hz, 2H), 8.24 (d, 8.6 Hz, 2H),
8.13 (t, 7.8 Hz, 2H), 4.40 (sept, 4.8 Hz, 1H), 2.21ꢀ2.31 (m, 2H),
1.81ꢀ1.91 (m, 2H), 1.33ꢀ1.44 (m, 8H), 0.87 (t, 7.3 Hz, 6H) 13C NMR
(400 MHz, CDCl3) δ14.2, 22.7, 29.3, 32.7, 52.3, 121.4, 122.8, 123.4,
124.2, 124.4, 127.0, 127.2, 127.3, 129.9, 130.0, 132.0, 170.5. FT-IR:
2956 cmꢀ1 (w), 2927 (w), 2859 (w), 1754 (w), 1694 (s), 1393 (w),
1357 (m), 1309 (w), 830 (s). HRMS (ESI): m/z = 471.22 (M)+ Anal.:
C33H29NO2 Calcd., C (84.05), H (6.20), N (2.97), O (6.97); Found,
C (83.88), H (6.19), N (3.07), O (6.86).
2-(Undecan-6-yl)-1H-peryleno[1,12-efg]isoindole-1,3(2H)-
dione (3c). A 1.45-g portion, 4.19 mmol, of (1) was added to a solution
of (2c) (1.50 g, 8.81 mmol) in DMA (100 mL) and refluxed overnight.
The solution was cooled to room temperature, and methanol (230 mL)
was added to complete crystallization of the imide. The obtained solid
was dissolved in hot 5:6 toluene/hexane and purified by column
chromatography (silica, toluene/hexane, Rf = 0.60), and final-
ly boiled out in 1:1 methanol/water (200 mL), leaving (3c) as a yellow
powder (1.81 g, 86%). Mp.: 221ꢀ223οC 1H NMR (400 MHz, CDCl3):
δ9.17 (d, J = 8.7 Hz, 2H), 8.90 (d, 7.8 Hz, 2H), 8.15 (d, 8.2 Hz, 2H), 8.12
(d, 9.2 Hz, 2H), 8.02 (t, 7.8 Hz, 2H), 4.40 (sept, 5.0 Hz, 1H), 2.21ꢀ2.33
(m, 2H), 1.82ꢀ1.93 (m, 2H), 1.25ꢀ1.48 (m, 12H), 0.86 (t, 7.3 Hz, 6H)
13C NMR (400 MHz, CDCl3) δ14.2, 22.7, 26.8, 31.8, 32.9, 52.3, 121.3,
122.7, 123.3, 124.1, 124.2, 126.8, 127.1, 127.2, 129.7, 129.9, 131.9, 170.5.
FT-IR: 2956 cmꢀ1(w), 2927 (w), 2859 (w), 1754 (w), 1694 (s), 1393
(w), 1357 (m), 1309 (w), 830 (s). HRMS (ESI): m/z = 499.25 (M)+
Anal.: C35H33NO2 Calcd., C (84.14), H (6.66), N (2.80), O (6.40);
Found, C (84.11), H (6.66), N (2.79), O (6.44).
2-(Tridecan-7-yl)-1H-peryleno[1,12-efg]isoindole-1,3(2H)-
dione (3d). A 1.2416-g portion of (1) (3.59 mmol) was dis-
solved in 75 mL DMA in a 250-mL two-neck, round-bottom equipped
with stir bar and condenser. The solution was brought to 125 οC with
stirring to which 1.5643 g (2d) (7.86 mmol) was added. The reaction
was allowed to stir overnight and an orange precipitate formed upon
cooling back to room temperature. A 50-mL portion of CHCl3 was
added and 1.5883 g crude product collected. Crude (3d) was washed
with 2 M HCl, followed by 75:25 MeOH/H2O, and then boiled in hot
hexane for 2 h before filtering hot. Recrystallization from hexane yielded
1.4370 g (3d) as a bright orange powder. (76%) Mp.: 186ꢀ188 οC 1H
NMR (400 MHz, CDCl3): δ9.30 (d, J = 7.5 Hz, 2H), 9.09 (d, 7.4 Hz,
2H), 8.25 (d, 6.8 Hz, 2H), 8.20 (d, 8.7 Hz, 2H), 8.12 (t, 5.0 Hz, 2H), 4.40
(sept, 1H), 2.20ꢀ2.30 (q, 2H), 1.80ꢀ1.90 (q, 2H), 1.20ꢀ1.45 (m,
16H), 0.82 (t, 6.9 Hz, 6H). 13C NMR (400 MHz, CDCl3) δ14.2, 22.7,
27.1, 29.3, 31.9, 33.0, 52.4, 121.4, 122.8, 123.4, 124.2, 124.4, 127.0, 127.3,
127.4, 129.9, 130.0, 132.0, 170.5. FT-IR: 2956 cmꢀ1(w), 2927(w),
2859(w), 1754 (w), 1694 (s), 1393 (w), 1357 (m), 1309 (w), 830 (s).
HRMS (ESI): m/z = 528.29 (M+1)+ Anal.: C37H37NO2 Calcd., C
’ EXPERIMENTAL SECTION
Benzo[ghi]perylene-1,2-dicarboxylic Anhydride (1). A
5.090-g portion of perylene (20.17 mmol) was dissolved in 80.57 g
melted maleic anhydride (0.82 mol) at 240οC in a 250 mL two neck
round-bottom flask equipped with stir bar and condenser. The mixture
was brought to a rolling boil and 11.20 g p-chloranil (recrystallized from
acetone) (45.60 mmol) was added in small portions over 10 min. The re-
action was allowed to reflux for 10 min, after which 100 mL of hot xylenes
was added and the flask brought to room T. Then, the thick red precipitate
was filtered off and washed with xylenes and ether (3 ꢁ 100 mL each).
Red solids were collected (99%) and boiled in 2:1 ethyl acetate/chloro-
form for 16 h and filtered hot to afford 5.793 g clean, dry product. (85%
recovered). mp > 320οC FT-IR: 1831 cmꢀ1(m), 1816(m), 1785(w),
1766 (s), 1757 (s), 1330 (w), 1293 (s), 1217 (w), 1181 (s).
1-Butylpentylamine (2b). Portions of 5-nonanone (5.01 g, 35.2
mmol) and ammonium acetate (27.76 g, 360.1 mmol) were stirred at
room temperature under N2 gas in methanol (150 mL) for 90 min.
Sodium cyanoborohydride (1.56 g, 24.8 mmol) was added and the
solution was stirred for 56 h. The reaction was quenched by adding con-
centrated HCl dropwise (7 mL) and concentrated on a rotary evapora-
tor. The white solid was dispersed in water (500 mL) and adjusted to pH
10.5 with KOH. The solution was extracted with methylene chloride
(400 mL). The pale yellow oil (4.32 g, 86%) was obtained by
1
concentrating the CH2Cl2 fractions. H NMR (400 MHz, CDCl3):
δ2.56 (m, 1H), 1.36 (s, 2H), 1.09ꢀ1.31 (m, 12H), 0.79 (t, J = 6.6 Hz,
6H). 13C NMR (400 MHz, CDCl3) δ13.8, 22.7, 28.2, 37.5, 50.9.
1-Pentylhexylamine (2c). Portions of 6-undecanone (5.03 g,
29.5 mmol) and ammonium acetate (20.06 g, 260.2 mmol) were stirred
at room temperature under N2 gas in methanol (150 mL) for 90 min.
NaCNBH3 (1.12 g, 17.8 mmol) was added and the solution was stirred
for 56 h. The reaction was quenched by adding concentrated HCl drop-
wise (4 mL) and concentrated on a rotary evaporator. The white solid
was dispersed in water (500 mL) and adjusted to pH 10.5 with KOH.
The solution was extracted with methylene chloride (200 mL, 100 mL,
and 100 mL). The pale yellow oil (4.8556 g, 96%) was obtained by
1
concentrating the CH2Cl2 fractions. H NMR (400 MHz, CDCl3):
δ2.48 (m, 1H), 1.00ꢀ1.24 (m, 18H), 0.70 (t, J = 6.2 Hz, 6H) 13C NMR
(400 MHz, CDCl3) δ13.7, 22.4, 25.6, 31.8, 38.0, 50.9.
1-Hexylheptylamine (2d). A 5.650-g portion of dihexyl ketone
(28.50 mmol) and a 21.97-g portion ammonium acetate (0.2850 mol)
were dissolved in 85 mL methanol under N2 for 30 min. 25 mL MeOH
and 1.250 g sodiumcyanoborohydride (19.90 mmol) added to initiate
reduction. The reaction was allowed to continue at room temperature
with vigorous stirring for 48 h. The mixture was quenched with 3 mL
concentrated HCl added dropwise and concentrated via rotary evapora-
tion. The white solid was taken up in 500 mL H2O and brought to pH 10
with KOH pellets. The solution was extracted with 400 and 200 mL
CHCl3. Organics collected, dried over NaSO4, and evaporated to afford
3.6019 g 1-hexylheptylamine as a light yellow oil. (63%) 1H NMR (400
MHz, CDCl3): δ2.48 (m, 1H), 0.93ꢀ1.25 (m, 22H), 0.69 (t, J = 6.6 Hz,
6H). 13CNMR(400 MHz, CDCl3) δ13.9, 22.6, 26.1, 29.4, 31.8, 38.2, 51.1.
2-Isopropyl-1H-peryleno[1,12-efg]isoindole-1,3(2H)-
dione (3a). A 1.02-g portion of (1) (2.95 mmol) was dissolved in a
solution of isopropylamine (0.5 g, 2.95 mmol) and 150 mL DMA. The
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dx.doi.org/10.1021/jo200529p |J. Org. Chem. 2011, 76, 6007–6013