Synthesis and characterization of six N-(long-alkyl)-carbaldehyde

Article abstract of DOI:10.1080/15533171003766667

Six carbazole aldehyde compounds were synthesized and characterized by 1H NMR, UV-Vis, and IR spectroscopy. Fluorescence spectroscopy was also discussed, and they all have strong fluorescence. The thermal properties of compounds were studied by TGA-DTA. The compounds are considered to be promising and assistant materials for organic photo-electronic functional materials. Copyright Taylor & Francis Group, LLC.

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Synthesis and Characterization of Six N-(long-alkyl)-
carbaldehyde
a
a
a
a
Jian Hui Shi , Miao Yu , Wen Ping Jian & Yu Jing Zhang
a
College of Chemistry , Jilin University , Chang Chun, P. R. China
Published online: 10 May 2010.
To cite this article: Jian Hui Shi , Miao Yu , Wen Ping Jian & Yu Jing Zhang (2010) Synthesis and Characterization of Six N-
(long-alkyl)-carbaldehyde, Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 40:4, 268-272
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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 40:268–272, 2010
Copyright © Taylor & Francis Group, LLC
ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533171003766667
Synthesis and Characterization of Six N-(long-alkyl)-carbaldehyde
Jian Hui Shi, Miao Yu, Wen Ping Jian, and Yu Jing Zhang
College of Chemistry, Jilin University, Chang Chun, P. R. China
DTA. These compounds are considered to be promising and
Six carbazole aldehyde compounds were synthesized and char- assistant materials for organic photo-electronic functional ma-
1
acterized by H NMR, UV-Vis, and IR spectroscopy. Fluorescence terials and further work on these complexes is in under investi-
spectroscopy was also discussed, and they all have strong fluo-
gation in our laboratory.
rescence. The thermal properties of compounds were studied by
TGA-DTA. The compounds are considered to be promising and
assistant materials for organic photo-electronic functional materi- EXPERIMENTAL
als.
Reagents and Materials
Keywords carbazole, aldehyde carbazole, synthesis, TGA-DTA
Carbazole (C. P. chemica purity), N, N-dimethylformamide
A. R. analytical reagent), 1-Bromododecane (C. P.), Bromote-
(
tradecane (C. P.), Cetyl bromide (C. P.). NaH (A. R.), Perroleum
ether (A. R.), Silica gel for Thin-layer Chromatography (C. P.).
INTRODUCTION
Carbazole and its many derivatives have been widely used Phosphorus oxychloride(A. R.), Dichloromethane (A. R.)
ꢀ
as organic photo-electronic functional materials due to their
conjugated structure, intermolecular charge transfer, and special
photo-electronic properties such as electro-photographic recep-
Apparatus and Measurements
UV-Vis spectra were recorded on a Shimadzu UV-240 spec-
trophotometer using dichloromethane as solvents. The IR spec-
tra were recorded on a Nicolet 5PC-FTIR spectrometer in the
[
1−5]
They have been covalently
tors and light-emitting diodes.
incorporated into polymeric systems both in main-chain
[
6,7]
as building blocks and in side-chains as pendant group.[8−11]
Carbazole-containing polymers acting as hole-transporting ma-
terials and optical materials have been extensively studied.
Carbazole molecules are also quite interesting due to their
own photophysical and redox properties: they exhibit relatively
intense luminescence and undergo reversible oxidation pro-
cesses which make them suitable as hole carriers. The prop-
erties of these carbazole systems prompted us to introduce car-
−1
1
region 400–4000 cm using KBr pellets. H NMR spectra were
collected on a Varian Unity-400 (MHz) NMR spectrometer
using CDCl3 as solvent, chemical shifts were expressed with
tetramethylsilane as the internal reference and reported as po-
sition (δH), relative integral. TGA were carried out by DTG-60
Simultaneous DTA-TGA Apparatus (Sample: 3–8 mg; heat-
[12]
[13]
◦
−1
−1
ing rate: 10 C min ; atmosphere: Air; Flow rate: 20 ml min ;
◦
◦
Range of temperature: 4 C-1000 C.). Fluorescencespectrawere
recorded at room temperature with a Shimadzu RF-5301PC
spectrofluorometer using dichloromethane as solvent in the re-
gion of 300–600 nm and excitation wavelength is 425 nm.
DSC (differential scanning calorimetry) was recorded on a
NETESCH DSC 204.
[14]
bazole branches in porphyrin complexes.
Construction of a
rigid carbazole dendron around a porphyrin core may result in
interesting photochemical, electrochemical, and catalytic prop-
erties. However the synthesis of carbazole aldehyde is also con-
siderablely important to incorporate carbazole unit to porphyrin.
Herein we report the synthesis of six long-chain N-alkyl
(
–CnH2n+1, n = 12, 14, 16) carbazole substitutes aldehyde.
Synthesis of the Compounds
Synthesis of the N-Bromododecaned Carbaldehyde (1) and N-
Bromododecaned-3, 6-diformylcarbazole (2)
1
(Scheme 1). The characterization was confirmed by H NMR,
UV-Vis, IR, fluorescence spectrometry, XRD, DSC and TGA-
Phosphoryl chloride (0.097 mol, 8.81 ml) was added slowly
to DMF (0.194 mol, 12.83 ml), with purging with nitrogen and
◦
Received 29 January 2010; accepted 5 February 2010.
The authors would like to thank the National Natural Science Foun-
dation of China (No. 20801022) for financial support of this work.
Address correspondence to Miao Yu, College of Chem-
istry, Jilin University, Chang Chun, P.R. China, 130023. E-mail:
yumiao@jlu.edu.cn
cooling to 0 C. The Vilsmeier reactant was then allowed to warm
◦
to room temperature, stirred for 1 h, and then cooled to 0 C.
After that, a solution of N-Bromododecaned carbazole (0.039
mol, 13 g) in 1, 2-dichloroethane (20 mL) was added, and af-
◦
ter 1 h the system was warmed to 90 C for 8 h. Finally, the
268

SYNTHESIS AND CHARACTERIZATION OF SIX N-(LONG-ALKYL)-CARBALDEHYDE
269
SCH. 1. Synthetic routes to N-(long-alkyl)-carbaldehyde (n = 12,14,16).
cooled solution was poured into water, extracted with CH2Cl2, 400 MHz): δ = 10.104 (s, 2 H, –HC = O), 7.26–8.68 (6 H,
and dried with anhydrous magnesium sulfate. The crude prod- Ar–H), 3.77–4.41 (t, 2 H, –NCH2–), 1.23–1.93 (20 H, –CH2–),
uct was purified by column chromatography on silica gel 0.85–0.89 (t, 3 H, –CH3) ppm.
(
(
CH2Cl2/Perroleum ether 1.5:1, v/v), the first band gives 9.16 g
65%) of a light yellow solid (1); the second gives 5.31 (35%) N-Bromotetradecaned Carbaldehyde (3)
of a white solid (2). [17] The other products was obtained by
Yield: 60%. UV-Vis (dichloromethane, λmax/nm, molar ex-
2
−1
the procedure used for the preparation of 1, 2 and purified by tinction coefficients are in parentheses, cm mol ) 238(4.47 ×
4
4
4
4
column chromatography.
10 ) 278(4.77 × 10 ) 294(4.36 × 10 ) 327 (2.01 × 10 ); IR
(
KBr): ν˜ =3049, 2953, 2917, 2850, 1690, 1625, 1593, 1567,
–
1 1
N-Bromododecaned Carbaldehyde (1)
1470, 809, 1381, 807 cm ; H NMR (CDCl , 400 MHz): δ =
3
Yield: 65%. UV-Vis (dichloromethane, λmax/nm, molar ex- 10.10 (s, 1 H, –HC = O), 7.26–8.62 (7 H, Ar–H), 4.32–4.36(t,
2
−1
tinction coefficients are in parentheses, cm mol ) 237(5.05 × 2 H, –NCH –), 1.23–1.91 (24 H, –CH –), 0.86–0.89 (t, 3 H,
2
2
4
4
4
4
1
0 ) 278(5.53 × 10 ) 294(5.41 × 10 ) 327 (2.30 × 10 ); IR –CH ) ppm.
3
(
1
KBr): ν˜ = 3049, 2953, 2918, 2850, 1691, 1625, 1593, 1566,
− −1
1
493, 1381, 807 cm ; a strong peak at 1691 cm is the νs of N-Bromododecaned-3, 6-diformylcarbazole (4)
a C = O moiety. 2850 (vs of a C-H in the CHO), 809 ( C-H
Yield: 37%. UV-Vis (dichloromethane, λmax / nm, mo-
1
2
−1
aromatic ring out-of-plane); H NMR (CDCl3, 400 MHz): δ = lar extinction coefficients are in parentheses, cm mol
)
4
4
1
2
–
0.10 (s, 1 H, –HC=O), 7.62–8.62 (7 H, Ar–H), 4.32–4.36(t, 269(6.41×10 ) 342(3.75×10 ); IR (KBr): ν˜ = 2954, 2918,
–1 1
H, –NCH2–), 1.23–1.91 ( 20 H, –CH2–), 0.86–0.89 (t, 3 H, 2848, 1684, 1626, 1594, 1570,1488, 1383, 806 cm ; H NMR
CH3) ppm.
(CDCl3, 400 MHz): δ = 10.104 (s, 2 H, –HC=O), 7.26–8.68
6 H, Ar–H), 3.49–4.41(t, 2 H, –NCH2–), 1.23–1.92 (24 H,
–CH –), 0.86–0.94 (t, 3 H, –CH ) ppm.
(
N-Bromododecaned-3, 6-diformylcarbazole (2)
2
3
Yield: 35%. UV-Vis (dichloromethane, λmax/nm, molar
2
−1
extinction coefficients are in parentheses, cm mol ) 270 N-Cetyl Bromided Carbaldehyde (5)
4
4
(
2
4.34 × 10 ) 343(2.64 × 10 ); IR (KBr): ν˜ = 2953, 2918,
Yield: 58%. UV-Vis (dichloromethane, λmax/nm, molar ex-
−
1
2
−
1
847, 1681, 1626, 1593, 1488, , 1383, 806 cm ; a strong peak tinction coefficients are in parentheses, cm mol ) 235(3.90
−
1
1
4
4
4
4
at 1681 cm is the νs of a C = O moiety.; H NMR (CDCl3, × 10 ) 276(4.20 × 10 ) 293(4.12 × 10 ) 329(1.77 × 10 ); IR
FIG. 1. (a) UV-Vis spectra of N-(long-alkyl)-carbaldehyde (1, 3, 5).(b) UV-Vis spectra of N-(long-alkyl)-3, 6-diformylcarbazole compounds (2, 4, 6).

270
J. H. SHI ET AL.
TABLE 1
UV-Vis spectra of compounds
−
1
−1
)
Max. absorption peaks( λ max nm); (ε max L mol cm
Compounds
I
II III
IV
4
4
4
4
1
2
3
4
5
6
237 (5.05 × 10 )
278 (5.53 × 10 )
294 (5.41 × 10 )
327 (2.30 × 10 )
4
4
270 (4.34 × 10 )
343 (2.64 × 10 )
4
4
4
4
238 (4.47 × 10 )
278 (4.77 × 10 )
294 (4.73 × 10 )
327 (2.01 × 10 )
4
4
269 (6.40 × 10 )
342 (3.75 × 10 )
4
4
4
4
235 (3.89 × 10 )
276 (4.20 × 10 )
293 (4.12 × 10 )
329 (1.77 × 10 )
4
4
270 (5.07 × 10 )
342 (2.99 × 10 )
(
KBr): ν˜ = 2954, 2912, 2850, 1692, 1595, 1567, 1471, 1381,
−
1 1
8
–
1
09 cm ; H NMR (CDCl3, 400 MHz): δ = 10.10 (s, 1 H,
HC=O), 7.26–8.62 (7 H, Ar–H), 4.32–4.36(t, 2 H, –NCH2–),
.23–1.91 ( 24 H, –CH2–), 0.86–0.89 (t, 3 H, –CH3) ppm.
N-Cetyl Bromided-3, 6-diformylcarbazole (6)
Yield: 38%. UV-Vis (dichloromethane, λmax/nm, molar ex-
2
−1
tinction coefficients are in parentheses, cm mol ) 270(5.07 ×
4
4
1
1
4
0 ) 342(2.99 × 10 ); IR (KBr): ν˜ = 2954, 2917, 2848, 1686,
−
1 1
627, 1594, 1570,1488, 1383, 807 cm ; H NMR (CDCl3,
00 MHz): δ = 10.14 (s, 2 H, –HC=O), 7.26–8.68 (6 H, Ar–
H), 3.77–4.41(t, 2 H, –NCH2–), 1.23–1.93 ( 28 H, –CH2–),
0.86–0.92 (t, 3 H, –CH3) ppm.
RESULTS AND DISCUSSION
UV-Vis Spectra
FIG. 2. UV-Vis spectra of compounds 3 and 4.
UV-Vis absorption spectra of the six compounds 1–6 in
dichloromethane at the room temperature are shown in Figure 1.
Table 1 gives the absorption spectrum of six compounds. In
FIG. 3. (a) Fluorescence spectra of N-(long-alkyl)-carbaldehyde (1, 3, 5). (b) Fluorescence spectra of N-(long-alkyl)-3, 6-diformylcarbazole compounds (2, 4,
).
6

SYNTHESIS AND CHARACTERIZATION OF SIX N-(LONG-ALKYL)-CARBALDEHYDE
271
TABLE 2
Detailed thermal analytical data
Compounds Dec. temp.(1) Dec. temp.(2) Com.temp. Lost weight Exothermal peaks
◦
◦
◦
◦
(
C)
( C)
( C)
(%)
( C)
1
2
3
4
5
6
318
351
323
333
355
349
495
553
518
529
528
540
354, 548
387, 473, 580
358,543
373, 467, 547
378, 552
440
431
453
57.87
65.02
61.16
384, 472, 561
the absorption spectrum of the N-(long-alkyl)-carbaldehyde (1,
, 5), the absorption bands at 235–238 nm originate from in-
3
traligand π − π* transition of carbazole unit, and the absorp-
tion bands at about 276–329 nm are due to n-π* transition in
carbazole ring. However, there are no absorption bands at about
2
35–238 nm in three N-(long-alkyl)-3, 6-diformylcarbazole
compounds (2, 4, 6). Their maximum absorption bands at about
70, 342 nm are all attributed to n-π* transition of the car-
2
bazole ring, and maybe the absorption bands arising from n-π*
transition in the carbazole ring lay over the one arising from
π − π* transition inner carbazole unit. The absorption band of
the compounds 2, 4, 6 exhibits a red shift comparing to that in
compounds1, 3, 5. (see Figure 2).
Fluorescence Spectra
Luminescent properties of the six compounds were investi-
gated in dichloromethane solution at room temperature. The flu-
orescence spectra of six compounds are shown in Figure 3. The
fluorescent spectra of the N-(long-alkyl)-carbaldehyde (1, 3, 5)
display maximum emission wavelengths (λem, max) at 405–410
nm with excitation wavelengths at 270 nm in dichloromethane
solution, and maximum emission wavelengths (λem, max) at
FIG. 4. Fluorescence spectra of compounds 3 and 4.
FIG. 5. TGA and DTA curves of compounds 3 and 4.

272
J. H. SHI ET AL.
3
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(long-alkyl)-3, 6-diformylcarbazole compounds (2, 4, 6) exhibit
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2
Thermal gravimetric analyses of the N-(long-alkyl)-
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gives the detailed thermal analytical data. These six compounds
7
◦
were seen to be thermally stable up to 300–350 C. However, the
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◦
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◦
◦
loss was 41.84%, in good agreement with the calculated weight
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1
1
◦ ◦
72.83 C while the process is complete up to 553.08 C, cor-
4
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