Regioselective ring-opening of epoxides by carbazole: A direct preparation of novel N-(β-hydroxyalkyl)carbazoles

Article abstract of DOI:10.3184/174751916X14538054606043

The influence of various parameters including solvent, base and temperature on the reaction between carbazole and epoxides was studied This led to the development of a regioselective ring-opening of epoxides by the potassium salt of carbazole in DMSO at 100 °C which is a straightforward way to prepare new N-(β-hydroxyalkyl)carbazoles in good to excellent yields. Fifteen new compounds are described.

Full text of DOI:10.3184/174751916X14538054606043

JOURNAL OF CHEMICAL RESEARCH 2016
VOL. 40 MARCH, 137–140
RESEARCH PAPER 137
Regioselective ring-opening of epoxides by carbazole: a direct preparation of
novel N-(β-hydroxyalkyl)carbazoles
Mohammad Navid Soltani Rad*, Somayeh Behrouz and Samira Ahrari
Medicinal Chemistry Research Laboratory, Department of Chemistry, Shiraz University of Technology, Shiraz 71555-313, Iran
The influence of various parameters including solvent, base and temperature on the reaction between carbazole and epoxides was studied.
This led to the development of a regioselective ring-opening of epoxides by the potassium salt of carbazole in DMSO at 100 °C which is
a straightforward way to prepare new N-(β-hydroxyalkyl)carbazoles in good to excellent yields. Fifteen new compounds are described.
Keywords: carbazole, carbazole potasium salt, epoxide, N-alkylation, N-(β-hydroxyalkyl)carbazole
alkyl halides via SN2-type reactions either under conventional10
or microwave assisted11 conditions, aryl halides using Cu-
catalysed SNAr-type reactions (Ullmann-type reactions)
under microwave irradiation12 and alcohols using Mitsunobu
condition.13 However, to the best of our knowledge, among the
carbon electrophiles used to react with carbazole, no report
has yet appeared for C–N bond formation via ring-opening of
epoxides with carbazole.
Introduction
Carbazole and its substituted derivatives have an undeniable
role in human life science,1 and are an important class of
nitrogen-containing heterocyclic compounds widely found
in nature mainly as naturally-occurring carbazole alkaloids.2
In addition, naturally-occurring carbazole alkaloids as well
as other synthetic carbazole derivatives are well known for
exhibiting many types of pharmacological activity including
anti-inflammatory, antibacterial, anti-tumour, anticonvulsant,
antipsychotic, anti-diabetic, anti-malarial, anticancer, and
anti-Alzheimer properties.3 Also carbazole and its substituted
derivatives have found widespread applications in various
industries,4 such as electroluminescent materials for fabrication
of organic light emitting devices (OLEDs),5 carbazole-based
polymers for solid-state organic dye-sensitised solar cells,6 in
electrochemistry7 and as pigments.8
Despite the importance of carbazole, however, this
compound has rarely found an application in its parental form.
The majority of carbazole scaffolds described above have
diverse organic functionalities either on the aryl residues or the
N-atom.9 The functionalisation of the N-atom in carbazole and
its derivatives is mostly achieved through C–N bond formation.
To accomplish this, a very weakly basic N-atom of carbazole
is activated to react with certain carbon electrophiles such as
Recently,
the
N-(3-phenylamino-2-hydroxypropyl)
carbazole P7C3 and related analogues were reported as new
neuroprotective and pro-neurogenic agents (Fig. 1).14 In the
search for new chemotherapeutic agents, having structural
features resembling P7C3, and also in continuation of our
interest in the design and synthesis of new β-adrenoceptor
blocking agents15–19 like carazolol,20 herein we describe the
regioselective ring-opening of epoxides with carbazole as
a straightforward way to prepare new N-(β-hydroxyalkyl)
carbazoles (Fig. 1).
Results and discussion
Our planned method of preparation of N-(β-hydroxyalkyl)
carbazoles 3 was by heating a variety of epoxides 2 with
carbazole 1 in a solvent in the presence of a base, as shown in
Scheme 1.
Br
CH3 OH
OH
NH
OH
N
O
N
H
R1
R2
H3C
N
N
Br
New compounds
Carazolol
P7C3
R1=aryloxymethyl, alkyloxymethyl, alkyl...
R2=H,alkyl
Fig. 1 The structure of P7C3, carazolol and general structure of synthesised compounds.
O
base, solvent, heat
R1
R2
N
N
H
OH
R1
1
2
3
R2
3a: R1= PhOCH2, R2= H
3h: R1= 2,4-Cl2-C6H3OCH2, R2= H
3i: R1= BuOCH2, R2= H
3j: R1= Me2CHOCH2, R2= H
3k: R1= MeC(=CH2)CO2CH2, R2= H
3l: R1= Me, R2= H
3o:
3b: R1= 4-MeO-C6H4OCH2, R2= H
3c: R1= 4-Et-C6H4OCH2, R2= H
3d: R1= 4-Me2CH-C6H4OCH2, R2= H
3e: R1= 3,4-Me2-C6H3OCH2, R2= H
3f: R1= 3-Me-4-Cl-C6H3OCH2, R2= H
3g: R1= 4-Cl-C6H4OCH2, R2= H
N
OH
3m: R1= Et, R2= H
3n: R1= Me, R2= Me
Scheme 1
* Correspondent. E-mail: soltani@sutech.ac.ir

138 JOURNAL OF CHEMICAL RESEARCH 2016
Table 2 Effects of solvent and temperature on the yields of N-(2-
hydroxycyclohexyl)carbazole 3o prepared by reaction of the potassium
salt of carbazole (1; K for H) and cyclohexene oxide (Scheme 1)a
Table 1 Effects of various bases, temperature and duration of
reaction on the yields of N-(2-hydroxycyclohexyl) carbazole 3o
prepared by reaction of carbazole 1 and cyclohexene oxide
(Scheme 1)a
Entry Solvent
Temperature/°C
Reflux
100
100
100
Time/h
48
10
7
Yield/%b
62
83
91
75
47
34
51
55
42
42
NRc
10
26
56
86
91
Entry Solvent Base
Temperature/°C Time/h Yield/%b
1
H2O
1
2
3
4
5
6
7
8
H2O
EtOH
MeOH
PEG200 KOH
DMF
DMSO
NMP
MeCN
acetone KOH
THF KOH
Toluene KOH
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMF
KOH
KOH
KOH
Reflux
Reflux
Reflux
100
100
100
72
72
72
72
15
10
24
48
48
48
36
10
9
18
25
21
27
46
52
43
35
12
28
NRc
54
56
58
60
61
NR
30
36
28
32
45
49
10
14
65
2
DMF
3
4
DMSO
NMP
14
36
48
24
24
24
36
48
72
48
18
12
7
5
6
MeCN
Acetone
Reflux
Reflux
KOH
KOH
KOH
KOH
7
8
[bmim][BF4] 100
[bmim][Br] 100
100
Reflux
Reflux
Reflux
Reflux
110
120
130
140
150
100
100
100
100
100
100
100
100
9
TBAC
100
Reflux
Reflux
r.t.
50
80
9
10
11
12
13
14
15
16
17
18
THF
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
Toluene
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
KOH
KOH
KOH
KOH
KOH
–
Et3N
DBU
DMAP
DABCO
K2CO3
Cs2CO3
MgO
8
8
90
110
130
150
10
72
24
12
15
14
11
11
48
48
14
7
6
92
92
aReaction conditions: Potassium carbazol-9-ide (0.01 mol), epoxide (0.015 mol) and
solvent (20 mL).
bIsolated yield.
cNo reaction.
fact that the N–H bond of carbazole has a weakly acidic nature
and thus exhibits low nucleophilic power at the N-atom.
To enhance the reaction yield, we then changed the procedure
and used the potassium salt of carbazole instead of a carbazole-
base combination in the reaction. We decided to pre-prepare
the potassium salt of carbazole by dissolving carbazole in a
refluxing ethanolic solution of KOH followed by evaporation of
solvent and recrystallisation from hot MeOH. Having prepared
the potassium salt of carbazole (1; K for H), we investigated
the effect of solvent and temperature on the ring-opening
of cyclohexene oxide with the potassium salt of carbazole
(Table 2). As can be seen among the studied solvents (entries
1–11), DMSO was the best solvent for progress of reaction
giving a yield of 91%. Thus, DMSO was selected for all
subsequent reactions (entry 3). Because of the ionic nature of
the potassium salt of carbazole, we also examined the influence
of some ionic liquids21 as solvents on the sample reaction but
contrary to our expectations no superiority over traditional
organic solvents was observed (entries 7–9). Other solvents
used in this experiment afforded 3o in low to moderate yields,
and the use of toluene failed to generate 3o (entry 11).
We then investigated the influence of temperature on the
sample reaction (entries 3, 12–18). Performing the reaction
at room temperature resulted in a low yield of 3o even if the
reaction time was prolonged. An incremental rise in temperature
improved the reaction yields up to 100 °C, but no improvement
in yield was seen between 100–150 °C.
Having obtained the optimised reaction conditions, the
generality and the scope of this method was investigated
by applying the optimised reaction conditions to a variety of
structurally diverse epoxides (Table 3).
Basic Al2O3 100
NaH 100
aReaction conditions: carbazole (0.01 mol), epoxide (0.015 mol), base (0.01 mol) and
solvent (20 mL).
bIsolated yield.
cNo reaction.
First we wished to establish the optimum conditions for the
reaction. For this purpose, the reaction of carbazole 1 with
cyclohexene oxide which affords 3o, regioselectively, was
selected as a test reaction. The influence of various parameters
including solvent, base and temperature was evaluated.
The results obtained are shown in Table 1. The choice of an
appropriate solvent is of great importance for the efficient
progress of the reaction, so we examined the effect of a variety
of protic and aprotic solvents in the presence of KOH as a base
(entries 1–11). In water, a low yield (18%) of 3o was obtained
after refluxing for 72 h. Other protic solvents were not much
better (entries 2–4). However, applying polar aprotic solvents
somewhat improved the yield (entries 5–10). DMSO gave the
best result (52%) (entry 6) and it was assigned as the solvent of
choice. With DMSO as the selected solvent, we tested the effect
of various temperatures on the yield of the reaction (entries 6,
12–16). As can be seen, by increasing the temperature up to
150 °C, an improvement in yield was observed; however, the
yields obtained were still moderate. As mentioned previously,
the N-atom of carbazole is an extremely weak base and requires
to be activated by an efficient base. In the absence of a base the
reaction, unsurprisingly, could not be achieved at all (entry 17).
We then screened the effect of some organic and inorganic bases
at 100 °C, but none of them were very effective (entries 18–26),
but using NaH as base was the most successful with a yield of
65%. The low yields obtained for products are attributed to the
As shown in Table 3, 14 terminal epoxides containing alkyl,
alkoxy and aryloxy substituents were used to prepare the
corresponding N-(β-hydroxyalkyl)carbazoles 3a–n in yields of
75–91%. In all reactions, the ring-openings of epoxides were
achieved regioselectively, the result of nucleophilic carbazole

JOURNAL OF CHEMICAL RESEARCH 2016 139
carbazole potassium salt was also reported in which 9H-carbazole and
Table 3 Yields and duration of reaction for the preparation of N-(β-
hydroxyalkyl)carbazoles 3a–o by reaction of the potassium salt of
carbazole (1; K for H) with various epoxides 1a–n (Scheme 1)a
KOH was heated in xylene.25
Synthesis of aryloxy glycidyl ethers (2c–f and 2h); general procedure
Entry
1
Productb
3a
Time/h
12
13
15
15
14
15
13
14
9
Yield/%c
87
In a round-bottomed flask (100 mL), a mixture of the appropriate
phenol (0.01 mol), epibromohydrin (2.05 g, 0.015 mol) and K2CO3
(1.38 g, 0.01 mol) in anhydrous MeCN (40 mL) was heated at reflux
for 12–24 h (TLC control). After completion of the reaction, the
solvent was evaporated in vacuo. The foam obtained was dissolved in
CHCl3 (100 mL) and subsequently washed with water (2 × 100 mL).
The organic layer was dried over anhydrous sodium sulphate and
evaporated. The crude aryloxy glycidyl ether was purified by short-
column chromatography on silica gel eluting with n-hexane.
2
3b
90
3
3c
89
4
3d
85
5
3e
87
6
3f
84
7
3g
86
8
9
3h
3i
83
92
Synthesis of 3a–o; general procedure
In a round bottom flask (50 mL), a mixture of potassium carbazol-
9-ide (0.01 mol) and the appropriate epoxide (0.015 mol) in DMSO
(20 mL) was heated at 100 °C until TLC monitoring indicated no
further improvement in the reaction (7–15 h). After completion of the
reaction, the solvent was evaporated in vacuo. The foam obtained was
dissolved in CHCl3 (100 mL) and subsequently washed with water
(2 × 100 mL). The organic layer was dried over anhydrous sodium
sulphate and evaporated. The crude product was purified by short-
column chromatography on silica gel eluting with n-hexane:EtOAc.
1-(9H-Carbazol-9-yl)-3-phenoxypropan-2-ol 3a: Yellow oil
(87%); IR (νmax): 3375, 3049, 2969, 1455, 1297, 1210 cm–1; 1H NMR: δ
3.79–3.82 (m, 1H, CHOH), 3.99 (s, 1H, OH, exchangeable with D2O),
4.20–4.24 (m, 2H, NCH2), 4.40–4.46 (m, 2H, OCH2), 6.78–6.84 (m,
2H, aryl), 7.18–7.49 (m, 11H, aryl); 13C NMR: δ 56.8, 65.1, 71.6, 112.0,
116.2, 117.9, 118.2, 119.8, 120.9, 121.7, 129.8, 132.4, 159.5; MS (EI) m/z
(%): 317 (23.7) (M+); Anal. calcd for: C21H19NO2: C, 79.47; H, 6.03; N,
4.41; found: C, 79.40; H, 6.12; N, 4.56%.
10
11
12
13
14
15
3j
3k
3l
3m
3n
3o
9
8
8
7
7
7
90
75
81
89
88
91
aReaction conditions: Potassium carbazol-9-ide (0.01 mol), epoxide (0.015 mol) and
DMSO (20 mL) at 100 °C.
bAll products were characterised by 1H NMR and 13C NMR, IR, CHN, and MS analysis.
cIsolated yield.
anion attacks predominantly at the less hindered side. Indeed,
in some cases, small amounts of isomers were also obtained
as indicated by GC-analysis (< 5–9%). All the reactions were
completed in 7–15 as indicated by a TLC check. The reaction
of the potassium salt of carbazole with 2-aryloxymethyl-
oxiranes is interesting since the obtained products 3a–h have
a close resemblance to a general structure known to be present
in β-adrenoceptor blocking agents (i.e. R1R2NCH2CH(OH)
CH2OAr).22
1-(9H-Carbazol-9-yl)-3-(4-methoxyphenoxy)propan-2-ol 3b: White
prisms (90%); m.p. 85–87 °C; IR (νmax): 3370, 3068, 2940, 1474, 1269,
1
1218 cm–1; H NMR: δ 2.16 (s, 3H, OCH3), 3.95 (dd, J = 4.9, 11.2 Hz,
2H, NCH2), 4.18 (s, 1H, OH, exchangeable with D2O), 4.37–4.41 (m,
3H, OCH2, CHOH), 6.79–6.85 (m, 4H, aryl), 7.20–7.24 (m, 6H, aryl),
7.46–7.51 (m, 2H, aryl); 13C NMR: δ 57.5, 59.4, 65.0, 71.9, 112.0, 115.8,
117.0, 118.7, 120.2, 121.8, 124.1, 133.0, 151.5, 158.6; MS (EI) m/z (%):
347 (11.3) (M+); Anal. calcd for: C22H21NO3: C, 76.06; H, 6.09; N, 4.03;
found: C, 75.94; H, 6.17; N, 3.90%.
The biological activities of the title compounds are currently
under investigation and will be reported in due course.
Experimental
1-(9H-Carbazol-9-yl)-3-(4-ethylphenoxy)propan-2-ol 3c: White
prisms (89%); m.p. 89–91 °C; IR (νmax): 3400, 3077, 2965, 1485, 1273,
All chemical reagents were purchased from Merck, Fluka or Sigma-
Aldrich companies. The aryloxy glycidyl ethers were either purchased
or synthesised via coupling of appropriate phenols and epibromohydrin
according to the reported procedure.23,24 Solvents were purified by
standard procedures, and stored over 3Å molecular sieves. Reactions
were followed by TLC using SILG/UV 254 silica-gel plates. Column
chromatography was performed on silica gel 60 (0.063–0.200 mm,
70–230 mesh; ASTM). Melting points were determined using an
Electrothermal IA 9000 melting point apparatus in open capillary
tubes and are uncorrected. IR spectra were obtained using a Shimadzu
1
1230 cm–1; H NMR: δ 1.43 (t, J = 7.3 Hz, 3H, CH3), 2.60 (q, J = 7.3
Hz, 2H, CH2CH3), 3.92–3.97 (m, 3H, NCH2CH), 4.17 (s, 1H, OH,
exchangeable with D2O), 4.52–4.61 (m, 2H, OCH2), 6.95 (d, J = 8.0
Hz, 2H, aryl), 7.38–7.46 (m, 10H, aryl); 13C NMR: δ 16.0, 34.1, 59.7,
65.8, 71.9, 112.8, 117.5, 119.8, 120.6, 122.0, 123.9, 129.1, 130.9, 131.6,
152.0; MS (EI) m/z (%): 345 (22.9) (M+); Anal. calcd for: C23H23NO2:
C, 79.97; H, 6.71; N, 4.05; found: C, 80.06; H, 6.80; N, 3.94%.
1-(9H-Carbazol-9-yl)-3-(4-isopropylphenoxy)propan-2-ol 3d: White
cubes (85%); m.p. 64–66 °C; IR (νmax): 3340, 3025, 2990, 1468, 1280,
1209 cm–1; 1H NMR: δ 1.64 (d, J = 7.5 Hz, 6H, 2CH3), 2.98–3.05 (m, 1H,
CH(CH3)2), 3.91–3.95 (m, 2H, NCH2), 4.13 (s, 1H, OH, exchangeable
with D2O), 4.45–4.52 (m, 3H, OCH2CH), 6.98–7.09 (m, 4H, aryl),
7.26–7.47 (m, 8H, aryl); 13C NMR: δ 23.9, 37.0, 59.7, 65.6, 71.5, 112.4,
117.8, 119.0, 120.7, 122.0, 124.1, 129.0, 131.0, 132.7, 153.9; MS (EI) m/z
(%): 359 (9.4) (M+); Anal. calcd for: C24H25NO2: C, 80.19; H, 7.01; N,
3.90; found: C, 80.26; H, 7.09; N, 3.95%.
1-(9H-Carbazol-9-yl)-3-(3,4-dimethylphenoxy)propan-2-ol 3e: White
needles (87%); m.p. 83–85 °C; IR (νmax): 3425, 3041, 2938, 1467, 1289,
1251 cm–1; 1H NMR: δ 2.29 (s, 3H, CH3), 3.04 (s, 3H, CH3), 3.68–3.77
(m, 3H, NCH2CH), 4.01 (s, 1H, OH, exchangeable with D2O), 4.16 (dd,
J = 6.9, 13.5 Hz, 1H, OCHAHB), 4.43 (dd, J = 3.1, 13.5 Hz, 1H, OCHAHB),
6.78–6.85 (m, 4H, aryl), 6.98–7.12 (m, 7H, aryl); 13C NMR: δ 24.1, 25.0,
59.3, 65.0, 72.3, 111.9, 112.7, 116.9, 118.7, 119.3, 120.9, 123.0, 129.8,
131.2, 132.9, 138.0, 159.1; MS (EI) m/z (%): 345 (15.7) (M+); Anal. calcd
for: C23H23NO2: C, 79.97; H, 6.71; N, 4.05; found: C, 80.04; H, 6.79; N,
3.92%.
FTIR-8300 spectrophotometer. H NMR and 13C NMR spectra were
1
recorded in CDCl3 on a Brüker Avance-DPX-250 spectrometer
operating at 250 and 62.5 MHz, respectively. Chemical shifts
are given in δ relative to tetramethylsilane (TMS) as an internal
standard, coupling constants J are given in Hz. Abbreviations used for
1H NMR signals are: s = singlet, d = doublet, t = triplet, q = quartet,
m = multiplet, br = broad. GC/MS was performed on a Shimadzu GC/
MS-QP 1000-EX apparatus (m/z; rel.%). Elemental analyses were
performed on a Perkin–Elmer 240-B micro-analyser.
Synthesis of potassium carbazol-9-ide (1; K for H); general procedure
In a round-bottomed flask (100 mL), a mixture of 9H-carbazole
(1.67 g, 0.01 mol) and KOH (0.67 g, 0.012 mol) in EtOH (40 mL) was
heated at reflux for 4 h (TLC control). The solvent was then evaporated
and dried to afford crude carbazole potassium salt (1; K for H), which
was recrystallised from hot methanol (50 mL) to give a bright yellow-
brown solid (1.95 g, 95%). An alternative method for preparation of

140 JOURNAL OF CHEMICAL RESEARCH 2016
1-(9H-Carbazol-9-yl)-3-(4-chloro-3-methylphenoxy)propan-2-ol 3f:
Yellow oil (84%); IR (νmax): 3364, 3100, 2950, 1469, 1304, 1227, 758 cm–1;
1H NMR: δ 2.37 (s, 3H, CH3), 3.98–4.03 (m, 2H, NCH2), 4.29 (s, 1H, OH,
exchangeable with D2O), 4.56–4.70 (m, 3H, OCH2, CHOH), 6.80–6.85
(m, 3H, aryl), 7.18–7.43 (m, 8H, aryl); 13C NMR: δ 21.9, 59.4, 65.0, 71.2,
112.0, 113.9, 118.1, 119.5, 120.3, 121.9, 122.3, 126.7, 130.9, 132.0, 138.1,
158.3; MS (EI) m/z (%): 365 (16.6) (M+); Anal. calcd for: C22H20ClNO2:
C, 72.22; H, 5.51; N, 3.83; found: C, 72.35; H, 5.65; N, 3.89%.
1-(9H-Carbazol-9-yl)-3-(4-chlorophenoxy)propan-2-ol 3g: Yellow oil
(86%); IR (νmax): 3395, 3050, 2977, 1483, 1275, 1213, 760 cm–1; 1H NMR:
δ 3.47 (d, J = 6.8 Hz, 1H, NCHAHB), 3.70 (s, 1H, OH, exchangeable with
D2O), 3.82 (d, J = 6.8 Hz, 1H, NCHAHB), 4.09 (dd, J = 6.4, 16.2 Hz, 2H,
OCH2), 4.28–4.33 (m, 1H, CHOH), 6.52–6.61 (m, 4H, aryl), 7.05–7.25
(m, 8H, aryl); 13C NMR: δ 58.8, 64.9, 73.0, 112.7, 117.0, 118.2, 119.6, 121.9,
123.2, 127.1, 130.5, 132.9, 159.1; MS (EI) m/z (%): 351 (18.9) (M+); Anal.
calcd for: C21H18ClNO2: C, 71.69; H, 5.16; N, 3.98, found: C, 71.58; H,
5.23; N, 4.06%.
(m, 8H, aryl); 13C NMR: δ 9.8, 28.5, 63.7, 72.0, 112.3, 119.8, 121.4,
122.1, 123.9, 132.7; MS (EI) m/z (%): 239 (18.9) (M+); Anal. calcd for:
C16H17NO: C, 80.30; H, 7.16; N, 5.85; found: C, 80.35; H, 7.24; N, 5.93%.
1-(9H-Carbazol-9-yl)-2-methylpropan-2-ol 3n: White cubes (88%);
m.p. 107–109 °C; IR (νmax): 3510, 3074, 2953, 1480, 1289, 1250 cm–1;
1H NMR: δ 0.95 (s, 6H, 2CH3), 2.94 (s, 1H, OH, exchangeable with D2O),
3.81 (s, 2H, NCH2), 7.18–7.24 (m, 4H, aryl), 7.40–7.48 (m, 4H, aryl);
13C NMR: δ 27.1, 66.2, 70.8, 112.6, 118.5, 120.3, 121.9, 122.8, 132.6; MS
(EI) m/z (%): 239 (15.3) (M+); Anal. calcd for: C16H17NO: C, 80.30; H,
7.16; N, 5.85; found: C, 80.43; H, 7.25; N, 5.80%.
2-(9H-Carbazol-9-yl)cyclohexanol 3o: Yellow oil (91%); IR (νmax):
3389, 3065, 2948, 1471, 1302 cm–1; 1H NMR: δ 1.31–1.37 (m, 4H, 2CH2),
1.69–1.78 (m, 4H, 2CH2), 2.97 (s, 1H, OH, exchangeable with D2O),
3.82–3.90 (m, 2H, NCHCHOH), 7.26–7.54 (m, 8H, aryl); 13C NMR: δ
21.9, 25.2, 28.0, 32.9, 59.9, 70.1, 112.9, 118.6, 120.3, 121.4, 123.7, 132.8;
MS (EI) m/z (%): 265 (19.8) (M+); Anal. calcd for: C18H19NO: C, 81.47;
H, 7.22; N, 5.28; found: C, 81.58; H, 7.14; N, 5.37%.
1-(9H-Carbazol-9-yl)-3-(2,4-dichlorophenoxy)propan-2-ol 3h: White
prisms (83%); m.p. 113–115 °C; IR (νmax): 3412, 3100, 2985, 1462, 1309,
The authors wish to thank Shiraz University of Technology
research council for partial support of this work.
1
1226, 820, 750 cm–1; H NMR: δ 3.62 (s, 1H, OH, exchangeable with
D2O), 3.94–3.97 (m, 2H, NCH2), 4.17–4.31 (m, 3H, OCH2CH), 6.67–7.29
(m, 9H, aryl), 7.90 (d, J = 8.1 Hz, 2H, aryl); 13C NMR: δ 57.9, 63.8, 71.3,
113.0, 118.1, 119.6, 120.5, 121.9, 122.4, 124.0, 127.9, 129.1, 131.9, 133.5,
152.7; MS (EI) m/z (%): 385 (21.6) (M+); Anal. calcd for: C21H17Cl2NO2:
C, 65.30; H, 4.44; N, 3.63; found: C, 65.19; H, 4.51; N, 3.67%.
Received 29 November 2015; accepted 29 December 2015
Paper 1503745 doi: 10.3184/174751916X14538054606043
Published online: 8 February 2016
1-Butoxy-3-(9H-carbazol-9-yl)propan-2-ol 3i: White needles (92%);
m.p. 111–113 °C; IR (νmax): 3350, 3100, 2985, 1473, 1295, 1217 cm–1;
1H NMR: δ 0.93 (t, J = 7.5 Hz, 3H, CH3), 1.34–1.41 (m, 2H, CH2CH3),
1.54–1.59 (m, 2H, OCH2CH2), 2.54 (s, 1H, OH, exchangeable with D2O),
3.25–3.40 (m, 4H, CH2OCH2), 4.20–4.22 (m, 1H, CHOH), 4.33–4.40
(m, 2H, NCH2), 7.18–7.24 (m, 2H, aryl), 7.43–7.48 (m, 4H, aryl), 8.04 (d,
J = 7.8 Hz, 2H, aryl); 13C NMR: δ 13.9, 20.8, 33.7, 59.0, 64.1, 72.9, 75.4,
112.5, 119.1, 120.9, 121.6, 122.3, 132.4; MS (EI) m/z (%): 297 (20.1) (M+);
Anal. calcd for: C19H23NO2: C, 76.73; H, 7.80; N, 4.71; found: C, 76.61; H,
7.73; N, 4.79%.
1-(9H-Carbazol-9-yl)-3-isopropoxypropan-2-ol 3j: Yellow oil (90%);
IR (νmax): 3400, 3050, 2956, 1479, 1297, 1225 cm–1; 1H NMR: δ 0.94 (d,
J = 7.3 Hz, 6H, 2CH3), 3.15 (dd, J = 4.1, 10.5 Hz, 2H, OCH2), 3.32–3.37
(m, 1H, CH(CH3)2), 3.49–3.54 (m, 1H, CHOH), 3.79 (s, 1H, OH,
exchangeable with D2O), 4.12 (dd, J = 6.5, 12.7 Hz, 1H, NCHAHB), 4.46
(dd, J = 3.4, 13.8 Hz, 1H, NCHAHB), 7.20–7.27 (m, 4H, aryl), 7.45–7.56
(m, 4H, aryl); 13C NMR: δ 24.1, 59.7, 65.6, 68.0, 74.1, 112.8, 118.6, 119.8,
121.0, 122.9, 133.5; MS (EI) m/z (%): 283 (18.2) (M+); Anal. calcd for:
C18H21NO2: C, 76.29; H, 7.47; N, 4.94; found: C, 76.37; H, 7.40; N, 5.02%.
3-(9H-Carbazol-9-yl)-2-hydroxypropyl methacrylate 3k: Green
prisms (75%); m.p. 114–116 °C; IR (νmax): 3370, 3100, 2982, 1740,
1459, 1310, 1240 cm–1; 1H NMR: δ 2.68 (s, 3H, CH3), 3.31–3.39 (m, 3H,
NCH2CH), 3.86 (s, 1H, OH, exchangeable with D2O), 4.05 (dd, J = 6.8,
13.5 Hz, 1H, OCHAHB), 4.56 (dd, J = 3.4, 13.6 Hz, 1H, OCHAHB), 4.91 (s,
1H, =CHAHB), 5.27 (s, 1H, =CHAHB), 7.26–7.34 (m, 2H, aryl), 7.50–7.58
(m, 2H, aryl), 7.83–7.89 (d, J = 8.0 Hz, 2H, aryl), 8.21 (d, J = 8.0 Hz, 2H,
aryl); 13C NMR: δ 20.6, 59.8, 65.3, 70.1, 111.8, 118.6, 119.9, 120.7, 122.9,
124.2, 133.7, 137.1, 170.2; MS (EI) m/z (%): 309 (16.9) (M+); Anal. calcd
for: C19H19NO3: C, 73.77; H, 6.19; N, 4.53; found: C, 73.85; H, 6.12; N,
4.67%.
References
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1-(9H-Carbazol-9-yl)propan-2-ol 3l: Creamy needle crystals (81%);
m.p. 103–105 °C; IR (νmax): 3410, 3020, 2946, 1460, 1315 cm–1; 1H NMR:
δ 1.21–1.31 (m, 3H, CH3), 2.44 (s, 1H, OH, exchangeable with D2O),
4.31–4.40 (m, 2H, NCH2), 4.69–4.77 (m, 1H, CHOH), 7.22–7.28 (m, 4H,
aryl), 7.47–7.49 (m, 4H, aryl); 13C NMR: δ 25.8, 65.0, 68.9, 112.0, 118.3,
119.1, 120.9, 123.1, 132.8; MS (EI) m/z (%): 225 (12.5) (M+); Anal. calcd
for: C15H15NO: C, 79.97; H, 6.71; N, 6.22; found: C, 80.05; H, 7.78; N,
6.34%.
1-(9H-Carbazol-9-yl)butan-2-ol 3m: White prisms (89%); m.p.
1
113–115 °C; IR (νmax): 3400, 3087, 2938, 1450, 1284 cm–1; H NMR:
δ 0.91 (t, J = 7.4 Hz, 3H, CH3), 1.41–1.45 (m, 2H, CH2CH3), 3.01 (s, 1H,
OH, exchangeable with D2O), 3.62–3.65 (m, 1H, CHOH), 3.89–3.96
(m, 1H, NCHAHB), 4.15 (dd, J = 2.9, 12.8 Hz, 1H, NCHAHB), 7.28–7.50
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