Nano sulfated titania as solid acid catalyst in direct synthesis of fatty acid amides

Article abstract of DOI:10.1021/jo2002769

Nanosized sulfated titania was prepared by a sol-gel hydrothermal process. X-ray diffraction (XRD), transmission electron, and scanning electron micrographs (TEM and SEM), FT-IR specific surface area, and BET N₂ adsorption were employed to characterize the properties of the synthesized sulfated TiO₂. The results indicate that both anatase and rutile TiO₂ are obtainable. This prepared sulfated titania showed high catalytic activity in direct amidation of fatty acids as well as benzoic acids with various amines under solvent-free conditions.

Full text of DOI:10.1021/jo2002769

ARTICLE
pubs.acs.org/joc
Nano Sulfated Titania as Solid Acid Catalyst in Direct Synthesis of Fatty
Acid Amides
Mona Hosseini-Sarvari,*,† Esmat Sodagar,† and Mohammad Mahdi Doroodmand†,‡
†Department of Chemistry and ‡Nanotechnology Research Institute, Shiraz University, Shiraz 71454, I. R. Iran
S Supporting Information
b
ABSTRACT: Nanosized sulfated titania was prepared by a
solꢀgel hydrothermal process. X-ray diffraction (XRD), trans-
mission electron, and scanning electron micrographs (TEM and
SEM), FT-IR specific surface area, and BET N2 adsorption were
employed to characterize the properties of the synthesized
sulfated TiO2. The results indicate that both anatase and rutile
TiO2 are obtainable. This prepared sulfated titania showed high catalytic activity in direct amidation of fatty acids as well as benzoic
acids with various amines under solvent-free conditions.
’ INTRODUCTION
In recent years, solid catalysts have been of considerable
interest because of their advantages such as nonhazardous nature,
selectivity, requirement in catalytic amounts, and easier reaction
workup. The ease of separation and option of reusability of the
solid catalysts render the process as green. Among the various
solid catalysts, sulfated metal oxides are potential catalysts for
many reactions. Sulfated titania has been proven one of the most
useful sulfated metal oxides.
In this paper, as a part of our continuing research works on
nano metal oxides catalysts,18 we report the preparation of a new
nano-sized sulfated titania by a solꢀgel method that have a large
specific surface area ∼218 m2 gꢀ1. Furthermore, the catalytic
activity of nano sulfated titania was applied to effective synthesis
of fatty amides in the absence of any coupling reagents and
solvents.
Amide bond linkage is a worldwide and important core
structure in pharmaceutical, chemical, and many natural pro-
ducts.1 Many procedures for the formation of amides are known
in the literature.2 The most common methods are the reaction
between carboxylic acid derivatives particularly acid halides, acid
anhydrides, and esters with the amines. Despite their wide scope,
limitations are associated with the use of acid halides, anhydrides,
and esters. Limitations are mostly due to the limited stability of
many acid chlorides and the need for preparation of hazardous
reagents (thionyl chlorides, etc.), which release corrosive and
volatile byproducts. Reactions with esters require strongly basic
or acidic catalysts.3 Thus, the reaction between carboxylic acids
and amines for the preparation of amides is preferred.
Fatty acid amides are of considerable interest due to their wide
rang of application in lubricants, surfactants, cosmetics, shampoo,
detergents, photographic materials, polyolefin foaming materials,
polymer stabilizers, photocurable developers, and pigments.4ꢀ10
Fatty acid amides have been prepared by reaction of fatty acids
with anhydrous ammonia under high temperature (200 °C) and
high pressure.11 In this procedure, an additional purification step
is also required to obtain pure fatty amide. To overcome these
drawbacks, enzymatic synthesis offers potential alternative
processes.12ꢀ15 However, in their preparation procedures, pri-
mary fatty amides such as oleamide from oleic acid and erucamide
from erucic acid have been prepared as the main products.
Recently, Sharma,16a Khare,16b and co-workers reported that
synthesis of bioactive N-alkyl fatty amide derivatives using
enzymes as catalyst. Terada16c and co-workers have also devel-
oped metal salts as versatile catalysts for amidation of fatty acids.
Therefore, amidation of fatty acids imparts a broad spectrum
of activity against bacteria, yeasts, and molds.17 Due to enhanced
functionality and significant bioactive properties in secondary
fatty amides, there is an increasing interest in their production
and characterization. Thus, a need to develop new methods for
environmentally friendly amidation is substantial.
’ RESULTS AND DISCUSSION
X-ray Diffraction (XRD) Analysis. Figure 1 shows the XRD
pattern of nano sulfated TiO2. Combination of both phases’
rutile TiO2 and anatase TiO2 morphologies are clearly shown
according to the XRD pattern. The peaks positioned at 2θ = 25ο,
32ο, and 38ο are related to the (110), (101), and (111) of rutile
TiO2, respectively, whereas the peaks situated at 2θ = 48ο and
72ο belong to the (211) and (220) phases of the anatase TiO2
structure.19 The average crystallite size was determined using the
Scherrer equation.20 Therefore, in accordance with the XRD
pattern, it is clearly implied that the proposed procedure majored
to the formation of both morphologies including rutile and
anatase TiO2.
SEM and TEM. The size and structure of the sulfated TiO2
were also evaluated using scanning electron microscopy (SEM)
and transmission electron microscopy (TEM). According to the
Received: February 5, 2011
Published: March 15, 2011
r
2011 American Chemical Society
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Figure 4. FT-IR spectrum of nano sulfated TiO2.
Figure 1. XRD pattern of nano sulfated TiO2.
Figure 2. SEM image of nano sulfated TiO2.
Figure 5. Thermograms revealing the thermal stability of (A) pure
TiO2 and (B) sulfated TiO2.
in the rutile form.21 This presence of a well-defined band
positioned at 666.90 cmꢀ1 is quite evident, which is related to
the formation of TiO2 in rutile morphology (see Figure 4). On
the basis of the literature,21 the absorbance bands related to the
TiꢀO stretching and TiꢀOꢀTi bending characterize the for-
mation of the anatase structure of TiO2. In this study according
to the FT-IR spectrum (Figure 4) only a broad absorbance band
positioned at 666.90 cmꢀ1 reveals the formation of TiO2 in both
rutile and anatase forms. This result is in accord with that
obtained from the XRD studies. Also, the peaks positioned at
1047.72 and 1138.83 cmꢀ1 are related to stretching of the SdO
band.22 It should be noted that one band at 1626.31 cmꢀ1
,
belongs to HꢀOꢀH bending during the adsorption of water
molecules. In addition, the strong peak at 3347.38 cmꢀ1 is due to
the stretching of OH groups caused during the adsorption of
water.23 In this study, the adsorption of water molecules was
shown using thermogravimetric (TG) analysis.
The thermal behavior of nano sulfated TiO2 and pure TiO2 is
shown in Figure 5. A significant decrease in the weight percen-
tage of the sulfated TiO2 at about ∼100 °C is related to
desorption of water molecules from the catalyst substrate. This
was evaluated to ∼0.7% according to the TG analysis. In
addition, the sharp decrease in the weight percentage at tem-
perature around 290 °C is due to the decomposition of sulfuric
acid and formation of sulfur dioxide. According to the thermo-
gram, the amount of sulfuric acid functionalized on TiO2 support
is evaluated to be ∼5.8% (w/w).
Figure 3. TEM image of nano sulfated TiO2.
SEM (Figure 2) and TEM (Figure 3), it was observed that the
synthesized sulfated TiO2 catalyst have nano dimension ranging
from ∼40 to 250 nm. It was also observed that, during the
sulfonation of TiO2, some of TiO2 morphologies are partially
aggregated with each other, resulting in the formation of larger
clusters of TiO2 nano particles.
FT-IR Spectroscopy and Thermogravimetric Analysis. In
this work, FT-IR spectroscopy is adopted as an applicable
technique for further characterization of the sulfated TiO2. The
IR spectrum of TiO2 has been reported in the literature, and two
well-defined bands at 646 and 552 cmꢀ1 were attributed to TiO2
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amount of stearic acid (Table 1). Excellent results were obtained
in each case affording the corresponding amide derivatives in
70ꢀ98% yields in 3ꢀ12 h at 115 °C under solvent-free
conditions.
As shown in Table 1, various aromatic and aliphatic amine as
well as heterocyclic and ambidentate amines react with stearic
acid to give the corresponding amides in good to high yields. In
most cases, the product obtained after the usual workup was pure
(spectral data), without requiring additional efforts of purifica-
tion. Wherever required, the purification was performed by
column chromatography.
Moreover, the mildness/efficiency and chemoselectivity of the
nano sulfated TiO2 were demonstrated with heteroaromatic and
aromatic diamines (entries 7, 8) that resulted in the formation of
the corresponding mono amide in excellent yield. It is interesting
to note that in the case of the amines 2g and 2h when we used 2
equiv of amines in the reaction conditions, selectively the
corresponding mono amides 3g and 3h were obtained in the
same yield, without any side product.
Figure 6. Nitrogen adsorption isotherms of (A) pure TiO2 and (B)
sulfated TiO2.
Scheme 1
In the case of amidation of morpholine with stearic acid, the
corresponding amide was obtained in a yield higher than that
reported by Taddei et al.24 by using solid supported chloro-
[1,3,5]triazine as catalyst. It is interesting to note that fatty
acid amides plasticizers have shown that the morpholides of
fatty acids such as oleic acid and stearic acids are compatible
and efficient plasticizers for homo- and copolymers of vinyl
chloride.25
Recently N-alkyl fatty acid amides have assumed great
important,26 so we planned to investigate the application of
nano sulfated TiO2 catalyst for synthesis of N-alkyl fatty amides.
The amidation of fatty amines such as dodecyl amine and
hexadecyl amine was performed with stearic acid using nano
sulfated TiO2 as catalyst. The amidation proceeded efficiently for
both fatty amines, resulting in the formation of corresponding
fatty acid amides in high yield (98%) (entries 12, 13). Nanosul-
fated TiO2 gave amides in high yields irrespective of the chain
length of fatty amine. These tendencies are different from recent
reports that the catalytic activity of various catalyst changed with
the changing of the chain length of amines.27
From further analysis of the synthesized catalyst, the value of
pH of sulfated TiO2 emulsion was studied. For this purpose, the
same amounts of pure TiO2 or sulfated TiO2 (∼0.02 g) were
sonicated inside two separated bottles containing 5.0 mL H2O.
Under similar conditions, it was observed that there is a
significant difference in the pH. This difference was evaluated
to ∼5.13 pH units, revealing the capability of the synthesized
catalyst to act as a suitable proton-donating agent during the
synthesis of organic compounds.
Nitrogen Adsorption Isotherm. The N2 adsorption iso-
therms of the synthesized sulfated TiO2 and pure TiO2 at
25 °C using a homemade TG analysis system are shown in
Figure 6. In accordance with the N2 adsorption isotherms,
significant increase to ∼0.8% was evaluated for TiO2 during
the sulfate process. According to the N2 adsorption isotherms,
there is a significant increase to ∼218 m2 gꢀ1 in the active surface
area of the TiO2 during the sulfate process.
Catalytic Activity of the Nano Sulfated TiO2 for Amidation
of Carboxylic Acids. The main objective of the present work is
to investigate and characterize the activity of nano sulfated TiO2
as the heterogeneous catalyst for direct amidation of carboxylic
acids. So far, it was tested as catalyst for the amidation of fatty
acids. To find out the activity of nano sulfated TiO2 as a general
amidation catalyst, we chose stearic acid 1a as a representative
substrate and treated 1a with aniline 2a under solvent-free
conditions. The amidation of 1a was completed in 3 h at
115 °C by using a catalytic amount of nano sulfated TiO2
(0.011 mo%) to give stearamide 3a in 98% yield (Scheme 1).
Performing the experiment in the absence of nano sulfated
TiO2 did not lead to any products even after 48 h. On the other
hand, this catalyst lost its efficiency in the presence of organic
solvents such as ethanol, acetonitrile, toluene, chloroform,
dichloromethane, and water. This observation gives the impres-
sion that the solvent-free condition plays an important role in this
reaction.
In addition, caprylic and lauric acids were also reacted with
aniline to form the corresponding amides in the same reaction
conditions. In both cases the corresponding amides obtained in
high yields (98%) after 3 h (Scheme 2).
In order to investigate and generalize the reaction condition, we
then chose a range of aromatic carboxylic acids in the amidation
reaction using nano sulfated titania under the same reaction
conditions (Scheme 3). The results are shown in Table 2.
In conclusion, the production of N-alkyl fatty acid amides from
the amidation of stearic acid, caprylic acid, and lauric acid with
various amines using nano sulfated TiO2 as a catalyst was
investigated in the present study. The nano sulfated TiO2 was
obtained by solꢀgel methodology and characterized in terms of
its acidity and structural aspects. Also, this catalyst is very active in
the amidation of fatty acids and also aromatic/aliphatic car-
boxylic acids with various amines. The advantages are as follows:
(a) the use of a cheap and easily prepared catalyst, (b) solvent-
free conditions, (c) short reaction times and high yields, (d) easy
reaction procedure and workup, (e) use of very low catalytic
amount of catalyst (0.011 mol %), and (f) stoichiometric
amounts of both components (acid and amine) in order to
avoid environmental waste and fulfill the philosophy of green
chemistry.28
To establish the general applicability of nano sulfated TiO2 as
an amidation catalyst, a wide range of anilines containing various
electron-donating and -withdrawing groups and primary and
secondary aliphatic amines were treated with an equimolar
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a
Table 1. Direct Amidation of Various Amines (2) with Stearic Acid 1a Catalyzed by Nano Sulfated TiO2
a Reaction conditions: stearic acid (1.0 mmol), amine (1.0 mmol), catalyst (0.011 mol %), in an oil bath at 115 °C. b Isolated yield.
Scheme 2
Scheme 3
Catalyst Preparation. Sulfated TiO2 nano powder was prepared
by a solꢀgel process. Titanium isobutoxide (98% Fluka) was used as the
source of TiO2. A 14.3 mL portion of Ti (OC4H9)4 was hydrolyzed in
150 mL of water containing 1.25 mL of nitric acid (65% Merck), and then
the aqueous solution was stirred continuously at room temperature for 2 h
to form a highly dispersed sol, which was concentrated and dried at 60 °C.
Sulfation was done using 0.5 M sulfuric acid solution (2.0 g mLꢀ1). The
samples, after 2 h of drying at 110 °C, were calcined for 5 h at 500 °C.
Amidation of Carboxylic Acids with Amines. Amidation
reaction was performed in a flux at atmospheric pressure equipped with
’ EXPERIMENTAL SECTION
Materials and Instruments for Preparation and Character-
ization of the Catalyst. Titanium isobutoxide (C16H36O4Ti) was
purchased from Fluka Company. Power X-ray diffraction (XRD) was
performed on a Bruker D8-advance X-ray diffractometer with Cu KR
(λ = 1.54178 Å) radiation. The morphology of the products were deter-
mined by using Leica Cambridge, model s360, version V03.03 Scanning
electron microscopy (SEM) performed at accelerating voltage of 25 Kv. The
size of the nano flakes was confirmed by a Philips CM10 TEM instrument.
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a
Table 2. Direct Amidation of Various Carboxylic Acids with Aniline Catalyzed by Nano Sulfated TiO2
a Reaction conditions: benzoic acids (1.0 mmol), aniline (1.0 mmol), in an oil bath at 115 °C. b Isolated yield.
a Teflon-coated magnetic stir bar. A mixture of carboxylic acid
(1.0 mmol), amine (1.0 mmol), and nano sulfated TiO2 (0.2 g,
0.011 mol %) was stirred magnetically at 115 °C and monitored by TLC
or GC. The reaction mixture was diluted with EtOAc (10 mL) and
centrifuged to remove the catalyst. The filtrate was washed with satd aq
NaHCO3 (3 ꢁ 10 mL) and water (3 ꢁ 10 mL) to afford the crude
product, which was dried over CaCl2 and concentrated by rotary vacuum
evaporation. Further purification was performed by column chromatog-
raphy using petroleum ether and EtOAc as solvent to yield the expected
products. All products were characterized by NMR, IR, mass spectra,
and CHN analysis data, which for known compounds were found to be
identical with the literature and only 1H and 13C NMR. The complete
spectroscopic data are described in Supporting Information.
N-(2-Chlorophenyl) Stearamide (3c)29. White solid; mp 68ꢀ
70 °C; 1H NMR (250 MHz, CDCl3) δ 0.87 (3H, t, J = 6.30 Hz), 1.25
(28H, m), 1.62ꢀ1.73 (2H, m), 2.3 (2H, t, J = 7.42 Hz), 6.98ꢀ7.04
(1H, m), 7.20ꢀ7.35 (2H, m), 7.68 (1H, s), 8.37 (1H, d, J = 8.05 Hz);
13C NMR (62.9 MHz, CDCl3) δ 14.1, 22.7, 24.7, 24.9, 25.5, 27.9, 29.1,
29.2, 29.3, 29.4, 29.4, 29.5, 29.5, 29.6, 29.7, 31.9, 37.9, 121.8, 122.7,
124.5, 127.6, 128.9, 134.5, 171.6.
N-(3-Chlorophenyl) Stearamide (3d)29. White solid; mp
51ꢀ53 °C; 1H NMR (250 MHz, CDCl3) δ 0.87 (3H, t, J = 6.30 Hz),
1.25 (28H, m), 1.62ꢀ1.73 (2H, m), 2.3 (2H, t, J = 7.42 Hz), 7.04
(1H, m), 7.22ꢀ7.28 (2H, m), 7.37 (1H, d, J = 8.05 Hz), 7.64 (1H, s);
13C NMR (62.9 MHz, CDCl3) δ 14.1, 22.7, 25.6, 29.3, 29.4, 29.4, 29.5,
29.6, 29.7, 29.7, 31.9, 37.7, 117.9, 120.1, 124.2, 129.8, 134.5, 139.2, 172.1
some peaks were overlapped.
N-Phenyl Stearamide (3a). White solid; mp 85ꢀ87 °C; 1H NMR
(250 MHz, CDCl3) δ 0.85 (3H, t, J = 6.59 Hz), 1.25 (28H, m),
1.69ꢀ1.71 (2H, m), 2.21 (2H, t, J = 7.46 Hz), 7.09 (1H, m), 7.26
(1H, s), 7.33 (2H, m), 7.50ꢀ7.53 (2H, m); 13C NMR (62.9 MHz,
CDCl3) δ 14.1, 22.7, 25.5, 29.3, 29.4, 29.5, 29.7, 31.9, 37.8, 119.8, 124.1,
128.9, 138.7, 173.5 some peaks were overlapped; IR cmꢀ1 (KBr) 1657,
2912, 3342; MS m/z (%) 359 (0.4) [Mþ]. Anal. Calcd for molecular
formula C24H41NO: C, 80.16; H, 11.49%. Found: C, 80.02, H, 11.33%.
N-(4-Clorophenyl) Stearamide (3e)29. White solid; mp 56ꢀ
58 °C; 1H NMR (250 MHz, CDCl3) δ 0.86 (3H, t, J = 6.86 Hz), 1.25
(28H, m), 1.47 (2H, m), 2.18 (2H, t, J = 7.40 Hz), 7.24 (1H, d, J = 8.83
Hz), 7.38 (1H, s), 7.45 (1H, d, J = 8.89 Hz); 13C NMR (62.9 MHz,
CDCl3) δ 14.1, 22.7, 25.5, 29.2, 29.4, 29.5, 29.6, 29.7, 31.9, 37.7, 120.9,
128.9, 136.6, 173.1 some peaks were overlapped.
N-(4-(4-Aminophenoxy)phenyl) Stearamide (3f)30. Yellow
solid; mp 116ꢀ118 °C; 1H NMR (250 MHz, DMSO-d6) δ 0.82 (3H, t,
J = 6.75 Hz), 1.20 28H, m), 1.46ꢀ1.53 (2H, m), 2.3 (2H, t, J = 7.20 Hz),
5.10 (1H, s), 6.56 (2H, d, J = 7.73 Hz), 6.69 (2H, d, J = 7.67 Hz), 6.77
(2H, d, J = 7.98 Hz), 7.47 (2H, d, J = 8.81 Hz), 9.74 (2H, s); 13C NMR
(62.9 MHz, CDCl3) δ 14.1, 22.7, 24.9, 25.4, 29.2, 29.4, 29.5, 29.7, 31.9,
29
1
N-P-Tolyl stearamide (3b) . White solid; mp 70ꢀ71 °C; H
NMR (250 MHz, CDCl3) δ 0.88 (3H, t, J = 6.92 Hz), 1.25 (28H, m),
1.68ꢀ1.74 (2H, m), 2.30 (3H, s), 2.33 (2H, t, J = 7.54 Hz), 7.11 (2H, d,
J = 8.17 Hz), 7.26 (1H, s), 7.39 (2H, d, J = 8.30 Hz); 13C NMR (62.9
MHz, CDCl3) δ 14.1, 20.8, 22.7, 25.7, 29.3, 29.4, 29.5, 29.6, 29.6, 29.7,
31.9, 37.8, 119.9, 129.4, 135.0, 173.0 some peaks were overlapped.
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34.4, 37.5, 103.3, 104.2, 141.5, 149.2, 156.0, 172.5 some peaks were
overlapped.
(2H, m), 7.72 (2H, d, J = 8.40 Hz); 13C NMR (62.9 MHz, CDCl3)
δ 13.8, 22.5, 24.8, 28.7, 29.0, 29.5, 29.8, 31.8, 36.1, 173.4 some peaks
were overlapped; IR cmꢀ1 (KBr) 1656, 2912, 3331; MS m/z (%) 275
(1.9) [Mþ]. Anal. Calcd for molecular formula C18H29NO: C, 78.49; H,
10.61%. Found: C, 78.40, H, 10.54%.
N-(6-Aminopyridin-2-yl) Stearamide (3g). White solid; mp
70.5ꢀ72 °C; 1H NMR (250 MHz, CDCl3) δ 0.62 (3H, t, J = 6.00 Hz),
0.99 (28 H, m), 1.35ꢀ1.44 (2H, m), 2.09 (2H, t, J = 7.32 Hz), 4.36
(2H, s), 5.96 (2H, d, J = 7.92 Hz), 7.13ꢀ7.32 (1H, m), 8.94 (1H, s); 13C
NMR (62.9 MHz, CDCl3) δ 14.1, 22.7, 25.4, 27.9, 29.3, 31.9, 34.7, 37.5,
140.6, 149.8, 156.8, 172.2 some peaks were overlapped; IR cmꢀ1 (KBr)
1667, 2912, 3310.60, 3495.20; MS m/z (%) 375 (0.10) [Mþ]. Anal.
Calcd for molecular formula C23H41N3O: C, 73.55; H, 11.00%. Found:
C, 73.46, H, 10.97%.
N-Phenyl Benzamide (6a)31. White solid; mp 162ꢀ164 °C (lit.35
1
162ꢀ163 °C); H NMR (250 MHz, CDCl3) δ 7.33ꢀ7.43 (3H, m),
7.49ꢀ7.54 (3H, m), 7.65 (2H, d, J = 8.17 Hz), 7.85 (2H, d, J = 8.30 Hz),
7.87 (1H, s); 13C NMR (62.9 MHz, CDCl3) δ 120.3, 124.6, 127.1,
128.7, 129.1, 131.8, 134.9, 137.9, 165.9 some peaks were overlapped.
4-Methyl-N-phenyl Benzamide (6b)31. White solid; mp 155ꢀ
1
157 °C (lit.36 149ꢀ150 °C) ; H NMR (250 MHz, CDCl3) δ 2.43
1-(Piperidin-1-yl) Octadeca-1-one (3h). Viscose liquid; 1H
NMR (250 MHz, CDCl3) δ 0.86 (3H, t, J = 6.03 Hz), 1.24 (28 H,
m), 1.55ꢀ1.60 (8 H, m), 2.31 (2H, t, J = 7.14 Hz), 3.46 (4H, m); 13C
NMR (62.9 MHz, CDCl3) δ 14.1, 22.7, 24.5, 24.8, 25.5, 26.1, 29.1, 29.3,
29.4, 29.5, 29.7, 31.9, 33.4, 33.9, 171.5 some peaks were overlapped;
IR cmꢀ1 (KBr) 1644.70, 2923.40, 3456; MS m/z (%) 351 (0.90) [Mþ].
Anal. Calcd for molecular formula C23H45NO: C, 78.57; H, 12.90%.
Found: C, 78.69; H, 12.84%.
1-Morpholineooctadeca-1-one (3i). White solid; mp 42ꢀ
44 °C; 1H NMR (250 MHz, CDCl3) δ 0.84 (3H, t, J = 6.17 Hz), 1.22
(28 H, m), 1.57ꢀ1.62 (2H, m), 2.29 (2H, t, J = 7.36 Hz), 3.44 (4H, m),
3.62ꢀ3.64 (4H, m); 13C NMR (62.9 MHz, CDCl3) δ 14.1, 22.7, 24.8,
25.3, 29.1, 29.3, 29.3, 29.4, 29.4, 29.5, 29.6, 29.6, 29.7, 29.9, 31.9, 33.1,
34.0, 41.8, 46.1, 66.8, 172.1 some peaks were overlapped; IR cmꢀ1 (KBr)
1628, 2922, 3457; MS m/z (%) 353 (0.80) [Mþ]. Anal. Calcd for
molecular formula C22H43NO2: C, 74.73; H, 12.26%. Found: C, 74.68;
H, 12.20%.
(s, 3H), 7.22 (2H, d, J = 8.17 Hz), 7.35ꢀ7.52 (5H, m), 7.78 (2H, d, J =
8.30 Hz), 7.93 (1H, s); 13C NMR (62.9 MHz, CDCl3) δ 23.2, 120.4,
127.6, 128.9, 129.5, 131.5, 134.5, 135.9, 134.0, 165.9 some peaks were
overlapped.
3-Chloro-N-phenyl Benzamide (6c)32. White solid; mp 186ꢀ
188 °C (lit.32 187ꢀ188 °C) ; 1H NMR (250 MHz, CDCl3) δ 7.11ꢀ7.20
(2H, m), 7.24ꢀ7.35 (2H, m), 7.39 (1H, m), 7.53 (1H, d, J = 8.01 Hz),
7.65 (2H, d, J = 8.40 Hz), 7.87 (1H, d, J = 8.14 Hz), 7.94 (1H, s), 8.06
(1H, s); 13C NMR (62.9 MHz, CDCl3) δ 121.4, 124.4, 125.8, 127.5,
129.0, 130.2, 132.5, 134.1, 135.9, 135.9, 164.6 some peaks were
overlapped.
4-Chloro-N-phenyl Benzamide (6d)33. White solid; mp 201ꢀ
202 °C (lit.36 195ꢀ196 °C); 1H NMR (250 MHz, CDCl3) δ 7.34 (2H,
d, J = 8.20 Hz), 7.42ꢀ7.59 (5H, m), 7.82 (2H, d, J = 8.14 Hz), 7.95
(1H, s); 13C NMR (62.9 MHz, CDCl3) δ 121.6, 124.3, 128.9, 129.2,
129.2, 132.1, 135.9, 137.7, 165.3 some peaks were overlapped.
2-Chloro-N-phenyl Benzamide (6e)34. White solid; mp 184ꢀ
186 °C (lit.34 180ꢀ182 °C); 1H NMR (250 MHz, CDCl3) δ 7.13ꢀ7.19
(1H, m), 7.32ꢀ7.39 (3H, m), 7.56 (2H, m), 7.73 (2H, d, J = 8.32 Hz),
7.85 (1H, d, J = 8.45 Hz), 8.24 (1H, s); 13C NMR (62.9 MHz, CDCl3)
δ 120.9, 124.4, 127.1, 128.9, 129.0, 132.6, 132.7, 134.1, 136.3, 165.8
some peaks were overlapped.
N-(3-Morpholinopropyl) Stearamide (3j). White solid; mp
59ꢀ61 °C; 1H NMR (250 MHz, CDCl3) δ 0.85 (3H, t, J = 6.39 Hz),
1.22 (28H, m), 1.59ꢀ1.68 (4H, m), 2.14 (2H, t, J = 7.16 Hz), 2.42 (6H,
m), 3.33 (2H, t, J = 6.80 Hz), 3.67ꢀ3.69 (4H, m), 6.29 (1H, s); 13C
NMR (62.9 MHz, CDCl3) δ 14.1, 22.6, 24.9, 25.2, 25.9, 29.3, 29.4, 29.5,
29.7, 31.9, 34.8, 36.9, 38.9, 53.5, 57.5, 66.7, 173.1 some peaks were
overlapped; IR cmꢀ1 (KBr) 1638, 2923, 3331; MS m/z (%) 411 (2.4)
[Mþþ1]. Anal. Calcd for molecular formula C25H50N2O2: C, 73.12; H,
12.27%. Found: C, 73.07; H, 12.21%.
4-Nitro-N-phenyl Benzamide (6f)33. Pale yellow solid; mp
198ꢀ199 °C (lit.36 217ꢀ218 °C); 1H NMR (250 MHz, CDCl3)
δ 7.55 (2H, d, J = 8.23 Hz), 7.58ꢀ7.65 (5H, m), 7.74 (2H, d, J = 8.14
Hz), 7.90 (1H, s); 13C NMR (62.9 MHz, CDCl3) δ 121.3, 121.7, 124.5,
128.6, 129.1, 135.8, 140.2, 151.7, 164.9 some peaks were overlapped.
1
N-Dodecyl Stearamide (3k). Brown solid; mp 90ꢀ91 °C; H
NMR (250 MHz, CDCl3) δ 0.63 (6H, t, J = 6.99 Hz), 0.99 (46H, m),
1.22ꢀ1.32 (4H, m), 1.93 (2H, t, J = 7.35 Hz), 2.60 (2H, t, J = 7.48 Hz),
5.40 (1H, s); 13C NMR (62.9 MHz, CDCl3) δ 14.1, 22.7, 24.7, 25.8,
26.9, 29.1, 29.3, 29.3, 29.4, 29.4, 29.5, 29.6, 29.7, 31.9, 34.1, 36.9, 39.5,
173.4 some peaks were overlapped; IR cmꢀ1 (KBr) 1633, 2912, 3320;
MS m/z (%) 451 (5.8) [Mþ]. Anal. Calcd for molecular formula
C30H61NO: C, 79.75; H, 13.61%. Found: C, 79.70; H, 13.58%.
N-Hexadecyl Stearamide (3l). Brown solid; mp 98ꢀ100 °C; 1H
NMR (250 MHz, CDCl3) δ 0.63 (6H, t, J = 6.99 Hz), 1.23 (56H, m),
1.37 (4H, m), 2.07 (2H, t, J = 7.35 Hz), 2.99 (2H, t, J = 7.48 Hz), 5.32
(1H, s); 13C NMR (62.9 MHz, CDCl3) δ 14.1, 22.7, 24.7, 25.8, 26.9,
28.1, 29.1, 29.3, 29.4, 29.5, 29.7, 31.9, 33.9, 39.5, 173.4 some peaks were
overlapped ; IR cmꢀ1 (KBr) 1638, 2912, 3331; MS m/z (%) 506 (3)
[Mþꢀ1]. Anal. Calcd for molecular formula C34H69NO: C, 80.40; H,
13.69%. Found: C, 80.36; H, 13.57%.
’ ASSOCIATED CONTENT
S
Supporting Information. Experimental procedures, spec-
b
1
troscopic data for all compounds, and H NMR spectra. This
material is available free of charge via the Internet at http://pubs.
acs.org.
’ AUTHOR INFORMATION
Corresponding Author
*E-mail: hossaini@susc.ac.ir; hossaini@shirazu.ac.ir.
1
N-Phenyl Octanamide (4a). White solid; mp 82ꢀ84 °C; H
’ ACKNOWLEDGMENT
NMR (250 MHz, CDCl3) δ 0.88 (3H, t, J = 6.46 Hz), 1.26 (10H, m),
2.24 (2H, t, J = 7.46 Hz), 7.15 (1H, m), 7.32 (1H, s), 7.43ꢀ7.52 (2H,
m), 7.63 (2H, d, J = 8.21 Hz); 13C NMR (62.9 MHz, CDCl3) δ 14.0,
22.6, 24.9, 29.1, 31.6, 34.4, 119.8, 124.1, 128.9, 138.5, 173.3 some peaks
were overlapped; IR cmꢀ1 (KBr) 1655, 2917, 3337; MS m/z (%) 219
(12) [Mþ]. Anal. Calcd for molecular formula C14H21NO: C, 76.67; H,
9.65%. Found: C, 76.61, H, 9.53%.
The authors thank the Shiraz University Research Council for
financial support.
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The Journal of Organic Chemistry
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