Nickel-Catalyzed Reductive Addition of Aryl/Benzyl Halides and Pseudohalides to Carbodiimides for the Synthesis of Amides

Article abstract of DOI:10.1002/ejoc.201501349

A Nickel-catalyzed reductive process is described for the direct amidation of benzyl and aryl halides using carbodiimides as the amidating agent. Moreover, aryl and benzyl C–O electrophiles such as triflate, acetate, tosylate, trityl ether, and pivalate were converted into amides using this method. The in-situ-generated Ni⁰acts as a catalyst for the reaction at room temperature for benzylic substrates, and 70 °C for aryl electrophiles. This new nickel-catalyzed reductive coupling protocol provides a general and operationally simple method for the synthesis of diverse amides using carbodiimides. Amides bearing bulky substituents can be synthesized by this strategy in high yield, which demonstrates its effectiveness in amide synthesis.

Full text of DOI:10.1002/ejoc.201501349

DOI: 10.1002/ejoc.201501349
Full Paper
Amide Synthesis
Nickel-Catalyzed Reductive Addition of Aryl/Benzyl Halides and
Pseudohalides to Carbodiimides for the Synthesis of Amides
Farhad Panahi,[a] Fereshteh Jamedi,[a] and Nasser Iranpoor*[a]
Abstract: A Nickel-catalyzed reductive process is described for philes. This new nickel-catalyzed reductive coupling protocol
the direct amidation of benzyl and aryl halides using carbodi-
imides as the amidating agent. Moreover, aryl and benzyl C–O
electrophiles such as triflate, acetate, tosylate, trityl ether, and
pivalate were converted into amides using this method. The in-
situ-generated Ni0 acts as a catalyst for the reaction at room
temperature for benzylic substrates, and 70 °C for aryl electro-
provides a general and operationally simple method for the
synthesis of diverse amides using carbodiimides. Amides bear-
ing bulky substituents can be synthesized by this strategy in
high yield, which demonstrates its effectiveness in amide syn-
thesis.
Introduction
The development of new organic transformations to open up
simple and efficient pathways for the synthesis of complex mo-
lecules is important in organic chemistry.[1] The use of such
methods for the synthesis of amides is of great importance, as
the amide motif can be used to generate several other organic
functionalities.[2] Amides are an important class of organic com-
pounds because of their uses in the synthesis of natural pro-
ducts, advanced materials, and biologically active com-
pounds.[3] Traditional methods for the synthesis of amides are
based on the condensation of carboxylic acid derivatives with
amines.[4] Despite the simplicity of such methods, they often
suffer from several limitations.[5] To avoid the problems associ-
ated with these traditional methods, and to enable rwactions
with a broad substrate scope for the synthesis of new amides,
a great deal of effort has been made towards the development
of new protocols. Some of the most widely used strategies in
amide synthesis are shown in Scheme 1.[6]
As shown in Scheme 1, most of these approaches used for
amide synthesis are based on transition-metal-catalyzed coup-
ling reactions.[6] One interesting method introduced recently by
Martin et al. is a reductive amidation approach using a nickel-
catalyzed reductive coupling reaction.[7] The reductive coupling
strategy is one of the most effective approaches to the forma-
tion of carbon–carbon and carbon–heteroatom bonds in mod-
ern organic chemistry.[8] Transition-metal-catalyzed reductive
cross-coupling reactions facilitate the coupling of two electro-
philes by converting of one of them into a nucleophile in situ.[9]
This strategy is attractive in terms both of experimental simplic-
ity and of step economy.
Scheme 1. Some synthetic approaches to amides. a) Traditional methods;
b) Beckmann rearrangement; c) aminocarbonylation of aryl halides and al-
kynes; d) acceptorless dehydrogenative coupling reactions; e) cross-coupling
of formamides with alkyl/aryl halides; f) umpolung reaction of amines with α-
halo nitro alkanes; g) oxidative amidation of aldehydes with amines; h) amid-
ation using isocyanides and nitriles.
As an example of this approach, the direct coupling of aryl/
alkyl halides and carbonyl compounds, both electrophilic sub-
strates that are readily available with a wide variety of struc-
tures, is possible.[10] In work by Martin et al., isocyanates were
used as amidating agents, and reductive coupling of different
aryl and benzyl electrophiles with isocyanates resulted in the
production of amides. Also, we have previously studied a Ni-
catalyzed reductive coupling process for the addition of benz-
ylic substrates to aldehydes for the synthesis of diverse benzylic
alcohols.[11] In a continuation of our work on Ni-catalyzed re-
ductive coupling,[11] we found that amides could be produced
by the reductive coupling of aryl/benzyl halides and carbodiim-
ides. In this new strategy, carbodiimides were used instead of
isocyanates in order to increase the variety of amidating agents
[a] Department of Chemistry, College of Sciences, Shiraz University,
Shiraz 71454, Iran
E-mail: iranpoor@chem.susc.ac.ir
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/ejoc.201501349.
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Figure 1. Structures of some biologically active compounds incorporating an N-cyclohexyl amide moiety.
that could be used in the reductive amidation process, and also
to avoid some of the problems associated with the use of iso-
cyanates in organic transformations.[12] Carbodiimides are an
important class of reagents for organic synthesis due to their
ready availability and their utility in coupling reactions.[13] Due
to the high reactivity of the carbon atom in carbodiimides, it
can be used as a counterpart electrophile in reductive coupling
reactions. Our new strategy resulted in the generation of
amides (Scheme 2), and, to the best of our knowledge, there is
no previous report in the literature on the use of carbodiimides
for the synthesis of amides through a nickel-catalyzed reductive
process.
Table 1. Optimization of reaction conditions for the Ni-catalyzed amidation
of benzyl chloride with DCC.[a]
Entry Ni catalyst (mol-%)
Solvent T [°C]
Time [h]
Yield
[%][b]
1
2
3
4
5
6
7
8
–
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMSO
THF
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
50
r.t.
r.t.
24
24
24
24
24
24
24
24
24
24
24
24 (48)
24 (30)
24
24
24
0
55
61
76
75
80
85
86
NiCl2·5H2O (10 mol-%)
NiCl2(PPh3)2 (10 mol-%)
NiCl2(PCy3)2 (10 mol-%)
NiCl2(dppe) (10 mol-%)
NiCl2(dppp) (10 mol-%)
NiCl2(dppf) (10 mol-%)
NiCl2(dppf) (10 mol-%)
NiCl2(dppf) (10 mol-%)
NiCl2(dppf) (10 mol-%)
NiCl2(dppf) (10 mol-%)
NiCl2(dppf) (5 mol-%)
NiCl2(dppf) (7.5 mol-%)
NiCl2(dppf) (12 mol-%)
NiCl2(dppf) (10 mol-%)
NiCl2(dppf) (10 mol-%)
NiCl2(dppf) (10 mol-%)
NiCl2(dppf) (10 mol-%)
9
50
58
40
10
11
12
13
14
15
16
17
18
toluene r.t.
DMF
DMF
DMF
DMF
DMF
DMF
DMF
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
78 (79)
82 (84)
85
Scheme 2. Our new strategy for the synthesis of amides using the reductive
coupling of aryl or benzyl halides and carbodiimides.
84[c]
75[d]
0[e]
43[f]
One of the most readily available carbodiimides is DCC (di-
cyclohexylmethanediimine). The reaction between benzylic
substrates and DCC resulted in the production of N-cyclohexyl-
2-phenylacetamides. This class of compounds has many biologi-
cal and synthetic applications. The structures of some biologi-
cally active compounds containing an N-cyclohexyl amide
moiety are shown in Figure 1.[14]
24
24
[a] Reaction conditions: benzylic substrate (1.0 mmol), DCC (1.2 mmol), Zn
(3.0 mmol), MgCl2 (2.0 mmol), solvent (3.0 mL); dppe = 1,2-bis(diphenylphos-
phino)ethane; dppp = 1,3-bis(diphenylphosphino)propane; dppf = 1,1′-bis(di-
phenylphosphino)ferrocene. [b] Isolated yield. [c] 2.5 mmol Zn was used.
[d] Mn was used instead of Zn. [e] Zn was not used. [f] MgCl2 was not used.
In addition, this class of amides is also important in organic
synthesis. For example, a range of N-cyclohexyl amides have
been used by Bechara et al. for the chemoselective synthesis of
ketones and ketimines.[15]
In the absence of Ni catalyst, no product was observed
(Table 1, entry 1). However, in the presence of NiCl2 as catalyst,
a 55 % yield of the product was obtained (Table 1, entry 2).
To try to improve the reaction yield, other Ni catalysts bearing
phosphine ligands were tested. When NiCl2(dppf) was used, an
85 % yield of the product was obtained (Table 1, entries 3–7).
Results and Discussion
We began by studying the reaction of benzyl chloride (1a) and When the temperature was increased to 50 °C, no improvement
dicyclohexylmethanediimine (DCC, a cheap and accessible in the reaction yield was observed, thus room temperature was
carbodiimide) as model substrates to find the optimum condi- selected as optimum (Table 1, entry 8). Different solvents were
tions (Table 1).
tested, but no better solvent was found, and DMF selected as
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the best solvent tested (Table 1, entries 9–11). Different catalyst halides. Next, we examined the generality of the reaction using
loadings were tested, and a catalyst loading of 10 mol-% of other benzylic substrates under the optimized reaction condi-
NiCl2(dppf) was found to be optimal (Table 1, entries 12–14). tions, as shown in Table 2.
Increasing the amount of Zn did not have a significant effect
on the reaction yield (Table 1, entry 15). When Mn was used
Table 2. Different benzylic substrates.[a]
Entry
X
Time [h]
Yield [%][b]
instead of Zn, no improvement in the reaction yield was ob-
served (Table 1, entry 15). In the absence of the Zn reducing
agent, no product was observed. According to the literature,
the role of Zn in this reaction is to reduce NiII to NiI/Ni0.[16]
When the MgCl2 was removed, the yield of the reaction de-
creased to 43 %, so this additive has a significant effect on the
reaction yield. It has been reported previously that in this type
of reaction, the use of MgCl2 as an additive improved the reac-
tion yields.[11,17]
1
2
3
4
5
6
7
8
9
Cl
Br
I
OTf
OAc
OTs
OTr
OPiv
OH
24
20
18
24
24
24
24
24
24
86
87
90
85
76
78
65
85
0
[a] Reaction conditions: benzylic substrate (1.0 mmol), DCC (1.2 mmol), Zn
(3.0 mmol), MgCl2 (2.0 mmol), NiCl2(dppf) (10.0 mol-%), DMF (3.0 mL). [b] Iso-
lated yield.
The results of optimization process (Table 1) show that the
maximum yield of product 3a was obtained in the presence of
NiCl2(dppf) (10 mol-%) as catalyst, Zn (3 mmol) as reducing
agent, and MgCl2 (2 mmol) as additive, in DMF (as solvent), at
room temperature.
We found that, in addition to benzyl halides (Cl, Br, and I),
other benzylic C–O electrophiles such as triflate, acetate, tosyl-
There is a great variety of benzylic C–O electrophiles, and ate, trityl ether, and pivalate also resulted in the formation of
they can be used as readily available alternatives to benzylic the desired product. This point reveals the importance of our
Scheme 3. Ni-catalyzed reductive amidation of benzylic substrates with DCC. Reaction conditions: benzylic substrate (1.0 mmol), DCC (1.2 mmol), Zn (3.0 mmol),
MgCl2 (2.0 mmol), NiCl2(dppf) (10.0 mol-%), DMF (3.0 mL); all yields refer to isolated products. [a] The reaction was carried out at 50 °C.
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protocol for the synthesis of diverse amides using a range of strates under the optimized conditions. The use of (1-bromo-
benzylic substrates. All of the used benzylic C–O electrophiles ethyl)benzene, (bromomethylene)dibenzene, and trityl chloride
gave the amide product in good yields. Benzyl alcohol failed to resulted in the formation of the corresponding products (i.e.,
produce the desired amide and remained unchanged.
3j–3l) in 67, 62, and 60 % yields, respectively.
The method was also used for the introduction of the amide
group into aromatic systems, bearing in mind the importance
of benzamides as valuable building blocks in medicinal chemis-
try.[18] In fact, synthetic routes often require the conversion of
aryl halides to amides, and this encouraged us to explore the
possibility of using our method for this conversion.[19] Thus,
iodobenzene and DCC were subjected to the optimized condi-
tions at room temperature, but no product was observed. For-
tunately, at the higher temperature of 70 °C, N-cyclohexyl-
benzamide was produced in 82 % yield. Different conditions
were also tested, but no improvement was observed. Thus, the
optimized conditions could also be used for the amidation of
aryl substrates using DCC.
To show the generality of this protocol in the synthesis of
other N-cyclohexyl amides, other benzylic derivatives were also
tested, and the results are shown in Scheme 3. Different types
of benzylic substrates can be used in this approach. Benzylic
substrates bearing electron-rich and electron-poor substituents
were both tolerated, and excellent yields of the desired pro-
ducts (i.e., 3b–3e) were obtained. When an anthracene deriva-
tive was used, the reaction occurred readily to give amide 3f in
good yield. To demonstrate the applicability of this reaction
with halogen-substituted substrates, 4-bromobenzyl chloride
and 4-fluorobenzyl chloride were also examined, and good
yields of the products (i.e., 3g and 3h) were obtained. 2,4,6-
Trimethylbenzyl chloride was also used as a sterically hindered
substrate, and compound 3i was obtained in 70 % isolated
To establish the scope of this new method, a number of
yield. We also examined secondary and tertiary benzylic sub- aromatic substrates were tested under the optimized conditions
Scheme 4. Ni-catalyzed reductive amidation of aryl halides with DCC. Reaction conditions: aryl–X (1.0 mmol), DCC (1.2 mmol), Zn (3.0 mmol), MgCl2 (2.0 mmol),
NiCl2(dppf) (10.0 mol-%), DMF (3.0 mL). All yields refer to isolated products.
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(Scheme 4). A range of substrates bearing an electron-donating
The scope of the reaction was further investigated by using
(4b and 4c) or an electron-withdrawing (4d and 4e) group on benzylic substrates instead of aryl halides (Table 3). We found
the phenyl ring gave the corresponding amides in good yields. that the protocol was efficient for synthesis of structurally differ-
Some substrates bearing two halogen groups were also tested, ent amides using benzylic substrates with carbodiimides. For
and these gave the desired monoamides (i.e., 4f–4h) in rela- carbodiimides with aromatic and bulky aliphatic substituents,
tively good yields, with selectivity between the two different such as tert-butyl, the yields were lower than with other sub-
halogens. 1-Bromonaphthalene was found to react, and the cor- strates.
responding amide (i.e., 4i) was obtained in 74 % yield. Naphth-
Table 3. Amidation of benzylic substrates with different carbodiimides.[a]
alen-1-tosylate also gave 4i in 71 % yield. 2-Iodotoluene was
produced N-cyclohexyl-2-methylbenzamide (4j) in 80 % yield.
1-Bromo-2,4-bis(methylsulfonyl)benzene, bearing an SO2Me
group, was also compatible with the optimized conditions and
gave 4k. A triflate derivative of estrone reacted with DCC under
the optimized conditions to give the corresponding amide de-
rivative (i.e., 4l) in 77 % yield.[20] Also, 9-(4-bromophenyl)-
3,3,6,6-tetramethyl-3,4,5,6,7,9-hexahydro-1H-xanthene-1,8(2H)-
dione was used in this reaction, and amide 4m was produced
in 72 % yield.[21]
Encouraged by these results, we examined the scope of our
Ni-catalyzed reductive amidation with other carbodiimides to
investigate the generality of this approach to amide synthesis
(Scheme 5). We found that the reaction of aryl halides with
bis(trimethylsilyl)methanediimine proceeded smoothly to give
primary amides 5a–5c in good yields. When di-p-tolylmethane-
diimine was used, the corresponding amides (i.e., 5d–5f) were
obtained in yields of 71, 73, and 70 %, respectively. Treatment
of aryl halides and aryl C–O electrophiles with tert-butyl, isopro-
pyl, and ethyl carbodiimides gave the corresponding amide
products in good yields. These results demonstrate that this
protocol can be used with different carbodiimides, thus repre-
Entry
X
R
Product 6
Yield [%][b]
1
2
3
4
5
6
7
8
Cl
H
H
H
Et
Et
iPr
iPr
tBu
tBu
p-tolyl
p-tolyl
6a
6a
6a
6b
6b
6c
6c
6d
6d
6e
6e
90
85
88
91
89
90
87
84
82
72
70
OTs
OPiv
Cl
OTf
Br
OTf
Cl
OTf
Cl
9
10
11
OPiv
[a] Reaction conditions: benzylic substrate (1 mmol), DCC (1.2 mmol), Zn
(3 mmol), MgCl2 (2 mmol), NiCl2(dppf) (10 mol-%), DMF (3 mL). [b] Isolated
yield.
An unsymmetrical carbodiimide was also tested in this pro-
senting an efficient route for the synthesis of diverse substi- cedure, and cleavage of the C=N bond connected to the less
tuted amides.
bulky substituent was observed (Scheme 6).[22]
Scheme 5. Amidation of aryl substrates with different carbodiimides. Reaction conditions: aryl substrate (1.0 mmol), DCC (1.2 mmol), Zn (3.0 mmol), MgCl2
(2.0 mmol), NiCl2(dppf) (10.0 mol-%), DMF (3.0 mL). All yields refer to isolated products.
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Scheme 6. Use of an unsymmetrical carbodiimide.
Although a detailed mechanistic understanding of this reac- Conclusions
tion requires further studies, a plausible reaction mechanism
In conclusion, we have established the first examples of the Ni-
catalyzed addition of benzylic and aryl substrates to carbodiim-
ides using a Ni/Zn catalytic system for synthesis of amide deriv-
atives. The reaction proceeds with a catalytic amount of Ni un-
der mild conditions, and the procedure was also applicable to
C–O electrophiles. This method is characterized by its opera-
tional simplicity, wide preparative scope, and the ready availa-
bility of the substrates used. The method also represents a sim-
ple choice for the synthesis of amides using carbodiimides as
an easily handled amidating agent without the need for the
preparation of sensitive organometallic reagents.
for benzylic substrates based on the literature is proposed
(Scheme 7).[11,16b] The catalytic cycle is initiated by the reduc-
tion of NiII to Ni0. It seems that in the presence of Zn, NiII is
reduced to Ni0, because in the absence of Zn the reaction did
not take place.[11] Furthermore, the reaction did take place
when Ni(PPh3)2(CO)2 was used as an Ni0 source. These results
confirm that this is a Ni0-catalyzed process. The Ni0 species un-
dergoes oxidative addition with the C–X bond to form NiII com-
plex i. Then, the carbodiimide coordinates with complex i to
form adduct ii. Next, the aryl or benzyl moiety adds to the
activated carbodiimide to form intermediate iii.[16a] Zn can then
regenerate the Ni0 complex to continue the catalytic cycle. Pro-
tonation of adduct iv results in the formation of amidine prod-
uct v.[23] The amidine product was isolated from the reaction
mixture. Further hydrolysis of the amidine resulted in the forma-
tion of the amide.[22] It should be mentioned that for benzylic
substrates the formation of NiI complexes in the presence of Zn
has been reported; this represents another possible pathway
for the formation of intermediate iii from i.[24]
Experimental Section
General Remarks: Chemicals were purchased from Fluka, Merck,
and Aldrich, and were used without further purification. Known pro-
ducts were characterized by comparison of their spectral and physi-
cal data with those reported in the literature. 1H (250 MHz) and
13C (62.9 MHz) NMR spectra were recorded with a Bruker Avance
spectrometer in CDCl3 and [D6]DMSO solutions, and tetramethyl-
silane (TMS) was used as an internal standard. FTIR spectra were
recorded with a Shimadzu FTIR 8300 spectrophotometer. Melting
points were determined in open capillary tubes with a Barnstead
electro-thermal 9100 BZ circulating oil melting-point apparatus. Re-
actions were monitored by TLC on silica gel PolyGram SILG/UV254
plates. Column chromatography was carried out on columns of sil-
ica gel 60 (70–230 mesh).
General Procedure for Ni-Catalyzed Reductive Amidation: A
mixture of carbodiimide (1.2 mmol), aryl/benzyl substrate
(1.0 mmol), Zn (3.0 mmol), MgCl2 (2.0 mmol), and NiCl2(dppf)
(10 mol-%) was stirred in dry DMF (3.0 mL) in a 50 mL flask for 24 h
at room temp. or 70 °C. After TLC indicated that the reaction was
complete, HCl (0.5 mM aq; 25 mL) was added, and the mixture was
stirred for 3 h. Then ethyl acetate (50 mL) and saturated NaHCO3
(25 mL) were added to the mixture. The aqueous and organic layers
were separated, then the aqueous phase was extracted with ethyl
acetate (2 × 25 mL). The combined organic layers were then dried
with anhydrous Na2SO4, filtered, and concentrated under vacuum.
The crude product was purified by column chromatography (n-hex-
ane/ethyl acetate) to give the desired pure product.
N-Cyclohexyl-2-phenylacetamide (3a):[25] Yield 86 % (186 mg). 1H
NMR (250 MHz, CDCl3/TMS): δ = 0.70–1.89 (m, 10 H), 3.39–3.43 (m,
1 H), 3.98–3.99 (m, 2 H), 6.67 (s, 1 H), 7.30–7.39 (m, 3 H), 7.55–7.63
(m, 2 H) ppm. 13C NMR (62.5 MHz, CDCl3/TMS): δ = 24.9, 25.6, 32.4,
44.2, 127.6, 129.0, 129.6, 135.2, 170.0 ppm. C14H19NO (217.31): calcd.
C 77.38, H 8.81, N 6.45; found C 77.31, H 8.76, N 6.37.
N-Cyclohexyl-2-(4-nitrophenyl)acetamide (3b): Yield 90 %
1
(236 mg). H NMR (250 MHz, CDCl3/TMS): δ = 1.1–2-1.93 (m, 10 H),
3.43–3.48 (m, 1 H), 4.12–4.15 (m, 2 H), 7.25–7.28 (m, 3 H), 8.11–8.14
Scheme 7. Proposed reaction mechanism for Ni-catalyzed amide synthesis
using carbodiimides.
(m, 2 H) ppm. 13C NMR (62.5 MHz, CDCl3/TMS): δ = 24.9, 25.6, 33.9,
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43.1, 49.1, 124.0, 129.1, 141.0, 146.0, 171.6 ppm. C14H18N2O3
(262.31): calcd. C 64.11, H 6.92, N 10.68; found C 63.97, H 6.83, N
10.76.
(m, 10 H), 4.00 (s, 1 H), 5.07 (s, 1 H), 7.31–7.39 (m, 4 H), 7.67–7.72
(m, 6 H), 9.81 (br. s, 1 H) ppm. 13C NMR (62.5 MHz, CDCl3/TMS): δ =
24.7, 25.1, 31.9, 50.8, 58.3, 126.9, 128.6, 129.3, 138.7, 171.4 ppm.
C20H23NO (293.41): calcd. C 81.87, H 7.90, N 4.77; found C 81.76, H
7.81, N 4.69.
N-Cyclohexyl-2-(2-nitrophenyl)acetamide (3c): Yield 76 %
1
(199 mg). H NMR (250 MHz, CDCl3/TMS): δ = 1.07–1.89 (m, 10 H),
3.38–3.42 (m, 1 H), 4.02–4.05 (m, 2 H), 7.55–7.57 (m, 2 H), 7.71–7.72 N-Cyclohexyl-2,2,2-triphenylacetamide (3l): Yield 60 % (221 mg).
(m, 1 H), 8.05 (s, 1 H), 9.91 (s, 1 H) ppm. 13C NMR (62.5 MHz, CDCl3/ 1H NMR (250 MHz, CDCl3/TMS): δ = 0.86–1.94 (m, 10 H), 3.46–3.48
TMS): δ = 24.9, 25.6, 33.9, 38.6, 49.1, 125.6, 128.5, 128.9, 130.6, 135.3,
149.8, 171.3 ppm. C14H18N2O3 (262.31): calcd. C 64.11, H 6.92, N
10.68; found C 64.01, H 6.84, N 10.59.
(m, 1 H), 7.19–7.54 (m, 15 H), 8.05 (br. s, 1 H) ppm. 13C NMR
(62.5 MHz, CDCl3/TMS): δ = 24.9, 25.6, 33.9, 49.1, 62.0, 126.2, 129.3,
129.4, 143.2, 174.6 ppm. C26H27NO (369.51): calcd. C 84.51, H 7.37,
N 3.79; found C 84.42, H 7.31, N 3.70.
N-Cyclohexyl-2-(p-tolyl)acetamide (3d): Yield 88 % (203 mg). 1H
NMR (250 MHz, CDCl3/TMS): δ = 0.99–1.87 (m, 10 H), 2.10 (s, 3 H), N-Cyclohexyl Benzamide (4a):[26] Yield 82 % (166 mg). 1H NMR
3.41 (s, 1 H), 3.91 (s, 2 H), 7.04–7.06 (m, 2 H), 7.40–7.43 (m, 2 H),
(250 MHz, CDCl3/TMS): δ = 0.96–1.70 (m, 10 H), 4.03–4.06 (m, 1 H),
7.72 (br. s, 1 H) ppm. 13C NMR (62.5 MHz, CDCl3/TMS): δ = 21.3,
7.23–7.28 (m, 2 H), 7.54–7.64 (m, 2 H), 9.59 (s, 1 H) ppm. 13C NMR
24.9, 25.6, 32.3, 43.5, 50.0, 229.5, 129.60, 129.61, 129.65, 132.6, 137.3, (62.5 MHz, CDCl3/TMS): δ = 24.4, 24.5, 33.1, 54.6, 126.6, 129.8, 131.9,
171.4 ppm. C15H21NO (231.34): calcd. C 77.88, H 9.15, N 6.05; found
C 77.79, H 9.09, N 6.00.
134.5, 166.6 ppm. C13H17NO (203.29): calcd. C 76.81, H 8.43, N 6.89;
found C 76.72, H 8.37, N 6.81.
N-Cyclohexyl-2-(4-methoxyphenyl)acetamide (3e): Yield 81 %
(200 mg). H NMR (250 MHz, CDCl3/TMS): δ = 1.09–1.88 (m, 10 H),
N-Cyclohexyl-4-methoxybenzamide (4b):[15] Yield 80 % (186 mg).
1
1H NMR (250 MHz, CDCl3/TMS): δ = 1.02–1.97 (m, 10 H), 3.86 (s, 3
3.39–3.84 (m, 1 H), 3.84 (s, 3 H), 4.01 (d, J = 1.5 Hz, 2 H), 6.90 (d, J = H), 4.03–4.09 (m, 1 H), 7.02–7.07 (m, 2 H), 7.20–7.26 (m, 2 H), 9.44
6.0 Hz, 2 H), 6.90 (d, J = 6.2 Hz, 2 H) ppm. 13C NMR (62.5 MHz, (br. s, 1 H) ppm. 13C NMR (62.5 MHz, CDCl3/TMS): δ = 24.4, 24.7, 33.3,
CDCl3/TMS): δ = 24.9, 25.7, 32.3, 43.7, 49.9, 55.8, 115.0, 127.9, 130.7, 52.7, 54.8, 115.5, 117.6, 128.6, 129.9, 162.5, 165.4 ppm. C14H19NO2
159.8, 171.5 ppm. C15H21NO2 (247.34): calcd. C 72.84, H 8.56, N 5.66;
found C 72.76, H 8.51, N 5.59.
(233.31): calcd. C 72.07, H 8.21, N 6.00; found C 72.01, H 8.16, N
5.91.
2-(Anthracen-9-yl)-N-cyclohexylacetamide (3f): Yield 73 %
(231 mg). H NMR (250 MHz, CDCl3/TMS): δ = 1.00–1.98 (m, 10 H),
N-Cyclohexyl-4-methylbenzamide (4c): Yield 79 % (171 mg). CAS
No: 53205–68–8. H NMR (250 MHz, CDCl3/TMS): δ = 0.90–1.88 (m,
1
1
3.39–3.43 (m, 1 H), 4.93 (s, 2 H), 7.49–7.54 (m, 4 H), 7.86–7.89 (m, 3
H), 8.30–8.32 (m, 2 H), 8.74 (s, 1 H) ppm. 13C NMR (62.5 MHz, CDCl3/
TMS): δ = 24.7, 25.3, 32.3, 37.5, 50.1, 124.9, 125.0, 127.2, 127.9, 128.1,
128.9, 129.1, 170.3 ppm. C22H23NO (317.43): calcd. C 83.24, H 7.30,
N 4.41; found C 83.16, H 7.22, N 4.33.
10 H), 2.42 (s, 3 H), 3.96 (s, 1 H), 7.11–7.13 (m, 2 H), 7.32 (d, J =
7.5 Hz, 2 H), 9.85 (br. s, 1 H) ppm. 13C NMR (62.5 MHz, CDCl3/TMS):
δ = 17.4, 29.3, 30.4, 49.2, 128.2, 128.4, 131.7, 131.8, 174.8 ppm.
C14H19NO (217.31): calcd. C 77.38, H 8.81, N 6.45; found C 77.31, H
8.75, N 6.37.
2-(4-Bromophenyl)-N-cyclohexylacetamide (3g): Yield 78 %
(231 mg). H NMR (250 MHz, CDCl3/TMS): δ = 0.87–1.88 (m, 10 H),
N-Cyclohexyl-4-nitrobenzamide (4d):[15] Yield 88 % (218 mg). CAS
1
No. 7506–46–9. 1H NMR (250 MHz, CDCl3/TMS): δ = 1.05–1.96 (m,
3.38–3.42 (m, 1 H), 3.98 (d, J = 4.2 Hz, 2 H), 6.88–6.94 (m, 2 H), 7.27– 10 H), 3.50–3.52 (m, 1 H), 7.96–7.99 (m, 2 H), 8.34–8.37 (m, 2 H),
7.33 (m, 3 H) ppm. 13C NMR (62.5 MHz, CDCl3/TMS): δ = 24.9, 25.6,
29.6, 33.9, 37.0, 49.1, 120.4, 130.2, 131.4, 140.1, 182.9 ppm.
C14H18BrNO (296.21): calcd. C 56.77, H 6.13, N 4.73; found C 56.68,
H 6.05, N 4.65.
8.91 (br. s, 1 H) ppm. 13C NMR (62.5 MHz, CDCl3/TMS): δ = 24.6,
24.9, 32.6, 52.6, 118.9, 123.9, 132.7, 153.6, 175.1 ppm. C13H16N2O3
(248.28): calcd. C 62.89, H 6.50, N 11.28; found C 62.80, H 6.43, N
11.22.
N-Cyclohexyl-2-(4-fluorophenyl)acetamide (3h): Yield 80 %
(188 mg). H NMR (250 MHz, CDCl3/TMS): δ = 0.78–1.89 (m, 10 H),
N-Cyclohexyl-3-nitrobenzamide (4e): Yield 70 % (173 mg). CAS
No. 2702–32–1. 1H NMR (250 MHz, CDCl3/TMS): δ = 0.90–1.59 (m,
10 H), 3.54 (br. s, 1 H), 7.48–7.53 (m, 1 H), 8.05–8.07 (m, 2 H), 8.37–
8.44 (m, 2 H) ppm. 13C NMR (62.5 MHz, CDCl3/TMS): δ = 24.8, 25.1,
32.2, 48.6, 121.9, 125.4, 129.7, 133.7, 136.1, 147.5, 163.0 ppm.
C13H16N2O3 (248.28): calcd. C 62.89, H 6.50, N 11.28; found C 62.80,
H 6.41, N 11.22.
1
3.65–3.67 (m, 1 H), 4.04 (t, J = 2.0 Hz, 2 H), 6.75–7.05 (m, 4 H), 7.35
(s, 1 H) ppm. 13C NMR (62.5 MHz, CDCl3/TMS): δ = 24.8, 25.5, 33.7,
45.1, 51.5, 115.1, 115.4, 127.5, 127.6, 130.9, 131.0, 167.9, 174.4 ppm.
C14H18FNO (235.30): calcd. C 71.46, H 7.71, N 5.95; found C 71.34, H
7.63, N 5.85.
N-Cyclohexyl-2-mesitylacetamide (3i): Yield 70 % (181 mg). 1H
NMR (250 MHz, CDCl3/TMS): δ = 1.09–1.87 (m, 10 H), 2.81 (s, 3 H), No. 57707–20–7. H NMR (250 MHz, CDCl3/TMS): δ = 1.09–1.77 (m,
4-Chloro-N-cyclohexylbenzamide (4f): Yield 73 % (173 mg). CAS
1
2.98 (s, 6 H), 3.32–3.35 (m, 1 H), 3.77 (s, 2 H), 7.38 (s, 1 H), 7.95 (br. 10 H), 3.72 (br. s, 1 H), 7.46 (d, J = 5.5 Hz, 2 H), 7.83–7.86 (m, 2 H),
s, 1 H) ppm. 13C NMR (62.5 MHz, CDCl3/TMS): δ = 16.5, 21.8, 24.8,
8.25 (br. s, 1 H) ppm. 13C NMR (62.5 MHz, CDCl3/TMS): δ = 24.8,
25.5, 32.1, 35.5, 51.0, 127.6, 133.0, 137.0, 171.8 ppm. C17H25NO 25.2, 32.3, 48.4, 128.0, 129.1, 133.5, 135.7, 164.1 ppm. C13H16ClNO
(259.39): calcd. C 78.72, H 9.71, N 5.40; found C 78.63, H 9.64, N
5.31.
(237.73): calcd. C 65.68, H 6.78, N 5.89; found C 65.60, H 6.71, N
5.82.
N-Cyclohexyl-2-phenylpropanamide (3j): Yield 67 % (154 mg). 1H
NMR (250 MHz, CDCl3/TMS): δ = 0.85–1.69 (m, 13 H), 4.11–4.14 (m,
3,4-Dichloro-N-cyclohexylbenzamide (4g): Yield 87 % (236 mg).
1H NMR (250 MHz, CDCl3/TMS): δ = 0.93–1.94 (m, 10 H), 3.40–3.44
1 H), 4.26 (s, 1 H), 7.52–7.80 (m, 5 H), 8.20 (s, 1 H) ppm. 13C NMR (m, 1 H), 7.64–7.88 (m, 3 H), 8.21 (s, 1 H) ppm. 13C NMR (62.5 MHz,
(62.5 MHz, CDCl3/TMS): δ = 15.4, 24.7, 25.1, 31.2, 43.4, 50.8, 126.9,
128.6, 136.9, 171.4 ppm. C15H21NO (231.34): calcd. C 77.88, H 9.15,
N 6.05; found C 77.76, H 9.06, N 5.94.
CDCl3/TMS): δ = 24.4, 24.5, 33.1, 54.5, 128.1, 129.0, 130.4, 133.1,
133.5, 136.4, 167.8 ppm. C13H15Cl2NO (272.17): calcd. C 57.37, H
5.56, N 5.15; found C 57.28, H 5.51, N 5.06.
N-Cyclohexyl-2,2-diphenylacetamide (3k): Yield 67 % (154 mg).
4-Bromo-N-cyclohexylbenzamide (4h):[15] Yield 71 % (200 mg).
CAS No: 24932–56–7. 1H NMR (250 MHz, CDCl3/TMS): δ = 1.08–2.10 CAS number: 223553-87-5. 1H NMR (250 MHz, CDCl3/TMS): δ = 0.92–
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1.65 (m, 10 H), 4.01–4.07 (m, 1 H), 7.15 (d, J = 8.5 Hz, 2 H), 7.70 (d,
J = 8.2 Hz, 2 H), 8.62 (br. s, 1 H) ppm. 13C NMR (62.5 MHz, CDCl3/
TMS): δ = 24.4, 24.5, 33.1, 54.7, 126.6, 128.2, 131.9, 133.3, 176.2 ppm.
C13H16BrNO (282.18): calcd. C 55.33, H 5.72, N 4.96; found C 55.33,
H 5.72, N 4.96.
N-Cyclohexyl-1-naphthamide (4i): Yield 74 % (187 mg). 1H NMR
(250 MHz, CDCl3/TMS): δ = 0.78–1.61 (m, 10 H), 4.04–4.07 (m, 1 H),
7.36–7.39 (m, 1 H), 7.55–7.65 (m, 3 H), 7.72–7.76 (m, 1 H), 7.93–8.07
(m, 2 H), 10.13 (s, 1 H) ppm. 13C NMR (62.5 MHz, CDCl3/TMS): δ =
24.4, 32.8, 33.4, 54.7, 123.1, 123.9, 125.1, 125.3, 127.8, 128.7, 129.1,
132.0, 163.1, 181.8 ppm. C17H19NO (253.35): calcd. C 80.60, H 7.56,
N 5.53; found C 80.51, H 7.51, N 5.42.
N-Cyclohexyl-2-methylbenzamide (4j): Yield 80 % (173 mg). 1H
NMR (250 MHz, CDCl3/TMS): δ = 0.98–1.66 (m, 10 H), 2.27 (s, 3 H),
3.38–3.44 (m, 1 H), 7.09–7.49 (m, 3 H), 7.91 (s, 1 H), 9.66 (br. s, 1 H)
ppm. 13C NMR (62.5 MHz, CDCl3/TMS): δ = 21.6, 24.47, 24.53, 29.7,
33.1, 54.5, 126.5, 128.4, 130.4, 132.5, 136.4, 140.3, 168.5 ppm.
C14H19NO (217.31): calcd. C 77.38, H 8.81, N 6.45; found C 77.38, H
8.81, N 6.45.
4-Chloro-N-(p-tolyl)benzamide (5d): Yield 71 % (174 mg). CAS No.
2447–95–2. H NMR (250 MHz, CDCl3/TMS): δ = 2.25 (s, 3 H), 7.11–
7.14 (m, 2 H), 7.46–7.67 (m, 4 H), 7.91–7.95 (m, 2 H), 10.15 (s, 1 H)
ppm. 13C NMR (62.5 MHz, CDCl3/TMS): δ = 127.38, 127.42, 128.07,
128.14, 131.1, 134.05, 134.15, 168.1 ppm. C14H12ClNO (245.71):
calcd. C 68.44, H 4.92, N 5.70; found C 68.38, H 4.86, N 5.63.
1
3-Nitro-N-(p-tolyl)benzamide (5e): Yield 73 % (187 mg). CAS No:
6911–92–8. 1H NMR (250 MHz, CDCl3/TMS): δ = 2.27 (s, 3 H), 7.17
(d, J = 8.2 Hz, 2 H), 7.62–7.84 (m, 4 H), 8.35–8.43 (m, 2 H), 8.75–8.77
(m, 1 H), 10.49 (s, 1 H) ppm. 13C NMR (62.5 MHz, CDCl3/TMS): δ =
20.4, 120.4, 120.5, 122.3, 126.0, 129.0, 130.1, 133.1, 134.0, 147.7,
162.9 ppm. C14H12N2O3 (256.26): calcd. C 65.62, H 4.72, N 10.93;
found C 65.55, H 4.67, N 10.88.
4-Nitro-N-(p-tolyl)benzamide (5f):[26] Yield 70 % (179 mg). CAS
No. 582–78–5. 1H NMR (250 MHz, CDCl3/TMS): δ = 2.26 (s, 3 H), 7.15
(d, J = 8.0 Hz, 2 H), 7.62–7.65 (m, 2 H), 8.13–8.16 (m, 2 H), 8.34 (d,
J = 8.7 Hz, 2 H), 10.45 (s, 1 H) ppm. 13C NMR (62.5 MHz, CDCl3/TMS):
δ = 20.4, 120.3, 120.4, 123.5, 129.0, 129.1, 133.1, 136.0, 136.1, 140.6,
149.0, 163.5 ppm. C14H12N2O3 (256.26): calcd. C 65.62, H 4.72, N
10.93; found C 65.57, H 4.67, N 10.88.
N-(tert-Butyl)-4-nitrobenzamide (5g):[28] Yield 80 % (177 mg). CAS
No. 42498–30–6. 1H NMR (250 MHz, CDCl3/TMS): δ = 1.37 (s, 9 H),
7.96–8.02 (m, 2 H), 8.11 (s, 1 H), 8.22–8.27 (m, 2 H) ppm. 13C NMR
(62.5 MHz, CDCl3/TMS): δ = 28.3, 123.2, 128.8, 141.5, 148.6,
164.6 ppm. C11H14N2O3 (222.24): calcd. C 59.45, H 6.35, N 12.61;
found C 59.38, H 6.31, N 12.55.
N-Cyclohexyl-2,4-bis(methylsulfonyl)benzamide (4k): Yield 58 %
1
(208 mg). H NMR (250 MHz, CDCl3/TMS): δ = 0.88–1.89 (m, 10 H),
3.07 (s, 6 H), 4.09–4.12 (m, 1 H), 7.20 (s, 1 H), 7.79 (d, J = 8.0 Hz, 1
H), 8.17–8.20 (d, J = 7.7 Hz, 1 H), 8.47 (s, 1 H) ppm. 13C NMR
(62.5 MHz, CDCl3/TMS): δ = 24.9, 25.6, 33.9, 44.3, 49.1, 126.7, 130.8,
132.4, 140.1, 141.1, 142.3, 168.2 ppm. C15H21NO5S2 (359.46): calcd.
C 50.12, H 5.89, N 3.90, S 17.84; found C 50.04, H 5.82, N 3.81, S
17.78.
N-Isopropyl-3-nitrobenzamide (5h): Yield 82 % (171 mg). CAS No.
(8R,9S,13S,14S)-N-Cyclohexyl-13-methyl-17-oxo-7,8,9,11,12,13,
14,15,16,17-decahydro-6H-cyclopenta[a]phenanthrene-3-carb-
1
50445–53–9. H NMR (250 MHz, CDCl3/TMS): δ = 1.13 (s, 3 H), 1.15
(s, 3 H), 4.04–4.12 (m, 1 H), 7.66–7.72 (m, 1 H), 8.24–8.30 (m, 2 H),
8.59–8.64 (m, 2 H) ppm. 13C NMR (62.5 MHz, CDCl3/TMS): δ = 22.0,
41.3, 121.8, 125.4, 129.7, 133.6, 136.0, 147.5 ppm. C10H12N2O3
(208.22): calcd. C 57.69, H 5.81, N 13.45; found C 57.61, H 5.76, N
13.40.
N-Ethylbenzamide (5i):[29] Yield 88 % (131 mg). CAS No. 614–17–
5. 1H NMR (250 MHz, CDCl3/TMS): δ = 1.10–1.13 (m, 3 H), 2.78–2.84
(m, 2 H), 7.22–7.34 (m, 3 H), 7.84–7.88 (m, 2 H), 8.74 (br. s, 1 H) ppm.
13C NMR (62.5 MHz, CDCl3/TMS): δ = 12.3, 34.2, 127.0, 128.1, 131.0,
134.1, 166.5 ppm. C9H11NO (149.19): calcd. C 72.46, H 7.43, N 9.39;
found C 72.41, H 7.37, N 9.32.
1
oxamide (4l): Yield 77 % (292 mg). H NMR (250 MHz, CDCl3/TMS):
δ = 0.80 (s, 1 H), 0.88–2.73 (m, 23 H), 3.34 (s, 2 H), 3.72 (s, 1 H), 7.24
(d, J = 4.7 Hz, 1 H), 7.68 (d, J = 2.7 Hz, 1 H), 7.81 (s, 1 H), 8.82 (br. s,
1 H) ppm. 13C NMR (62.5 MHz, CDCl3/TMS): δ = 18.7, 24.6, 25.6, 26.3,
30.7, 31.3, 32.9, 34.2, 36.5, 40.5, 48.6, 51.7, 52.5, 54.8, 124.2, 126.9,
131.2, 135.1, 142.3, 168.0, 219.7 ppm. C25H33NO2 (379.54): calcd. C
79.11, H 8.76, N 3.69; found C 79.04, H 8.70, N 3.61.
N-Cyclohexyl-4-(3,3,6,6-tetramethyl-1,8-dioxo-2,3,4,5,6,7,8,9-
octahydro-1H-xanthen-9-yl)benzamide
(4m):
Yield
72 %
1
(342 mg). H NMR (250 MHz, CDCl3/TMS): δ = 0.97 (s, 6 H), 1.06 (s,
6 H), 1.08–1.73 (m, 10 H), 2.12–2.26 (m, 4 H), 2.49 (s, 4 H), 4.08 (s, 1
H), 4.69 (s, 1 H), 7.12–7.19 (m, 2 H), 7.26–7.35 (m, 2 H), 8.82 (br. s, 1
H) ppm. 13C NMR (62.5 MHz, CDCl3/TMS): δ = 24.9, 25.9, 27.3, 29.3,
31.5, 32.2, 40.8, 50.7, 51.2, 115.1, 127.3, 127.7, 131.1, 147.4, 154.7,
167.8, 196.3 ppm. C30H37NO4 (475.63): calcd. C 75.76, H 7.84, N 2.94;
found C 75.68, H 7.76, N 2.85.
2-Phenylacetamide (6a): Yield 90 % (121.6 mg). CAS No. 103–81–
1. 1H NMR (250 MHz, CDCl3/TMS): δ = 3.35 (s, 2 H), 6.87 (s, 1 H),
7.16–7.31 (m, 5 H), 7.46 (s, 1 H) ppm. 13C NMR (62.5 MHz, CDCl3/
TMS): δ = 42.2, 126.2, 128.1, 129.0, 136.4, 172.2 ppm. C8H9NO
(135.17): calcd. C 71.09, H 6.71, N 10.36; found C 71.00, H 6.64, N
10.31.
Benzamide (5a):[27] Yield 85 % (102 mg). CAS No. 55–21–0. 1H NMR
(250 MHz, CDCl3/TMS): δ = 7.38–7.48 (m, 3 H), 7.87–7.91 (m, 2 H),
8.02 (s, 1 H) ppm. 13C NMR (62.5 MHz, CDCl3/TMS): δ = 127.4, 128.1,
131.1, 134.1, 168.1 ppm. C7H7NO (121.14): calcd. C 69.41, H 5.82, N
11.56; found C 69.34, H 5.78, N 11.51.
Nicotinamide (5b): Yield 75 % (91.5 mg). CAS No. 98–92–0. 1H NMR
(250 MHz, CDCl3/TMS): δ = 7.44–7.59 (m, 2 H), 7.59 (s, 1 H), 8.15–
8.20 (m, 3 H), 8.66–8.67 (m, 1 H), 9.00 (s, 1 H) ppm. 13C NMR
(62.5 MHz, CDCl3/TMS): δ = 123.3, 129.6, 135.1, 148.6, 151.8,
166.4 ppm. C6H6N2O (122.13): calcd. C 59.01, H 4.95, N 22.94; found
C 58.95, H 4.91, N 22.88.
N-Ethyl-2-phenylacetamide (6b): Yield 91 % (148 mg). CAS No.
1
5465–00–9. H NMR (250 MHz, CDCl3/TMS): δ = 1.11 (s, 3 H), 2.73–
2.76 (m, 2 H), 3.42 (s, 2 H), 7.09–7.26 (m, 5 H), 8.45 (s, 1 H) ppm. 13
C
NMR (62.5 MHz, CDCl3/TMS): δ = 12.3, 34.1, 42.9, 125.9, 128.0, 128.1,
128.8, 129.0, 136.4, 174.7 ppm. C10H13NO (163.22): calcd. C 73.59, H
8.03, N 8.58; found C 73.51, H 7.98, N 8.52.
N-Isopropyl-2-phenylacetamide (6c): Yield 90 % (159 mg). 1H
NMR (250 MHz, CDCl3/TMS): δ = 1.14–1.18 (m, 6 H), 3.18–3.20 (m, 1
H), 3.34–3.52 (m, 2 H), 7.10–7.29 (m, 5 H), 8.17 (br. s, 1 H) ppm. 13C
NMR (62.5 MHz, CDCl3/TMS): δ = 20.2, 40.7, 42.9, 126.5, 128.1, 129.2,
134.9, 169.2 ppm. C11H15NO (177.25): calcd. C 74.54, H 8.53, N 7.90;
found C 74.48, H 8.47, N 7.85.
4-Chlorobenzamide (5c):[27] Yield 86 % (134 mg). CAS No. 619–56–
7. 1H NMR (250 MHz, CDCl3/TMS): δ = 7.19–7.59 (m, 3 H), 7.84–7.88
(m. 2 H), 8.11 (s, 1 H) ppm. 13C NMR (62.5 MHz, CDCl3/TMS): δ =
N-(tert-Butyl)-2-phenylacetamide (6d): Yield 84 % (161 mg). CAS
128.1, 129.3, 131.0, 136.1, 166.9 ppm. C7H6ClNO (155.58): calcd. C No. 6941–21–5. 1H NMR (250 MHz, CDCl3/TMS): δ = 1.23 (s, 9 H),
54.04, H 3.89, N 9.00; found C 53.98, H 3.83, N 8.94.
3.28–3.34 (m, 2 H), 7.11–7.27 (m, 4 H), 7.61–7.65 (m, 1 H) ppm. 13C
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NMR (62.5 MHz, CDCl3/TMS): δ = 28.4, 42.9, 50.0, 126.0, 128.0, 128.8,
136.9, 169.5 ppm. C12H17NO (191.27): calcd. C 75.35, H 8.96, N 7.32;
found C 75.27, H 8.91, N 7.25.
1
2-Phenyl-N-(p-tolyl)acetamide (6e): Yield 72 % (162 mg). H NMR
(250 MHz, CDCl3/TMS): δ = 2.21 (s, 3 H), 3.59 (s, 2 H), 7.06 (d, J =
7.5 Hz, 2 H), 7.22–7.32 (m, 4 H), 7.44–7.47 (m, 2 H), 10.04 (s, 1 H)
ppm. 13C NMR (62.5 MHz, CDCl3/TMS): δ = 20.3, 43.2, 118.9, 119.0,
126.4, 128.18, 128.21, 129.0, 132.0, 136.0, 136.6, 168.8 ppm.
C15H15NO (225.29): calcd. C 79.97, H 6.71, N 6.22; found C 79.91, H
6.64, N 6.17.
Acknowledgments
Financial support from the research councils of Shiraz Univer-
sity, Iran and a grant from the Iran National Elite Foundation
are gratefully acknowledged.
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Keywords: Synthetic methods · Homogeneous catalysis · C–C
coupling · Amides · Nickel · Carbodiimides
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Published Online: December 23, 2015
Eur. J. Org. Chem. 2016, 780–788
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