Synthesis of N-acetoxy-N-arylamides via diacetoxyiodobenzene promoted double acylation reaction of hydroxylamines with aldehydes

Article abstract of DOI:10.1039/c7ob00855d

A facile and efficient synthesis of N-acetoxy-N-arylamides through double acylations of hydroxylamines with aldehydes and diacetoxyiodobenzene is reported. The yields of the products are good to excellent.

Full text of DOI:10.1039/c7ob00855d

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Takeharu Haino et al.
Solvent-induced emission of organogels based on tris(phenylisoxazolyl)
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DOI: 10.1039/C7OB00855D
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Synthesis of N‐acetoxy‐N‐arylamides via Diacetoxyiodobenzene
Promoted Double Acylation Reaction of Hydroxylamines with
Aldehydes†
Received 00th April 2017,
Accepted 00th April 2017
Huaiyuan Zhang,a Yingpeng Su,a Ke‐Hu Wang,a Danfeng Huang,a Jun Li,a Yulai Hu*a,b
DOI: 10.1039/x0xx00000x
A facile and efficient synthesis of N‐acetoxy‐N‐arylamides through double acylations of hydroxylamines with
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aldehydes and diacetoxyiodobenzene is reported. The yields of the products are good to excellent.
oxidative
rearrangement,16 allylation,17 azidation,18 dearomatization,19
spirocyclization,20 thiocyanation,21 selenylation,22
and
transformations
such
as
halogenation,15
Introduction
Amides are prevalent structural motifs that are found in
proteins, natural products, polymers, pharmaceuticals and
materials.1 For example, more than 25% of drugs on the
market contain amide groups.2 Thus, methods for synthesis of
amides have received extensive attention. To date, many
synthetic approaches have been developed for the synthesis of
amides. The conventional methods are based on the
condensation of carboxylic acids and amines.3 These methods
usually suffered from very harsh conditions such as high
temperature above 100 °C or poor atom economy. To
overcome these limitations, alternative methods are
developed, such as the Schmidt reaction,4 the Ritter reaction,5
the Ugi‐type multicomponent reactions,6 the Beckmann
rearrangement,7 aminocarbonylation of aryl halides,8 catalytic
amidation of carboxylic acids with amines9 or their
surrogates10, amidation of carboxylic acid surrogates such as
aldehydes, ketones, alcohols, esters, thioacids, alkenes,
alkynes, etc.11 Within these emerging amide formation
methods, oxidative amidation of aldehydes with different
kinds of amines is a very attractive and efficient method
because of easy availability and cheap price of aldehydes and
amines in industry. These reactions were usually carried out in
the presence of transition‐metal catalysts.12 In recent years,
several metal‐free procedures have also been reported. For
instance, N‐heterocyclic carbenes,13a‐13c iodine13d and Bu4NI
catalyzed13e‐13f amidation of aldehydes provided efficient
protocols for synthesis of amides.
oxidative coupling23 reaction resulting in the formation of new
C‐C, C‐N and other C‐heteroatom or heteroatom‐heteroatom
bonds.24 In addition, PhI(OAc)2 has showed a particularly
important application as selective reagents in the total
synthesis of natural products.25 Meanwhile, PhI(OAc)2 can be
used in the amidation of aldehydes with amines (Scheme 1). In
2012, Tiwari’s group reported the amidation of aldehydes
using PhI(OAc)2 in the presence of ionic liquid (Scheme 1, a).26
In 2015, Mal’s group also reported coupling of aldehydes with
primary amines into amides via C−H acꢀvaꢀon using
diacetoxyiodobenzene (Scheme 1, b).27 Furthermore, N‐
acetoxy‐N‐arylamides, derivatives of hydroxamic acids, are
important synthetic intermediates,28 which were usually
obtained from the lead tetraacetate mediated oxidative
rearrangement of nitrones.28a,29 Herein, we would like to
report a convenient method for the preparation of N‐acetoxy‐
N‐arylamides from PhI(OAc)2‐promoted double acylation
reaction of hydroxylamines with aldehydes (Scheme 1, c).
Mal's work
O
PhI(OAc)2
NaHSO4
O
R2
R1
N
R2 NH2
+
b
On the other hand, PhI(OAc)2 has emerged as versatile and
environmentally benign reagents for organic chemistry in
recent years.14 First of all, PhI(OAc)2 has showed diverse
R1
H
H
ball milling, rt
a. College of Chemistry and Chemical Engineering, Northwest Normal University,
Lanzhou, Gansu, 730070.
b. State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou
730000, P. R. China.
Scheme 1. Amidation of aldehydes mediated by diacetoxyiodobenzene.
E‐mail: huyl@nwnu.edu.cn.
†
Electronic
Supplementary
Information
(ESI)
available:
See
DOI: 10.1039/x0xx00000x
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Table 1. Optimization of the reaction conditions.a
Results and discussion
View Article Online
DOI: 10.1039/C7OB00855D
At the outset of the study, mixture of benzaldehyde 1a (1
equiv) and N‐phenylhydroxylamine 2a (1 equiv) in DCM was
stirred at room temperature for 10 hours. After removing the
solvent under vacuum, the residue was dissolved in dry
acetonitrile, and diacetoxyiodobenzene 3a (1 equiv) was
added under nitrogen atmosphere. After stirring the mixture
at room temperature for one hour, the double acylated
product 4a was obtained in 45% yield (Table 1, entry 1). In
order to improve the yield, the reaction conditions were
examined in detail. Firstly, the mole ratio of the substrate 3a
was screened when 1a and 2a was fixed to 1:130. As mole ratio
of 3a was gradually increased, the yield of 4a was slightly
Entry
Mole Ratio
of 1a/2a/3a
Temp. (oC)
Solvent
Isolated
yield (%)
1
2
3
4
5
6
7
8
1/1/1
1/1/1.5
1/1/2
1/1/2.5
1/1/2
1/1/2
1/1/2
1/1/2
1/1/2
1/1/2
1/1/2
1/1/2
1/1/2
1/1/2
rt
rt
rt
rt
rt
rt
rt
rt
rt
rt
rt
rt
MeCN
MeCN
MeCN
MeCN
CH2Cl2
PhMe
THF
DMF
MeNO2
CH3OH
CH3CH2OH
CH3COOH
CH3COOH
CH3COOH
45
43
51
46
62
38
40
25
71
49
71
75
67
48
improved. The 1:1:2 mole ratio of 1a:2a:3a was finally
determined to be the best one, and used to optimize other
conditions (Table 1, entry 3). Next, various solvents were
investigated. As shown in Table 1, both of aprotic and protic
solvents could give desired product 4a, but the product yields
in most of aprotic solvents were lower than those in protic
solvents. The best result was obtained in acetic acid with the
yield of 4a going up to 75% (Table 1, entries 5‐12). Then, the
effect of temperature on the reaction was also checked. It was
found that the room temperature was the most suitable
temperature (Table 1, entries 12‐14). Finally, other
commercially available hypervalent iodine compounds such as
9
10
11
12
13
14
0
reflux
aReactions were carried out on a 0.47 mmol scale of 1a and 2a in 5 mL of DCM. After
formation of nitrone, DCM was removed and 4 mL of new solvent and 3a were added.
Table 2. Scope of the aldehydes.a
O
phenyliodine
bis(trifluoroacetate)
(PIFA)
and
AcO
OAc
O
I
R
N
[hydroxy(tosyloxy)iodo]benzene (HTIB, Koser’s reagent) were
applied in the reactions. However, no corresponding products
were obtained when PIFA or HTIB was used in the reaction.
Thus, the best reaction condition was treatment of aldehydes
with 1 equiv of hydroxylamines in CH2Cl2 at room temperature
overnight. After removing the solvent, the residue was
dissolved in acetic acid, and diacetoxyiodobenzene 3a (2 equiv)
was added under nitrogen atmosphere to give the target
products.
H
N
O
CH3COOH
OH
RCHO
+
+
nitrogen atmosphere
room temperature
1
3a
4
2a
The scope and generality of the process was next explored
under the optimized conditions. Firstly, a variety of aromatic
aldehydes
were
employed
to
react
with
N‐
phenylhydroxylamine 2a. As shown in Table 2, most of
aromatic aldehydes could give desired products regardless of
whether the substituents on the phenyl ring were electron‐
donating or electron‐withdrawing groups. In some cases, the
position of substituents on phenyl rings of aromatic aldehydes
had great influence on the reactions. For instance, the p‐
nitrobenzaldehyde could make the reaction occurred smoothly
to afford the product 4l in 73% yield, but the o‐
nitrobenzaldehyde could not produce the product 4j in the
same reaction (Table 2, 4l and 4j). Heterocyclic aromatic
O
O
O
O
N
O
O
O
O
N
N
O
O
O
NC
O2N
4m: 71% yield
4l: 73% yield
X-ray structure of 4l
4n: 52% yield
O
O
N
aldehydes
such
as
2‐furaldehyde
and
2‐
N
O
O
O
N
N
pyridinecarboxaldehyde provided the corresponding products
in good yields (Table 2, 4n and 4o). Unfortunately, aliphatic
aldehydes, such as n‐butyraldehyde and heptanal, could not
give the corresponding products (Table 2, 4p and 4q).
O
O
O
4q: 0% yield
4o: 77%
4p: 0% yield
aReactions were carried out on a 0.47 mmol scale of 1 and 2a in 5 mL of DCM. After
formation of nitrones, DCM was removed and 4 mL of AcOH and 0.94 mmol of 3a were
added. Isolated yield (SiO2).
2 | J. Name., 2012, 00, 1‐3
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Table 3. Scope of the hydroxylamines.a
Table 4. Scope of various aldehydes and hydroxylamines.a
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DOI: 10.1039/C7OB00855D
AcO
OAc
O
I
CHO
O
N
CH3COOH
RNHOH
R
O
nitrogen atmosphere
room temperature
1a
2
3a
4
O
N
O
O
O
O
O
Cl
O
O
O
F
O
O
N
O
O
O
O
O
O
O
N
N
N
N
N
N
O
O
O
O
O
O
Cl
F3C
F3C
Cl
Cl
Cl
4ac: 96% yield
4ad: 83% yield
4u:
65% yield
4r:
4t:
4ae: 78% yield
4af: 70% yield
51% yield
73% yield
4s: 57% yield
aReactions were carried out on a 0.47 mmol scale of 1 and 2 in 5 mL of DCM. After
formation of nitrone, DCM was removed and 4 mL of AcOH and 0.94 mmol of 3a were
added. Isolated yield (SiO2).
aReactions were carried out on a 0.47 mmol scale of 1a and 2 in 5 mL of DCM. After
formation of nitrone, DCM was removed and 4 mL of AcOH and 0.94 mmol of 3a were
added. Isolated yield (SiO2).
Then, the substrate scope of hydroxylamines
2 was
examined. Various N‐aromatic hydroxylamines containing
methyl, chloro, bromo, acetyl and ester groups reacted with
benzaldehyde 1a smoothly to afford the corresponding
products in 45‐75% yields (Table 3, 4r to 4z). However,
aliphatic hydroxylamines such as N‐methylhydroxylamine and
N‐(t‐butyl)hydroxylamine could not provide the desired
products 4aa and 4ab (Table 3, 4aa and 4ab).
Next, compatibility of the substituents on aromatic
aldehydes and aromatic hydroxylamines was also investigated
as showed in Table 4. The products would be obtained in
higher yields when more electron‐withdrawing groups were
attached on aromatic aldehydes. In contrast, if the electron‐
donating groups were attached on the aldehydes, the yields of
the products would decrease. For example, product 4ac, which
came from 4‐trifluoromethylbenzaldehyde, was obtained in 96%
Scheme 2. Transformation of product 4g.
To explore the application of the products
synthesis, the compound 4g was chose for further
transformations. It could be easily hydrolyzed to N‐hydroxyl
4 in organic
yield, but product 4ak
,
which came from 4‐
amide
5 in 73% yield when the compound 4g was exposed to
methoxybenzaldehyde, was produced only in 25% yield. The
same results could be observed between product 4ad and
product 4al. On the other hand, when the aldehydes were the
same, the aromatic hydroxylamines with electron‐donating
groups on their phenyl rings would give the products in higher
yields than those with electron‐withdrawing groups. For
instance, the product 4ac was produced in higher yield than
the product 4ad. At last, if the aromatic ketones, such as
acetophenone or 4‐bromoacetophenone, were used in the
reactions instead of aldehydes, no corresponding products
would be formed.
Ba(OH)2∙8H2O in ethanol. If 4g was treated with SmI2 in THF,
acetoxyl group would be removed to afford amide
yield (Scheme 2).
To investigate the reaction mechanism, nitrones were
assumed to be the intermediates in the reactions. Thus, some
nitrones were prepared firstly, and then reacted with
PhI(OAc)2 under the optimized reaction conditions. It was
found that the corresponding products were also obtained in
about the same yields as above (Table 5). These indicated that
nitrones were formed at the beginning of the reactions.
6 in 95%
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Table 5. Reactions of nitrones with diacetoxyiodobenzene for the synthesis of N‐
acetoxy‐N‐arylamides.a
Experimental Section
General Procedure for the Synthesis of CDoOmI:p1o0u.1n0d3s9/C47fOroB0m0815,5D2
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and 3a
The aldehyde
1 (0.47 mmol, 1 equiv) and hydroxylamine 2
(0.47 mmol, 1 equiv) was put in a dried round‐bottom flask (50
mL) fitted with a magnetic bar. Then dichloromethane (5 mL)
was added. The mixture was stirred at room temperature and
the reaction was monitored by TLC. After complete generation
of nitrones, the reaction mixture was concentrated under
reduced pressure, and diacetoxyiodobenzene 3a (0.94 mmol, 2
equiv) in acetic acid (4 mL) were added into the flask. The
resulting mixture was stirred at room temperature under
nitrogen atmosphere for 1 h, and then the saturated Na2CO3
solution (10 mL) was poured into the flask. After stirring for 10
min, the mixture was extracted with EtOAc (3 × 10 mL). The
organic layer were combined, dried over anhydrous MgSO4
and then concentrated under reduced pressure. The residue
was purified by silica gel column chromatography using PE : EA
aReactions were carried out on a scale of 0.25 mmol scale of 7 and 0.50 mmol of 3a in 4
mL of AcOH. Isolated yield (SiO2).
Based on the above experimental results and literature
reports29b, 31, a plausible mechanism for this reaction was
proposed in scheme 3. At the beginning, aldehyde 1a reacted
with hydroxylamine 2a to form nitrone 7a. The ligand
(10:1) as eluent to afford the product 4.
General Procedure for the Synthesis of Compounds 4 from 7 and
3a
exchange of 7a and PIDA 3a produced intermediate
conducted intramolecular rearrangement to produce
intermediate . Deprotonation of intermediate by acetate
8, which
The nitrone
7 (0.25 mmol, 1 equiv) and diacetoxyiodobenzene
3a (0.50 mmol, 2 equiv) were put in a dried round‐bottom
flask (50 mL) fitted with a magnetic bar. Then acetic acid (4 mL)
was added under nitrogen atmosphere. The mixture was
stirred at room temperature for 1 h, and then the saturated
Na2CO3 solution was poured into the flask. After stirring for 10
min, the mixture was extracted with EtOAc (3 × 10 mL). The
organic layer were combined, dried over anhydrous MgSO4
and then concentrated under reduced pressure. The residue
was purified by silica gel column chromatography using PE : EA
9
9
afforded intermediate 10, which gave the final product 4a
after migration of acyl group and isomerization.
(10:1) as eluent to afford the product
4.
N
‐acetoxy‐
N
‐phenylbenzamide (4a).29b White solid, 90.0 mg,
o
1
yield 75%. m.p. 47−48 C; H NMR (600 MHz, CDCl3) δ (ppm)
7.53−7.52 (m, 2H), 7.38−7.35 (m, 1H), 7.31−7.25 (m, 7H), 2.18
(s, 3H); 13C NMR (100 MHz, CDCl3) δ (ppm) 167.9, 166.8, 140.6,
133.2, 131.0, 129.2, 128.8, 128.4, 128.1, 126.9, 18.4; HRMS
(ESI) M/Z calcd for C15H14NO3 [M+H+] 256.0968, found:
256.0970.
N
‐acetoxy‐2‐methyl‐N‐phenylbenzamide (4b). White solid,
Scheme 3. Plausible mechanism.
78.5 mg, yield 62%. m.p. 61−62 oC; 1H NMR (600 MHz, CDCl3) δ
(ppm) 7.30−7.19 (m, 7H), 7.13 (d, J = 7.8 Hz, 1H), 7.06 (t, J = 7.2
Hz, 1H), 2.44 (s, 3H), 2.13 (s, 3H); 13C NMR (150 MHz, CDCl3) δ
(ppm) 167.9, 139.4, 135.9, 133.9, 130.5, 129.8, 129.0, 128.3,
127.5, 126.1, 125.3, 19.3, 18.2; HRMS (ESI) M/Z calcd for
C16H16NO3 [M+H+] 270.1125, found: 270.1123.
Conclusions
In summary, an efficient double acylation protocol for the
preparation of N‐acetoxy‐N‐arylamides has been developed.
The method couples the aromatic aldehydes and
N
‐acetoxy‐3‐methyl‐N‐phenylbenzamide (4c). White solid,
81.0 mg, yield 64%. m.p. 90−91 oC; 1H NMR (600 MHz, CDCl3) δ
(ppm) 7.40 (s, 1H), 7.31−7.29 (m, 4H), 7.27−7.25 (m, 2H), 7.17
(d, J = 7.2 Hz, 1H), 7.13 (t, J = 7.2 Hz, 1H), 2.28 (s, 3H), 2.18 (s,
3H); 13C NMR (150 MHz, CDCl3) δ (ppm) 167.8, 167.0, 140.6,
138.0, 133.1, 131.8, 129.3, 129.1, 128.3, 127.8, 126.8, 125.8,
21.2, 18.4; HRMS (ESI) M/Z calcd for C16H16NO3 [M+H+]
270.1125, found: 270.1122.
hydroxylamines
directly
in
the
presence
of
diacetoxyiodobenzene to afford the N‐acetoxy‐N‐arylamides in
good to excellent yields. One advantage of the method is
double acylation between N‐acylation and O‐acylation of
hydroxylamines. The nitrogen atoms in hydroxylamines are
only acylated by acyl groups of aldehydes, but the oxygen
atoms in hydroxylamines are acylated by acetyl group of
diacetoxyiodobenzene. Another advantage is that the two acyl
groups were introduced into the same amide molecules at the
same time.
N
‐acetoxy‐4‐methyl‐N
‐phenylbenzamide (4d).32 White solid,
75.9 mg, yield 60%. m.p. 88−89 oC; 1H NMR (600 MHz, CDCl3) δ
(ppm) 7.42 (d, J = 7.8 Hz, 2H), 7.30−7.25 (m, 5H), 7.06 (d, J =
4 | J. Name., 2012, 00, 1‐3
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7.8 Hz, 2H), 2.30 (s, 3H), 2.19 (s, 3H); 13C NMR (150 MHz, CDCl3) (ppm) 167.6, 164.6, 139.6, 137.5, 131.9, 129.5, 129.2, 129.1,
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DOI: 10.1039/C7OB00855D
δ (ppm) 167.9, 166.8, 141.5, 140.8, 130.2, 129.1, 128.9, 128.7, 127.0, 117.8, 114.6, 18.2; HRMS (ESI) M/Z calcd for
128.3, 126.9, 21.4, 18.4; HRMS (ESI) M/Z calcd for C16H16NO3 C16H12N2O3Na [M+Na+] 303.0740, found: 303.0737.
[M+H+] 270.1125, found: 270.1123.
‐acetoxy‐3‐methoxy‐
N
‐acetoxy‐
N‐phenylfuran‐2‐carboxamide (4n). White solid,
N
N
‐phenylbenzamide (4e). White solid, 59.9 mg, yield 52%. m.p. 70−71 oC; 1H NMR (600 MHz, CDCl3) δ
100.6 mg, yield 75%. m.p. 68−69 oC; 1H NMR (600 MHz, CDCl3) (ppm) 7.50−7.48 (m, 2H), 7.44−7.40 (m, 4H), 6.66 (d, J = 3.0 Hz,
δ (ppm) 7.31−7.28 (m, 4H), 7.27−7.24 (m, 1H), 7.14 (t, J = 7.8 1H), 6.38 (dd, J = 3.6, 1.8 Hz, 1H), 2.25 (s, 3H); 13C NMR (150
Hz, 1H), 7.07−7.05 (m, 2H), 6.89−6.88 (m, 1H), 3.69 (s, 3H), MHz, CDCl3) δ (ppm) 167.9, 164.6, 151.7, 148.5, 140.1, 136.6,
2.17 (s, 3H); 13C NMR (150 MHz, CDCl3) δ (ppm) 167.8, 166.4, 128.9, 128.2, 125.2, 124.4, 18.3; HRMS (ESI) M/Z calcd for
159.1, 140.5, 134.3, 129.1, 129.0, 128.4, 126.8, 121.0, 117.4, C13H12NO4 [M+H+] 246.0761, found: 246.0758.
113.5, 55.2, 18.3; HRMS (ESI) M/Z calcd for C16H15NO4Na
[M+Na+] 308.0893, found: 308.0889.
N
‐acetoxy‐
N‐phenylpicolinamide (4o). White solid, 92.7 mg,
o
1
yield 77%. m.p. 75−76 C; H NMR (600 MHz, CDCl3) δ (ppm)
N
‐acetoxy‐4‐methoxy‐N‐phenylbenzamide (4f). White solid, 8.45 (s, 1H), 7.79−7.72 (m, 2H), 7.39−7.25 (m, 6H), 2.19 (s, 3H);
83.1 mg, yield 62%. m.p. 74−75 oC; 1H NMR (600 MHz, CDCl3) δ 13C NMR (150 MHz, CDCl3) δ (ppm) 167.9, 156.2, 145.4, 145.3,
(ppm) 7.51 (d, J = 9.0 Hz, 2H), 7.33−7.27 (m, 5H), 6.76 (d, J = 140.0, 129.3, 129.2, 127.4, 118.2, 111.5, 18.4; HRMS (ESI) M/Z
9.0 Hz, 2H), 3.78 (s, 3H), 2.20 (s, 3H); 13C NMR (150 MHz, CDCl3) calcd for C14H13N2O3 [M+H+] 257.0921, found: 257.0918.
δ (ppm) 168.0, 166.5, 161.8, 141.2, 131.0, 129.2, 128.3, 127.0,
125.1, 113.4, 55.3, 18.5; HRMS (ESI) M/Z calcd for yield 51%. m.p. 65−66 C; H NMR (600 MHz, CDCl3) δ (ppm)
C16H15NO4Na [M+Na+] 308.0893, found: 308.0889.
7.49 (d, J = 7.2 Hz, 2H), 7.35−7.32 (m, 2H), 7.25−7.22 (m, 4H),
‐acetoxy‐2‐chloro‐
‐phenylbenzamide (4g). White solid, 7.12 (d, J = 4.8 Hz, 1H), 2.38 (s, 3H), 2.16 (s, 3H); 13C NMR (150
N‐acetoxy‐N‐(o‐tolyl)benzamide (4r). White solid, 64.6 mg,
o
1
N
N
87.1 mg, yield 64%. m.p. 88−89 oC; 1H NMR (600 MHz, CDCl3) δ MHz, CDCl3) δ (ppm) 167.5, 139.0, 137.0, 133.0, 131.1, 131.0,
(ppm) 7.38−7.26 (m, 9H), 2.25 (s, 3H); 13C NMR (150 MHz, 129.9, 129.7, 128.4, 127.9, 126.7, 18.3, 17.9; HRMS (ESI) M/Z
CDCl3) δ (ppm) 167.6, 162.8, 138.8, 134.0, 131.1, 130.9, 129.7, calcd for C16H15NO3Na [M+Na+] 292.0944, found: 292.0950.
129.0, 127.6, 126.5, 110.0, 18.1; HRMS (ESI) M/Z calcd for
C15H12ClNO3Na [M+Na+] 312.0398, found: 312.0399.
N‐acetoxy‐N‐(m‐tolyl)benzamide (4s). White solid, 72.1 mg,
yield 57%. m.p. 70−71 C; H NMR (600 MHz, CDCl3) δ (ppm)
o
1
N
‐acetoxy‐3‐chloro‐
N
‐phenylbenzamide (4h). White solid,
7.53 (d, J = 7.8 Hz, 2H), 7.35 (t, J = 7.2 Hz, 1H), 7.26 (t, J = 7.8 Hz,
o
1
104.3 mg, yield 76%. m.p. 102−103 C; H NMR (600 MHz, 2H), 7.16 (t, J = 8.4 Hz, 2H), 7.07 (t, J = 10.2 Hz, 2H), 2.28 (s, 3H),
CDCl3) δ (ppm) 7.55 (s, 1H), 7.37−7.28 (m, 7H), 7.20 (t, J = 7.8 2.16 (s, 3H); 13C NMR (150 MHz, CDCl3) δ (ppm) 167.8, 166.8,
Hz, 1H), 2.19 (s, 3H); 13C NMR (150 MHz, CDCl3) δ (ppm) 167.7, 140.4, 139.2, 133.3, 130.9, 129.2, 128.8, 128.6, 128.0, 127.3,
165.3, 140.1, 135.0, 134.2, 131.1, 129.4, 129.3, 128.9, 128.8, 124.0, 21.1, 18.3; HRMS (ESI) M/Z calcd for C16H15NO3Na
127.0, 126.8, 18.3; HRMS (ESI) M/Z calcd for C15H12ClNO3Na [M+Na+] 292.0944, found: 292.0952.
[M+Na+] 312.0398, found: 312.0401.
N
N‐acetoxy‐N
‐(p‐tolyl)benzamide (4t).29b White solid, 92.4 mg,
o
1
‐acetoxy‐4‐chloro‐
N
‐phenylbenzamide (4i).32 White solid, yield 73%. m.p. 88−89 C; H NMR (600 MHz, CDCl3) δ (ppm)
81.7 mg, yield 60%. m.p. 105−107 oC; 1H NMR (600 MHz, CDCl3) 7.52 (d, J = 7.8 Hz, 2H), 7.34 (t, J = 7.2 Hz, 1H), 7.25 (t, J = 7.8 Hz,
δ (ppm) 7.47 (d, J = 7.8 Hz, 2H), 7.34−7.27 (m, 5H), 7.25 (d, J = 2H), 7.19 (d, J = 8.4 Hz, 2H), 7.09 (d, J = 7.8 Hz, 2H), 2.30 (s, 3H),
8.4 Hz, 2H), 2.19 (s, 3H); 13C NMR (150 MHz, CDCl3) δ (ppm) 2.17 (s, 3H); 13C NMR (150 MHz, CDCl3) δ (ppm) 167.8, 166.7,
167.7, 165.6, 140.2, 137.2, 131.6, 130.2, 129.3, 128.6, 128.4, 138.8, 138.0, 133.3, 130.9, 129.8, 128.7, 128.0, 127.2, 21.1,
126.9, 18.3; HRMS (ESI) M/Z calcd for C15H13ClNO3 [M+H+] 18.3; HRMS (ESI) M/Z calcd for C16H16NO3 [M+H+] 270.1125,
290.0578, found: 290.0576.
‐acetoxy‐3‐nitro‐ ‐phenylbenzamide (4k). Yellow oil, 119.9
found: 270.1122.
‐acetoxy‐ ‐(2‐chlorophenyl)benzamide (4u). White solid,
N
N
N
N
mg, yield 85%. 1H NMR (600 MHz, CDCl3) δ (ppm) 8.38 (s, 1H), 88.5 mg, yield 65%. m.p. 80−81 oC; 1H NMR (600 MHz, CDCl3) δ
8.23 (d, J = 8.4 Hz, 1H), 7.86 (d, J = 7.8 Hz, 1H), 7.49 (t, J = 6.0 (ppm) 7.56 (d, J = 7.8 Hz, 2H), 7.51 (d, J = 7.2 Hz, 1H), 7.42 (d, J
Hz, 1H), 7.36−7.32 (m, 5H), 2.21 (s, 3H); 13C NMR (150 MHz, = 7.8 Hz, 1H), 7.36 (t, J = 7.2 Hz, 1H), 7.29−7.26 (m, 3H), 7.22 (t,
CDCl3) δ (ppm) 167.6, 147.7, 139.6, 134.9, 134.5, 129.6, 129.4, J = 7.8 Hz, 1H), 2.19 (s, 3H); 13C NMR (150 MHz, CDCl3) δ (ppm)
129.3, 127.3, 125.6, 123.9, 18.3; HRMS (ESI) M/Z calcd for 167.7, 137.9, 133.8, 132.9, 132.2, 131.2, 131.0, 130.6, 128.5,
C15H12N2O5Na [M+Na+] 323.0638, found: 323.0635.
‐acetoxy‐4‐nitro‐
‐phenylbenzamide (4l).33 White solid, [M+H+] 290.0578, found: 290.0580.
103.0 mg, yield 73%. m.p. 157−158 C; H NMR (600 MHz, ‐acetoxy‐N‐(3‐chlorophenyl)benzamide (4v). Yellow liquid,
128.1, 127.6, 18.4; HRMS (ESI) M/Z calcd for C15H13ClNO3
N
N
o
1
N
CDCl3) δ (ppm) 8.14 (d, J = 9.0 Hz, 2H), 7.69 (d, J = 8.4 Hz, 2H), 102.1 mg, yield 75%. 1H NMR (600 MHz, CDCl3) δ (ppm)
7.35−7.32 (m, 5H), 2.21 (s, 3H); 13C NMR (150 MHz, CDCl3) δ 7.55−7.53 (m, 2H), 7.42−7.39 (m, 2H), 7.32 (t, J = 7.8 Hz, 2H),
(ppm) 167.6, 148.9, 139.4, 129.7, 129.5, 129.3, 127.1, 123.4, 7.24−7.19 (m, 3H), 2.16 (s, 3H); 13C NMR (150 MHz, CDCl3) δ
110.0, 18.3; HRMS (ESI) M/Z calcd for C15H12N2O5Na [M+Na+] (ppm) 167.8, 166.9, 141.5, 134.6, 132.9, 131.3, 129.9, 128.5,
323.0638, found: 323.0634.
128.2, 128.1, 125.9, 124.3, 18.3; HRMS (ESI) M/Z calcd for
N
‐acetoxy‐4‐cyano‐
N
‐phenylbenzamide (4m). White solid, C15H13ClNO3 [M+H+] 290.0578, found: 290.0577.
93.5 mg, yield 71%. m.p. 105−106 oC; 1H NMR (600 MHz, CDCl3)
N‐acetoxy‐N
‐(4‐chlorophenyl)benzamide (4w).29b White solid,
δ (ppm) 7.61 (d, J = 8.4 Hz, 2H), 7.57 (d, J = 8.4 Hz, 2H), 61.3 mg, yield 45%. m.p. 108−109 oC; 1H NMR (600 MHz, CDCl3)
7.35−7.29 (m, 5H), 2.19 (s, 3H); 13C NMR (150 MHz, CDCl3) δ δ (ppm) 7.53−7.52 (m, 2H), 7.41−7.38 (m, 1H), 7.32−7.26 (m,
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J. Name., 2013, 00, 1‐3 | 5
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Organic & Biomolecular Chemistry
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ARTICLE
Journal Name
6H), 2.16 (s, 3H); 13C NMR (150 MHz, CDCl3) δ (ppm) 167.8, 129.3, 126.7, 18.1; HRMS (ESI) M/Z calcd for C15H15Cl2N2O3
View Article Online
+
DOI: 10.1039/C7OB00855D
166.8, 139.0, 134.0, 133.0, 131.2, 129.3, 128.6, 128.2, 127.8, [M+NH4 ] 341.0454, found: 341.0453.
18.3; HRMS (ESI) M/Z calcd for C15H12ClNO3Na [M+Na+]
312.0398, found: 312.0403.
N
‐acetoxy‐4‐chloro‐
White solid, 114.27 mg, yield 75%. m.p. 75−77 C; H NMR
N
‐(4‐chlorophenyl)benzamide
(4ag).
o
1
N
‐acetoxy‐N‐(4‐bromophenyl)benzamide (4x). White solid, (600 MHz, CDCl3) δ (ppm) 7.47 (d, J = 7.8 Hz, 2H), 7.31−7.25 (m,
108.4 mg, yield 69%. m.p. 66−67 oC; 1H NMR (600 MHz, CDCl3) 6H), 2.17 (s, 3H); 13C NMR (150 MHz, CDCl3) δ (ppm) 167.9,
δ (ppm) 7.52 (d, J = 7.2 Hz, 2H), 7.44−7.39 (m, 3H), 7.31 (t, J = 166.8, 140.6, 133.2, 131.0, 129.2, 128.8, 128.4, 128.1, 126.9,
7.8 Hz, 2H), 7.20 (d, J = 8.4 Hz, 2H), 2.16 (s, 3H); 13C NMR (150 18.4; HRMS (ESI) M/Z calcd for C15H11Cl2NO3Na [M+Na+]
MHz, CDCl3) δ (ppm) 167.8, 166.8, 139.5, 132.9, 132.3, 131.3, 346.0008, found: 346.0012.
128.6, 128.2, 128.0, 122.0, 18.3; HRMS (ESI) M/Z calcd for
C15H12BrNO3Na [M+Na+] 355.9893, found: 355.9905.
N
‐acetoxy‐4‐bromo‐
N
‐(4‐chlorophenyl)benzamide
(4ah).
White solid, 128.2 mg, yield 74%. m.p. 70−71 oC; 1H NMR (600
N
‐acetoxy‐N‐(4‐acetylphenyl)benzamide (4y). White solid, MHz, CDCl3) δ (ppm) 7.45 (d, J = 8.4 Hz, 2H), 7.40 (d, J = 8.4 Hz,
86.6 mg, yield 62%. m.p. 116−117 oC; 1H NMR (600 MHz, CDCl3) 2H), 7.30 (d, J = 9.0 Hz, 2H), 7.26 (d, J = 8.4 Hz, 2H), 2.17 (s, 3H);
δ (ppm) 7.90 (d, J = 8.4 Hz, 2H), 7.56 (d, J = 7.2 Hz, 2H), 13C NMR (150 MHz, CDCl3) δ (ppm) 167.7, 165.9, 138.7, 134.4,
7.45−7.39 (m, 3H), 7.34 (t, J = 7.2 Hz, 2H), 2.57 (s, 3H), 2.17 (s, 131.8, 131.5, 130.2, 129.5, 127.9, 126.0, 18.3; HRMS (ESI) M/Z
3H); 13C NMR (150 MHz, CDCl3) δ (ppm) 196.6, 167.8, 166.9, calcd for C15H11BrClNO3Na [M+Na+] 389.9503, found: 389.9499.
144.1, 135.4, 133.0, 131.5, 129.2, 128.5, 128.3, 124.2, 26.5,
18.2; HRMS (ESI) M/Z calcd for C17H15NO4Na [M+Na+] 320.0893, White solid, 114.8 mg, yield 73%. m.p. 166−167 C; H NMR
found: 320.0901. (600 MHz, CDCl3) δ (ppm) 8.18 (d, J = 8.4 Hz, 2H), 7.70 (d, J =
Ethyl 4‐(
‐acetoxybenzamido)benzoate (4z). White solid, 93.8 8.4 Hz, 2H), 7.34−7.27 (m, 4H), 2.18 (s, 3H); 13C NMR (150 MHz,
N
‐acetoxy‐
N
‐(4‐chlorophenyl)‐4‐nitrobenzamide
(4ai).33
o
1
N
mg, yield 61%. m.p. 72−73 oC; 1H NMR (600 MHz, CDCl3) δ 7.98 CDCl3) δ (ppm) 167.6, 149.1, 139.0, 137.9, 135.0, 129.7, 128.0,
(d, J = 8.4 Hz, 2H), 7.55 (d, J = 7.8 Hz, 2H), 7.42 (t, J = 7.2 Hz, 123.5, 109.9, 18.2; HRMS (ESI) M/Z calcd for C15H11ClN2O5Na
1H), 7.36 (d, J = 7.8 Hz, 2H), 7.32 (t, J = 7.2 Hz, 2H), 4.35 (q, J = [M+Na+] 357.0249, found: 357.0246.
7.2 Hz, 2H), 2.17 (s, 3H), 1.37 (t, J = 7.2 Hz, 3H); 13C NMR (100
N‐acetoxy‐N‐(p‐tolyl)furan‐2‐carboxamide (4aj). White solid,
MHz, CDCl3) δ 167.8, 166.8, 165.5, 144.1, 133.1, 131.4, 130.4, 81.6 mg, yield 67%. m.p. 107−108 oC; 1H NMR (600 MHz, CDCl3)
129.2, 128.6, 128.3, 124.4, 61.2, 18.2, 14.2; HRMS (ESI) M/Z δ (ppm) 7.42 (d, J = 1.2 Hz, 1H), 7.37 (d, J = 7.8 Hz, 2H), 7.23 (d,
calcd for C18H18NO5 [M+H+] 328.1179, found: 328.1176.
J = 8.4 Hz, 2H), 6.55 (s, 1H), 6.36 (dd, J = 3.6, 1.2 Hz, 1H), 2.40
N
‐acetoxy‐
N
‐(p‐tolyl)‐4‐(trifluoromethyl)benzamide
(4ac). (s, 3H), 2.23 (s, 3H); 13C NMR (100 MHz, CDCl3) δ (ppm) 167.9,
White solid, 152.2 mg, yield 96%. m.p. 67−68 oC; 1H NMR (600 156.2, 145.4, 145.2, 139.8, 137.3, 130.0, 127.8, 118.0, 111.4,
MHz, CDCl3) δ (ppm) 7.63 (d, J = 7.8 Hz, 2H), 7.53 (d, J = 8.4 Hz, 21.3, 18.5; HRMS (ESI) M/Z calcd for C14H14NO4 [M+H+]
2H), 7.20 (d, J = 7.8 Hz, 2H), 7.12 (d, J = 8.4 Hz, 2H), 2.32 (s, 3H), 260.0917, found: 260.0914.
2.19 (s, 3H); 13C NMR (150 MHz, CDCl3) δ (ppm) 167.7, 165.3,
N
‐acetoxy‐
N
‐(4‐chlorophenyl)‐4‐methoxybenzamide
(4ak).
1
139.4, 137.3, 136.9, 132.5 (q, JC‐F = 33.0 Hz), 130.0, 129.1, Yellow oil, 37.5 mg, yield 25%. H NMR (600 MHz, CDCl3) δ
127.3, 125.1 (q, JC‐F = 3.0 Hz), 123.5 (q, JC‐F = 271.5 Hz), 21.1, (ppm) 7.50 (d, J = 9.0 Hz, 2H), 7.30−7.28 (m, 2H), 7.25−7.24 (m,
18.3; HRMS (ESI) M/Z calcd for C17H15F3NO3 [M+H+] 338.0999, 2H), 6.79 (d, J = 9.0 Hz, 2H), 3.80 (s, 3H), 2.19 (s, 3H); 13C NMR
found: 338.0998.
(150 MHz, CDCl3) δ (ppm) 167.9, 162.1, 134.0, 131.0, 129.4,
128.0, 124.7, 113.5, 110.0, 55.3, 18.4; HRMS (ESI) M/Z calcd
N
‐acetoxy‐
N
‐(4‐chlorophenyl)‐4‐(trifluoromethyl)benzamide
(4ad). Yellow oil, 139.3 mg, yield 83%. H NMR (600 MHz, for C16H14ClNO4Na [M+Na+] 342.0604, found: 342.0608.
1
CDCl3) δ (ppm) 7.65 (d, J = 8.4 Hz, 2H), 7.59 (d, J = 7.8 Hz, 2H),
N
‐acetoxy‐
N
‐(4‐chlorophenyl)‐4‐methylbenzamide
(4al).
1
7.33−7.27 (m, 4H), 2.17 (s, 3H); 13C NMR (150 MHz, CDCl3) δ yellow oil, 44.1 mg, yield 31%. H NMR (600 MHz, CDCl3) δ
(ppm) 167.7, 165.5, 138.3, 136.5, 134.6, 132.9 (q, JC‐F = 33.0 (ppm) 7.42 (d, J = 8.4 Hz, 2H), 7.29−7.24 (m, 4H), 7.10 (d, J =
Hz), 129.6, 129.0, 127.9, 125.3 (q, JC‐F = 4.5 Hz), 123.4 (q, JC‐F
=
7.8 Hz, 2H), 2.33 (s, 3H), 2.18 (s, 3H); 13C NMR (150 MHz, CDCl3)
271.5 Hz), 18.2; HRMS (ESI) M/Z calcd for C16H11ClF3NO3Na δ (ppm) 167.9, 166.9, 141.9, 139.4, 134.0, 130.0, 129.4, 128.9,
[M+Na+] 380.0272, found: 380.0278.
‐acetoxy‐ ‐(4‐chlorophenyl)‐2‐fluorobenzamide
128.8, 128.0, 21.5, 18.4; HRMS (ESI) M/Z calcd for
(4ae). C16H14ClNO3Na [M+Na+] 326.0554, found: 326.0558.
N
N
White solid, 112.8 mg, yield 78%. m.p. 98−99 oC; 1H NMR (600 General Procedure for the Synthesis of Compounds 5
MHz, CDCl3) δ (ppm) 7.48 (t, J = 7.2 Hz, 1H), 7.37−7.27 (m, 5H), Hydrated barium hydroxide (1.47 mmol, 7 equiv) was added to
7.14 (t, J = 7.2 Hz, 1H), 6.98 (s, 1H), 2.12 (s, 3H); 13C NMR (150 a solution of the N‐acetoxy‐2‐chloro‐N‐phenylbenzamide 4g in
MHz, CDCl3) δ (ppm) 167.5, 158.4 (d, JC‐F = 250.5 Hz), 137.5, ethanol (7 ml) under nitrogen atmosphere and the mixture
134.3, 132.5 (d, JC‐F = 7.5 Hz), 129.6, 129.1, 127.9, 124.3 (d, JC‐F was stirred at room temperature for 1.5 h. Then, hydrochloric
= 3.0 Hz), 122.3 (d, JC‐F = 15.0 Hz), 115.8 (d, JC‐F = 21.0 Hz), 18.0; acid was added to acidify the mixture to pH 1. The resulting
HRMS (ESI) M/Z calcd for C15H11ClFNO3Na [M+Na+] 330.0304, mixture was extracted with EtOAc (3 × 10 mL). The organic
found: 330.0303.
‐acetoxy‐2‐chloro‐
layer were combined, dried over anhydrous MgSO4 and then
(4af). concentrated under reduced pressure. The residue was
White solid, 106.6 mg, yield 70%. m.p. 72−73 oC; 1H NMR (600 purified by silica gel column chromatography using PE : EA (5:3)
N
N
‐(4‐chlorophenyl)benzamide
MHz, CDCl3) δ (ppm) 7.38−7.27 (m, 8H), 2.25 (s, 3H); 13C NMR as eluent to afford the product
(150 MHz, CDCl3) δ (ppm) 167.6, 137.3, 133.8, 131.1, 129.7,
5.
6 | J. Name., 2012, 00, 1‐3
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Organic & Biomolecular Chemistry
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Journal Name
2‐chloro‐ ‐hydroxy‐N
‐phenylbenzamide (5).34 White solid,
38.0 mg, yield 73%. m.p. 103−104 oC; 1H NMR (400 MHz, CDCl3)
δ (ppm) 9.46 (s, 1H), 7.29−7.21 (m, 9H); 13C NMR (150 MHz,
CDCl3) δ (ppm) 162.5, 137.8, 133.1, 131.6, 131.2, 129.9, 129.4,
128.8, 128.2, 126.7, 125.1.
ARTICLE
Wu, J. K. Ekegren, Mats. Larhed, Organometallics, 2006, 25
1434; (c) J. Ju, M. Jeong, J. Moon, HD. OMI:.10Ju.1n0g3V9,i/eSCw.7AOLretBice0le,0O8On5rl5ingDe.
Lett., 2007, , 4615.
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,
N
9
9
,
3405; (b) C. Singh, V. Kumar, U. Sharma, N. Kumar, B. Singh,
Curr. Org. Synth., 2013, 10, 241; (c) C. Wang, H.‐Z. Yu, Y. Fu,
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Figueiredo, J.‐S. Suppo, J.‐M. Campagne, Chem. Rev., 2016,
116, 12029.
General Procedure for the Synthesis of Com.p.ounds 6
To a stirring solution of the N‐acetoxy‐2‐chloro‐N‐phenylbenzamide
4g (0.21 mmol, 1 equiv) in dry THF (5 mL), maintained under
nitrogen atmosphere at room temperature, was added a freshly
prepared solution of SmI2 in THF dropwise. After TLC analysis
indicated complete reaction, the mixture was diluted with CH2Cl2
(10 mL), then quenched with 10 ml of 10% aqueous sodium
thiosulfate solution. The resulting mixture was extracted with
CH2Cl2 (3 × 10 mL). The organic layer were combined, dried over
anhydrous MgSO4 and then concentrated under reduced pressure.
The residue was purified by silica gel column chromatography using
PE : EA (100:1) as eluent to afford the product 6.
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2013, 15, 2506; (b) S. Kegnæs, J. Mielby, U. V. Mentzel, T.
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,
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2‐chloro‐N
‐phenylbenzamide (6).35 White solid, 46.2 mg, yield
95%. m.p. 116−118 oC; 1H NMR (400 MHz, CDCl3) δ (ppm) 8.02
(s, 1H), 7.70 (d, J = 7.2 Hz, 1H), 7.64 (d, J = 8.4 Hz, 2H),
7.44−7.32 (m, 5H), 7.17 (t, J = 7.6 Hz, 1H); 13C NMR (150 MHz,
CDCl3) δ (ppm) 164.5, 137.5, 135.2, 131.6, 130.6, 130.3, 130.2,
129.1, 127.2, 124.8, 120.1.
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Acknowledgements
We are thankful for financial support from the National
Natural Science Foundation of China (Grant No. 21662030 and
21362033); Key Laboratory Polymer Materials of Gansu
Province (Northwest Normal University); Bioactive Product
Engineering Research Center for Gansu Distinctive Plants; and
State Key Laboratory of Applied Organic Chemistry, Lanzhou
University.
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5014; (h) S. Gaspa, A. Porcheddu, L. De Luca, Tetrahedron
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Z. Wu, P. Wang, W Xue,. B. Song, S. Yang, Tetrahedron Lett.,
2015, 56, 831; (j) K. R. Reddy, C. U. Maheswari, M.
Venkateshwar, M. L. Kantam, Eur. J. Org. Chem., 2008, 3619;
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Notes and references
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Organic & Biomolecular Chemistry
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Journal Name
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8 | J. Name., 2012, 00, 1‐3
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DOI: 10.1039/C7OB00855D
Journal Name
ARTICLE
Synthesis of N-acetoxy-N-arylamidesvia Diacetoxyiodobenzene Promoted Double
Acylation Reaction of Hydroxylamines with Aldehydes
Huaiyuan Zhang, Yingpeng Su, Ke-Hu Wang, Danfeng Huang, Jun Li, Yulai Hu*
A facile and efficient synthesis of N-acetoxy-N-
arylamides through double acylations of
hydroxylamines
with
aldehydes
and
diacetoxyiodobenzene is reported. The yields of
the products are good to excellent.
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