Hypervalent Iodine(III)-Promoted Phenyl Transfer Reaction from Phenyl Hydrazides to Nitriles

Article abstract of DOI:10.1021/acs.joc.7b01215

A useful transformation of nitriles to N-phenyl amides has been achieved through a novel intermolecular phenyl transfer reaction from phenyl hydrazides and N-addition to nitriles in the presence of PIFA under mild and solvent-free conditions. This cross-coupling reaction includes the oxidative cleavage of sp² C-N bonds of phenyl hydrazides to form a phenyl radical and the subsequent N-addition to cyanos to form new sp² C-N bonds and provides efficient access to various N-phenyl amides in moderate to good yields under mild reaction conditions.

Full text of DOI:10.1021/acs.joc.7b01215

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Article
Hypervalent Iodine(III)-Promoted Phenyl Transfer
Reaction from Phenyl Hydrazides to Nitriles
Yan Yan, Zhiguo Zhang, Yameng Wan, Guisheng Zhang, Nana Ma, and Qingfeng Liu
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.7b01215 • Publication Date (Web): 07 Jul 2017
Downloaded from http://pubs.acs.org on July 7, 2017
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Hypervalent Iodine(III)-Promoted Phenyl Transfer Reaction from Phenyl Hydrazides to
Nitriles
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Yan Yan,a Zhiguo Zhang,*a,b Yameng Wan,a Guisheng Zhang,*a Nana Ma,a Qingfeng Liua
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a
Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals, Key
Laboratory of Green Chemical Media and Reactions, Ministry of Education, School of Chemistry and Chemical
Engineering, Henan Normal University, Xinxiang, Henan 453007, P. R. China.
* Fax: (+86)-373-332-5250; E-mail: zhangzg@htu.edu.cn or zgs6668@yahoo.com
b
Jilin Province Key Laboratory of Organic Functional Molecular Design & Synthesis, Northeast Normal
University, Jilin, Changchun, 130024, P. R. China
Abstract: A useful transformation of nitriles to N-phenyl amides has been achieved through a
novel intermolecular phenyl transfer reaction from phenyl hydrazides and N-addition to nitriles in
the presence of PIFA under mild and solvent-free conditions. This cross-coupling reaction includes
the oxidative cleavage of sp2 C-N bonds of phenylhydrazides to form a phenyl radical and the
subsequent N-addition to cyanos to form new sp2 C-N bonds, and provides efficient access to
various N-phenyl amides in moderate to good yields under mild reaction conditions.
Keywords: Phenyl hydrazides; Nitrile N-addition; Phenyl transfer reaction; Cross-coupling;
Hypervalent iodine; PIFA; Primary amides
INTRODUCTION
Nitriles are commercially available and commonly used for functional group conversions in
organic reactions, including the formation of amides, aldehydes, carboxyl derivatives, amines, and
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heterocycles.1-7 When nitriles react with aryl donors, such as sodium arylsulfinates,8 arylsulfinic
acids,9,10 potassium aryltrifluoroborates,11 arylboronic acids,12-16 aryl iodides,17 and arenes,18 the
arylketone or ketimine products are afforded via an aryl transfer reaction, frequently in the
presence of transition-metal catalysts (Scheme 1, a). These C-addition reactions directly add the
aryl group to the carbon atom of the cyano group. However, a review of the literature showed that
a direct N-addition reaction by tethering the aryl and nitrile portion to afford amides or their
analogs is relatively rare. To the best of our knowledge, only two examples of this type reaction
have been reported, and both involve copper catalysis. In 2013, Chen and co-workers19 established
a regioselective [2+2+2] cyclization for the synthesis of substituted quinolines, involving a
diaryliodonium salt, a nitrile, and an alkyne. The aryl group of the diaryliodoniums served as the
aryl source in this three-component reaction. The reaction proceeded through a key N-
phenylnitrilium intermediate, which upon hydrolysis gave the anilides (only one case was listed in
their work) or formal [4+2] annulation to the quinolines via direct N-addition assisted by Cu(OTf)2
(Scheme 1, b). Soon after, they found that this aryl transfer reaction could be extended to the
preparation of tricyclic quinolines starting from an alkyne and nitriles.20 In light of the above
results, we were interested in developing a new route using both the aryl and nitrile portions as the
reaction partners to construct a new carbon–nitrogen bond in the presence of non-metallic reagents
under mild and green conditions. We now present the first example of furnishing N-phenyl amides
via [bis-(trifluoroacetoxy)iodo]benzene (PIFA)-promoted intermolecular direct N-addition of a
phenyl radical (generated in situ from phenyl hydrazides) to nitriles under solvent-free conditions
at 40 °C (Scheme 1, c).
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Scheme 1. C/N-Addition reaction of aryl and nitrile portion.
Hydrazines and their analogs are versatile synthetic building blocks in the construction of
various nitrogen-containing compounds in organic chemistry.21-28 It is well-known that
dehydrogenation of aryl hydrazines by a variety of oxidants will produce arenes and nitrogen via a
transient aryl diazene (Scheme 2).29-31 Hydrazine derivatives can serve as an aryl donorin the
presence of a palladium catalyst,32-35 as well as donor of sulfonyl,36-38 amino39 and other groups40,41
in transfer reactions to construct new C-C, C-P, C-S, and C-N bonds by cleavage of the hydrazide
linker. However, new methods which proceed efficiently under relatively mild and catalytic
reaction conditions are in high demand.
Scheme 2. Oxidative cleavage of an aryl hydrazide.
RESULTS AND DISCUSSION
Very recently, we developed42 a PIFA-promoted ring-closing reaction for the synthesis of
spirocyclopropane quinolinediones in good to excellent yields from readily available 2,2-
disubstituted-2-benzoylacetamides under mild conditions. The spirocyclopropane quinolinedione
products can readily convert to pyrrolo[3,2-c]quinolinones via an intermolecular amine ring-
opening cyclization reaction. Based on our recent research42-46 and that of others19,20 related to the
synthesis of nitrogen-containing functional small molecules, it was envisioned that N’-
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phenylacetohydrazide (1) would react with nitriles (2) leading to N-phenylamides (3) via
intermolecular direct N-addition (Scheme 1, c).
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Initially, several solvents were screened for the reaction, including CH2Cl2, dimethyl sulfoxide
(DMSO), dimethylformamide (DMF), methamol (CH3OH), 2,2,2-trifluoroethanol (TFE),
hexafluoroisopropanol (HFIP), and ethyl acetate (EtOAc). It was found that the rate of the reaction
gradually accelerated as the CH2Cl2 (1 mL) evaporated. The desired product 3a was isolated in
69% yield as a white solid when we treated the mixture of 1a (0.3 mmol) and 2a (0.6 mmol) with
1.5 equivalent of PIFA at 40 °C (Table 1, entry 1). However, none of compound 3a was obtained
in other higher boiling-point solvents under the same conditions, and mostly starting material 1a
was recovered. These observations indicate that increasing the concentration of the reactants is
favourable for this phenyl transfer reaction. Therefore, we decided to carry out the reaction in the
absence of solvent. To our delight, the desired product 3a was isolated in 76% yield, along with 16%
of N′-acetyl-N′-phenyl-acetohydrazide (4a) generated from 1a (Table 1, entry 3).47 Further
investigation revealed that increasing the amount of PIFA had almost no effect on the yield of 3a
(Table 1, entry 4), but a significantly lower yield of 3a was obtained if we decreased the amount of
PIFA to 1.0 equivalent (Table 1, entry 2). In addition, we found that it was detrimental to the
transformation if the amount of 2a was reduced (Table 1, entries 5 and 6). Similar results were
observed during temperature optimization experiments (Table 1, entries 7 and 8). Further
investigation was carried out into other oxidants including PIDA, PhIO, and IBX. All of these
showed a lower oxidative activity than PIFA, and mostly starting material 2a was recovered (Table
1, entries 9–11).
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TABLE 1. Optimization of the reaction conditionsa
Entry 2a/equiv
Hypervalent iodine
T(°C) Yield of 3a(%) Yield of 4a(%)
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reagent(equiv)
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1b
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2.0
2.0
2.0
2.0
1.0
1.5
2.0
2.0
2.0
2.0
2.0
PIFA (1.5)
PIFA (1.0)
PIFA (1.5)
PIFA (2.0)
PIFA (1.5)
PIFA (1.5)
PIFA (1.5)
PIFA (1.5)
PIDA (1.5)
PhIO (1.5)
IBX (1.5)
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9c
10d
11e
trace
trace
0
a
Unless otherwise indicated, all reactions were carried out with 1a (0.3 mmol) for 3 h under
solvent-free conditions; b Reaction was performed in CH2Cl2 (1 mL). c 88% of 2a was recovered.
d 90% of 2a was recovered. e 87% of 2a was recovered.
The optimal conditions were established as a ratio of 1, 2 and PIFA of 1:2:1.5 at 40 °C for this
phenyl transfer process (Table 1, entry 3). The scope of the reaction was then inbestigated, and the
results are summarized in Table 2. The scope of nitriles 2 was investigated first (entries 1-21 in
Table 2). A phenyl group (2e) and a variety of phenyl groups substituted with electron-donating
groups (EDGs, e.g. Me and OMe) (2a–d) and electron-withdrawing groups (EWGs, e.g. Cl and
CO2Et) (2f–j) at the ortho-, meta-, or para-positions were well tolerated, and afforded the
corresponding primary amides 3a–j in 36–76% yields. The reaction also proceeded well with
furan-2-carbonitrile (2k), thiophene-2-carbonitrile (2l), and 1-methyl-1H-pyrrole-2-carbonitrile
(2m), and afforded the desired products (3k–m) in 36–71% yield. Aliphatic-substituted nitriles
were more active, and a range of amides 3n–p were isolated in 68–79% yields. It is noteworthy
that this method has been proven to be efficient for the synthesis of some useful α-substituted
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primary amides, including 2-cyano-N-phenylacetamide (3q), N-2-diphenylacetamide (3r), and
methyl 3-oxo-3-(phenylamino)propanoate (3s), with a lower loading of 2 (1.5 equiv). The case of
3q is expecially interesting, as this application demonstrated high chemoselectivity, and no double
N-addition product was detected by LCMS. Moreover, the reaction also proceeded smoothly to
afford the desired products 3t and 3u in moderate yields without affecting the alkenyl and carbonyl
functional groups at the α-position.
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TABLE 2. Extension of the substrate scopea
3: Yield
4: Yield
Entry
Substrates 1
Substrates 2
Time(h)
(%)
(%)
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2
1a
1a
3
3
3a: 76
3b: 63
4a: 16
4a: 25
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2b
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3c: 39
4a: 42
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3d: 55
3e: 53
4a: 25
4a: 29
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3i: 45
4a: 43
4a: 30
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1a
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3j: 41
4a: 33
2j
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1a
1a
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3k: 71b
3l: 62b
3m: 36
4a: 19
4a: 24
4a: 45
2k
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2
2l
2
2m
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1a
1a
2
3n: 79b
3o: 68b
4a: 12
4a: 24
2n
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2o
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1a
2
3p: 69b
4a: 22
2p
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19
20
1a
1a
1a
1a
2
3q: 74b
3r: 72b
3s: 59b
3t: 57b
4a: 16
4a: 19
4a: 29
4a: 27
2q
2
2r
2
2s
2
2t
21
22
23
1a
2
3u: 54b
3a: 49
4a: 31
--
2u
2a
2a
3
3
1b
3a: tracec
4c: 0
1c
24
25
2a
2a
3
2
3ad: 0d
4d: 59e
4e: 23
1d
1e
3ae: 54d
26
27
2a
2a
2
3
3af: 69
3a: 67
4f: 11
4g: 0
1f
1g
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2a
2a
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3
3a: 72
3a: 59
4h: 0
4i: 0
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a Unless otherwise indicated, all reactions were carried out with 1 (0.3 mmol), 2a (0.6
mmol) and PIFA (0.45 mmol) under solvent-free conditions at 40 °C. b 1.5 mmol of 2
was used. c Complex mixture was observed. d The reaction was performed at 80 °C. e
Mixture of N-acetyl-N’-(4-methoxyphenyl)acetohydrazide and N’-acetyl-N’-(4-
methoxyphenyl)acetohydrazide in a ratio of 2:1.
Encouraged by the above-mentioned results (entries 22–21), the scope of the direct N-addition
protocol was further expanded using various hydrazides 1 (entries 22–29, Table 2). We observed
that phenylhydrazine 1b only gave the desired 3a in 49% yield (entry 22). Starting materials 1c and
1d converted to the oxidative dehydrogenation products 4c and 4d in the yields of 0% and 59%,
respectively, instead of compounds 3a and 3ad (entries 23 and 24). The substrate with a CF3 group
on the benzene was transformed to the corresponding cross-coupled amide 3ae in 54% yield (entry
25). To our delight, the tert-butyl group on 1f was also easily transferred to the nitrile, and gave
3af in 69% yield (entry 26). Several other sulfamides 1g−i were also successfully reacted, and
product 3a was obtained in 59–72% (entries 27–29). It should be noted that the relatively low
yields of products 3 were due to the formation of the diacetylhydrazine 4, which was generated
from starting material 1. Several control experiments were performed to clarify the mechanism for
this by-product formation. It was found that an oxidative dehydrogenation intermediate 5a was
afforded in 63% yield when we treated compound 1a (1.0 equiv) in MeCN (5.0 equiv) at 0 °C for 5
min in the presence of 1.5 equiv of PIFA (Eq. 1).48 The isolated intermediate 5a was then smoothly
transformed to the desired compound 3n in 85% yield under the optimized conditions, without the
formation of by-product 4a (Eq. 2). A blank experiment performed with 1a in the absence of
carbonitriles 2 under the optimized conditions afforded by-product 4a in 82% yield (Eq. 3). These
observation indicated that 4a was being formed directly form 1a, not from 5a. Furthermore, a
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separate experiment performed under an atmosphere of N2 still proceeded smoothly to give the
target compound 3a in 71% yield (Eq. 4). This observation indicates that the oxygen atom of 2
may come from the PIFA.29-31,49 To further clarify the source of the nitrogen atom in the product 3,
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an experiment was conducted using 1a (1.0 equiv) and N-labeled MeC15N (5.0 equiv) under the
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optimized conditions (Eq. 5). Mass spectrometry (MS) analysis suggested that 15N was
incorporated in product 3, which indicated that the CN group served as the nitrogen donor and
attacked to the phenyl group of the phenyl hydrazides. Radical trapping experiments were also
conducted to determine whether a radical process was involved in this reaction (Table 3). It was
found that compound 3a could be isolated in 19% and 22% yield in the presence of one equivalent
of 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) and 1,1-diphenyltehylene, respectively, under
the optimized conditions. However, none of 3a was generated with N-tert-butyl-alpha-
phenylnitrone (PBN) and galvinoxyl. These results indicate that radicals might be involved in the
transformation.50-53
TABLE 3. Radical trapping experiments
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Radical scavengers None TEMPO 1,1-Diphenylethylene PBN Galvinoxyl
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Yield of 3a(%)
76
19
22
0
0
Based on the results of these control experiments and information from previous work, a
plausible mechanism is proposed in Scheme 3. Initially, phenylhydrazide 1a is oxidized by the
oxidant PIFA to form dehydrogenation intermediate 5, which is subsequently decomposed into
phenyl radical A.29-31,49 The radical A reacts intermolecularly with 2a to form a new radical
intermediate B.19 This intermediate is then oxidized to give the non-isolable positively charged
imine ion C,54,55 which is trapped by a free ligand delivered by PIFA. This result in the formation
of the non-isolable carbocation D,54 and subsequently leads to the amide 3a after workup. It should
be noted that, byproduct 4a might be formed from the acetyl radical (MeCO‧) and 1 via a radical
coupling reaction.
Scheme 3. Proposed mechanism.
CONCLUSION
A PIFA-promoted intermolecular tandem amidation and successive oxidation reaction of phenyl
hydrazides and nitriles was developed for the synthesis of various secondary amide derivatives.
Advantages of this aryl transfer reaction over existing methods include the use of metal-free
reagents, readily available starting materials, good yields, and the drug-like nature of the products.
EXPERIMENTAL SECTION
General Remarks. All reactions were carried out under air atmosphere, unless otherwise
indicated. Other all reagents were purchased from commercial sources and used without further
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treatment, unless otherwise indicated. Petroleum ether (PE) used refers to the 60-90 C boiling
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point fraction of petroleum. H NMR and C NMR spectra were recorded on Bruker Avance/600
(1H: 600 MHz, 13C: 150 MHz at 25 ºC) or Bruker Avance/400 (1H: 400 MHz, 13C: 100 MHz at 25
ºC) and TMS as internal standard. Data are represented as follows: chemical shift, integration,
multiplicity (br = broad, s = singlet, d = doublet, dd = double doublet, t = triplet, q = quartet, m =
multiplet), coupling constants in Hertz (Hz). All high-resolution mass spectra (HRMS) were
measured on a mass spectrometer by using electrospray ionization (ESI-oa-TOF), and the purity of
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all samples used for HRMS (>95%) were confirmed by H NMR and 13C NMR spectroscopic
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analysis. Melting points were measured on a melting point apparatus equipped with a thermometer
and were uncorrected. All reactions were monitored by TLC with GF254 silica gel coated plates.
Flash chromatography was carried out on SiO2 (silica gel 200−300 mesh).
Typical experimental procedure for 3 (3a as an example): To a tube was added N’-
phenylacetohydrazide 1a (45 mg, 0.3 mmol), 4-methoxybenzonitrile 2a (80 mg, 0.6 mmol), and
o
PIFA (194 mg, 0.45 mmol). The mixture was well stirred for 3 h at 40 C (the whole process was
closely monitored by TLC). After cooling, the reaction mixture was purified by a flash silica gel
column chromatography with ethyl acetate and PE as eluent to give N-(4-
methoxyphenyl)benzamide 3a as white solid (52 mg, 76%).
4-methoxy-N-phenylbenzamide (3a).56 The product was isolated by flash chromatography
o
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(eluent: PE/EA = 20/1) as a white solid (52 mg, 76%). mp 165-167 C; H NMR (400 MHz,
CDCl3) δ 7.85 (d, J = 8.8 Hz, 2H), 7.71 (s, 1H), 7.63 (d, J = 7.6 Hz, 2H), 7.37 (t, J = 7.6 Hz, 2H),
13
7.14 (t, J = 7.6 Hz, 1H), 6.98 (d, J = 8.8 Hz, 2H), 3.88 (s, 3H). C NMR (100 MHz, CDCl3) δ
165.4, 162.6, 138.3, 129.2, 129.0, 127.3, 124.5, 120.6, 114.1, 55.6. HRMS (ESI), m/z calcd. for
C14H13NO2Na ([M+Na]+) 250.0838, found: 250.0838.
3-methoxy-N-phenylbenzamide (3b).57 The product was isolated by flash chromatography
(eluent: PE/EA = 20/1) as a white solid (43 mg, 63%). mp 111-114 oC; 1H NMR (400 MHz, CDCl3)
δ 7.78 (s, 1H), 7.64 (d, J = 7.6 Hz, 2H), 7.45 (s, 1H), 7.41-7.34 (m, 4H), 7.16 (t, J = 7.6 Hz, 1H),
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7.11-7.08 (m, 1H), 3.88 (s, 3H). 13C NMR (150 MHz, CDCl3) δ 160.2, 138.0, 136.7, 130.0, 129.3,
124.8, 120.3, 118.8, 118.2, 112.7, 55.7. (One carbon is not observed). HRMS (ESI), m/z calcd. for
C14H13NO2Na ([M+Na]+) 250.0838, found: 250.0843.
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2-methoxy-N-phenylbenzamide (3c).57 The product was isolated by flash chromatography
(eluent: PE/EA = 50/1) as a white solid (26 mg, 39%). mp 75-76 oC; 1H NMR (400 MHz, CDCl3) δ
9.80 (s, 1H), 8.30 (dd, J = 7.6, 2.0 Hz, 1H), 7.68 (d, J = 7.6 Hz, 2H), 7.51-7.48 (m, 1H), 7.37 (t, J =
8.0 Hz, 2H), 7.16-7.11 (m, 2H), 7.04 (d, J = 8.0 Hz, 1H), 4.06 (s, 3H). 13C NMR (100 MHz,
CDCl3) δ 163.4, 157.4, 138.6, 133.4, 132.7, 129.1, 124.3, 121.9, 120.6, 111.7, 56.4. HRMS (ESI),
m/z calcd. for C14H13NO2Na ([M+Na]+) 250.0838, found: 250.0842.
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4-methyl-N-phenylbenzamide (3d).56 The product was isolated by flash chromatography (eluent:
PE/EA = 20/1) as a white solid (35 mg, 55%). mp 140-143 oC; 1H NMR (600 MHz, CDCl3) δ 7.77
(d, J = 7.8 Hz, 3H), 7.64 (d, J = 7.8 Hz, 2H), 7.37 (t, J = 7.2 Hz, 2H), 7.29 (d, J = 7.8 Hz, 2H), 7.15
(t, J = 7.8 Hz, 1H), 2.43 (s, 3H). 13C NMR (150 MHz, CDCl3) δ 142.6, 138.1, 132.3, 129.6, 129.2,
127.2, 124.6, 120.2, 21.6. (One carbon is not observed). HRMS (ESI), m/z calcd. for C14H13NONa
([M+Na]+) 234.0889, found: 234.0883.
N-phenylbenzamide (3e).56 The product was isolated by flash chromatography (eluent: PE/EA =
o
20/1) as a white solid (31 mg, 53%). mp 164-167 C; 1H NMR (400 MHz, CDCl3) δ 7.87 (d, J =
6.8 Hz, 2H), 7.83 (s, 1H), 7.65 (d, J = 7.6 Hz, 2H), 7.56 (t, J = 7.2 Hz, 1H), 7.49 (t, J = 7.2 Hz,
2H), 7.38 (t, J = 7.6 Hz, 2H), 7.16 (t, J = 7.6 Hz, 1H). 13C NMR (150 MHz, CDCl3) δ 165.9, 138.1,
135.2, 132.0, 129.3, 129.0, 127.2, 124.7, 120.3. HRMS (ESI), m/z calcd. for C13H11NONa
([M+Na]+) 220.0733, found: 220.0741.
4-chloro-N-phenylbenzamide (3f).56 The product was isolated by flash chromatography (eluent:
PE/EA = 20/1) as a white solid (28 mg, 41%). mp 192-193 oC; 1H NMR (400 MHz, CDCl3) δ 7.82
(d, J = 8.4 Hz, 2H), 7.74 (s, 1H), 7.62 (d, J = 7.6 Hz, 2H), 7.47 (d, J = 8.4 Hz, 2H), 7.38 (t, J = 7.6
Hz, 2H), 7.17 (t, J = 7.6 Hz, 1H). 13C NMR (150 MHz, CDCl3) δ 138.3, 137.8, 133.5, 129.3, 129.2,
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128.6, 125.0, 120.4. (One carbon is not observed). HRMS (ESI), m/z calcd. for C13H10ClNONa
([M+Na]+) 254.0343, found: 254.0337.
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2,6-dichloro-N-phenylbenzamide (3g).58 The product was isolated by flash chromatography
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(eluent: PE/EA = 30/1) as a white solid (29 mg, 36%). mp 140-143 C; 1H NMR (400 MHz,
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CDCl3) δ 7.64 (d, J = 7.6 Hz, 2H), 7.45-7.34 (m, 5H), 7.33-7.29 (m, 1H), 7.20 (t, J = 7.6 Hz, 1H).
13C NMR (150 MHz, CDCl3) δ 162.5, 137.3, 136.1, 132.6, 131.1, 129.4, 128.4, 125.4, 120.5.
HRMS (ESI), m/z calcd. for C13H9Cl2NONa ([M+Na]+) 287.9953, found: 287.9953.
methyl 4-(phenylcarbamoyl)benzoate (3h).59 The product was isolated by flash chromatography
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(eluent: PE/EA = 20/1) as a white solid (24 mg, 32%). mp 184-187 C; H NMR (400 MHz,
CDCl3) δ 8.16 (d, J = 8.4 Hz, 2H), 7.93 (d, J = 8.8 Hz, 2H), 7.81 (s, 1H), 7.65 (d, J = 7.6 Hz, 2H),
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7.39 (t, J = 7.6 Hz, 2H), 7.18 (t, J = 7.6 Hz, 1H), 3.96 (s, 3H). C NMR (150 MHz, CDCl3) δ
166.3, 139.0, 137.7, 133.2, 130.2, 129.3, 127.2, 125.1, 120.4, 52.6. HRMS (ESI), m/z calcd. for
C15H13NO3Na ([M+Na]+) 278.0788, found: 278.0793.
methyl 3-(phenylcarbamoyl)benzoate (3i).60 The product was isolated by flash chromatography
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(eluent: PE/EA = 20/1) as a white solid (34 mg, 45%). mp 131-133 C; H NMR (400 MHz,
CDCl3) δ 8.49 (s, 1H), 8.22 (d, J = 7.6 Hz, 1H), 8.14 (d, J = 7.6 Hz, 1H), 7.88 (s, 1H), 7.67 (d, J =
7.6 Hz, 2H), 7.60 (t, J = 7.6 Hz, 1H), 7.40 (t, J = 7.6 Hz, 2H), 7.18 (t, J = 7.6 Hz, 1H), 3.97 (s, 3H).
13C NMR (150 MHz, CDCl3) δ 166.4, 137.8, 135.5, 132.9, 132.2, 130.8, 129.4, 127.6, 125.0,
120.5, 52.6. HRMS (ESI), m/z calcd. for C15H13NO3Na ([M+Na]+) 278.0788, found: 278.0792.
methyl 2-(phenylcarbamoyl)benzoate (3j).61 The product was isolated by flash chromatography
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(eluent: PE/EA = 10/1) as a white solid (31 mg, 41%). mp 110-113 C; H NMR (400 MHz,
CDCl3) δ 7.94 (d, J = 7.2 Hz, 1H), 7.70-7.56 (m, 5H), 7.53 (s, 1H), 7.37 (t, J = 6.2 Hz, 2H), 7.16 (t,
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J = 6.3 Hz, 1H), 3.87 (s, 3H). C NMR (150 MHz, CDCl3) δ 167.4, 167.3, 138.4, 138.1, 132.4,
130.5, 130.1, 129.3, 129.1, 127.9, 124.8, 120.2, 52.9. HRMS (ESI), m/z calcd. for C15H13NO3Na
([M+Na]+) 278.0788, found: 278.0789.
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N-phenylfuran-2-carboxamide (3k).56,62 The product was isolated by flash chromatography
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(eluent: PE/EA = 20/1) as a white solid (40 mg, 71%). mp 123-125 C; 1H NMR (400 MHz,
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CDCl3) δ 8.06 (s, 1H), 7.65 (d, J = 7.6 Hz, 2H), 7.52 (m, 1H), 7.37 (t, J = 7.2 Hz, 2H), 7.24 (m,
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1H), 7.15 (t, J = 7.6 Hz, 1H), 6.57 (m, 1H). C NMR (100 MHz, CDCl3) δ 156.2, 147.9, 144.3,
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137.5, 129.3, 124.7, 120.0, 115.4, 112.8. HRMS (ESI), m/z calcd. for C11H9NO2Na ([M+Na]+)
210.0525, found: 210.0547.
N-phenylthiophene-2-carboxamide (3l).56,62 The product was isolated by flash chromatography
o
(eluent: PE/EA = 30/1) as a white solid (38 mg, 62%). mp 140-143 C; 1H NMR (400 MHz,
CDCl3) δ 7.63-7.62 (m, 3H), 7.60 (s, 1H), 7.56-7.54 (m, 1H), 7.37 (t, J = 7.2 Hz, 2H), 7.17-7.13
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(m, 2H). C NMR (150 MHz, CDCl3) δ 160.0, 137.7, 130.9, 129.3, 128.6, 128.0, 124.8, 120.3.
HRMS (ESI), m/z calcd. for C11H9NONaS ([M+Na]+) 226.0297, found: 226.0298.
1-methyl-N-phenyl-1H-pyrrole-2-carboxamide (3m).62 The product was isolated by flash
o
chromatography (eluent: PE/EA = 10/1) as a white solid (22 mg, 36%). mp 114-116 C; 1H NMR
(400 MHz, CDCl3) δ 7.55 (d, J = 7.6 Hz, 3H), 7.35 (t, J = 7.6 Hz, 2H), 7.11 (t, J = 7.6 Hz, 1H),
6.81-6.77 (m, 1H), 6.70-6.69 (m, 1H), 6.16-6.14 (m, 1H), 3.98 (s, 3H). 13C NMR (150 MHz,
CDCl3) δ 138.2, 129.2, 129.0, 124.2, 120.8, 120.1, 112.2, 107.6. HRMS (ESI), m/z calcd. for
C12H12N2ONa ([M+Na]+) 223.0842, found: 223.0844.
N-phenylacetamide (3n).56 The product was isolated by flash chromatography (eluent: PE/EA =
o
5/1) as a white solid (32 mg, 79%). mp 113-116 C; 1H NMR (400 MHz, CDCl3) δ 7.55 (s, 1H),
7.50 (d, J = 8.0 Hz, 2H), 7.30 (t, J = 8.0 Hz, 2H), 7.10 (t, J = 7.6 Hz, 1H), 2.16 (s, 3H). 13C NMR
(100 MHz, CDCl3) δ 168.2, 139.3, 128.6, 122.9, 119.0, 24.0. HRMS (ESI), m/z calcd. for
C8H9NONa ([M+Na]+) 158.0576, found: 158.0574.
N-phenylpentanamide (3o).56 The product was isolated by flash chromatography (eluent: PE/EA
= 10/1) as a white solid (36 mg, 68%). mp 60-62 oC; 1H NMR (400 MHz, CDCl3) δ 7.51 (d, J = 7.6
Hz, 2H), 7.31 (t, J = 7.6 Hz, 2H), 7.20 (s, 1H), 7.10 (t, J = 7.6 Hz, 1H), 2.36 (t, J = 7.2 Hz, 2H),
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1.77-1.67 (m, 2H), 1.46-1.35 (m, 2H), 0.95 (t, J = 7.2 Hz, 3H). C NMR (150 MHz, CDCl3) δ
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171.5, 138.1, 129.1, 124.3, 119.9, 37.7, 27.8, 22.5, 14.0. HRMS (ESI), m/z calcd. for C11H16NO
([M+H]+) 178.1226, found: 178.1232.
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N-phenylpivalamide (3p).63 The product was isolated by flash chromatography (eluent: PE/EA =
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20/1) as a white solid (37 mg, 69%). mp 129-132 C; 1H NMR (400 MHz, CDCl3) δ 7.53 (d, J =
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7.6 Hz, 2H), 7.32 (t, J = 7.6 Hz, 3H), 7.10 (t, J = 7.6 Hz, 1H), 1.32 (s, 9H). C NMR (150 MHz,
CDCl3) δ 176.7, 138.2, 129.1, 124.3, 120.1, 39.8, 27.8. HRMS (ESI), m/z calcd. for C11H15NONa
([M+Na]+) 200.1046, found: 200.1047.
2-cyano-N-phenylacetamide (3q).64 The product was isolated by flash chromatography (eluent:
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PE/EA = 5/1) as a white solid (36 mg, 74%). mp 197-199 C; H NMR (400 MHz, DMSO-d6) δ
10.30 (s, 1H), 7.54 (d, J = 7.6 Hz, 2H), 7.33 (t, J = 8.0 Hz, 2H), 7.09 (t, J = 7.6 Hz, 1H), 3.90 (s,
2H). 13C NMR (150 MHz, DMSO-d6) δ 161.0, 138.4, 128.9, 123.9, 119.2, 115.9, 26.7. HRMS
(ESI), m/z calcd. for C9H8N2ONa ([M+Na]+) 183.0529, found: 183.0534.
N,2-diphenylacetamide (3r).56 The product was isolated by flash chromatography (eluent:
PE/EA = 20/1) as a white solid (46 mg, 72%). mp 119-120 oC; 1H NMR (400 MHz, CDCl3) δ 7.45-
7.38 (m, 4H), 7.36-7.33 (m, 3H), 7.29 (d, J = 7.6 Hz, 2H), 7.08 (t, J = 7.6 Hz, 2H), 3.74 (s, 2H).
13C NMR (150 MHz, CDCl3) δ 169.2, 137.6, 134.5, 129.7, 129.4, 129.1, 127.9, 124.6, 119.8, 45.0.
HRMS (ESI), m/z calcd. for C14H13NONa ([M+Na]+) 234.0889, found: 234.0888.
methyl 3-oxo-3-(phenylamino)propanoate (3s).65 The product was isolated by flash
chromatography (eluent: PE/EA = 10/1) as a white solid (34 mg, 59%). mp 43-46 C; 1H NMR
o
(400 MHz, CDCl3) δ 9.14 (s, 1H), 7.55 (d, J = 7.6 Hz, 2H), 7.34 (t, J = 7.6 Hz, 2H), 7.13 (t, J = 7.6
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Hz, 1H), 3.81 (s, 3H), 3.49 (s, 2H). C NMR (150 MHz, CDCl3) δ 170.6, 162.8, 137.6, 129.2,
124.8, 120.3, 52.8, 41.4. HRMS (ESI), m/z calcd. for C10H11NO3Na ([M+Na]+) 216.0631, found:
216.0631.
N-phenylcinnamamide (3t).62 The product was isolated by flash chromatography (eluent: PE/EA
= 10/1) as a white solid (38 mg, 57%). mp 151-154 oC; 1H NMR (400 MHz, CDCl3) δ 7.76 (d, J =
15.6 Hz, 1H), 7.63 (d, J = 7.2 Hz, 2H), 7.55-7.52 (m, 2H), 7.42 (s, 1H), 7.40-7.34 (m, 5H), 7.14 (t,
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J = 7.2 Hz, 1H), 6.56 (d, J = 15.6 Hz, 1H). C NMR (150 MHz, CDCl3) δ 164.0, 142.6, 138.1,
134.8, 130.2, 129.3, 129.0, 128.1, 124.6, 120.9, 120.0. HRMS (ESI), m/z calcd. for C15H13NONa
([M+Na]+) 246.0889, found: 246.0889.
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2-oxo-N,2-diphenylacetamide (3u).66 The product was isolated by flash chromatography (eluent:
PE/EA = 40/1) as a white solid (36 mg, 54%). mp 62-65 oC; 1H NMR (400 MHz, CDCl3) δ 8.93 (s,
1H), 8.43 (d, J = 7.2 Hz, 2H), 7.71 (d, J = 7.6 Hz, 2H), 7.67 (t, J = 7.2 Hz, 1H), 7.52 (t, J = 7.6 Hz,
2H), 7.41 (t, J = 7.6 Hz, 2H), 7.21 (t, J = 7.6 Hz, 1H). 13C NMR (150 MHz, CDCl3) δ 187.5, 159.0,
136.8, 134.8, 133.2, 131.7, 129.4, 128.7, 125.5, 120.1. HRMS (ESI), m/z calcd. for C14H11NO2Na
([M+Na]+) 248.0682, found: 248.0682.
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4-methoxy-N-(4-(trifluoromethyl)phenyl)benzamide (3ae).67 The product was isolated by flash
o
chromatography (eluent: PE/EA = 20/1) as a white solid (48 mg, 54%). mp 212-214 C; 1H NMR
(600 MHz, DMSO-d6) δ 10.41 (s, 1H), 8.01-7.97 (m, 4H), 7.70 (d, J = 8.4 Hz, 2H), 7.08 (d, J = 9.0
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Hz, 2H), 3.85 (s, 3H). C NMR (150 MHz, CDCl3) δ 165.4, 162.2, 143.0, 129.8, 126.4, 125.88,
125.85, 120.0, 113.7, 55.5. HRMS (ESI), m/z calcd. for C15H12F3NO2Na ([M+Na]+) 318.0712,
found: 318.0718.
N-(tert-butyl)-4-methoxybenzamide (3af).68 The product was isolated by flash chromatography
o
(eluent: PE/EA = 40/1) as a white solid (48 mg, 54%). mp 112-113 C; 1H NMR (400 MHz,
CDCl3) δ 7.68 (d, J = 8.8 Hz, 2H), 6.90 (d, J = 8.8 Hz, 2H), 5.85 (s, 1H), 3.84 (s, 3H), 1.46 (s, 9H).
13C NMR (150 MHz, CDCl3) δ 166.6, 162.0, 128.6, 128.4, 113.8, 55.5, 51.6, 29.1. HRMS (ESI),
m/z calcd. for C12H17NO2Na ([M+Na]+) 230.1151, found: 230.1150.
acetic acid, 2-acetyl-2-phenylhydrazide (4a) and N-acetyl-N'-phenylacetohydrazide.69 The
product was isolated by flash chromatography (eluent: PE/EA = 1/2) as a colorless oil (9 mg,
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16%). H NMR (600 MHz, DMSO-d6) δ 10.88 (s, 1H), 10.38 (s, 1H), 7.36 (s, 5H), 7.19 (s, 1H),
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2.07 (s, 3H), 1.96 (s, 3H), 1.87 (d, J = 27.6 Hz, 1H). C NMR (150 MHz, DMSO-d6) δ 171.2,
168.8, 141.5, 128.5, 125.7, 123.4, 21.7, 20.5. HRMS (ESI), m/z calcd. for C10H12N2O2Na
([M+Na]+) 215.0791, found: 215.0800.
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acetic acid, 2-acetyl-2-(4-methoxyphenyl)hydrazide (4d) and N-acetyl-N'-(4-methoxyphenyl)
acetohydrazide. The product was isolated by flash chromatography (eluent: PE/EA = 1/3) as a
yellow oil (39 mg, 59%). 1H NMR (600 MHz, DMSO-d6) δ 10.81 (s, 1H), 10.29 (s, 1H), 7.32 (d, J
= 7.2 Hz, 1H), 7.24 (d, J = 7.8 Hz, 2H), 6.97 (d, J = 7.2 Hz, 1H), 6.90 (d, J = 7.8 Hz, 2H), 3.77 (s,
1H), 3.74 (s, 3H), 2.03 (s, 3H), 1.92 (s, 3H), 1.83 (d, J = 7.9 Hz, 3H). 13C NMR (150 MHz,
DMSO-d6) δ 171.1, 168.6, 157.3, 134.6, 128.6, 125.8, 114.4, 113.6, 55.3, 21.3, 20.5. HRMS (ESI),
m/z calcd. for C11H14N2O3Na ([M+Na]+) 245.0897, found: 245.0907.
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acetic acid, 2-acetyl-2-(4-(trifluoromethyl)phenyl)hydrazide (4e). The product was isolated by
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flash chromatography (eluent: PE/EA = 1/2) as a white solid (18 mg, 23%). mp 106-108 C; H
NMR (600 MHz, DMSO-d6) δ 10.99 (s, 1H), 7.73 (d, J = 7.8 Hz, 2H), 7.63 (d, J = 8.4 Hz, 2H),
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2.11 (s, 3H), 2.01 (s, 3H). C NMR (150 MHz, DMSO-d6) δ 171.6, 168.9, 144.7, 126.8, 125.7,
125.0, 123.2, 122.6, 121.4, 22.0, 20.4. HRMS (ESI), m/z calcd. for C11H12F3N2O2 ([M+H]+)
261.0845, found: 261.0854.
acetic acid, 2-acetyl-2-(tert-butyl)hydrazide (4f). The product was isolated by flash
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chromatography (eluent: PE/EA = 1/2) as a colorless oil (6 mg, 11%). H NMR (600 MHz,
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DMSO-d6) δ 10.15 (s, 1H), 1.87 (s, 3H), 1.81 (s, 3H), 1.29 (s, 9H). C NMR (150 MHz, DMSO-
d6) δ 171.6, 169.0, 59.2, 27.5, 23.0, 20.2. HRMS (ESI), m/z calcd. for C8H16N2O2Na ([M+Na]+)
195.1104, found: 195.1114.
(E)-1-(phenyldiazenyl)ethan-1-one (5a).70 The product was isolated by flash chromatography
(eluent: PE/EA = 2/1) as a red oil (28 mg, 63%). 1H NMR (600 MHz, CDCl3) δ 7.90 (d, J = 7.2 Hz,
2H), 7.58 (t, J = 7.8 Hz, 1H), 7.53 (t, J = 7.2 Hz, 2H), 2.44 (s, 3H). 13C NMR (150 MHz, CDCl3) δ
188.7, 151.6, 133.7, 129.5, 123.8, 21.4. HRMS (ESI), m/z calcd. for C8H8N2ONa ([M+Na]+)
171.0529, found: 171.0529.
ASSOCIATED CONTENT
Supporting Information
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The Supporting Information is available free of charge on the ACS Publications website at
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experiments (PDF)
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AUTHOR INFORMATION
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Corresponding Author
*E-mail: zhangzg@htu.edu.cn or zgs6668@yahoo.com. Fax: (+86)-373-332-5250.
ORCID
Zhiguo Zhang: 0000-0001-6920-0471
ACKNOWLEDGMENTS
We thank the NSFC (21272057, 21372065 and U1604285), Young Backbone Teachers Fund of
Henan (2014GGJS-049), Key Project of Henan Educational Committee (15A150015 and
18A150009), Science & Technology Innovation Talents in Universities of Henan Province
(17HASTIT002), Outstanding Young Talent Cultivation Project Funding of Henan Normal
University (14YR002), and Jilin Province Key Laboratory of Organic Functional Molecular
Design & Synthesis (130028742).
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