Cu(OAc)2-mediated reaction of C60 with ureas for the preparation of fulleroimidazolidinones

Article abstract of DOI:10.1021/acs.joc.5b02682

The Cu(OAc)₂-mediated intermolecular diamination reaction of C₆₀ with ureas allows the concise and efficient preparation of fulleroimidazolidinones involving the cleavage of two N-H bonds and formation of two C-N bonds. Both dialkylated and diarylated fulleroimidazolidinones can be synthesized using this method.

Full text of DOI:10.1021/acs.joc.5b02682

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Article
Cu(OAc)2-Mediated Reaction of C60 with Ureas
for the Preparation of Fulleroimidazolidinones
Hai-Tao Yang, Yi-Chen Tan, Yang Yang, Xiao-Qiang Sun, and Chun-Bao Miao
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.5b02682 • Publication Date (Web): 15 Jan 2016
Downloaded from http://pubs.acs.org on January 16, 2016
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Cu(OAc)2-Mediated Reaction of C60 with Ureas for the Preparation of
Fulleroimidazolidinones
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HaiꢀTao Yang,* YiꢀChen Tan, Yang Yang, XiaoꢀQiang Sun, and ChunꢀBao Miao
Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology, Advanced Catalysis and
Green Manufacturing Collaborative Innovation Center, School of Petrochemical Engineering,
Changzhou University, Changzhou 213164, China.
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Email: yht898@yahoo.com
O
R'
R''
N
N
O
⋅
Cu(OAc)2, Phen H2O
R'
R''
N
H
N
H
+
R' = Ts, alkyl, aryl
R'' = alky, aryl
Abstract
The Cu(OAc)2ꢀmediated intermolecular diamination reaction of C60 with ureas allows the concise
and efficient preparation of fulleroimidazolidinones involving the cleavage of two N−H bonds and
formation of two C−N bonds. Both dialkylated and diarylated fulleroimidazolidinones can be
synthesized using this method.
Introduction
Chemical modification of fullerenes has been widely investigated over the past two decades for
the preparation of a diversity of fullerene derivatives, some of which have shown potential
applications in medicinal and material science.1 New methods are continuously being explored for
the synthesis of organofullerenes with novel architectures.2 Free radical reactions have proved to be
a powerful tool for the functionalization of fullerenes.1a Various transitionꢀmetal reagents, including
Mn(III),3 Fe(II or III),4 Pb(IV),5 Co(0),6 Ni(0),7 and Ag(I)8 have been continuously explored to
induce the radical addition reactions of fullerenes.1a Cu(I or II) salts are inexpensive, readily
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available, insensitive to air and water, and lowꢀtoxicity reagents which have been found to catalyze
or promote various organic transformations, especially XꢀN (X = C, N) bond formation.9 The first
example of Cu(II) mediated reaction of fullerenes with ketonic compounds was reported by the
Wang group.10 After that, there were no reports on the application of Cu(I or II) reagents to the
functionalization of C60 for several years. The past five years, Cu(I/II) catalyzed or mediated
transformations of fullerenes has gained much more attention once more.11ꢀ15 The groups of Matsuo
and Nakamura have reported the oxidation of a fullerene radical or a fullerene anion with a Cu(II)
salt to generate fullerene cationic species for further transformations.12 The Jin group described the
Cu(II)ꢀcatalyzed dimerization or CꢀH amination of hydrofullerenes.13 Liu and coworkers explored
the Cu(OAc)2ꢀpromoted Nꢀheteroannulation reaction of C60 for the construction of novel C60ꢀfused
tetrahydroꢀazepinones and ꢀazepinonimines. 14 The Wang group reported the CuBrꢀcatalyzed
heteroannulation reaction of [60]fullerene with ketoxime acetates for the preparation of
1ꢀfulleropyrrolines.15 In contrast to the most investigated addition of Cꢀcentered and Oꢀcentered
radicals to fullerenes,1a the addition of Nꢀcentered radicals to fullerenes are rather rare16 and we
have been interested in this less developed field. In our previous work, the Cu(I or II) reagents17
and a hypervalent iodine/I2 system18 have proven efficient to generate a Nꢀradical from amine
compounds and their addition to C60 produces a variety of C60ꢀfused five of six membered ring
derivatives with bonding of one or two nitrogen atoms to the C60 core. In continuation of our
interest in the fullerene chemistry, we reported here the Cu(OAc)2ꢀpromoted reaction of C60 with
ureas for the easy preparation of fulleroimidazolidinones.
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Scheme 1 The Preparation of Fulleroimidazolidinones
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R' = Ts, alkyl, aryl; R'' = alkyl, aryl
O
O
R'
R''
Ts
N
N
N
Minakata's work
R'
R''
N
H
H
N
reserve of TsN unit
Cu (II)
This work
ArN=C=O
ref. 9
SO2Ph
PhO2S
N
F
ref. 10
O
O
R'
R''
N
N
N
N
H
H
H
H
9
R' = Electron withdrawing group
Our previous work, release of TsN unit
ref. 2a
Gan's work
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The preparation of fulleroimidazolidinones (Scheme 1) was first reported by the Minakata group
through PCy3ꢀcatalyzed formal [3+2] reaction of Nꢀsulfonylated aziridinofullerene with aryl
isocyanates.19 In the conversion, the TsN unit was reserved in the product and the substrates were
limited to aryl isocyanates. Later, we developed the Lewis baseꢀcatalyzed double nucleophilic
substitution reaction of Nꢀtosylaziridinofullerene with ureas along with the release of the TsN unit,
solving the problem of synthesis of alkyl substituted fulleroimidazolidinones.20 However these
strategies could not realize the preparation of dialkylꢀ or diarylꢀsubstituted fulleroimidazolidinones
as an electronꢀwithdrawing group on the nitrogen atom was necessary. Most recently, the Gan group
reported the synthesis of N,N'ꢀdimethylfulleroimidazolidinone from the precursor 1,2ꢀadduct of C60
with NFSI, albeit in very low yield.2a These approaches are not direct synthetic routes from pristine
C60 and the preparation of dialkylꢀ or diarylꢀsubstituted fulleroimidazolidinones still remains a
challenge.
Results and Discussion
Table 1 Screening of the Reaction Conditions
O
Ts
N
N
O
conditions
Ts
+
N
N
H
H
1a
2a
entr
y
molar ratio
[C60/1a/condition]
conditions
PhI(OAc)2:I2
T (ºC)
time (h)
yield (%)a
1
1:2:2:2
rt
rt
6
6
8
8
0
0
0
0
2
PhIO:I2
1:2:2:2
3
Pd(OAc)2,PhI(OAc)2,NaOAc
Pd(OAc)2, CuBr2, NaOAc
1:4:2.2:2.2:1.2
1:4:2.2:3:1.2
100
100
4
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Cu(OAc)2
1:2:2
140
140
140
140
140
140
140
140
140
140
140
8
8
8
8
4
4
4
8
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8
7
0
CuCl2
1:2:2
0
0
7
CuI
1:2:2
8
9b
Cu(OAc)2, Cs2CO3
Cu(OAc)2, Phen•H2O
1:2:2:2
1:2:2:2
1:2:0.4:0.4
1:3:3:3
1:3:3:3
1:3:3:3
1:2:2:2
1:2:2:2
0
16 (74)
trace
21 (65)
0
10 Cu(OAc)2, Phen•H2O
11
9
Cu(OAc)2, Phen•H2O
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12 Cu(OAc)2,PMDETA
13 Cu(OAc)2,TMEDA
0
14 Cu(OAc)2, 2,2'ꢀBipyridine
15 Cu(OAc)2, 2ꢀPicolinic acid
12 (57)
trace
O
O
16
1:2:2:2
140
5.5
14 (79)
N
N
Cu(OAc)2,
a Isolated yield; the values in parentheses are based on consumed C60. b Carried out under a N2 atomosphere.
In the documented intramolecular diamination of olefins, the urea moities always contained a
sulfonyl group on the nitrogen atom.21 So, the NꢀtosylꢀN'ꢀbutylurea 1a was selected as a model
substrate to react with C60 (Table 1). Encouraged by our recently developed diamination reactions
of C60 with sulfamides or phosphoryl diamides promoted by a hypervalent iodine/I2 system, 18a we
envisioned that a similar reaction process could occur with the ureas due to their structural analogy
with sulfamides. However, under either PhI(OAc)2/I2 or PhIO/I2 conditions, no anticipated product
2a was obtained (Table 1, entries 1 and 2). The classic conditions of Pdꢀcatalyzed intramolecular
diamination of ureas with alkenes21a did not work at all for the reaction of C60 with 1a (Table 1,
entries 3 and 4). Then, Cu(OAc)2, CuCl2, or CuI as the reagent was tried, which have proven to be
efficient to promote the reaction of C60 with amine derivatives in our previous work.17aꢀc It was
frustrating to find that employing Cu(I or II) reagents alone was totally ineffective in the
transformation (Table 1, entries 5ꢀ7). Next, different bases or ligands such as Cs2CO3, TMEDA
(N,N,N',N'ꢀtetramethylethylenediamine),
PMDETA
(pentamethyldiethylenetriamine),
Bpy
(2,2'ꢀbipyridine), Phen⋅H2O (1,10ꢀphenanthroline monohydrate), 2ꢀpicolinic acid, or
2,2'ꢀisopropylidenebisoxazoline (BOX) were added with Cu(OAc)2 as the oxidant to trigger the
reaction (Table 1, entries 8ꢀ16). Gratifyingly, the combination of Cu(OAc)2 with Bpy, Phen⋅H2O, or
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BOX were found to be effective systems for the reaction of C60 with urea 1a (Table 1, entries 9, 14
and 16). The Phen⋅H2O gave a higher yield than BOX and Bpy, affording 2a in 16% yield.
Increasing the amount of Cu(OAc)2 and Phen⋅H2O to 3 equiv improved the yield to 21% (Table 1,
entry 11). Reducing the Phen⋅H2O to catalytic amount only gave a trace amount of 2a (Table 1,
entry 10). Further increasing the amount of Cu(OAc)2 and Phen⋅H2O could just accelerate the
reaction, but there was no increase in the yield. The reaction time could not be too long as the
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product decomposed slowly under the harsh conditions.
Table 2 Cu(OAc)2ꢀMediated Reaction of
C60 with Ureas Connecting a Tosyl Group.
O
Ts
R
N
N
O
Cu(OAc)2 (3 equiv)
Ts
R
N
N
+
Phen•H2O (3 equiv)
PhCl, 140 oC
H
H
1
(3 equiv)
2
O
O
O
OEt
Ts
Ts
Ts
N
N
N
N
N
N
O
2c, 7 h, 12%
2b
, 6 h, 23%
2a, 4.5 h, 21%
O
O
Me
OMe
OMe
Ts
Ts
N
N
N
N
2d, 4.5 h, 19%
2e, 4 h, 9%
Under the optimal conditions, several ureas bearing a tosyl group on the nitrogen atom were
introduced to this diamination reaction (Table 2). The alkylatedꢀureas showed a higher activity than
that of arylatedꢀureas. Both ester and acetal groups were tolerated under these conditions.
We next turned our attention to investigate the reactivity of more challenging dialkylꢀ or
diarylꢀsubstituted ureas (Table 3). Excitingly, the reaction proceeded smoothly to give the desired
fulleroimidazolidinones bearing two alkyl or aryl groups. The dialkyl substitutedꢀureas gave a better
results than that of diarylꢀsubstituted ureas. In terms of the diarylꢀsubstituted ureas, an obvious
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substituent electronic effect was observed and electron donating groups on the phenyl ring
performed better than that of electron withdrawing groups. No reaction occurred for substrate 3h,
which bears a nitro group on each phenyl ring. An ortho substituted group on the phenyl ring led to
noticeable decrease in the yield of product (4i) probably due to the steric hindrance. The ureas
having an alkyl and an aryl group on each of the nitrogen atom also worked to give the desired
products 4j and 4k.
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Table
3
Substrate Scope for the
Cu(OAc)2ꢀMediated Reaction of C60 with
Alkylated or Arylated Ureas.
O
R1
R2
N
N
O
R1
R2
Cu(OAc)2 (3 equiv)
Phen•H2O (3 equiv)
+
N
N
H
H
3
PhCl, 140 o
C
4
(3 equiv)
O
O
O
N
N
N
N
N
N
4b
4c
, 3.5 h, 27%
, 4 h, 17%
4a
, 4 h, 21%
MeO
OMe
O
O
O
N
N
N
N
N
N
4e, 6 h, 20%
4d, 6 h, 18%
4f, 5.5 h, 18%
Cl
Cl O2N
NO2
O
O
O
N
N
N
N
N
N
OMe
4g, 7.5 h, 12%
4h
, 6 h, 0%
4i
, 5 h, 9%
CO2Et
O
O
N
N
N
N
4j, 4.5 h, 20%
4k, 5 h, 17%
In order to further evaluate the influence of steric hindrance, ureas 3lꢀo were treated with C60
under the standard reaction conditions (Scheme 2). For the dialkyl ureas, a noticeable steric effect
was observed. The secondary and tertiary carbon connecting on the nitrogen atom (3lꢀn) resulted in
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the failed reactions. At present, we had no reasonable explanation to these resluts. If
NꢀphenylꢀN'ꢀtertiary butyl urea 3o was employed, no anticipated product was formed. Instead,
diphenylꢀsubstituted fulleroimidazolidinone 4f was produced in 14% yield. Further investigation
revealed that the starting material 3o was transform to N,N'ꢀdiphenylurea 3f completely upon
heating with Cu(OAc)2 and Phen⋅H2O in chlorobenzene at 140 ºC for 4 h, which resulted in the
formation of 4f.
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Scheme 2 Reaction of C60 with Sterically Hindered Ureas .
O
(3l)
N
N
H
H
N. R.
6 h
O
(3m)
(3n)
N
H
N
H
N. R.
6 h
O
Cu(OAc)2 (3 equiv)
Phen•H2O (3 equiv)
PhCl, 140 o
C
N
H
N
H
trace of product
5 h
O
(3o)
N
N
H
H
4f (14%)
5 h
To further investigate the effect of other electronꢀwithdrawing groups such as
diethoxylphosphoryl, ethoxylcarbonyl, and benzoyl, the ureas 5ꢀ8 were prepared and treated with
C60 under the standard reation conditions (Scheme 3). No reaction occurred for the
NꢀdiethoxylphosphorylꢀN'ꢀphenyl urea 5 and the NꢀethoxylcrabonylꢀN'ꢀbenzyl urea 6. In terms of
the benzoylꢀsubstituted ureas, the substituents on the other nitrogen atom display significant
influence on the reaction. The reaction of C60 with NꢀbenzoylꢀN'ꢀbenzyl urea 7 under the standard
conditions furnished the desired product 9 in 6% yield along with the formation of the unexpected
fullerooxazoline 10 in 19% yield. For the NꢀbenzoylꢀN'ꢀpheny urea 8 , the fullerooxazoline 10 was
obtained as the sole product in 26% yield instead of the anticipated unsymmetrical diaminated
product.
Scheme 3 Reaction of C60 with Diethoxylphosphorylꢀ, Ethoxylcarbonylꢀ, and BenzoylꢀSubstituted
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Ureasa
4
5
6
7
5
( )
O
P
O
EtO
N
N
EtO
H
H
N. R.
4.5 h
8
9
6
( )
O
O
O
Bn
Bn
N
H
N
EtO
H
N. R.
10
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60
5 h
Ph
O
O
Bn
N
O
N
N
7
( )
O
N
H
N
H
+
4.5 h
10
(19%)
9 (6%)
Ph
N
O
8
( )
O
O
N
H
N
H
5 h
10 (26%)
a The reactions were carried out with the ratio of C60/ureas/Cu(OAc)2/Phen⋅H2O as 1:3:3:3 at 140 ºC.
The known products 2a-d, 9,20 and 1018c were confirmed through comparison of their TLC
mobilities with those obtained compounds using our previous reported method and their spectral
data with those reported in the literatures. The new compounds 2e, 4a–g, and 4i–k were
unambiguously characterized by their HRMS, H NMR, 13C NMR, and UVꢀvis spectra (see
1
Supporting Information).
To gain more insight into the reaction mechanism, the reaction of C60 with 3d in the presence of a
free radical scavenger was performed (Scheme 4). Adding 2,2,6,6ꢀtetramethylpiperidineꢀ1ꢀoxyl
(TEMPO), 2,6ꢀditertbutylꢀ4ꢀmethylphenol (BHT), or 2,2ꢀazobisisobutyronitrile (AIBN) blocked the
reaction completely. While the exact reaction mechanism is still uncertain, the results implied that a
radical pathway might be involved in the reaction.
Scheme 4 Reaction in the Presence of Radical Scavenger
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O
N
N
4
5
6
7
Cu(OAc)2 (3 equiv)
O
C60
+
×
Phen•H2O (3 equiv)
N
N
H
H
(a), (b), or (c)
3d
(3 equiv)
4d
8
(a) TEMPO (3 equiv), (b) BHT (3 equiv), (c) AIBN (3 equiv)
9
Base on the literature Cuꢀcatalyzed or promoted CꢀN bond formation reactions10,13b,14,17,21b and
the control experiment, a proposed mechanism is depicted in Scheme 5. Coordination of urea with
Cu(OAc)2 will provide intermeditate 12. Homolytical cleavage of the NꢀCu bond generates the
nitrogen radical 13,22 which adds to C60 to form the fullerenyl radical 14. Similar reaction pathway
takes place once more to generate intermediate 15 and the further intramolecular cyclization along
with release of CuOAc provides the product (path A). A mechanism involving a fullerene cationic
species is also feasible (path B).12 Oxidation of the fullerene radical by Cu(OAc)2 produces the
fullerenyl cation 16. A subsequent intramolecular nucleophilic reaction then affords the observed
product. In case of the reaction of C60 with 7 or 8, two reaction pathways may exist after the
generation of fullerenyl cation 16. Attack of the other nitrogen atom to the fullerenyl cation affords
the normal product 9 (path a). Alternatively, the attack of the oxygen atom of the benzoxy group to
the fullerenyl cation followed by extrusion of isocyanate and a proton ion will produce the
undesired fullerooxazoline 10 (path b).
10
11
12
13
14
15
16
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Scheme 5 Proposed Mechanism.
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O
O
O
R1
R2
R1
R2
Cu(OAc)2
-CuOAc
R2
C60
R1
R2
N
N
N
N
N
N
⋅
Phen H2O
H
H
H
H
Cu
13
OAc
12
L
O
N
N
L
R1
Cu
OAc
O
R2
N
H
8
9
O
path A
R1
R2
N
N
R1
N
10
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Cu(OAc)2
O
N
R2
N
H
⋅
Phen H2O
R1
14
-H+
path B
16
O
O
Bn
N
Ph
N
R
O
N
(b)
path a
-H+
R = Bn
N
O
(a)H
Ph
9
Ph
Ph
O
O
N
R
O
N
N
H
16
-H+
-RN=C=O
R1 = PhCO
R2 = Bn, Ph
path b
R = Bn, Ph
17
10
Conclusion
In summary, a concise synthetic method toward the preparation of fulleroimidazolidinones has
been developed through the Cu(OAc)2ꢀpromoted intermolecular diamination reaction C60 with ureas.
Both dialkyl and diaryl ureas are suitable in the transformation. A radical pathway is proposed for
the formation of fulleroimidazolidinones.
Experimental Section
General Information.
1
13
All reactions were conducted under an air atmosphere. H and C NMR spectra were recorded
on 300, 400, and 500 MHz (75, 100, and 125 MHz for 13C NMR) spectrometer at ambient
temperature, using TMS as an internal standard. Flash column chromatography was performed over
silica gel (200−300 mesh). The MALDIꢀTOF MS were measured in positive ion mode using DCTB
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Eꢀ(2ꢀ[3ꢀ(4ꢀtertbutylphenyl)ꢀ2ꢀmethylꢀ2ꢀpropenylidene]malononitrile) as the matrix.
Ureas 2a−e were prepared from tosyl isocyanate and the corresponding amines according to
reported procedure.23 Ureas 3 were prepared as described in literature.24 Symmetric ureas 3a, 3b,
3d, 3e, 3f, 3g, 3h, 3l, and 3m were prepared form amines and triphosgene. The unsymmetric ureas
3c, 3j, and 3n were prepared from nꢀbutylisocyanate and the corresponding amines. Ureas 3i and 3o
were synthesized from phenylisocyanate and amines. Urea 6 was prepared using our previous
reported method.20 Ureas 7 and 8 were synthesized according to the described method.25
Preparation of 3k.
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CO2Et
O
CH2Cl2
n-Bu
H2N
+
CO2Et
n-Bu N C O
N
N
rt.
H
H
3k
Butyl isocyanate (0.338 mL, 3 mmol, 1.0 equiv) was added to a stirred solution of ethyl
pꢀaminobenzoate (545 mg, 3.3 mmol, 1.1 equiv) in CH2Cl2 (5 mL) via syringe at 0 ºC. The mixture
was continuing stir for 2 h at room temperature. The generated white solid in the mixture was
filtered, dried, and then purified on silica gel (CH2Cl2/MeOH = 20/1) to give the compond 3k (365
mg, 46%) as a white solid.
1
Ethyl 4ꢀ(3ꢀbutylureido)benzoate (3k): mp 98–99 °C; H NMR (300 MHz, CDCl3) δ 7.93 (d, J =
8.7 Hz, 2H), 7.39 (d, J = 8.8 Hz, 2H), 7.31 (br, 1H), 5.23 (br, 1H), 4.34 (q, J = 7.1 Hz, 2H), 3.24 (q,
J = 6.5 Hz, 2H), 1.48 (quint, J = 7.2 Hz, 2H), 1.25 ~ 1.42 (m, 5H), 0.89 (t, J = 7.2 Hz, 3H); 13C
NMR (75 MHz, CDCl3) δ 166.8, 156.3, 144.1, 130.9, 123.8, 119.0, 60.9, 40.0, 32.2, 20.1, 14.4, 13.8;
HRMS (ESIꢀQꢀTOF) m/z: [M+H]+ Calcd for C14H21N2O3 265.1552; Found 265.1547.
Urea 5 was Prepared from Dimethyl Phosphorisocyanatidate and Aniline.26
Diethyl isocyanatidophosphate (120 mg, 0.67 mmol) was added slowly to a solution of aniline
(76 mg, 0.82 mmol) in toluene (3 mL) in an ice bath with magnetic stirring. After completion of the
addition, the mixture was allowed to heat to 60 ºC and stirred for 1 h. Then the mixture was
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chromatographed on silica gel (petroleun ether / ethyl acetate = 2:1) to give the compound 5 (130
mg, 71%) as a white solid.
6
7
8
9
Diethyl phenylcarbamoylphosphoramidate (5): 1H NMR (300 MHz, CDCl3) δ 9.23 (br, 1H), 7.48
(d, J = 7.7 Hz, 2H), 7.31 (t, J = 7.9 Hz, 2H), 7.08 (d, J = 7.4 Hz, 1H), 4.12ꢀ4.32 (m, 4H), 1.39 (td, J
= 7.1, 0.9 Hz, 6H); 13C NMR (75 MHz, CDCl3) δ 152.5 (d, J2, CꢀP = 4.4 Hz), 152.5, 138.1, 129.0,
123.8, 119.7, 64.4 (d, J2, CꢀP = 5.9 Hz), 16.2 (d, J3, CꢀP = 7.2 Hz).
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General Procedure for the Cu(OAc)2-Mediated Reaction of C60 with Ureas 1 and 3.
A mixture of C60 (54.0 mg, 0.075 mmol), 1,10ꢀphenanthroline monohydrate (44.6 mg, 0.225
mmol), corresponding ureas (1a−e and 3a−k, 0.225 mmol), and Cu(OAc)2 (27.0 mg, 0.225 mmol)
was stirred vigorously in chlorobenzene (13 mL) at 140 °C. The reaction was monitored by TLC
analysis and stopped at the designated time. The solvent was evaporated in vacuo, and the residue
was purified by column chromatography on silica gel eluted with CS2/toluene to give corresponding
products 2a−e and 4a−k.
1
2a: (brown solid, 15.6 mg, 21%, mp > 300 °C): H NMR (500 MHz, CDCl3ꢀCS2) δ 8.09 (d, J =
8.3 Hz, 2H), 7.39 (d, J = 8.2 Hz, 2H), 4.03 (t, J = 7.8 Hz, 2H), 2.51 (s, 3H), 1.93 (quint, J = 7.7 Hz,
13
2H), 1.45 (sextet, J = 7.5 Hz, 2H), 0.96 (t, J = 7.3 Hz, 3H); C NMR (125 MHz, CDCl3ꢀCS2) δ
152.23, 148.14, 148.06, 146.82, 146.62, 146.59, 146.43, 146.33, 146.21, 146.06, 145.61, 145.26,
145.20, 145.11, 145.06, 145.01, 144.73, 144.42, 143.67, 143.10, 142.99, 142.92, 142.88, 142.73,
142.18, 142.10, 142.04, 141.68, 141.38, 139.92, 138.45, 136.65, 136.56, 136.48, 129.55, 128.95,
80.00 (sp3ꢀC of C60), 79.02 (sp3ꢀC of C60), 43.17, 31.70, 21.91, 20.61, 13.99.
1
2b: (brown solid, 17.5 mg, 23%, mp > 300 °C): H NMR (500 MHz, CDCl3ꢀCS2) δ 8.14 (d, J =
8.4 Hz, 2H), 7.42 (d, J = 8.2 Hz, 2H), 7.39 (d, J = 7.0 Hz, 2H), 7.17 ~ 7.25 (m, 3H), 5.27 (s, 2H),
13
2.54 (s, 3H). C NMR (125 MHz, CDCl3ꢀCS2) δ 152.77, 148.08, 148.00, 146.83, 146.57, 146.39,
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146.31, 146.16, 145.98, 145.54, 145.22, 145.17, 144.96, 144.80, 144.64, 144.37, 143.73, 142.96,
142.88, 142.81, 142.66, 142.19, 142.04, 142.00, 141.50, 141.29, 139.49, 138.43, 136.60, 136.58,
136.31, 136.21, 129.61, 129.00, 128.74, 128.47, 128.05, 79.95 (sp3ꢀC of C60), 79.07 (sp3ꢀC of C60),
46.78, 21.94.
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2c: (brown solid, 9.4 mg, 12%, mp > 300 °C): 1H NMR (500 MHz, CDCl3ꢀCS2) δ 8.10 (d, J = 8.3
Hz, 2H), 7.39 (d, J = 8.1 Hz, 2H), 4.76 (s, 2H), 4.16 (q, J = 7.1 Hz, 2H), 2.51 (s, 3H), 1.20 (t, J =
7.1 Hz, 3H).
1
2d: (brown solid, 14.4 mg, 19%, mp > 300 °C): H NMR (500 MHz, CDCl3ꢀCS2) δ 8.10 (d, J =
8.3 Hz, 2H), 7.39 (d, J = 8.1 Hz, 2H), 4.94 (t, J = 5.4 Hz, 1H), 4.10 (d, J = 5.4 Hz, 2H), 3.42 (s, 6H),
2.51 (s, 3H).
2e: (brown solid, 7.1 mg, 9%, mp > 300 °C): 1H NMR (500 MHz, CDCl3ꢀCS2) δ 8.15 (d, J = 8.4
Hz, 2H), 7.49 (d, J = 8.3 Hz, 2H), 7.40 (d, J = 8.1 Hz, 2H), 7.25 (d, J = 8.1 Hz, 2H), 2.51 (s, 3H),
2.36 (s, 3H); 13C NMR (125 MHz, CDCl3ꢀCS2) δ 152.31, 148.25, 148.15, 146.85, 146.72, 146.70,
146.50, 146.48, 146.30, 146.11, 145.72, 145.43, 145.39, 145.34, 145.27, 144.87, 144.76, 144.52,
144.27, 143.05, 142.95, 142.90, 142.81, 142.23, 142.13, 142.07, 141.67, 141.53, 139.83, 139.78,
138.55, 136.76, 136.48, 136.26, 131.67, 130.64, 130.49, 129.72, 129.21, 81.68 (sp3ꢀC of C60), 79.14
(sp3ꢀC of C60), 21.96, 21.43; UV−vis (CHCl3) λmax/nm 256, 318, 679; HRMS (MALDIꢀTOF) m/z
[M + Na]+ calcd for C75H14N2NaO3S 1045.0623, found 1045.0616.
4a (brown solid, 14.0 mg, 21%, mp > 300 °C): 1H NMR (500 MHz, CDCl3ꢀCS2) δ 4.41 (t, J = 7.7
13
Hz, 4H), 1.98 (quint, J = 7.6 Hz, 4H), 1.54 (sextet, J = 7.5 Hz, 4H), 1.01 (t, J = 7.4 Hz, 6H); C
NMR (125 MHz, CDCl3ꢀCS2) δ 157.01, 148.15, 146.73, 146.43, 146.26, 146.10, 145.58, 145.21,
144.61, 144.40, 143.04, 142.85, 142.23, 142.11, 142.08, 139.79, 136.72, 79.85 (sp3ꢀC of C60), 42.93,
32.57, 20.64, 14.12; UV−vis (CHCl3) λmax/nm 256, 316, 690; HRMS (MALDIꢀTOF MS) m/z [M +
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H]+ calcd for C69H19N2O 891.1497, found 891.1483.
4
5
6
1
4b (brown solid, 19.6 mg, 27%, mp > 300 °C): H NMR (500 MHz, CDCl3ꢀCS2) δ 7.56 (d, J =
7
8
13
7.4 Hz, 4H), 7.28 (t, J = 7.6 Hz, 4H), 7.21 (t, J = 7.4 Hz, 2H), 5.41 (s, 4H); C NMR (125 MHz,
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CDCl3ꢀCS2) δ 157.36, 148.05, 146.41, 146.36, 146.19, 146.03, 145.43, 145.16, 144.48, 144.42,
142.91, 142.77, 142.18, 141.99, 141.83, 139.36, 138.03, 136.47, 128.65, 128.61, 127.76, 79.67
(sp3ꢀC of C60), 46.97; UV−vis (CHCl3) λmax/nm 257, 318, 689; HRMS (MALDIꢀTOF) m/z [M +
Na]+ calcd for C75H14N2NaO 981.1004, found 981.1013, [M + K]+ calcd for C75H14N2KO 997.0743,
found 997.0729.
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4c (brown solid, 11.9 mg, 17%, mp > 300 °C): H NMR (500 MHz, CDCl3ꢀCS2) δ 7.50 (d, J =
7.1 Hz, 2H), 7.26 (d, J = 7.2 Hz, 2H), 7.18 (t, J = 7.3 Hz, 1H), 5.32 (s, 2H), 4.17 (t, J = 7.7 Hz, 2H),
2.03 (quint, J = 7.6 Hz, 2H), 1.58 (sextet, J = 7.5 Hz, 2H), 1.04 (t, J = 7.4 Hz, 3H); 13C NMR (125
MHz, CDCl3ꢀCS2) δ 157.06, 148.08, 148.07, 146.75, 146.41, 146.35, 146.21, 146.20, 146.08,
146.01, 145.48, 145.16, 144.55, 144.51, 144.39, 142.96, 142.80, 142.78, 142.22, 142.15, 142.08,
142.00, 141.96, 141.90, 139.74, 139.36, 138.06, 136.73, 136.41, 128.57, 127.66, 79.74 (sp3ꢀC of
C60), 79.70 (sp3ꢀC of C60), 46.79, 43.09, 32.64, 20.69, 14.15; UV−vis (CHCl3) λmax/nm 256, 317,
689; HRMS (MALDIꢀTOF) m/z [M + H]+ calcd for C72H17N2O 925.1342, found 925.1348;
1
4d (brown solid, 12.7 mg, 18%, mp > 300 °C): H NMR (500 MHz, CDCl3ꢀCS2) δ 7.65 (d, J =
8.3Hz, 4H), 7.28 (d, J = 8.2 Hz, 4H), 2.40 (s, 6H); 13C NMR (125 MHz, CDCl3ꢀCS2) δ 155.90,
148.12, 146.51, 146.42, 146.20, 146.09, 145.58, 145.14, 144.80, 144.53, 142.89, 142.75, 142.17,
142.00, 141.94, 139.60, 138.67, 136.52, 133.49, 130.73, 130.29, 81.05 (sp3ꢀC of C60), 21.44;
UV−vis (CHCl3) λmax/nm 257, 318, 687; HRMS (MALDIꢀTOF) m/z [M + Na]+ calcd for
C75H14N2NaO 981.1004, found 981.0998, [M + K]+ calcd for C75H14N2KO 997.0743, found
997.0738.
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4e (brown solid, 14.8 mg, 20%, mp > 300 °C): 1H NMR (300 MHz, CDCl3ꢀCS2) δ 7.68 (d, J =
4
5
6
13
9.0 Hz, 4H), 6.98 (d, J = 9.0 Hz, 4H), 3.82 (s, 6H); C NMR (125 MHz, CDCl3ꢀCS2) δ 159.69,
7
8
9
156.16, 148.15, 146.51, 146.44, 146.23, 146.12, 145.57, 145.16, 144.80, 144.55, 142.91, 142.77,
142.18, 142.03, 141.96, 139.64, 136.52, 132.16, 128.63, 114.84, 81.12 (2C, sp3ꢀC of C60), 55.26;
UV−vis (CHCl3) λmax/nm 257, 318, 686; HRMS (MALDIꢀTOF) m/z [M + H]+ calcd for
C75H15N2O3 991.1083, found 991.1085, [M + Na]+ calcd for C75H14N2NaO3 1013.0902, found
1013.0901.
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4f (brown solid, 12.8 mg, 18%, mp > 300 °C): H NMR (300 MHz, CDCl3ꢀCS2) δ 7.80 (d, J =
7.2 Hz, 4H), 7.51 (t, J = 7.8 Hz, 4H), 7.42 (t, J = 7.5 Hz, 2H); 13C NMR (100 MHz, CDCl3ꢀCS2) δ
155.79, 148.17, 146.48, 146.41, 146.26, 146.15, 145.60, 145.20, 144.72, 144.57, 142.94, 142.81,
142.21, 142.01, 141.98, 139.66, 136.59, 136.24, 130.92, 129.64, 128.80, 81.10 (sp3ꢀC of C60);
UV−vis (CHCl3) λmax/nm 256, 317, 687; HRMS (MALDIꢀTOF) m/z [M + H]+ calcd for C73H11N2O
931.0872, found 931.0868, [M + Na]+ calcd for C73H10N2NaO 953.0691, found 953.0668.
4g (brown solid, 9.2 mg, 12%, mp > 300 °C): 1H NMR (500 MHz, CDCl3ꢀCS2) δ 7.74 (d, J = 8.6
Hz, 4H), 7.47 (d, J = 8.8 Hz, 4H); 13C NMR (125 MHz, CDCl3ꢀCS2) δ 155.36, 148.21, 146.52,
146.32, 146.23, 145.83, 145.50, 145.24, 144.56, 144.44, 142.99, 142.87, 142.21, 142.03, 141.92,
139.78, 136.62, 135.14, 134.60, 132.05, 129.93, 80.92 (2C, sp3ꢀC of C60); UV−vis (CHCl3) λmax/nm
256, 318, 685 HRMS (MALDIꢀTOF) m/z [M + H]+ calcd for C73H9Cl2N2O 999.0093, found
999.0076.
4i (brown solid, 6.6 mg, 9%, mp > 300 °C): 1H NMR (500 MHz, CDCl3ꢀCS2) δ 7.80 (d, J = 7.8
Hz, 2H), 7.69 (dd, J = 7.7, 1.5 Hz, 1H), 7.49 (t, J = 7.8 Hz, 2H), 7.37ꢀ7.42 (m, 2H), 7.06 (d, J = 8.3
Hz, 1H), 7.04 (t, J = 7.7 Hz, 1H), 3.98 (s, 3H); 13C NMR (125 MHz, CDCl3ꢀCS2) δ 157.28, 156.16,
148.16, 148.13, 147.25, 146.84, 146.67, 146.61, 146.46, 146.42, 146.38, 146.23, 146.17, 146.09,
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146.06, 145.88, 145.67, 145.60, 145.18, 145.15, 145.12, 145.08, 144.96, 144.74, 144.71, 144.62,
144.59, 144.53, 142.94, 142.93, 142.80, 142.75, 142.67, 142.19, 142.03, 141.99, 141.91, 141.88,
139.83, 139.57, 139.43, 139.35, 136.93, 136.70, 136.62, 136.53, 136.30, 132.74, 130.83, 130.71,
129.53, 128.57, 125.34, 121.17, 112.98, 81.17 (sp3ꢀC of C60), 81.05 (sp3ꢀC of C60), 55.95; UV−vis
(CHCl3) λmax/nm 257, 318, 687; HRMS (MALDIꢀTOF) m/z [M + H]+ calcd for C74H13N2O2
961.0978, found 961.0976, [M + Na]+ calcd for C74H12N2NaO2 983.0797, found 983.0792.
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1
4j (brown solid, 13.9 mg, 20%, mp > 300 °C): H NMR (500 MHz, CDCl3ꢀCS2) δ 7.71 (d, J =
7.3 Hz, 2H), 7.48 (t, J = 7.8 Hz, 2H), 7.39 (t, J = 7.5 Hz, 1H), 4.19 (t, J = 7.7 Hz, 2H), 2.06 (quint, J
= 7.6 Hz, 2H), 1.58 (sextet, J = 7.4 Hz, 2H), 1.03 (t, J = 7.4 Hz, 3H); 13C NMR (125 MHz,
CDCl3ꢀCS2) δ 156.48, 148.19, 146.83, 146.50, 146.45, 146.32, 146.30, 146.27, 146.18, 146.10,
145.61, 145.23, 144.82, 144.62, 144.59, 144.34, 143.01, 142.88, 142.83, 142.27, 142.22, 142.15,
142.10, 142.00, 139.83, 139.67, 136.82, 136.54, 136.52, 130.89, 129.58, 128.58, 81.18 (sp3ꢀC of
C60), 79.85 (sp3ꢀC of C60), 43.12, 32.42, 20.67, 14.12; UV−vis (CHCl3) λmax/nm 256, 317, 687;
HRMS (MALDIꢀTOF) m/z [M + H]+ calcd for C71H15N2O 911.1185, found 911.1174.
1
4k (brown solid, 12.3 mg, 17%, mp > 300 °C): H NMR (400 MHz, CDCl3ꢀCS2) δ 8.19 (d, J =
8.5 Hz, 2H), 7.87 (d, J = 8.5 Hz, 2H), 4.38 (q, J = 7.1 Hz, 2H), 4.24 (t, J = 7.7 Hz, 2H), 2.08 (quint,
J = 7.5 Hz, 2H), 1.60 (sextet, J = 7.5 Hz, 2H), 1.39 (t, J = 7.1 Hz, 3H), 1.03 (t, J = 7.4 Hz, 3H);
13C NMR (100 MHz, CDCl3ꢀCS2) δ 166.09, 156.63, 148.35, 146.65, 146.62, 146.51, 146.46, 146.44,
146.33, 146.28, 146.17, 145.71, 145.40, 145.38, 144.72, 144.36, 143.16, 143.03, 142.97, 142.41,
142.37, 142.23, 142.21, 142.13, 142.03, 141.02, 139.99, 139.80, 136.87, 136.81, 131.01, 130.52,
130.44, 81.10 (sp3ꢀC of C60), 80.16 (sp3ꢀC of C60), 61.39, 43.29, 32.34, 20.53, 14.47, 14.08; UV−vis
(CHCl3) λmax/nm 256, 317, 697; HRMS (MALDIꢀTOF) m/z [M + H]+ calcd for C74H19N2O3
983.1396, found 983.1390, [M + Na]+ calcd for C74H18N2NaO3 1005.1215, found 1005.1210.
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The Cu(OAc)2-mediated reaction of C60 with urea 3o.
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A mixture of C60 (54.0 mg, 0.075 mmol), urea 3o (43.2 mg, 0.225 mmol), 1,10ꢀPhenanthroline
monohydrate (44.6 mg, 0.225 mmol), and Cu(OAc)2 (27.0 mg, 0.225 mmol) was stirred vigorously
in chlorobenzene (13 mL) at 140 °C for 5 h. The solvent was evaporated in vacuo, and the residue
was purified by column chromatography on silica gel using CS2/toluene as the eluent to give the
product 4f (9.9 mg, 14%).
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The Reaction of 3o with Cu(OAc)2 and Phen⋅H2O in Chlorobenzene.
O
O
Cu(OAc)2 (1 equiv)
N
N
N
N
Phen (1 equiv)
PhCl, 140 oC
H
H
H
H
3o
3f
A mixture of 3o (43.2 mg, 0.225 mmol), Cu(OAc)2 (27.0 mg, 0.225 mmol), and Phen⋅H2O (44.6
mg, 0.225 mmol) was vigorously stirred in in chlorobenzene (10 mL) at 140 ºC for 4 h until the
TLC showed that full conversion of 3o to 3f occurred. The solvent was evaporated in vacuo, and the
residue was purified by column chromatography on silica gel eluting with ethyl acetate/petroleum
to give the product 3f (20.5 mg, 86%).
The Cu(OAc)2-Mediated Reaction of C60 with N-Diethoxylphosphoryl-N'-Phenyl Urea 5.
A mixture of C60 (54.0 mg, 0.075 mmol), urea 5 (61.2 mg, 0.225 mmol), Phen⋅H2O (44.6 mg,
0.225 mmol), and Cu(OAc)2 (27.0 mg, 0.225 mmol) was stirred vigorously in chlorobenzene (13
mL) at 140 °C for 4.5 h. The solvent was evaporated in vacuo, and the residue was purified by
column chromatography on silica gel eluting with CS2/toluene to give the product 4f (7.8 mg, 11%).
The Cu(OAc)2-Mediated Reaction of C60 with N-Benzoyl-N'-benzyl Urea 7.
A mixture of C60 (54.0 mg, 0.075 mmol), urea 7 (57.2 mg, 0.225 mmol), Phen⋅H2O (44.6 mg,
0.225 mmol), and Cu(OAc)2 (27.0 mg, 0.225 mmol) was stirred vigorously in chlorobenzene (13
mL) at 140 °C for 4 h. The solvent was evaporated in vacuo, and the residue was purified by
column chromatography on silica gel eluting with CS2/toluene to give the product 920 (4.6 mg, 6%,
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higher polarity) and 1018c (12.2 mg, 19%, lower polarity).
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9: 1H NMR (400 MHz, CDCl3ꢀCS2) δ 7.92 (d, J = 7.0 Hz, 2H), 7.63 (t, J = 7.3 Hz, 1H), 7.56 (t, J
= 7.3 Hz, 2H), 7.50 (d, J = 7.1 Hz, 2H), 7.29 (t, J = 7.3 Hz, 2H), 7.23 (t, J = 7.3 Hz, 1H), 5.40 (s,
2H).
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10: 1H NMR (300 MHz, CDCl3ꢀCS2) δ 8.37ꢀ8.49 (m, 2H), 7.55ꢀ7.73 (m, 3H).
The Cu(OAc)2-Mediated Reaction of C60 with N-Benzoyl-N'-Pheny Urea 8.
A mixture of C60 (54.0 mg, 0.075 mmol), urea 8 (54.2 mg, 0.225 mmol), Phen⋅H2O (44.6 mg,
0.225 mmol), and Cu(OAc)2 (27.0 mg, 0.225 mmol) was stirred vigorously in chlorobenzene (13
mL) at 140 °C for 4 h. The solvent was evaporated in vacuo, and the residue was purified by
column chromatography on silica gel using CS2 as the eluent to give the product 10 (16.5 mg,
26%).
Acknowledgments
We are grateful for financial support from the National Natural Science Foundation of China
(Nos. 21202011), Natural Science Foundation of Jiangsu Province (BK20141171), the Jiangsu Key
Laboratory of Advanced Catalytic Materials and Technology (BM2012110), and Advanced
Catalysis and Green Manufacturing Collaborative Innovation Center.
Supporting Information
13
1H and C NMR spectra of 2a−e, 3k, 4a−g, 4i−k, 5, 9, and 10 and the UVꢀvis spectra of new
fullerene derivatives. This material is available free of charge via the Internet at http://pubs.acs.org.
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