Carbene adduct of cyclopalladated ferrocenylimine as an efficient catalyst for the amination of aryl chlorides

Article abstract of DOI:10.1016/j.jorganchem.2007.05.022

A novel air- and moisture-stable carbene adduct of cyclopalladated ferrocenylimine has been synthesized and characterized. The structure of this compound was determined by X-ray crystal structure analysis. This adduct has been applied as an efficient catalyst for the amination of aryl chlorides.

Full text of DOI:10.1016/j.jorganchem.2007.05.022

Journal of Organometallic Chemistry 692 (2007) 3732–3742
www.elsevier.com/locate/jorganchem
Carbene adduct of cyclopalladated ferrocenylimine as an
efficient catalyst for the amination of aryl chlorides
*
Jingya Li, Mengjun Cui, Ajuan Yu, Yangjie Wu
Department of Chemistry, Henan key Laboratory of Chemical Biology and Organic Chemistry, Key Laboratory of Applied Chemistry of Henan
Universities, Zhengzhou University, Zhengzhou 450052, PR China
Received 4 April 2007; received in revised form 8 May 2007; accepted 15 May 2007
Available online 23 May 2007
Abstract
A novel air- and moisture-stable carbene adduct of cyclopalladated ferrocenylimine has been synthesized and characterized. The
structure of this compound was determined by X-ray crystal structure analysis. This adduct has been applied as an efficient catalyst
for the amination of aryl chlorides.
ꢀ 2007 Published by Elsevier B.V.
Keywords: Cyclopalladated ferrocenylimine; N-Heterocyclic carbene; Amination; Aryl chlorides
1. Introduction
As an alternative, N-heterocyclic carbenes have been
proved to be excellent ligands in numerous palladium cat-
alyzed coupling reactions by the virtue of their strong elec-
tron-donating properties and their hedge-like steric bulk
[11]. In the earlier work, the NHC-palladium moiety has
been generated in situ by the reaction of a base with a
imidazolium salt precursor followed by addition of a palla-
dium source [12]. To circumvent the drawbacks associated
with in situ generated catalytic systems, some air- and mois-
ture-stable NHC-bearing palladium (NHC = N-heterocy-
clic carbene) complexes has been reported for the cross
coupling reactions [13]. Among these NHC-bearing palla-
dium complexes, only several examples about carbene
adducts of palladacycle were reported by the groups of
Nolan [14], Herrmann [15], Iyer [16] and Bedford [17].
These catalysts combine the stability induced by the pres-
ence of a palladacycle framework with the high activity
commonly associated with palladium/carbene complexes,
and was also demonstrated to be highly active. Especially
the carbene–palladacycle complex reported by the group
of Nolan has been successfully applied to the Suzuki–
Miyaura reaction, a-ketone arylation, dehalogenation reac-
tion and Buchwald–Hartwig amination [14]. However,
unlike the Suzuki reaction and Heck arylation, the report
The palladium catalyzed amination of aryl halides
(Buchwald–Hartwig amination) is a rapidly developing
field due to the importance of the products in many fields,
e.g. pharmaceuticals, xerography, electronic materials and
ligands for transition metals [1]. Employing aryl chlorides
for this reaction has been focused recently because aryl
chlorides are cheaper and more available than their bro-
mide and iodide counterparts. Not surprisingly, a plethora
of palladium catalyst systems, featuring a palladium-bound
ligand, are now accessible for accomplishing the transfor-
mation involving aryl chlorides. Typically, electron-rich
sterically hindered phosphine ligands such as trialkylphos-
phines [2], aryldialkylphosphines [3–5], ferrocenyldialkyl-
phosphines [6], dialkylphosphinous acids [7], bicyclic
triaminophosphines [8] and phosphorinanes [9], have been
investigated in these reactions. And a number of reports
have shown that Pd complexes derived from sterically hin-
dered and electron-rich phosphines are effective catalysts
for this transformation [10].
*
Corresponding author. Tel./fax: +86 371 67766667.
E-mail address: wyj@zzu.edu.cn (Y. Wu).
0022-328X/$ - see front matter ꢀ 2007 Published by Elsevier B.V.
doi:10.1016/j.jorganchem.2007.05.022

J. Li et al. / Journal of Organometallic Chemistry 692 (2007) 3732–3742
3733
Fe
R
R
N
R
R
N
N
N
THF, rt
Pd Cl
R
+
Fe
Pd Cl
R
2
N
N
R
R
2
1
R= i-Pr
Scheme 1. Synthesis of compound 2.
of Buchwald–Hartwig amination catalyzed by carbene–
palladacycle complex remains elusive. To the best of our
knowledge, only one example of carbene adduct of amine-
based palladacycle for this reaction has been reported
[14b].
Over the past decade, part of our research effort has
focused on the synthesis and application of cyclopalladated
ferrocenylimines [18], we have found that catalyst 1 is an
effective catalyst for various coupling reactions [19]. Taking
the advantage of the NHC properties, we synthesized car-
bene adduct 2, and studied the catalytic activity of 2 for the
amination of aryl chlorides. The results are present below.
cyclopalladated ferrocenylimine 1 at room temperature
under N2 (Scheme 1). The compound 2 was isolated as a
red solid. It is stable to air and moisture. It is very soluble
in chloroform, dichloromethane and acetone, but insoluble
in petroleum ether and n-hexane. Recrystallization from
dichloromethane/petroleum ether afforded the correspond-
ing red crystal. This new compound was characterized by
IR, 1H NMR, 13C NMR, DEPT 135, HSQC, MS and
high-resolution mass spectra. These spectra were well con-
sistent with the title compound. Moreover, the molecular
structure of 2 has also been ascertained by means of
X-ray studies. The structure of 2 together with selected
bond distances and angles is shown in Fig. 1.
2. Results and discussion
Crystallographic data are presented in Table 1. The Pd
atom in 2 is in a slightly distorted square-planar environ-
ment bonded to the carbon atom of the carbene, the chlo-
rine atom, the nitrogen atom and the carbon atom of the
ferrocenyl moiety. In all cases the plane of Pd is defined
by N, C (Cp ring), Cl, C (carbene) atoms with the deviation
2.1. Synthesis and characterization of complex 2
The carbene adduct 2 was prepared in good yield by
simple addition of THF solution of the carbene to the
˚
of Pd1 at 0.0384 A. The bicyclic system formed by the pal-
ladacycle and the C5H3 moiety is approximately coplanar
(dihedral angle 6.4ꢁ), and the dihedral angle between two
Table 1
Crystallographic and data collection parameters for complex 2
Compound
2
Empirical formula
Formula weight
Temperature (K)
Crystal system
Space group
C48 H58Cl5 Fe N3Pd
1016.47
291(2)
Orthorhombic
P2(1)2(1)2(1)
˚
a (A)
12.371(3)
˚
b (A)
15.248(3)
26.771(5)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
90
90
90
3
˚
Volume (A )
Calculated density (g cmꢀ3
5050.1(18)
1.337
)
Z
4
Absorption coefficient (mmꢀ1
F(000)
)
0.942
2096
Crystal size (mm)
0.20 · 0.18 · 0.17
8586/4/504
1.073
R1 = 0.0600, wR2 = 0.1469
R1 = 0.0685, wR2 = 0.1530
˚
Fig. 1. Molecular structure of compound 2. Selected bond distances (A)
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I > 2r(I)]
R indices (all data)
and angles (ꢁ): Pd1–C6 1.983(4), Pd1–C20 1.998(3), Pd1–Cl1 2.379(1),
Pd1–N1 2.114(3); C6–Pd1–C20 96.46(15), C6–Pd1–Cl1 170.94(12), C6–
Pd1–N1 79.83(14), C20–Pd1–Cl1 90.47(15), C20–Pd1–N1 175.78(13), N1–
Pd1–Cl1 93.01(9).

3734
J. Li et al. / Journal of Organometallic Chemistry 692 (2007) 3732–3742
Cp rings in 2 is 3.1ꢁ. The Pd–C (carbene) bond length
However, the yields were influenced by the steric hindrance
of aryl chlorides. 2-Chloroanisole reacted with morpholine
giving 87% isolated yield (Table 2, entry 5), while the very
sterically hindered 2-chloro-m-xylene reacted with mor-
pholine gave 77% isolated yields (Table 2, entry 6).
We then studied the reaction of aryl chlorides with
N-methylaniline. As shown in Table 3, unlike the reaction
of aryl chlorides with morpholine, the yields of aryl chlo-
rides reacted with N-methylaniline in this system were
slightly low.
˚
(1.998 A) is similar to the reported data [14b]. The Pd–C
˚
˚
(Cp ring) (1.983 A) and Pd–N (2.114 A) bond lengths in
2 are longer than those of 1 [20].
2.2. Catalytic activity
2.2.1. Palladacycle 2 catalyzed aryl chlorides with secondary
amines
In order to test the catalytic activity of palladacycle 2,
we initially conducted the reaction of various aryl chlorides
with secondary amine morpholine. The results are summa-
rized in Table 2. To our delight, using 1 mol% of 2, these
reactions indeed proceeded smoothly to afford the corre-
sponding products in moderate to good yields. Both elec-
tron-poor and electron-rich aryl chlorides reacted to
afford the product in high yields (Table 2, entries 1–4,7).
2.2.2. Palladacycle 2 catalyzed aryl chlorides with various
anilines
Having successfully demonstrated the activity of
palladacycle 2 catalyzed amination of aryl chlorides with
secondary amines, we used this system for the reaction of
aryl chlorides with aniline. The results are listed in
Table 4. In all the cases aniline could be arylated with elec-
Table 2
Palladacycle 2 catalyzed amination of aryl chlorides with morpholine
Cat. 2 1 mol%, t
Dioxane, 110 oC, 3h
BuOK
+
Cl
Table 3
HN
O
N
O
R
R
Palladacycle 2 catalyzed amination of aryl chlorides with N-methylaniline
Entrya
1
Aryl chloride
Product
Yield (%)b
99
Me
HN
Ph
Me
N
Ph
Yield (%)b
85
Cat. 2 1 mol%,t
Dioxane, 110 oC, 3h
BuOK
+
Cl
R
R
MeO
Cl
MeO
Me
N
O
Entrya
1
Aryl chloride
Product
Me
N
Ph
2
3
4
98
99
99
MeO
Cl
H3CO
H3C
Me
Cl
N
O
2
3
4
90
92
88
Me
N
Ph
Cl
N
N
O
Me
Cl
Cl
O
O
Me
N
Ph
Cl
Me
Me
5
6
87
77
Me
N
Ph
Cl
N
Cl
OMe
Me
OMe
Me
Me
Me
N
5
81
92
Me
N
Ph
Cl
Cl
O
OMe
OMe
Me
Me
6
Me
7
98
Cl
Cl
N
O
N
Ph
F3C
F3C
F3C
F3C
a
a
Reaction conditions: cat. 2, 0.01 mmol, aryl chloride 1.0 mmol,
Reaction conditions: cat. 2, 0.01 mmol, aryl chloride 1.0 mmol, mor-
t
t
N-methylaniline 1.2 mmol, BuOK 1.5 mmol, dioxane 2 ml.
b
phline 1.2 mmol, BuOK 1.5 mmol, dioxane 2 ml.
b
Islolated yields based on aryl chloride.
Islolated yields based on aryl chloride.

J. Li et al. / Journal of Organometallic Chemistry 692 (2007) 3732–3742
3735
Table 5
tronically diverse aryl chlorides. Reaction of ortho-substi-
tuted aryl chlorides with aniline afforded higher yields. This
is mainly due to that the ortho-substituent of aryl chlorides
prevent the formation of triarylamine.
Table 5 summarizes the results of the couplings of vari-
ous aryl chlorides with 2,5-dimethylaniline. As shown in
Table 5, palladacycle 2 was very effective for the arylation
of 2,5-dimethylaniline. Nearly all the aryl chlorides reacted
with 2,5-dimethylaniline to afford good to excellent yields.
Ortho-substituted aryl chlorides showed no deleterious
effect on this reaction. The ortho-substituent of aniline
could also promote this reaction.
Palladacycle 2 catalyzed amination of aryl chlorides with 2,5-dimethylan-
iline
NH2
H
N
Me
Cat. 2 1 mol%, t
Dioxane, 110 oC, 3h
Me
BuOK
Cl
+
R
Me
R
Me
Entrya Aryl chloride
Product
Yield (%)b
95
1
H
N
Me
Cl
Me
Me
Me
We also examined the amination of aryl chlorides with
sterically hindered 2,6-dimethylaniline. As shown in Table
6, the yields are better than the yields of aniline in most
cases. The presence of an ortho-substituent on the aryl
chloride had no deleterious effect and in fact, coupling
occurred in nearly quantitative yield. Especially, the
reaction of 2-chloro-m-xylene with 2,6-dimethylaniline pro-
vided tetra-ortho-substituted diarylamine in 99% isolated
yield (Table 6, entry 5).
2
96
99
H
N
Me
Me
Cl
Me
3
Me
H
N
Cl
Me
Me
Table 4
Palladacycle 2 catalyzed amination of aryl chlorides with aniline
4
99
98
OMe
H
Cl
Cat. 2 1 mol%, t
Dioxane, 110 oC, 3h
BuOK
H
N
Me
Me
+
Cl
NH2
N
R
R
OMe
Me
Entrya
1
Aryl chloride
Product
Yield (%)b
H
65
88
96
Me
Cl
Me
N
5
Me
Me
H
Cl
N
2
3
H
N
Cl
Me
Me Me
6
89
H
H
N
Cl
F3C
N
Me
Cl
F3C
Me
Me
Me
a
Reaction conditions: cat. 2, 0.01 mmol, aryl chloride 1.0 mmol, 2,5-
t
dimethylaniline 1.2 mmol, BuOK 1.5 mmol, dioxane 2 ml.
b
4
5
99
89
H
N
Islolated yields based on aryl chloride.
Cl
OMe
OMe
2.2.3. Palladacycle 2 catalyzed aryl chlorides with aliphatic
amines
Me
Cl
Me
It is well known that reactions of primary aliphatic
amines with aryl chlorides are not common in amination
reaction. We first investigated the efficiency of 2 in the ary-
lation of cyclohexylamine. As shown in Table 7, moderate
to good yields were obtained. The steric hindrances of aryl
chlorides are favored in this reaction. The reaction of
2-chloro-m-xylene with cyclohexylamine provided 99% iso-
lated yield (Table 7, entry 6).
Encouraged by these results, we evaluated the efficiency
of palladacycle 2 for the arylation of n-dodecylamine under
the same condition (Table 7, entries 8–11). In case of ortho-
substituted phenyl chlorides, high yields of coupled amines
H
N
Me
Me
6
76
H
Cl
N
F3C
F3C
a
Reaction conditions: cat. 2, 0.01 mmol, aryl chloride 1.0 mmol, aniline
t
1.2 mmol, BuOK 1.5 mmol, dioxane 2 ml.
b
Islolated yields based on aryl chloride.

3736
J. Li et al. / Journal of Organometallic Chemistry 692 (2007) 3732–3742
Table 6
3. Conclusion
Palladacycle 2 catalyzed amination of aryl chlorides with sterically
hindered 2,6-dimethylaniline
A novel air- and moisture-stable carbene–palladacycle
complex has been synthesized. The new complex
showed good activity as catalyst for the Buchwald–
Hartwig amination of a range of aryl chlorides with
amines.
Me
NH2
H
N
tBuOK
Dioxane, 110 oC, 3h
Me
Me
Cat. 2 1 mol%,
Cl
+
R
Me
R
Entrya
1
Aryl chloride
Product
Yield (%)b
66
94
99
99
99
Me
4. Experimental
H
N
Me
Cl
4.1. General comments
Me
Me
Melting points were measured on a WC-1 microscopic
apparatus and are uncorrected. IR spectra were recorded
2
3
4
5
Me
H
N
1
Cl
on a Bruker VECTOR22 spectrophotometer. H NMR,
13C NMR, DEPT and C, H-COSY spectra were recorded
on a Bruker DPX-400 spectrometer in CDCl3 with TMS
as an internal standard. Mass spectra were measured on
a LC-MSD-Trap-XCT instrument. High-resolution mass
spectra were measured on a Waters Q-T of Micro spec-
trometer.
Me
Me
Me
Me
H
N
Cl
Me
All the solvents were purified by the standard methods.
The chloride-bridged palladacyclic dimer [21] and N-het-
erocyclic carbene [22] were prepared according to the pub-
lished procedures. The liquid amines were distilled before
used, n-dodecylamine was used without purification. The
aryl chlorides were obtained from commercial sources
and used without purification.
Me
OMe
H
Cl
N
OMe
Me
4.2. Preparation of adduct 2
Me
Cl
Me Me
H
N
The palladacycle dimer 1 (0.1 mmol) was put in a
Schlenk tube. Then under the protection of N2, 5 ml
THF solution of carbene (0.3 mmol) was added slowly
to the dimer via a syringe, stir at room tempera-
ture for 2 h. The mixture was filtered, THF was removed
in vacuum. The crude product was purified by silica
gel column chromatography (ethyl acetate/petroleum
ether = 1:5) to yield the complex (153 mg, 90%). IR
(KBr pellet): 2963, 2925, 1569, 1466, 1398, 1325, 1107,
Me
Me Me
6
84
Me
H
Cl
F3C
N
F3C
Me
a
806, 758 cmꢀ1 1H NMR: d 7.51 (2H, d, J = 4.6 Hz),
.
Reaction conditions: cat, 2, 0.01 mmol, aryl chloride 1.0 mmol, 2,6-
t
dimethylaniline 1.2 mmol, BuOK 1.5 mmol, dioxane 2 ml.
b
7.45–7.36 (2H, m), 7.26 (1H, d, J = 8.0 Hz), 7.14–7.12
(3H, m), 7.00 (2H, d, J = 8.0 Hz), 6.57 (2H, d,
J = 7.0 Hz), 4.67–4.63 (1H, m), 4.30–4.27 (2H, m), 3.96
(1H, s), 3.63 (5H, s), 3.41–3.24 (1H, m), 2.93–2.89 (1H,
m), 2.80–2.77 (1H, m), 2.24 (3H, s), 1.83 (3H, s), 1.60
(3H, d, J = 6.5 Hz), 1.54 (3H, d, J = 6.5 Hz), 1.41 (3H,
d, J = 6.5 Hz), 1.38 (3H, d, J = 6.5 Hz), 1.13 (3H, d,
J = 6.8 Hz), 0.90 (3H, d, J = 6.8 Hz), 0.88 (3H, d,
J = 6.9 Hz), 0.72 (3H, d, J = 6.5 Hz). 13C NMR: d
181.1, 175.4, 148.2, 147.2, 145.2, 144.3, 136.7, 136.5,
133.9, 129.9, 129.4, 128.3, 125.3, 124.6, 124.5, 124.4,
124.2, 123.4, 122.9, 89.9, 77.6, 70.4, 68.9, 66.1, 28.9,
28.7, 28.2, 27.8, 27.0, 25.3, 24.8, 23.7, 23.3, 23.2,
21.7, 21.0, 16.9. Ms: 810.2 [MꢀCl]+. HRMS (positive
ESI) calc. for [C46H54ClN3FePd–Cl]+: 810.2702, found:
810.2686.
Islolated yields based on aryl chloride.
were obtained (Table 7, entries 10,11). In case of aryl chlo-
rides without ortho-substituent, both mono and di-substi-
tuted amines were obtained (Table 7, entries 8, 9).
Overall, the results above-mentioned that palladacycle 2
is clearly comparable in efficacy to other popular catalysts
or ligands currently employed. However, as to the typical
amination catalysts or ligands developed by the groups of
Buchwald, Hartwig, Nolan and others, due to their wide
research and excellent work, the amination can be carried
out at room temperature [2b,3a,6a] with a lower catalyst
loading [6c,13f,13g] and a weaker base [3e]. So our further
research will focus on the development of more efficient
catalytic systems for this reaction.

J. Li et al. / Journal of Organometallic Chemistry 692 (2007) 3732–3742
3737
Table 7
Palladacycle 2 catalyzed amination of aryl chlorides with aliphatic amines
Cat.2 1 mol%,t
Dioxane, 110 oC, 3h
BuOK
H
+
Cl
R2 NH2
N R2
R1
Cl
R1
Entrya
1
Aryl chloride
Amine
Product
Yield (%)b
91
H
MeO
NH2
NH2
NH2
NH2
MeO
N
2
3
4
93
85
99
H
Me
Cl
Me
N
H
N
Cl
H
N
Cl
Me
Me
5
6
72
99
H
N
Cl
NH2
NH2
OMe
OMe
Me
Cl
Me
H
N
Me
Me
7
90
H
NH2
Cl
N
F3C
F3C
8
H2N(n-C12H25
)
)
)
39c
59d
99
MeO
Cl
MeO
NH
n-C12H25
9
H2N(n-C12H25
Cl
NH
n-C12H25
10
H2N(n-C12H25
Cl
NH
n-C12H25
Me
Me
Me
Me
Cl
11
H2N(n-C12H25
)
96
NH
n-C12H25
Me
Me
a
t
Reaction conditions: cat. 2, 0.01 mmol, aryl chloride 1.0 mmol, aliphatic amine 1.2 mmol, BuOK 1.5 mmol, dioxane 2 ml.
Islolated yields based on aryl chloride.
b
c
Fifty-five percent of diarylamine (N-dodecyl-4,40-dimethoxydiphenylamine) was also isolated.
Forty percent of diarylamine (N-dodecyldiphenylamine) was also isolated.
d

3738
J. Li et al. / Journal of Organometallic Chemistry 692 (2007) 3732–3742
4.3. General procedure for the coupling reaction
J = 7.9 Hz), 3.77 (3H, s), 3.22 (3H, s). 13C NMR: d
156.3, 149.8, 142.3, 129.0, 126.3, 118.4, 115.7, 114.8, 55.5,
40.5. MS: 213.6 [M+H]+.
N-Methyl-N-(4-methylphenyl)aniline (Table 3, entry 2)
[5c]. Yellow oil; 1H NMR: d 7.20 (2H, t, J = 7.9 Hz),
7.08 (2H, d, J = 8.2 Hz), 6.97 (2H, d, J = 8.3 Hz), 6.90
(2H, d, J = 8.0 Hz), 6.84 (1H, t, J = 7.3 Hz), 3.25 (3H, s),
2.29 (3H, s). 13C NMR: d 149.5, 146.7, 132.1, 130.0,
129.1, 122.7, 119.9, 118.3, 40.4, 20.9. MS: 219.9
[M+Na]+,197.9 [M+H]+.
N-Methyldiphenylamine (Table 3, entry 3) [4c]. Pale yel-
low oil; 1H NMR: d 7.26–7.22 (4H, m), 7.01–6.99 (4H, m),
6.95–6.91 (2H, m), 3.28 (3H, s). 13C NMR: d 149.1,
129.3, 121.3, 120.5, 40.3. MS: 205.7 [M+Na]+, 183.7
[M+H]+.
Under the protection of N2, 8.45 mg (1 mol%) of cata-
lyst 2, 168 mg of KOtBu, 1 mmol aryl chloride, 1.2 mmol
amine and 2 ml dry dioxane were added into oven-dried
vials. The reaction was run at indicated temperature with
the protection of N2 for 3 h. The reaction mixture was
allowed to cool to room temperature and was quenched
by filtering through a short silica column (eluent: ethyl ace-
tate) and then concentrated under reduced pressure. After
purification by flash chromatography (eluent: ethyl ace-
tate/petroleum ether), the yield was calculated based on
the aryl chlorides.
N-(4-Methoxyphenyl)morpholine (Table 2, entry 1)
[23]. White solid, m.p.: 72–74 ꢁC (lit. 72–74 ꢁC); 1H
NMR: d 6.89–6.83 (4H, m), 3.85 (4H, t, J = 4.7 Hz), 3.76
(3H, s), 3.05 (4H, t, J = 4.7 Hz).13C NMR: d 153.9,
145.6, 117.8, 114.4, 67.0, 55.5, 50.8. MS: 193.8 [M+H]+.
N-(4-Methylphenyl)morpholine (Table 2, entry 2) [24].
White solid, m.p.: 47–49 ꢁC;1H NMR: d 7.08 (2H, d,
J = 8.5 Hz), 6.83 (2H, d, J = 8.5 Hz), 3.85 (4H, t,
J = 4.8 Hz), 3.10 (4H, t, J = 4.8 Hz), 2.27 (3H, s). 13C
NMR: d 149.2, 129.7, 129.5, 116.0, 66.9, 49.9, 20.4. MS:
177.9 [M+H]+.
N-Methyl-N-(2-methylphenyl)aniline (Table 3, entry 4)
1
[5a]. Pale yellow oil; H NMR: d 7.27–7.11 (6H, m), 6.69
(1H, t, J = 6.8 Hz), 6.52 (2H, d, J = 7.8 Hz), 3.19 (3H, s),
2.12 (3H, s). 13C NMR: d 149.0, 146.7, 136.7, 131.2,
128.9, 128.2, 127.4, 126.3, 116.7, 112.7, 38.9, 17.8. MS:
236.8 [M+K]+,197.8 [M+H]+.
N-Methyl-N-phenyl-2-methoxyaniline (Table 3, entry 5)
[26]. Pale yellow oil; 1H NMR: d 7.19–7.12 ( 4H, m),
6.95–6.94 (2H, m), 6.70 (1H, t, J = 7.3 Hz), 6.64–6.62
(2H, m), 3.72 (3H, s), 3.19 (3H, s). 13C NMR: d 156.0,
149.4, 136.8, 129.2, 128.8, 127.0, 121.3, 117.2, 113.4,
112.6, 55.6, 39.1. MS: 235.8 [M+Na]+, 213.9 [M+H]+.
N-Methyl-N-[3-(trifluoromethyl)phenyl]aniline (Table
N-Phenylmorpholine (Table 2, entry 3) [23]. White
solid, m.p.: 52–54 ꢁC (lit. 51–54 ꢁC); 1H NMR: d 7.30–
7.26 (2H, m), 6.93–6.86 (3H, m), 3.86 (4H, t, J = 4.8 Hz),
3.15 (4H, t, J = 4.8 Hz). 13C NMR: d 151.1, 129.1, 120.0,
115.6, 66.8, 49.2. MS: 163.9 [M+H]+.
1
3, entry 6) [5a]. Colorless oil; H NMR: d 7.34–7.31 (2H,
N-(2-Methylphenyl)morpholine (Table 2, entry 4) [13h].
Colorless oil; H NMR: d 7.19–7.15 (2H, m), 7.02–6.97
m), 7.26 (1H, t, J = 7.9 Hz), 7.12–7.05 (5H, m), 7.03–7.00
(1H, m), 3.31 (3H, s). 13C NMR: d 149.3, 148.1, 131.5 (q,
2J(C,F) = 31.6 Hz), 129.7, 129.4, 124.3 (q, 1J(C,F)
1
(2H, m), 3.84 (4H, t, J = 4.5 Hz), 2.89 (4H, t, J = 4.5 Hz),
2.31 (3H, s). 13C NMR: d 151.2, 132.5, 131.1, 126.6, 123.3,
118.8, 67.4, 52.1, 17.8. MS: 177.9 [M+H]+.
N-(2-Methoxyphenyl)morpholine (Table 2, entry 5)
[13h]. Pale yellow oil; 1H NMR: d 7.03–6.98 (1H, m),
6.93 (2H, d, J = 4.3 Hz), 6.87 (1H, d, J = 7.9 Hz), 3.89
(4H, t, J = 4.6 Hz), 3.86 (3H, s), 3.07 (4H, t, J =
4.5 Hz). 13C NMR: d 151.6, 140.5, 122.6, 120.5, 117.4,
110.7, 66.6, 54.8, 50.6. MS: 215.8 [M+Na]+, 193.8
[M+H]+.
= 270.9 Hz),
123.8,
123.6,
120.4,
115.9
(d,
3
3J(C,F) = 3.7 Hz), 113.9 (d, J(C,F) = 3.7 Hz), 40.3. MS:
252.0 [M+H]+.
N-Phenyl-4-methylaniline (Table 4, entry 1) [27]. White
solid, m.p.: 86–87 ꢁC (lit. 86–87 ꢁC); 1H NMR: d 7.25–7.20
(2H, m), 7.08 (2H, d, J = 8.2 Hz), 7.01–6.98 (4H, m), 6.87
(1H, t, J = 7.3 Hz), 5.68 (1H, s), 2.30 (3H, s). 13C NMR: d
143.8, 140.2, 130.9, 129.8, 129.3, 120.3, 118.9, 116.8, 20.7.
MS: 183.9 [M+H]+.
N-(2,6-Dimethylphenyl)morpholine (Table 2, entry 6)
[3b]. White solid, m.p.: 87–89 ꢁC (lit. 86–87 ꢁC); 1H
NMR: d 7.02–6.95 (3H, m), 3.81 (4H, t, J = 4.5 Hz), 3.10
(4H, t, J = 4.5 Hz), 2.35 (6H, s). 13C NMR: d 147.7,
136.9, 129.0, 125.3, 68.1, 49.9, 19.6. MS: 192.0 [M+H]+.
N-[3-(Trifluoromethyl)phenyl]morpholine (Table 2,
entry 7) [25]. Pale yellow oil; 1H NMR: d 7.37–7.33
(1H, m), 7.10 (2H, d, J = 2.3 Hz), 7.05–7.03 (1H, m),
3.86 (4H, t, J = 4.8 Hz), 3.18 (4H, t, J = 4.8 Hz). 13C
Diphenylamine (Table 4, entry 2) [23]. White solid,
m.p.: 52–53 ꢁC (lit. 52–53 ꢁC); 1H NMR: d 7.27–7.22
(4H, m), 7.07–7.05 (4H, m), 6.92 (2H, t, J = 7.3 Hz), 5.74
(1H, s). 13C NMR: d 143.0, 129.3, 121.0, 117.8. MS:
169.9 [M+H]+.
N-Phenyl-2-methylaniline (Table 4, entry 3) [5a]. Yellow
oil; 1H NMR: d 7.25–7.17 (4H, m), 7.14–7.10 (1H, m),
6.95–6.86 (4H, m), 5.35 (1H, s), 2.23 (3H, s). 13C NMR:
d 143.9, 141.2, 130.9, 129.3, 128.2, 126.7, 121.9, 120.4,
118.7, 117.4, 17.9. MS: 206 [M+Na]+, 183.9 [M+H]+.
N-(2-Methoxyphenyl)aniline (Table 4, entry 4) [23].
2
NMR: d 151.4, 131.5 (q, J(C,F) = 31.7 Hz), 129.6, 124.3
(q, 2J(C,F) = 270.9 Hz), 118.4, 116.2 (d, 3J(C,F) = 3.7 Hz),
111.8 (d, 3J(C,F) = 3.7 Hz), 66.7, 48.8. MS: 231.8
[M+H]+.
1
Pale yellow oil; H NMR: d 7.31–7.24 (3H, m), 7.14–7.12
(2H, m), 6.94–6.91 (1H, m), 6.89–6.83 (3H, m), 6.14 (1H,
s), 3.86 (3H, s). 13C NMR: d 148.2, 142.7, 132.9, 129.2,
121.1, 120.8, 119.8, 118.5, 114.6, 110.5, 55.5. MS: 199.9
[M+H]+.
N-Methyl-N-phenyl-4-methoxyaniline (Table 3, entry 1)
1
[5a]. Pale yellow oil; H NMR: d 7.17 (2H, t, J = 7.9 Hz),
7.07 (2H, d, J = 8.9 Hz), 6.87–6.85 (2H, m), 6.77 (3H, d,

J. Li et al. / Journal of Organometallic Chemistry 692 (2007) 3732–3742
3739
N-Phenyl-3-(trifluoromethyl)aniline (Table 4, entry 6)
[3g]. Yellow oil; 1H NMR: d 7.32–7.28 (3H, m), 7.24
(1H, s), 7.18–7.15 (1H, m), 7.12–7.07 (3H, m), 7.02–6.99
(1H, m), 5.80 (1H, s). 13C NMR: d 144.0, 141.7, 131.7 (q,
2J(C,F) = 31.9 Hz), 129.8, 129.5, 124.1 (q, 1J(C,F) =
2,6-Dimethyl-N-(4-methylphenyl)aniline (Table 6, entry
1) [29]. Yellow oil; 1H NMR: d 7.11–7.09 (2H, m),
7.07–7.03 (1H, m), 6.96 (2H, d, J = 8.3 Hz), 6.44–6.41
(2H, m), 5.12 (1H, s), 2.23 (3H, s), 2.19 (6H, s). 13C
NMR: d 143.8, 138.6, 135.4, 129.7, 128.5, 127.4, 125.3,
113.7, 20.4, 18.3. MS: 211.9 [M+H]+.
3
270.7 Hz), 122.3, 119.6, 118.9, 116.9 (d, J(C,F) = 3.8 Hz),
3
113.2 (d, J(C,F) = 3.8 Hz). MS: 238.0 [M+H]+.
N-(4-Methylphenyl)-2,5-dimethylaniline (Table 5, entry
N-(2,6-Dimethylphenyl)aniline (Table 4, entry 5; Table
6, entry 2) [23]. White solid, m.p.: 52–53 ꢁC (lit.
1
1
1) [28]. Orange solid, m.p.: 46–48 ꢁC; H NMR: d 7.06
53–56 ꢁC) [30]; H NMR: d 7.16–7.06 (5H, m), 6.73 (1H,
(3H, t, J = 8.5 Hz), 6.98 (1H, s), 6.89 (2H, d, J = 8.0 Hz),
6.69 (1H, d, J = 7.4 Hz), 5.25 (1H, s), 2.29 (3H, s), 2.24
(3H, s), 2.18 (3H, s). 13C NMR: d 141.7, 141.0, 136.4,
130.6, 130.3, 129.7, 123.9, 121.8, 118.6, 117.9, 21.1, 20.6,
17.3. MS: 212.0 [M+H]+.
t, J = 7.3 Hz), 6.49 (2H, d, J = 7.7 Hz), 5.14 (1H, s), 2.20
(6H, s). 13C NMR: d 146.3, 138.2, 135.9, 129.3, 128.6,
125.8, 118.2, 113.5, 18.4. MS: 198.0 [M+H]+.
2,6-Dimethyl-N-(2-methylphenyl)aniline (Table 6, entry
3) [29]. White solid, m.p.: 61–63 ꢁC (lit. 64–66 ꢁC) [30];
1H NMR: d 7.12–7.04 (4H, m), 6.95 (1H, t, J = 7.3 Hz),
6.69 (1H, t, J = 7.3 Hz), 6.14 (1H, d, J = 8.0 Hz), 4.91
(1H, s), 2.31 (3H, s), 2.17 (6H, s). 13C NMR: d 144.1,
138.7, 135.5, 130.2, 128.5, 126.9, 125.5, 122.4, 118.0,
111.7, 18.2, 17.6. MS: 212.1 [M+H]+.
N-(2-Methoxyphenyl)-2,6-dimethylaniline (Table 6,
entry 4) [2c]. White solid, m.p.: 81–83 ꢁC; 1H NMR: d
7.12–7.04 (3H, m), 6.86–6.83 (1H, m), 6.74–6.66 (2H, m),
6.13–6.11 (1H, m), 5.52 (1H, s), 3.93 (3H, s), 2.20 (6H, s).
13C NMR: d 146.2, 137.8, 135.6, 135.4, 127.9, 125.1,
120.5, 116.7, 110.5, 109.3, 55.1, 17.7. MS: 228.1 [M+H]+.
Bis(2,6-dimethylphenyl)amine (Table 6, entry 5) [2c].
White solid, m.p.: 97–99 ꢁC; 1H NMR: d 6.97 (4H, d,
J = 7.4 Hz), 6.83 (2H, t, J = 7.4 Hz), 4.75 (1H, s), 2.00
(12H, s). 13C NMR: d 141.6, 129.4, 128.6, 121.6, 19.0.
MS: 226.0 [M+H]+.
N-Phenyl-2,5-dimethylaniline (Table 5, entry 2) [5d].
1
Yellow oil; H NMR: d 7.24–7.20 (2H, m), 7.06 (2H, d,
J = 8.2 Hz), 6.93–6.91 (2H, m), 6.87 (1H, t, J = 7.3 Hz),
6.74 (1H, d, J = 7.4 Hz), 5.32 (1H, s), 2.25 (3H, s), 2.18
(3H, s). 13C NMR: d 144.0, 140.9, 136.4, 130.7, 129.3,
125.3, 122.8, 120.3, 119.5, 117.4, 21.1, 17.4. MS: 198.0
[M+H]+.
N-(2-Methylphenyl)-2,5-dimethylaniline (Table 5, entry
1
3). White solid, m.p.: 72–73 ꢁC; H NMR: d 7.17 (1H, d,
J = 7.4 Hz), 7.10–7.05 (2H, m), 6.97 (1H, d, J = 7.8 Hz),
6.88 (1H, t, J = 7.4 Hz), 6.81 (1H, s), 6.71 (1H, d,
J = 7.6 Hz), 5.07 (1H, s), 2.24 (6H, s), 2.19 (3H, s). 13C
NMR: d 142.1, 141.7, 136.5, 130.8, 130.7, 127.4, 126.8,
124.6, 122.3, 121.2, 119.1, 118.2, 21.2, 17.9, 17.4. MS:
212.1 [M+H]+. HRMS (positive ESI) calc. for
[C15H17N+H]+: 212.1440, found: 212.1439.
N-(2-Methoxyphenyl)-2,5-dimethylaniline (Table 5,
1
2,6-Dimethyl-N-[3-(trifluoromethyl)phenyl]aniline (Table 6,
1
entry 4) [3b]. White solid, m.p.: 85–86 ꢁC; H NMR: d
entry 6). Yellow oil; H NMR: d 7.21 (1H, t, J = 7.9 Hz),
7.19 (1H, s), 7.14 (1H, d, J = 7.6 Hz), 7.09–7.06 (1H, m),
6.95–6.84 (3H, m), 6.82 (1H, d, J = 7.5 Hz), 5.88 (1H, s),
3.95 (3H, s), 2.33 (3H, s), 2.28 (3H, s). 13C NMR: d
147.7, 140.0, 135.8, 133.4, 130.1, 125.7, 122.4, 120.3,
119.7, 118.6, 113.9, 109.8, 55.1, 20.6, 16.9. MS: 249.9
[M+Na]+, 227.9 [M+H]+.
7.15–7.09 (3H, m), 6.96 (1H, d, J = 7.6 Hz), 6.71 (1H, s),
6.58 (1H, d, J = 8.2 Hz), 5.30 (1H, s), 2.19 (6H, s). 13C
2
NMR: d 146.6, 137.1, 136.2, 131.7 (q, J(C,F) = 31.6 Hz),
1
129.7, 128.8, 126.5, 124.3 (q, J(C,F) = 270.8 Hz), 116.1,
114.5 (d, 3J(C,F) = 3.7 Hz), 109.2 (d, 3J(C,F) = 3.7 Hz),
18.3. MS: 266.1 [M+H]+. HRMS (positive ESI) calc. for
[C15H14F3N+H]+: 266.1157, found: 266.1155.
N-(2,6-Dimethylphenyl)-2,5-dimethylaniline (Table 5,
1
entry 5). Orange solid, m.p.: 66–68 ꢁC; H NMR: d 7.12–
N-Cyclohexyl-4-methoxyaniline (Table 7, entry 1) [31].
White solid, m.p.: 42–43 ꢁC; 1H NMR: d 6.78–6.74
(2H, m), 6.58–6.55 (2H, m), 3.73 (3H, s), 3.18–3.12 (1H,
m), 3.08 (1H, s), 2.05–2.01 (2H, m), 1.77–1.72 (2H, m),
1.65–1.61 (1H, m), 1.39–1.29 (2H, m), 1.25–1.18 (1H, m),
1.15–1.05 (2H, m). 13C NMR: d 151.8, 141.5, 114.9,
114.8, 55.7, 52.7, 33.6, 25.9, 25.0. MS: 205.9 [M+H]+.
N-Cyclohexyl-4-methylaniline (Table 7, entry 2) [32].
7.04 (3H, m), 7.00 (1H, d, J = 7.5 Hz), 6.52 (1H, d,
J = 7.3 Hz), 5.96 (1H, s), 4.83 (1H, s), 2.27 (3H, s), 2.17
(6H, s), 2.12 (3H, s). 13C NMR: d 143.3, 138.3, 136.0,
134.9, 129.5, 128.0, 124.9, 119.0, 118.3, 111.9, 20.8, 17.7,
16.7. MS: 226.1 [M+H]+. HRMS (positive ESI) calc. for
[C16H19N+H]+: 226.1596, found: 226.1596.
N-[3-(Trifluoromethyl)phenyl]-2,5-dimethylaniline (Table 5,
1
1
entry 6). White solid, m.p.: 36–37 ꢁC; H NMR: d 7.30–
White solid, m.p.: 40–41ꢁC (lit. 39ꢁC); H NMR: d 6.96
7.26 (1H, m), 7.11 (1H, d, J = 7.6 Hz), 7.06–7.03 (3H,
m), 6.99 (1H, d, J = 7.8 Hz), 6.85–6.83 (1H, m), 5.45
(1H, s), 2.28 (3H, s), 2.18 (3H, s). 13C NMR: d 144.7,
139.0, 136.2, 131.2 (q, 2J(C,F) = 31.7 Hz), 130.5, 129.2,
126.7, 124.0, 123.7 (q, 1J(C,F) = 270.8 Hz), 121.2,
118.4, 115.5 (d, 3J(C,F) = 3.7 Hz), 112.0 (d, 3J(C,F) =
3.7 Hz), 20.5, 16.9. MS: 266.1 [M+H]+. HRMS (posi-
tive ESI) calc. for [C15H14F3N+H]+: 266.1157, found:
266.1151.
(2H, d, J = 8.3 Hz), 6.52 (2H, d, J = 8.3 Hz), 3.34 (1H, s),
3.23–3.18 (1H, m), 2.22 (3H, s), 2.06–2.02 (2H, m),
1.76–1.71 (2H, m), 1.66–1.61 (1H, m), 1.40–1.29 (2H, m),
1.25–1.17 (1H, m), 1.16–1.06 (2H, m). 13C NMR: d 145.0,
129.7, 126.1, 113.5, 52.0, 33.5, 25.9, 25.0, 20.3. MS: 189.9
[M+H]+.
N-Cyclohexylaniline (Table 7, entry 3) [23]. Pale yellow
oil; 1H NMR: d 7.19–7.13 (2H, m), 6.67–6.66 (1H, m),
6.64–6.58 (2H, m), 3.46 (1H, s), 3.27–3.21 (1H, m),

3740
J. Li et al. / Journal of Organometallic Chemistry 692 (2007) 3732–3742
2.08–2.04 (2H, m), 1.79–1.64 (3H, m), 1.39–1.32 (2H, m),
1.23–1.12 (3H, m). 13C NMR: d 147.3, 129.2, 116.8,
113.1, 51.6, 33.4, 25.9, 25.0. MS: 175.8 [M+H]+.
J = 7.9 Hz ), 6.93 (2H, t, J = 7.3 Hz), 3.66 (2H, t,
J = 7.8 Hz), 1.66–1.61 (2H, m), 1.28–1.24 (18H, m), 0.87
(3H, t, J = 6.7 Hz). 13C NMR: d 148.0, 129.2, 121.0,
120.8, 52.4, 31.9, 29.7, 29.6, 29.5, 29.4, 27.4, 27.1, 22.7,
14.2. MS: 338.3 [M+H]+. HRMS (positive ESI) calc. for
[C24H35N+H]+: 338.2849, found: 338.2840.
N-Cyclohexyl-2-methylaniline (Table 7, entry 4) [8c].
1
Colorless oil; H NMR: d 7.10–7.01 (2H, m), 6.62–6.58
(2H, m), 3.35–3.26 (2H, m), 2.10–2.05 (5H, m), 1.77–1.73
(2H, m), 1.66–1.62 (1H, m), 1.39–1.33 (2H, m), 1.24–1.16
(3H, m). 13C NMR: d 145.2, 130.2, 127.0, 121.5, 116.2,
110.1, 51.4, 33.6, 26.0, 25.0, 17.5. MS: 189.9 [M+H]+.
N-Cyclohexyl-2-methoxyaniline (Table 7, entry 5) [6c].
N-Dodecyl-2-methylaniline (Table 7, entry 10). Pale yel-
1
low oil; H NMR: d 7.12 (1H, t, J = 7.6 Hz), 7.03 (1H, d,
J = 7.2 Hz), 6.65–6.58 (2H, m), 3.43 (1H, s), 3.14–3.10
(2H, m), 2.12 (3H, s), 1.68–1.61 (2H, m), 1.40–1.26 (18H,
m), 0.89–0.86 (3H, m). 13C NMR: d 146.4, 130.0, 127.1,
121.6, 116.6, 109.6, 44.0, 32.0, 29.7, 29.6, 29.5, 29.4, 27.3,
22.7, 17.5, 14.2. MS: 276.1 [M+H]+. HRMS (positive
ESI) calc. for [C19H33N+H]+: 276.2692, found: 276.2686.
N-Dodecyl-2,6-dimethylaniline (Table 7, entry 11). Col-
1
Pale yellow oil; H NMR: d 6.84–6.81 (1H, m), 6.76–6.73
(1H, m), 6.63–6.59 (2H, m), 4.12 (1H, s), 3.82 (3H, s),
3.27–3.21 (1H, m), 2.08–2.04 (2H, m), 1.78–1.62 (3H, m),
1.39–1.17 (5H, m). 13C NMR: d 146.6, 137.2, 121.2,
115.7, 110.1, 109.5, 55.3, 51.3, 33.4, 26.0, 25.1. MS: 227.9
[M+Na]+, 205.9 [M+H]+.
1
orless oil; H NMR: d 6.97 (2H, d, J = 7.4 Hz), 6.80 (1H,
N-Cyclohexyl-2,6-dimethylaniline (Table 7, entry 6)
1
t, J = 7.4 Hz), 2.96 (3H, t, J = 7.2 Hz), 2.27 (6H, s),
1.58–1.53 (2H, m), 1.38–1.25 (18H, m), 0.88 (3H, t,
J = 6.8 Hz). 13C NMR: d 146.4, 129.1, 128.8, 121.5, 48.7,
32.0, 31.2, 29.7, 29.6, 29.4, 27.2, 22.7, 18.6, 14.2. MS:
290.1 [M+H]+. HRMS (positive ESI) calc. for [C20H35
N+H]+: 290.2849, found: 290.2849.
[33]. Colorless oil; H NMR: d 6.97 (2H, d, J = 7.4 Hz),
6.77 (1H, t, J = 7.4 Hz), 2.97–2.90 (2H, m), 2.25 (6H, s),
1.96–1.93 (2H, m), 1.75–1.71 (2H, m), 1.63–1.60 (1H, m),
1.26–1.08 (5H, m). 13C NMR: d 145.0, 128.9, 128.6,
121.0, 56.1, 34.9, 25.9, 25.5, 19.0. MS: 203.9 [M+H]+.
N-Cyclohexyl-3-trifluoromethylaniline (Table 7, entry 7).
1
Colorless oil; H NMR: d 7.21 (1H, t, J = 7.9 Hz), 6.87
4.4. Crystal structure determination
(1H, d, J = 7.5 Hz), 6.75 (1H, s), 6.70–6.67 (1H, m), 3.73
(1H, s), 3.28–3.22 (1H, m), 2.05–2.01 (2H, m), 1.78–1.73
(2H, m), 1.67–1.62 (1H, m), 1.42–1.31 (2H, m), 1.27–1.09
Intensity data of 2 was measured on a Rigaku-Raxis-IV
X-ray diffractometer using graphite monochromated Mo
2
(3H, m). 13C NMR: d 147.5, 131.6 (q, J(C,F) = 31.4 Hz),
Ka radiation (k = 0.71073 A). The data were corrected
˚
129.6, 124.5 (q, 1J(C,F) = 270.7 Hz), 115.9, 113.1 (d,
for Lorentz and polarization factors. The structure was
solved by direct methods [36] and expanded using Fourier
techniques and refined by full-matrix least-squares meth-
ods. All calculations were performed using the TEXSAN
[37] crystallographic software package of Molecular Struc-
ture corporation.
3
3J(C,F) = 3.7 Hz), 109.1 (d, J(C,F) = 3.7 Hz), 51.5, 33.2,
25.8, 24.9. MS: 243.9 [M+H]+. HRMS (positive ESI) calc.
for [C13H16F3N+H]+: 244.1314, found: 244.1320.
N-Dodecyl-4-methoxyaniline (Table 7, entry 8) [34].
1
White solid, m.p.: 34–35ꢁC; H NMR: d 6.79–6.75 (2H,
m), 6.60–6.56 (2H, m), 3.74 (3H, s), 3.40 (1H, m), 3.05
(2H, t, J = 7.1 Hz), 1.63–1.56 (2H, m), 1.39–1.23 (18H,
m), 0.88 (3H, t, J = 6.8 Hz). 13C NMR: d 150.4, 141.1,
113.3, 112.5, 54.2, 43.5, 30.3, 28.1, 28.0, 27.9, 27.8, 25.6,
21.1, 12.5. MS: 292.2 [M+H]+.
5. Supplementary material
CCDC 634736 contains the supplementary crystallo-
graphic data for 2. These data can be obtained free of charge
via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or
from the Cambridge Crystallographic Data Centre, 12
Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-
336-033; or e-mail: deposit@ccdc.cam.ac.uk.
N-Dodecyl-4,40-dimethoxydiphenylamine (Table 7, entry
1
8). White solid, mp: 41–43 ꢁC; H NMR: d 6.86 (4H, d,
J = 9.0 Hz), 6.82–6.79 (4H, m), 3.77 (6H, s), 3.54 (2H, t,
J = 7.6 Hz), 1.61–1.57 (2H, m), 1.28–1.24 (18H, m), 0.87
(3H, t, J = 6.8 Hz). 13C NMR: d 154.1, 142.5, 122.0,
114.5, 55.6, 52.9, 31.9, 29.68, 29.66, 29.63, 29.5,
29.3, 27.5, 27.1, 22.7, 14.1. MS: 398.4 [M+H]+. HRMS
(positive ESI) calc. for [C26H39NO2+H]+: 398.3060, found:
398.3061.
Acknowledgements
We are grateful to the National Natural Science Foun-
dation of China (Project 20472074) and the Innovation
Found for Outstanding Scholar of Henan Province (Pro-
ject 0621001100) for the financial support on this research.
N-Dodecylaniline (Table 7, entry 9) [23]. White solid,
1
m.p.: 25–26 ꢁC; H NMR: d 7.18–7.14 (2H, m), 6.69–6.66
(1H, m), 6.61–6.58 (2H, m), 3.62 (1H, m), 3.09 (2H, t,
J = 7.1 Hz), 1.62–1.56 (2H, m), 1.40–1.26 (18H, m), 0.88
(3H, t, J = 6.7 Hz). 13C NMR: d 146.9, 127.6, 115.5,
111.1, 42.4, 30.3, 28.1, 28.0, 27.9, 27.8, 25.6, 21.1, 12.5.
MS: 262.1 [M+H]+.
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1
less oil; H NMR: d 7.24 (4H, t, J = 7.9 Hz), 6.98 (4H, d,

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