RSC Advances
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recovered by ltration and washed by methanol. Then the
reaction mixture was distilled to separate and recover methanol
Computational details
and light component and the product N,N-dimethyl-n-butyl- DFT calculations were carried out by using the CASTEP program
32–34
amine was obtained in 93% yield.
N,N-Dimethyl-n-butylamine. Yield 93%. H NMR (400 MHz, dew, Burke, Erzenhof gradient corrected functional (GGA-PBE)
CDCl
) d 2.31–2.12 (m, 8H), 1.52–1.38 (m, 2H), 1.32 (dq, J ¼ 14.3, is chosen together with plane wave basis functions with spin
package in Materials Studio of Accelrys Inc,
where the Per-
1
3
1
3
35–38
7
5
.1 Hz, 2H), 0.92 (t, J ¼ 7.3 Hz, 3H). C NMR (100 MHz, CDCl
3
) d polarization.
The linear and quadratic synchronous transit
9.62, 45.48, 29.90, 20.61, 14.01. MS (EI, 70 eV), m/z (rel abun- (LST/QST) complete search was chose to search for transition
+
39
dance): 101(M , 8), 86(5), 58(100), 44(13), 39(18), 30(88).
state of the reaction. The simulation of core electron was
1
40
N,N-Dimethyl-2-hydroxyethylamine. Yield 90%. H NMR performed by Ultraso pseudopotential (USP). In order to
(
2
400 MHz, CDCl ) d 4.00 (s, 1H), 3.54 (dd, J ¼ 10.2, 5.0 Hz, 2H), improve computational performance, energy cut-off was set
3
1
3
.38 (dd, J ¼ 10.6, 5.3 Hz, 2H), 2.18 (d, J ¼ 5.3 Hz, 6H). C NMR 400.0 eV.
(100 MHz, CDCl
3
) d 61.16, 58.81, 45.25. MS (EI, 70 eV), m/z (rel
Ni(111) surface was modeled by using a three-layer periodic
slab model with a (5 ꢂ 5) super cell. Then by building a 10 A˚
+
abundance): 89(M , 8), 58(100), 42(31), 30(15).
0
0
1
N,N,N ,N -Tetramethylethylenediamine. Yield 89%. H NMR vacuum slab, the adsorption and reaction occurs in this cell.
1
3
(400 MHz, CDCl
3
) d 2.39 (s, 4H), 2.24 (s, 12H). C NMR (100 The reciprocal space of the (5 ꢂ 5) super cell was sampled using
) d 57.58, 45.78. MS (EI, 70 eV), m/z (rel abundance): the 3 ꢂ 3 ꢂ 1 k-points grid. Larger k-points sets were needed if
more accurate energy value wanted. Study in this work focused
MHz, CDCl
1
3
+
14(M , 99), 99(11), 71(65), 56(32), 43(100), 28(17).
0
0
1
N,N,N ,N -Tetramethylpropanediamine. Yield 85%. H NMR on the relative results of different systems, so the k-points set of
(
400 MHz, CDCl ) d 2.33–2.25 (m, 4H), 2.22 (s, 12H), 1.70–1.57 (3 ꢂ 3 ꢂ 1) should be enough. For the geometry optimization,
3
1
3
3
(m, 2H). C NMR (100 MHz, CDCl ) d 57.80, 45.43, 25.94. MS all Ni atoms were constrained except the uppermost layer, with
+
(
5
EI, 70 eV), m/z (rel abundance): 130(M , 5), 85(79), 70(52), setting the convergence tolerances of energy and displacement
ꢁ
5
ꢁ3
8(100), 42(49), 30(11).
to 2 ꢂ 10 eV per atom and 2 ꢂ 10 A˚ , respectively, and
1
ꢁ6
N,N-Diisopropylmethylamine. Yield 90%. H NMR (400 setting the SCF tolerance to 2 ꢂ 10 eV per atom.
MHz, CDCl
(
2
3
) d 2.91 (dt, J ¼ 12.5, 6.2 Hz, 2H), 2.49 (s, 3H), 1.04
Chemisorption energies were calculated using the following
1
3
d, J ¼ 6.3 Hz, 12H). C NMR (100 MHz, CDCl ) d 59.68, 35.07, formulas:
3
+
3.30. MS (EI, 70 eV), m/z (rel abundance): 115(M , 33), 100(96),
7
2(18), 58(100), 42(22), 30(13).
N-Methylmorpholine. Yield 97%. H NMR (400 MHz, CDCl
DEads ¼ Eadsorbate–Ni ꢁ Eadsorbate ꢁ ENi
1
3
)
1
3
where DEads represented the adsorption energy of the adsorbate
on Ni(111) surface, Eadsorbate was the energy of free adsorbate,
ENi was the energy of clean slab and Eadsorbate–Ni was the energy
of adsorbate–Ni adsorption system.
For a reaction, such as A + B / C + D, the energy barrier was
calculated as follows:
d 3.79–3.59 (m, 4H), 2.41 (s, 4H), 2.29 (s, 3H). C NMR (100
MHz, CDCl ) d 66.87, 55.39, 46.40. MS (EI, 70 eV), m/z (rel
abundance): 101(M , 48), 71(31), 56(6), 43(100), 29(15).
3
+
1
1,4-Dimethylpiperazine. Yield 95%. H NMR (400 MHz,
1
3
CDCl ) d 2.45 (s, 8H), 2.29 (s, 6H). C NMR (100 MHz, CDCl ) d
3
3
+
5
9
5.03, 45.95. MS (EI, 70 eV), m/z (rel abundance): 114(M , 99),
9(11), 71(65), 56(32), 43(100), 28(17).
1
DEReact ¼ ETs ꢁ EA + B ꢁ Ni
N-Methyl-diethanolamine. Yield 92%. H NMR (400 MHz,
3
CDCl ) d 4.50 (s, 2H), 3.76–3.49 (m, 4H), 2.64–2.38 (m, 4H), 2.29
where ETs is the energy of the transition state and EA + B ꢁ Ni is
the energy of A + B ꢁ Ni adsorption system.
1
3
(
3
s, 3H). C NMR (100 MHz, CDCl ) d 59.51, 58.92, 42.09. MS (EI,
+
70 eV), m/z (rel abundance): 119(M , 3), 88(100), 58(12), 44(91),
3
1(20).
1
N,N-Dimethylaniline. Yield 65%. H NMR (400 MHz, CDCl )
3
Acknowledgements
d 7.35–7.14 (m, 2H), 6.72 (dd, J ¼ 13.2, 7.6 Hz, 3H), 2.93 (s, 6H).
1
3
C NMR (100 MHz, CDCl ) d 150.72, 129.09, 116.68, 112.71,
3
The authors are grateful for the nancial support from the
Natural Science Foundation of China (21376213), the Research
Fund for the Doctoral Program of Higher Education of China
+
4
9
0.64. MS (EI, 70 eV), m/z (rel abundance): 120(M , 100), 104(18),
1(7), 77(30), 51(14), 42(9).
1
3
-Dimethylamino-phenol. Yield 21%. H NMR (400 MHz,
(20120101110062) and the Low Carbon Fatty Amine Engi-
CDCl
3
) d 7.07 (t, J ¼ 8.3 Hz, 1H), 6.37–6.29 (m, 1H), 6.24–6.17 (m,
neering Research Center of Zhejiang Province (2012E10033).
Shang Zhicai group is thanked for helping us with calculations.
13
2H), 2.88 (s, 6H). C NMR (100 MHz, CDCl
3
) d 156.67, 152.22,
1
30.01, 105.68, 104.12, 100.17, 40.72. MS (EI, 70 eV), m/z (rel
+
abundance): 136(M , 100), 121(15), 108(9), 94(13), 65(14), 39(7).
1
N,N-Dimethyl-1-phenylmethanamine. Yield 80%. H NMR
References
(
(
400 MHz, CDCl
s, 2H), 2.23 (s, 6H). C NMR (100 MHz, CDCl
3
) d 7.36–7.27 (m, 4H), 7.27–7.18 (m, 1H), 3.41
1
3
3
) d 138.88, 129.13,
1 A. Ricci, Modern Amination Methods, Wiley-VCH, New York,
1
1
3
28.25, 127.05, 64.44, 45.38. MS (EI, 70 eV), m/z (rel abundance):
35(M , 77), 118(9), 91(80), 77(7), 65(25), 58(100), 51(10), 42(25),
0(3).
2000.
+
2 D. A. Horton, G. T. Bourne and M. L. Smythe, Chem. Rev.,
2003, 103, 893–930.
43202 | RSC Adv., 2014, 4, 43195–43203
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