electronic supporting information hydrosilanes catalysed ... · methylation of secondary amines...
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Electronic Supporting Information
Methylation of secondary amines with dialkylcarbonates and hydrosilanes catalysed by iron complexes
Jianxia Zheng, Christophe Darcel* and Jean-Baptiste Sortais*
Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS-Universit Rennes 1,
Team Organometallics: Materials and Catalysis
Centre for Catalysis and Green Chemistry
Campus de Beaulieu, Ave Gnral Leclerc
35042 Rennes, France
Fax: (+)33 2 23 23 69 39
E-mail: [email protected], [email protected]
Electronic Supplementary Material (ESI) for ChemComm.This journal is The Royal Society of Chemistry 2014
mailto:[email protected]:[email protected]
I. General information.All reagents were obtained from commercial sources and used as received. All reactions were carried out with oven-dried glassware using standard Schlenk techniques under an inert atmosphere of dry argon. Toluene, THF, diethyl ether (Et2O), and CH2Cl2 were dried over Braun MB-SPS-800 solvent purification system. Technical grade pentane, diethyl ether were used for chromatography column. Analytical TLC was performed on Merck 60F254 silica gel plates (0.25 mm thickness). Column chromatography was performed on Acros Organics Ultrapure silica gel (mesh size 40-60 m, 60).
1H NMR spectra were recorded in CDCl3 at ambient temperature on Bruker AVANCE 400 spectrometers at 400.1 MHz, using the solvent as internal standard (CDCl3 7.26 ppm). 13C NMR spectra were obtained at 100.6 MHz and referenced to the internal solvent signals (CDCl3, central peak is 77.00 ppm). 19F NMR spectra were obtained at 376 MHz. Chemical shift () and coupling constants (J) are given in ppm and in Hz respectively. The peak patterns are indicated as follows: (s, singlet; d, doublet; t, triplet; q, quartet; quin, quintet; m, multiplet, and br. for broad).
GCMS were measured by GCMS-QP2010S (Shimadzu) with GC-2010 equipped with a 30-m capillary column (Supelco, SLBTM-5ms, fused silica capillary column, 30 M 0.25 mm 0.25 mm film thickness), which was used with helium as vector gas. The following GC-MS conditions were used: Initial temperature 100 C, for 2 minutes, then rate 10 C/min. until 250 C and 250 C for 10 minutes.
Fe(CO)5, Fe2(CO)9 were purchased from commercial supply, Stream and used as received. All the well-defined iron complexes were prepared as described in the literature: [CpFe(CO)2(IMes)][I][1], [CpFe(CO)2(PCy)3][I][2], [CpFe(CO)2(PCy)3][PF6][2], [CpFe(CO)2(PCy)3][BF4][3], Fe(CO)4(IMes) [4].
II. General procedures for the iron-catalyzed methylation reactionsA 20 mL oven dried Schlenk tube, containing a stirring bar, was charged with [CpFe(CO)2(IMes)]I (12 mg, 0.025 mmol). After purging with argon (argon-vacuum three cycles), dimethyl carbonate or diethyl carbonate (1.5 mL) was added followed by amine (0.5 mmol) and PhSiH3 (309 L, 2.5 mmol). The reaction mixture was stirred at 100 oC for 24 h or 48 h under visible light irradiation (24 Watt compact fluorescent lamp). At the end of the reaction, the crude reaction mixture was filtered through a plug of silica gel with CH2Cl2 as an eluent. The filtrate was evaporated and then analyzed by 1H NMR using 1,3,5-trimethoxybenzene or pyridine as internal standard to determine the yield. The residue was purified by silica gel column chromatography using diethyl ether-pentane mixture as the eluent to achieve the desired product.
III Optimization III.1 Optimization table for the silane
HN N
5 mol% [CpFe(CO)2(IMes)]I
1mL DMC, 100 oC, 24h, hv
2 equiv. Silane
III.2 Table S1 : Competitive experimentsa
HN
3 (5 mol%)
DMC (1.5 mL)PhSiH3 (5 equiv.)
100 oC, 24h, hv
N+ functionalized
substrate1a 2a
reducedfunctionalized
substrate+
Entry Functionalized substrateYield of 2a (%)b Others observed products
1
Ph
O 30 100% PhCH(OH)CH3.
2
Ph O
O 31 17% Ph-(CH2)3-OH83% unreacted ester
3
Ph N
O < 5 62% PhCH2NMe2 38% unreacted amide
4 Ph CN 10 100% unreacted PhCN
5 Ph NO2 < 5 50% PhNH250% unreacted PhNO2.
67
88 100% unreacted 1-decene
a. 0.5 mmol of N-ethylaniline, 0.5 mmol competitive substrate, 5 mol% catalyst 3, 5 equiv. PhSiH3, 1.5 mL DMC, at 100 C for 24 h under visible light irradiation.b. Yield was determined by 1H NMR of the crude mixture after the evaporation of the solvent using 1,3,5-trimethoxybenzene
as internal standard.
Table S2: Supplementary catalytic results.a
HN N5 mol% [CpFe(CO)2(IMes)]I
100 oC, 24h, hv+ DMC + PhSiH3
Entry DMC PhSiH3 Yield (%)b1 42 L (1 equiv.) 5 equiv. 602 1.5 mL (36 equiv.) 2 equiv. 353 1.5 mL (36 equiv.) 4 equiv. 784 1.5mL (36 equiv.) 5 equiv. 96a. 0.5 mmol of N-ethylaniline, 5 mol% catalyst 3, at 100 C for 24 h under visible light irradiation.b. Yield was determined by 1H NMR of the crude mixture after the evaporation of the solvent using 1,3,5-trimethoxybenzene as internal standard.
Table S3: methylation of primary amines.
RNH2
3 (5 mol%)
DMC (1.5 mL)Silane (5 equiv.)
100 oC, 48h, hvR
NH
0.5 mmol
+R
N
8 1 2
Entry Functionalized substrates Yield of 1 (%)a Yield of 2 (%)a
1 R = Ph 10 (1e) 20 (2e)2 R = 4-(CH3O)-Ph 11 (1f) 11 (2f)3 R = PhCH2- 0 (1r) 8 (2r)
a. Yield was determined by 1H NMR of the crude mixture after the evaporation of the solvent using 1,3,5-trimethoxybenzene as internal standard and confirmed by GC/GC-MS.
IV. Characterization of the methylated products
N-Ethyl-N-methylaniline[5]
The compound was prepared as described in the general procedure (m
N
= 57 mg, 84% isolated yield). 1H NMR (400 MHz, CDCl3): 7.25-7.21 (m, 2H), 6.73-6.66 (m, 3H), 3.40 (q, J = 7.1, 2H), 2.91 (s, 3H), 1.12 (t, J = 7.1, 3H). 13C{1H} NMR (100 MHz, CDCl3): 149.1, 129.1(2C), 116.0, 112.4(2C), 46.8, 37.4, 11.2.
N-Ethyl-N-methyl-4-methylaniline
The compound was prepared as described in the general procedure
N
(m = 71 mg, 95% isolated yield). 1H NMR (400 MHz, CDCl3): 7.04 (d, J = 8.4, 2H), 6.66 (d, J = 8.4, 2H), 3.36 (q, J = 7.0, 2H), 2.87 (s, 3H), 2.25 (s, 3H), 1.10 (t, J = 7.0, 3H). 13C{1H} NMR (100 MHz, CDCl3): 147.2, 129.6(2C), 125.4, 113.0(2C), 47.1, 37.6, 20.2, 11.0. GC-MS: m/z (%) 149 (M+, 26), 134(100), 119(18), 105(3), 91(22), 77(6), 65(12), 51(5).N-Ethyl-N-methyl-2-methylaniline
The compound was prepared as described in the general procedure (m
N
= 59 mg, 79% isolated yield). 1H NMR (400 MHz, CDCl3): 7.18-7.13 (m, 2H), 7.05-7.03 (m, 1H), 6.97-6.93 (m, 1H), 2.91 (q, J = 7.1, 2H), 2.68 (s, 3H), 2.31 (s, 3H), 1.10 (t, J = 7.1, 3H). 13C{1H} NMR (100 MHz, CDCl3): 152.2, 133.1, 131.0, 126.2, 122.6, 119.8, 50.4, 40.9, 18.3, 12.8. GC-MS: m/z (%) 149 (M+, 22), 134(100), 118(20), 106(3), 91(22), 77(9), 65(16), 51(11).
N-Ethyl-N-methyl-3-methylaniline
The compound was prepared as described in the general procedure
N
(m = 45 mg, 60% isolated yield). 1H NMR (400 MHz, CDCl3): 7.14-7.10 (m, 1H), 6.55-6.51 (m, 3H), 3.38 (q, J = 7.1, 2H), 2.89 (s, 3H), 2.31 (s, 3H), 1.12 (t, J = 7.1, 3H). 13C{1H} NMR (100 MHz, CDCl3): 149.2, 138.8, 129.0, 117.0, 113.2, 109.7, 46.8, 37.5, 21.9, 11.2. GC-MS: m/z (%) 149 (M+, 28), 134(100), 119(14), 105(3), 91(23), 77(6), 65(13), 51(4).
N,N-Dimethylaniline[6]
The compound was prepared as described in the general procedure (m = N
45 mg, 75% isolated yield). 1H NMR (400 MHz, CDCl3): 7.27-7.24 (m, 2H), 6.76-6.71 (m, 3H), 2.95 (s, 6H). 13C{1H} NMR (100 MHz, CDCl3): 150.6, 129.0(2C), 116.6, 112.6(2C), 40.6(2C).
4-Methoxy-N,N-dimethylaniline[7]
The compound was prepared as described in the general procedure
N
MeO
(m = 55 mg, 72% isolated yield). 1H NMR (400 MHz, CDCl3): 6.86-6.82 (m, 2H), 6.77-6.73 (m, 2H), 3.76 (s, 3H), 2.87 (s, 6H). 13C{1H} NMR (100 MHz, CDCl3): 151.9, 145.7, 114.8(2C), 114.6(2C), 55.7, 41.8(2C).
4-Chloro-N,N-dimethylaniline[8]
The compound was prepared as described in the general procedure (m
N
Cl
= 78 mg, 98% isolated yield). 1H NMR (400 MHz, CDCl3): 7.19-7.15 (m, 2H), 6.66-6.62 (m, 2H), 2.93 (s, 6H). 13C{1H} NMR (100 MHz, CDCl3): 149.2, 128.8(2C), 121.4, 113.7(2C), 40.7.4-Fluoro-N,N-dimethylaniline(ZJX1775 redo After c)[9]
The compound was prepared as described in the general procedure (m NF
= 52 mg, 75% isolated yield). 1H NMR (400 MHz, CDCl3): 6.97-6.91 (m, 2H), 6.71-6.66 (m, 2H), 2.90 (s, 6H). 13C{1H} NMR (100 MHz, CDCl3): 155.6 (d, JC-F = 235.2), 147.5 (d, JC-F = 1.7), 115.3 (d, JC-F = 22.0, 2C), 113.9 (d, JC-F = 7.3, 2C), 41.3. 19F NMR (376 MHz. CDCl3): -129.0.
N,N-Dimethyl-4-(trifluoromethyl)aniline[10]
The compound was prepared as described in the general procedure NF3C
(m = 71 mg, 75% isolated yield). 1H NMR (400 MHz, CDCl3): 7.45 (d, J = 8.8, 2H), 6.70 (d, J = 8.8, 2H), 3.01 (s, 6H). 13C{1H} NMR (100 MHz, CDCl3): 152.3, 125.2 (q, JC-F = 270.0), 126.3 (q, JC-F = 3.8), 117.4 (q, JC-F = 32.6), 111.1, 40.0(2C). 19F NMR (376 MHz. CDCl3): -60.8.
N-Methyl-N-propylaniline[11]
The compound was prepared as described in the general procedure
N
(m = 40 mg, 54% isolated yield). 1H NMR (400 MHz, CDCl3): 7.24-7.20 (m, 2H), 6.71-6.65 (m, 3H), 3.27 (t, J = 7.4, 2H), 2.93 (s, 3H), 1.61 (m, 2H), 0.92 (t, J = 7.4, 3H). 13C{1H} NMR (100 MHz, CDCl3): 149.4, 129.1(2C), 115.7, 112.0(2C), 54.5, 38.3, 19.9, 11.5.
N-Benzyl-N-methylaniline[8]
The compound was prepared as described in the general
N
procedure (m = 85 mg, 86% isolated yield). 1H NMR (400 MHz, CDCl3): 7.32-7.30 (m, 2H), 7.25-7.20 (m, 5H), 6.77-6.70 (m, 3H), 4.54 (s, 2H), 3.02 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3): 149.7, 139.0, 129.1(2C), 128.5(2C), 126.8, 126.7(2C), 116.5, 112.3(2C), 56.6, 38.4.
N-Methyl-N-phenylaniline[12]
The compound was prepared as described in the general procedure
N
(m = 79 mg, 86% isolated yield). 1H NMR (400 MHz, CDCl3): 7.30-7.26 (m, 4H), 7.04-7.02 (m, 4H), 6.98-6.94 (m, 2H), 3.32 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3): 149.0(2C), 129.2(4C), 121.2(2C), 120.4(4C), 40.2.
N-Benzyl-2-bromo-N-methylaniline[13]
The compound was prepared as described in the general procedure
NBr
(m = 89 mg, 64% isolated yield). 1H NMR (400 MHz, CDCl3): 7.59-7.57 (m, 1H), 7.24-7.20 (m, 3H), 7.14-7.10 (m, 2H), 6.74-6.66 (m, 3H), 4.55 (s, 2H), 3.09 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3): 149.1, 137.3, 132.8, 129.2(2C), 128.3, 127.8, 127.5, 122.7, 116.6, 111.9(2C), 57.3, 38.7.
N-Benzyl-N-methyl-1-phenylmethanamine[14]
The compound was prepared as described in the general N
procedure (m = 60 mg, 57% isolated yield). 1H NMR (400 MHz, CDCl3): 7.38-7.22 (m, 10H), 3.53 (s, 4H), 2.19 (s, 4H). 13C{1H} NMR (100 MHz, CDCl3): 139.3(2C), 128.9(4C), 1281.2(4C), 126.9(2C), 61.8(2C), 42.2.
1-Methyl-1,2,3,4-tetrahydroquinoline[15]
The compound was prepared as described in the general procedure (m = N
44 mg, 60% isolated yield). 1H NMR (400 MHz, CDCl3): 7.09-7.05 (m, 1H), 6.96-6.94 (m, 1H), 6.62-6.58 (m, 2H), 3.22 (t, J = 5.6, 2H), 2.88 (s, 3H), 2.77 (t, J = 6.4, 2H), 1.98 (m, 2H). 13C{1H} NMR (100 MHz, CDCl3): 146.7, 128.8, 127.0, 122.8, 116.2, 110.9, 51.2, 39.1, 27.8, 22.4.
1-Methylindoline[8]
The compound was prepared as described in the general procedure (m = N
41 mg, 61% isolated yield). 1H NMR (400 MHz, CDCl3): 7.10-7.07 (m, 2H), 6.99-6.95 (m, 1H), 6.50-6.48 (m, 1H), 3.29 (t, J = 8.1, 2H), 2.94 (t, J = 8.1, 2H), 2.76 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3): 153.4, 130.3, 127.3, 124.2, 117.7, 107.2, 56.1, 36.2, 28.7.
N-methyl-N-octyloctan-1-amine[16]
The compound was prepared as described in the general procedure N
6 6
(m = 84 mg, 66% isolated yield). 1H NMR (400 MHz, CDCl3): 2.31-2.27 (m, 4H),.20 (s, 3H), 1.48-1.27 (m, 26H), 0.88 (t, J = 6.8, 3H). 13C{1H} NMR (100 MHz, CDCl3): 58.0(2C), 42.4, 31.8(2C), 29.6(2C), 29.3(2C), 27.6(2C), 27.3(2C), 22.6(2C), 14.1(2C).
V. References[1] P. Buchgraber, L. Toupet and V. Guerchais, Organometallics 2003, 22, 5144.[2] J. Zheng, L. C. Misal Castro, T. Roisnel, C Darcel and J.-B. Sortais, Inorg. Chim.
Acta., 2012, 380, 301.[3] D. Bzier, G. T. Venkanna, L. C. Misal Castro, J Zheng,T. Roisnel, J.-B. Sortais
and C. Darcel, Adv. Synth. Catal., 2012, 354, 1879.[4] H. Li, L. C. Misal Castro, J. Zheng, T. Roisnel, V. Dorcet, J.-B. Sortais and C.
Darcel, Angew. Chem. Int. Ed., 2013, 52, 8045.[5] K. Selvakumar, K. Rangareddy and J. F. Harrod, Can. J. Chem., 2004, 82, 1244.[6] A. Modak, A. Deb, T. Patra, S. Rana, S. Maity and D. Maiti, Chem. Commun.,
2012, 48, 4253.[7] S. Sato and H. Nakamura, Angew. Chem. Int. Ed., 2013, 52, 8681.[8] Y. Li, X. Fang, K. Junge and M. Beller, Angew. Chem. Int. Ed., 2013, 52, 9568.[9] L.-T. Li, H.-Y. Li, L.J. Xing, L.-J. Wen, P. Wang and B. Wang, Org. Biomol. Chem.,
2012, 10, 9519.[10] S. Seo, J.B. Taylorb and M. F. Greaney, Chem. Commun., 2013, 49, 6385.[11] R. A. Totah and R. P. Hanzlik, Biochemistry, 2004, 43, 7907.[12] M. Al-Amin, S. Arai, N. Hoshiya, T. Honma, Y. Tamenori, T. Sato, M. Yokoyama,
A. Ishii, M. Takeuchi, T. Maruko, S. Shuto and M. Arisawa, J. Org. Chem., 2013, 78, 7575.
[13] D. Sustac Roman, Y. Takahashi and A. B. Charette, Org. Lett., 2011, 13, 3242.[14] Q. Lei, Y.Wei, D. Talwar, C. Wang, D. Xue and J. Xiao, Chem. Eur. J., 2013, 19, 4021.
[15] C. L. Shaffer, M. D. Morton and R. P. Hanzlik. J. Am. Chem. Soc., 2001, 123, 8502.
[16] P. H. Toy, T. S. Reger and K. D. Janda, Org. Lett., 2000, 2, 2205.
N-Ethyl-N-methylaniline
ppm (f1)0.05.010.0
0
5000
10000
15000
7.26
07.
248
7.23
07.
226
7.20
8
6.73
46.
714
6.70
16.
683
6.66
5
3.42
83.
411
3.39
33.
375
2.90
6
1.14
01.
123
1.10
5
2.07
3.00
3.00
3.03
2.02
Frequency (MHz):(f1) 400.162 Original Points Count:(f1) 32768 Actual Points Count:(f1) 65536 Acquisition Time (sec):(f1) 3.9846 Spectral Width (ppm):(f1) 20.551 Pulse Program:ZG30Temperature:299.1204Number of Scans:16
ppm (f1)050100150
0
5000
10000
15000149.
137
129.
137
116.
020
112.
392
77.3
1777
.000
76.6
83
46.7
97
37.4
14
11.1
97 Frequency (MHz):(f1) 100.630 Original Points Count:(f1) 32768 Actual Points Count:(f1) 65536 Acquisition Time (sec):(f1) 1.3631 Spectral Width (ppm):(f1) 238.879 Pulse Program:ZGPG30Temperature:299.1165Number of Scans:800
N-Ethyl-N-methyl-4-methylaniline
ppm (f1)0.05.010.0
0
5000
10000
7.26
07.
053
7.03
2
6.67
36.
652
3.39
03.
372
3.35
43.
337
2.86
8
2.25
2
1.11
71.
099
1.08
2
1.94
1.90
2.04
2.96
3.06
3.06
Frequency (MHz):(f1) 400.162 Original Points Count:(f1) 32768 Actual Points Count:(f1) 65536 Acquisition Time (sec):(f1) 3.9846 Spectral Width (ppm):(f1) 20.551 Pulse Program:ZG30Temperature:299.1152Number of Scans:16
ppm (f1)050100150
0
5000
10000
15000
147.
171
129.
641
125.
432
112.
986
77.3
1777
.000
76.6
82
47.1
27
37.6
43
20.1
88
11.0
15 Frequency (MHz):(f1) 100.630 Original Points Count:(f1) 32768 Actual Points Count:(f1) 65536 Acquisition Time (sec):(f1) 1.3631 Spectral Width (ppm):(f1) 238.879 Pulse Program:ZGPG30Temperature:299.1328Number of Scans:512
N-Ethyl-N-methyl-2-methylaniline
ppm (f1)0.05.010.0
0
5000
10000
15000
200007.
260
7.17
87.
171
7.16
07.
152
7.13
3
7.04
87.
029
6.97
06.
968
6.95
26.
933
6.93
2
2.94
02.
922
2.90
42.
886
2.67
6
2.30
6
1.11
51.
098
1.08
0
1.991.031.00
3.04
2.023.06
3.00
Frequency (MHz):(f1) 400.162 Original Points Count:(f1) 32768 Actual Points Count:(f1) 65536 Acquisition Time (sec):(f1) 3.9846 Spectral Width (ppm):(f1) 20.551 Pulse Program:ZG30Temperature:299.0905Number of Scans:16
ppm (f1)050100150
0
5000
10000
15000
152.
196
133.
101
130.
981
126.
202
122.
626
119.
763
77.3
1777
.000
76.6
83
50.4
30
40.8
67
18.2
7012
.808 Frequency (MHz):
(f1) 100.630 Original Points Count:(f1) 32768 Actual Points Count:(f1) 65536 Acquisition Time (sec):(f1) 1.3631 Spectral Width (ppm):(f1) 238.879 Pulse Program:ZGPG30Temperature:299.1197Number of Scans:512
N-Ethyl-N-methyl-3-methylaniline
ppm (f1)0.05.010.0
-1000
0
1000
2000
3000
4000
5000
6000
7000
8000
7.26
0
7.13
67.
115
7.09
66.
550
6.53
56.
507
3.41
23.
394
3.37
63.
359
2.89
32.
314
1.13
41.
116
1.09
8
0.91
2.91
2.05
3.00
3.09
3.08
Frequency (MHz):(f1) 400.162 Original Points Count:(f1) 32768 Actual Points Count:(f1) 65536 Acquisition Time (sec):(f1) 3.9846 Spectral Width (ppm):(f1) 20.551 Pulse Program:ZG30Temperature:299.1208Number of Scans:16
ppm (f1)050100150
0
5000
149.
209
138.
758
128.
988
117.
022
113.
172
109.
658
77.3
1877
.000
76.6
82
46.8
23
37.4
58
21.9
20
11.2
43 Frequency (MHz):(f1) 100.630 Original Points Count:(f1) 32768 Actual Points Count:(f1) 65536 Acquisition Time (sec):(f1) 1.3631 Spectral Width (ppm):(f1) 238.879 Pulse Program:ZGPG30Temperature:299.1311Number of Scans:512
N,N-Dimethylaniline
ppm (f1)0.05.010.0
0
5000
100007.
267
7.26
07.
249
7.24
5
6.76
26.
742
6.72
56.
706
2.94
7
5.97
3.00
4.96
Frequency (MHz):(f1) 400.162 Original Points Count:(f1) 32768 Actual Points Count:(f1) 65536 Acquisition Time (sec):(f1) 3.9846 Spectral Width (ppm):(f1) 20.551 Pulse Program:ZG30Temperature:307.0851Number of Scans:8
ppm (f1)050100150
0
5000
10000
150.
632
129.
035
116.
610
112.
640
77.3
1877
.000
76.6
83
40.6
05 Frequency (MHz):(f1) 100.630 Original Points Count:(f1) 32768 Actual Points Count:(f1) 65536 Acquisition Time (sec):(f1) 1.3631 Spectral Width (ppm):(f1) 238.879 Pulse Program:ZGPG30Temperature:308.9454Number of Scans:256
4-Methoxy-N,N-dimethylaniline
ppm (f1)0.05.010.0
0
5000
10000
15000
20000
25000
7.26
06.
865
6.85
66.
851
6.83
96.
834
6.82
56.
775
6.76
66.
760
6.74
96.
743
6.73
4
3.76
5
2.86
6
1.922.00
2.97
5.96
Frequency (MHz):(f1) 400.162 Original Points Count:(f1) 32768 Actual Points Count:(f1) 65536 Acquisition Time (sec):(f1) 3.9846 Spectral Width (ppm):(f1) 20.551 Pulse Program:ZG30Temperature:299.0779Number of Scans:16
ppm (f1)050100150
0
5000
10000
15000
20000
25000
30000
35000
151.
947
145.
743
114.
866
114.
590
77.3
1877
.000
76.6
82
55.7
13
41.7
86 Frequency (MHz):(f1) 100.630 Original Points Count:(f1) 32768 Actual Points Count:(f1) 65536 Acquisition Time (sec):(f1) 1.3631 Spectral Width (ppm):(f1) 238.879 Pulse Program:ZGPG30Temperature:307.7891Number of Scans:512
4-Chloro-N,N-dimethylaniline
ppm (f1)0.05.010.0
0
10000
20000
30000
40000
7.26
07.
190
7.18
17.
176
7.16
47.
158
7.15
0
6.65
86.
649
6.64
46.
627
6.61
8
2.92
6
1.96
2.00
6.03
Frequency (MHz):(f1) 400.162 Original Points Count:(f1) 32768 Actual Points Count:(f1) 65536 Acquisition Time (sec):(f1) 3.9846 Spectral Width (ppm):(f1) 20.551 Pulse Program:ZG30Temperature:299.1163Number of Scans:16
ppm (f1)050100150
0
10000
20000
30000
149.
147
128.
759
121.
377
113.
601
77.3
1877
.000
76.6
83
40.6
24 Frequency (MHz):(f1) 100.630 Original Points Count:(f1) 32768 Actual Points Count:(f1) 65536 Acquisition Time (sec):(f1) 1.3631 Spectral Width (ppm):(f1) 238.879 Pulse Program:ZGPG30Temperature:299.1245Number of Scans:512
4-Fluoro-N,N-dimethylaniline
ppm (f1)0.05.010.0
-10000
0
10000
20000
30000
40000
50000
600007.
260
6.97
76.
967
6.96
16.
956
6.94
56.
923
6.91
46.
709
6.69
96.
693
6.68
86.
682
6.67
66.
672
6.66
56.
656
2.90
1
1.962.00
6.08
Frequency (MHz):(f1) 400.162 Original Points Count:(f1) 32768 Actual Points Count:(f1) 65536 Acquisition Time (sec):(f1) 3.9846 Spectral Width (ppm):(f1) 20.551 Pulse Program:ZG30Temperature:299.1177Number of Scans:16
ppm (f1)50100150200
0
5000
10000
15000
20000
156.
758
154.
420
147.
503
147.
487
115.
447
115.
229
113.
961
113.
888
77.3
1777
.000
76.6
82
41.3
47 Frequency (MHz):(f1) 100.631 Original Points Count:(f1) 32768 Actual Points Count:(f1) 65536 Acquisition Time (sec):(f1) 1.2583 Spectral Width (ppm):(f1) 258.783 Pulse Program:ZGPG30Temperature:299.1181Number of Scans:1024
ppm (f1)-200-150-100-500
0
500
1000
-129
.052
Frequency (MHz):(f1) 376.489 Original Points Count:(f1) 65536 Actual Points Count:(f1) 131072 Acquisition Time (sec):(f1) 0.5767 Spectral Width (ppm):(f1) 301.832 Pulse Program:ZGFLQNTemperature:299.1196Number of Scans:16
N,N-Dimethyl-4-(trifluoromethyl)aniline
ppm (f1)0.05.010.0
-5000
0
5000
10000
15000
20000
25000
300007.46
57.
443
7.26
06.
711
6.68
9
3.01
4
1.94
2.00
6.04
Frequency (MHz):(f1) 400.162 Original Points Count:(f1) 32768 Actual Points Count:(f1) 65536 Acquisition Time (sec):(f1) 3.9846 Spectral Width (ppm):(f1) 20.551 Pulse Program:ZG30Temperature:299.0996Number of Scans:8
ppm (f1)050100150
0
10000
20000
30000
40000
152.
281
129.
233
126.
550
126.
337
126.
299
126.
262
126.
224
123.
866
121.
182
117.
934
117.
610
117.
286
116.
962
111.
121
77.3
1877
.000
76.6
82
40.0
50 Frequency (MHz):(f1) 100.631 Original Points Count:(f1) 32768 Actual Points Count:(f1) 65536 Acquisition Time (sec):(f1) 1.2583 Spectral Width (ppm):(f1) 258.783 Pulse Program:ZGPG30Temperature:299.096Number of Scans:1024
ppm (f1)-200-150-100-500
0
50000
100000
150000
200000
250000
300000-60.
795
Frequency (MHz):(f1) 376.489 Original Points Count:(f1) 65536 Actual Points Count:(f1) 131072 Acquisition Time (sec):(f1) 0.7340 Spectral Width (ppm):(f1) 237.154 Pulse Program:ZGFLQNTemperature:299.1309Number of Scans:16
N-Methyl-N-propylaniline
ppm (f1)0.05.010.0
0
5000
10000
7.26
07.
240
7.22
27.
218
7.20
0
6.70
76.
686
6.66
66.
648
3.28
83.
270
3.25
12.
929
1.65
11.
633
1.61
41.
595
1.57
71.
558
0.94
30.
924
0.90
63.00
1.962.97
3.02
1.99
2.02
Frequency (MHz):(f1) 400.162 Original Points Count:(f1) 32768 Actual Points Count:(f1) 65536 Acquisition Time (sec):(f1) 3.9846 Spectral Width (ppm):(f1) 20.551 Pulse Program:ZG30Temperature:308.3398Number of Scans:16
ppm (f1)050100150
0
5000
10000
15000
149.
392
129.
091
115.
756
112.
026
77.3
1777
.000
76.6
82
54.5
36
38.2
98
19.9
23
11.5
09 Frequency (MHz):(f1) 100.630 Original Points Count:(f1) 32768 Actual Points Count:(f1) 65536 Acquisition Time (sec):(f1) 1.3631 Spectral Width (ppm):(f1) 238.879 Pulse Program:ZGPG30Temperature:308.6516Number of Scans:512
N-Methyl-N-phenylaniline
ppm (f1)0.05.010.0
0
5000
10000
15000
200007.
296
7.27
87.
275
7.26
0
7.03
77.
037
7.01
86.
976
6.95
86.
940
3.32
13.07
4.002.036.19
Frequency (MHz):(f1) 400.162 Original Points Count:(f1) 32768 Actual Points Count:(f1) 65536 Acquisition Time (sec):(f1) 3.9846 Spectral Width (ppm):(f1) 20.551 Pulse Program:ZG30Temperature:299.1177Number of Scans:16
ppm (f1)050100150
0
5000
10000
15000
149.
020
129.
160
121.
230
120.
424
77.3
1777
.000
76.6
83
40.2
18 Frequency (MHz):(f1) 100.631 Original Points Count:(f1) 32768 Actual Points Count:(f1) 65536 Acquisition Time (sec):(f1) 1.2583 Spectral Width (ppm):(f1) 258.783 Pulse Program:ZGPG30Temperature:299.1333Number of Scans:800
N-Benzyl-N-methylaniline
ppm (f1)0.05.010.0
0
5000
10000
15000
20000
7.31
87.
301
7.26
07.
248
7.24
57.
227
7.20
56.
771
6.75
16.
735
6.71
76.
698
4.54
2
3.02
2
2.06
3.00
3.06
1.914.93
Spectrum Title:
Frequency (MHz):(f1) 400.162 Original Points Count:(f1) 32768 Actual Points Count:(f1) 65536 Acquisition Time (sec):(f1) 3.9846 Spectral Width (ppm):(f1) 20.551 Pulse Program:ZG30Temperature:299.1243Number of Scans:16
ppm (f1)050100150
0
5000
10000
15000
20000
25000
30000
35000
149.
721
138.
993
129.
131
128.
509
126.
806
126.
696
116.
498
112.
328
77.3
1877
.000
76.6
82
56.5
91
38.4
48 Frequency (MHz):(f1) 100.630 Original Points Count:(f1) 32768 Actual Points Count:(f1) 65536 Acquisition Time (sec):(f1) 1.3631 Spectral Width (ppm):(f1) 238.879 Pulse Program:ZGPG30Temperature:299.1289Number of Scans:512
N-Benzyl-2-bromo-N-methylaniline
ppm (f1)0.05.010.0
-1000
0
1000
2000
3000
4000
5000
6000
70007.5
887.
570
7.56
87.
260
7.23
97.
221
7.20
27.
199
7.14
97.
140
7.13
47.
121
7.10
37.
099
6.73
86.
720
6.70
26.
678
6.65
84.
546
3.09
4
2.06
3.05
1.03
3.00
2.013.07
Frequency (MHz):(f1) 400.162 Original Points Count:(f1) 32768 Actual Points Count:(f1) 65536 Acquisition Time (sec):(f1) 3.9846 Spectral Width (ppm):(f1) 20.551 Pulse Program:ZG30Temperature:299.12Number of Scans:8
* H2O
ppm (f1)050100150
0
5000
10000
15000
20000
149.
154
137.
330
132.
766
129.
192
128.
323
127.
857
127.
483
122.
690
116.
584
111.
907
77.3
1877
.000
76.6
82
57.3
38
38.7
17 Frequency (MHz):(f1) 100.631 Original Points Count:(f1) 32768 Actual Points Count:(f1) 65536 Acquisition Time (sec):(f1) 1.2583 Spectral Width (ppm):(f1) 258.783 Pulse Program:ZGPG30Temperature:299.1229Number of Scans:1024
N-Benzyl-N-methyl-1-phenylmethanamine
ppm (f1)0.05.010.0
0
5000
10000
150007.
376
7.35
87.
358
7.33
87.
320
7.30
17.
260
7.24
37.
225
3.52
4
2.18
6
4.00
3.05
13.50
Frequency (MHz):(f1) 400.162 Original Points Count:(f1) 32768 Actual Points Count:(f1) 65536 Acquisition Time (sec):(f1) 3.9846 Spectral Width (ppm):(f1) 20.551 Pulse Program:ZG30Temperature:307.4398Number of Scans:16
ppm (f1)050100150
-10000
0
10000
20000
30000
40000
50000
60000
70000
80000
139.
293
128.
885
128.
176
126.
880
77.3
1877
.000
76.6
82
61.8
36
42.2
11 Frequency (MHz):(f1) 100.630 Original Points Count:(f1) 32768 Actual Points Count:(f1) 65536 Acquisition Time (sec):(f1) 1.3631 Spectral Width (ppm):(f1) 238.879 Pulse Program:ZGPG30Temperature:308.6099Number of Scans:512
1-Methyl-1,2,3,4-tetrahydroquinoline
ppm (f1)0.05.010.0
0
5000
100007.
260
7.09
27.
072
7.05
3
6.96
16.
943
6.62
16.
604
6.58
5
3.23
13.
217
3.20
32.
883
2.78
52.
769
2.75
3
2.01
41.
998
1.98
41.
969
1.95
31.
542
1.020.99
1.93
1.982.942.00
2.05
Frequency (MHz):(f1) 400.162 Original Points Count:(f1) 32768 Actual Points Count:(f1) 65536 Acquisition Time (sec):(f1) 3.9846 Spectral Width (ppm):(f1) 20.551 Pulse Program:ZG30Temperature:299.3297Number of Scans:16
*H2O
ppm (f1)050100150
0
5000
10000
146.
714
128.
773
127.
005
122.
819
116.
154
110.
915
77.3
1877
.000
76.6
82
51.2
49
39.0
93
27.7
6622
.436 Frequency (MHz):
(f1) 100.630 Original Points Count:(f1) 32768 Actual Points Count:(f1) 65536 Acquisition Time (sec):(f1) 1.3631 Spectral Width (ppm):(f1) 238.879 Pulse Program:ZGPG30Temperature:299.9301Number of Scans:512
1-Methylindoline
ppm (f1)0.05.010.0
0
5000
10000
15000
7.26
07.
104
7.09
27.
086
7.07
77.
074
7.06
8
6.69
06.
672
6.65
46.
503
6.48
3
3.31
13.
291
3.27
02.
965
2.94
52.
925
2.76
0
2.01
1.051.00
2.00
2.043.02
Frequency (MHz):(f1) 400.162 Original Points Count:(f1) 32768 Actual Points Count:(f1) 65536 Acquisition Time (sec):(f1) 3.9846 Spectral Width (ppm):(f1) 20.551 Pulse Program:ZG30Temperature:307.9774Number of Scans:16
ppm (f1)050100150
0
5000
10000
153.
367
130.
257
127.
273
124.
219
117.
719
107.
178
77.3
1777
.000
76.6
82
56.1
30
36.2
46
28.7
18 Frequency (MHz):(f1) 100.630 Original Points Count:(f1) 32768 Actual Points Count:(f1) 65536 Acquisition Time (sec):(f1) 1.3631 Spectral Width (ppm):(f1) 238.879 Pulse Program:ZGPG30Temperature:308.5442Number of Scans:512
N-Methyl-N-octyloctan-1-amine
ppm (f1)0.05.010.0
0
1000
2000
3000
4000
5000
7.26
0
2.30
82.
290
2.27
02.
195
1.48
21.
463
1.45
91.
445
1.43
11.
274
0.89
40.
878
0.86
0
6.01
3.973.00
24.03
Frequency (MHz):(f1) 400.162 Original Points Count:(f1) 32768 Actual Points Count:(f1) 65536 Acquisition Time (sec):(f1) 3.9846 Spectral Width (ppm):(f1) 20.551 Pulse Program:ZG30Temperature:307.4061Number of Scans:8
ppm (f1)010203040506070
-5000
0
5000
10000
15000
20000
25000
30000
35000
77.3
1877
.000
76.6
83
57.9
59
42.3
60
31.8
4429
.589
29.2
8527
.637
27.3
5822
.646
14.0
64 Frequency (MHz):(f1) 100.630 Original Points Count:(f1) 32768 Actual Points Count:(f1) 65536 Acquisition Time (sec):(f1) 1.3631 Spectral Width (ppm):(f1) 238.879 Pulse Program:ZGPG30Temperature:308.4551Number of Scans:512