Electronic Supporting Information hydrosilanes catalysed ... · Methylation of secondary amines with dialkylcarbonates and hydrosilanes catalysed by iron complexes Jianxia Zheng,

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


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

(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]


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]


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]


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]


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]


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]


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]


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


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


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



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


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


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


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


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


ppm (f1)050100150

0

5000

10000

150.

632

129.

035

116.

610

112.

640

77.3

1877

.000

76.6

83

40.6


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


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


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


ppm (f1)050100150

0

10000

20000

30000

149.

147

128.

759

121.

377

113.

601

77.3

1877

.000

76.6

83

40.6


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


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


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


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


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


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


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


ppm (f1)050100150

0

5000

10000

15000

149.

020

129.

160

121.

230

120.

424

77.3

1777

.000

76.6

83

40.2


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:


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


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


* 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


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


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


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


*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


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


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


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


Electronic Supporting Information hydrosilanes catalysed ... · Methylation of secondary amines with dialkylcarbonates and hydrosilanes catalysed by iron complexes Jianxia Zheng,

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