Electronic Supplementary Material (ESI) for RSC Advances.
This journal is © The Royal Society of Chemistry 2015
Supporting Information
Multiple Deuteration of Alkanes Synergistically-Catalyzed
by Platinum and Rhodium on Carbon
as a Mixed Catalytic System
Tsuyoshi Yamada,† Yoshinari Sawama,*† Kyoshiro Shibata,† Kosuke Morita, †
Yasunari Monguchi† and Hironao Sajiki*†
†
Laboratory of Organic Chemistry, Gifu Pharmaceutical University, 1-25-4
Daigaku-nishi, Gifu 501-1196, Japan
Contents
1. General
2. Procedures for Pt/C and Rh/C-catalyzed multi-deuteration of alkanes
3. Spectroscopic data of multi-deuterated alkanes
4. 1H and 2H NMR spectra of multi-deuterated alkanes
1. General
10% Pt/C catalyst was obtained from N.E. Chemcat Corporation, Japan. 5% Rh/C
catalyst was purchased from the Aldrich Chemical Co. D2O (>99.9% D atom) was
purchased from Spectra Gases, Inc. i-PrOD-d8 (>99.5% D atom) was purchased from
the Aldrich Chemical Co. All other reagents were purchased from commercial sources
and used without further purification. 1H and 2H NMR spectra were recorded by a JEOL
AL-400, EX-400 (1H: 400 MHz) or ECA-500 spectrometer (1H: 500 MHz, 2H: 61 MHz).
Chemical shifts (δ) are expressed in ppm and are internally referenced (7.26 ppm for
CDCl3 for 1H and 2H NMR or 7.16 ppm for benzene-d6 for 1H and 2H NMR). All H-D
exchange reactions were carried out using a 6 mL stainless-steel sealed tube. The
deuterium contents were determined by the 1H NMR using 1,4-dioxane as the internal
standard as a value of integral. The deuterium incorporation was also assigned by the 2H
NMR.
S1
2. Procedures for Pt/C and Rh/C-catalyzed multi-deuteration of
alkanes
2-1. Typical procedure for Pt/C and Rh/C-catalyzed multi-deuteration of alkanes
(Table 1 and Table 2, entries 1-2, 4-7 and 9)
A suspension of an alkane (0.25mmol), 10% Pt/C (15 mol%) and 5% Rh/C (15 mol%)
in i-PrOD-d8 (0.5 mL) and D2O (2 mL) in a 6 mL stainless-steel sealed tube was stirred
at 120 °C under atmospheric conditions. After stirring for 24 h, the mixture was cooled
to room temperature and filtered by a membrane filter (Milipore, Millex®-LH, 0.2 µm)
to remove the catalysts. The filtrate was extracted with Et2O (20 mL) and H2O (20 mL),
and then the aqueous layer was further extracted with Et2O (10 mL x 3). The combined
organic layers were dried over anhydrous MgSO4, filtrated and concentrated in vacuo to
give the deuterated product.
2-2. Procedure for Pt/C and Rh/C-catalyzed multi-deuteration of alkane (Table 2.
entry 3)
A suspension of an alkane (0.125 mmol), 10% Pt/C (30 mol%) and 5% Rh/C (30 mol%)
in i-PrOD-d8 (0.5 mL) and D2O (2 mL) in a 6 mL stainless-steel sealed tube was stirred
at 120 °C under atmospheric conditions. After stirring for 24 h, the mixture was cooled
to room temperature and filtered by a membrane filter (Milipore, Millex®-LH, 0.2 µm)
to remove the catalysts. The filtrate was extracted with hexane (20 mL) and H2O (20
mL), and then the aqueous layer was further extracted with hexane (10 mL x 3). The
combined organic layers were dried over anhydrous MgSO4, filtrated and concentrated
in vacuo to give the deuterated product.
2-3. Procedure for Pt/C and Rh/C-catalyzed multi-deuteration of alkane (Table 2.
entry 8)
A suspension of an alkane (0.125 mmol), 10% Pt/C (30 mol%) and 5% Rh/C (30 mol%) in
i-PrOD-d8 (0.5 mL), D2O (2 mL) and cyclohexane (0.1 mL) in a 6 mL stainless-steel
sealed tube was stirred at 120 °C under atmospheric conditions. After stirring for 24 h,
the mixture was cooled to room temperature and filtered by a membrane filter (Milipore,
Millex®-LH, 0.2 µm) to remove the catalysts. The filtrate was extracted with hexane (20
mL : Table 2, entries 3 and 9) and H2O (20 mL), and then the aqueous layer was further
extracted with hexane (10 mL x 3). The combined organic layers were dried over
anhydrous MgSO4, filtrated and concentrated in vacuo to give the deuterated product.
S2
3. Spectroscopic data of multi-deuterated alkanes
n-Dodecane-d26 (Table 1, entry 5) : 100% (49.1 mg, 250 μmol) as a colorless oil, 1H
NMR (500 MHz, CDCl3): δ 1.24–1.18 (m, 1.26H), 0.80 (m, 0.27H); 2H NMR
(61 MHz, CHCl3): δ 1.20 (brs), 0.83 (brs).
n-Pentadecane-d32 (Table 2, entry 1) : 92% (56.9 mg, 230 μmol) as a colorless oil, 1H
NMR (400 MHz, CDCl3): δ 1.24–1.17 (m, 1.52H), 0.81 (m, 0.15H); 2H NMR
(61 MHz, CHCl3): δ 1.20 (brs), 0.83 (brs).
n-Eicosane-d42 (Table 2, entry 2) : 95% (77.4 mg, 238 μmol) as a colorless oil, 1H
NMR (500 MHz, Benzene-d6): δ 1.28–1.50 (m, 1.17H), 0.86 (m, 0.32H); 2H
NMR (61 MHz, Benzene): δ 1.20 (brs), 0.82 (brs).
n-Hexatriacontane-d74 (Table 2, entry 3) : 69% (49.3 mg, 86 μmol) as a colorless oil,
1H
NMR (500 MHz, CDCl3): δ 1.19–1.25 (m, 6.66H), 0.86 (m, 1.35H); 2H NMR
(61 MHz, CHCl3): δ 1.20 (brs), 0.83 (brs).
n-Hexatriacontane-d74 (Table 2, entry 3c) : 69% (62.6 mg, 86 μmol) as a colorless oil,
1H
NMR (500 MHz, CDCl3): δ 1.19–1.25 (m, 8.26H), 0.82–0.89 (m, 0.68H); 2H
NMR (61 MHz, CHCl3): δ 1.19 (brs), 0.82 (brs).
2,2,4,4,6,8,8,-Heptamethylnonane-d34 (Table 2, entry 4) : 100% (62.2 mg, 250 μmol)
as a colorless oil, 1H NMR (500 MHz, CDCl3): δ 1.59 (m, 0.47H), 1.03–1.27 (m,
4.97H), 0.85–0.97 (m, 10.21H); 2H NMR (61 MHz, CHCl3): δ 1.57 (brs), 1.22
(brs), 0.87–0.94 (brd).
2,2,4,4,6,8,8,-Heptamethylnonane-d34 (Table 2, entry 4c) : 100% (60.1 mg, 250 μmol)
as a colorless oil, 1H NMR (500 MHz, CDCl3): δ 1.59 (m, 0.56H), 1.04–1.24 (m,
5.08H), 0.85–0.97 (m, 7.03H); 2H NMR (61 MHz, CHCl3): δ 1.54 (brs),
1.18–1.20 (brs), 0.84–0.91 (brd).
Bicyclohexyl-d22 (Table 2, entry 5) : 86% (39.7 mg, 215 μmol) as a colorless oil, 1H
NMR (500 MHz, CDCl3): δ 1.62–1.64 (m, 2.14H), 0.88–1.24 (m, 3.00H); 2H
NMR (61 MHz, CHCl3): δ 1.65 (m), 0.90–1.13 (m).
trans-Decaline-d18 (Table 2, entry 6) : 85% (32.1 mg, 213 μmol) as a colorless oil, 1H
NMR (500 MHz, CDCl3): δ 1.66 (m, 0.12H), 1.41 (m, 0.18H), 1.23 (m, 0.44H),
S3
0.86 (m, 0.32H); 2H NMR (61 MHz, CHCl3): δ 1.61 (brs), 1.49 (brs), 1.17 (brs),
0.87 (brs).
Adamantane-d16 (Table 2, entry 7) : 99% (34.6 mg, 248 μmol) as a colorless oil, 1H
NMR (500 MHz, CDCl3): δ 1.85 (m, 2.60H), 1.75 (brd, 7.20H); 2H NMR (61
MHz, CHCl3): δ 1.81 (brs), 1.69 (brs).
α-Cholestane-d48 (Table 2, entry 8c) : 82% (38.1 mg, 112.5 μmol) as a colorless oil, 1H
NMR (500 MHz, CDCl3): δ 0.63–1.95 (m, 33.84H); 2H NMR (61 MHz, CHCl3):
δ 0.92–1.16 (m).
α-Cholestane-d48 (Table 2, entry 8d) : 90% (44.7 mg, 112.5 μmol) as a colorless oil,
1H
NMR (500 MHz, CDCl3): δ 0.63–1.93 (m, 26.67H); 2H NMR (61 MHz,
CHCl3): δ 0.82–1.78 (m).
Cyclopentadecane-d30 (Table 2, entry 9) : 99% (59.7 mg, 248 μmol) as a colorless oil,
H NMR (400 MHz, CDCl3): δ 1.25 (s, 0.91H); 2H NMR (61 MHz, CHCl3): δ 1.27
(brs).
1
4. 1H and 2H NMR spectra of multi-deuterated alkanes
S4
120.0
8.00
110.0
TP-7-56
1
80.0
90.0
100.0
H NMR (CDCl3)
CD3(CD2)10CD3
With 1,4-dioxane (0.25 mmol)
96
as the internal standard
94
96
0.27
abundance
0
10.0
20.0
1.26
30.0
40.0
50.0
60.0
70.0
(Table 1, entry 5)
5.0
4.0
3.0
2.0
3.0
2.0
1.0
0
-0.019
4.0
1.413
1.410
1.401
1.238
1.230
1.205
1.188
1.177
0.800
5.0
3.680
3.668
6.0
7.260
7.0
X : parts per Million : Proton
27.0
29.0
TP-7-56-2H
2
25.0
H NMR
21.0
23.0
(CHCl3 + slight CDCl3)
19.0
CD3(CD2)10CD3
17.0
96
94
96
abundance
-1.0
1.0
3.0
5.0
7.0
9.0
11.0
13.0
15.0
(Table 1, entry 5)
1.0
X : parts per Million : 2H
S5
0
0.831
6.0
1.202
7.0
7.260
8.0
0.17
8.00
0.15
0.16
TP-7-123
1
0.11
0.12
0.13
0.14
H NMR (CDCl3)
CD3(CD2)13CD3
With 1,4-dioxane (0.25 mmol)
97
as the internal standard
92
97
4.0
5.0
4.0
3.0
2.0
3.0
2.0
1.0
0
0.803
5.0
1.239
1.174
6.0
3.684
7.0
7.260
8.0
-0.018
abundance
0
0.01
0.15
0.02
0.03
1.52
0.04
0.05
0.06
0.07
0.08
0.09
0.1
(Table 2, entry 1)
X : parts per Million : 1H
100.0 120.0 140.0 160.0 180.0 200.0 220.0 240.0 260.0 280.0 300.0
TP-7-123-2H
2
H NMR
(CHCl3 + slight CDCl3)
CD3(CD2)13CD3
97
92
97
abundance
-20.0 0
20.0
40.0
60.0
80.0
(Table 2, entry 1)
1.0
X : parts per Million : 2H
S6
0
0.830
6.0
1.196
7.0
7.260
8.0
8.00
70.0
TP-7-104-Benzene-d6
1
With 1,4-dioxane (0.25 mmol)
60.0
H NMR (Benzene-d6)
as the internal standard
50.0
CD3(CD2)18CD3
94
94
94
abundance
0
0.32
10.0
1.17
20.0
30.0
40.0
(Table 2, entry 2)
3.0
2.0
1.0
0
0.855
4.0
1.275
1.249
5.0
3.358
6.0
7.160
7.0
TP-7-104-2H-benzened6
2
H NMR
(Benzene + slight Benzene-d6)
CD3(CD2)18CD3
94
94
94
(Table 2, entry 2)
abundance
-20.0
0
20.0
40.0
60.0
80.0
100.0 120.0 140.0 160.0 180.0 200.0 220.0 240.0 260.0 280.0 300.0
X : parts per Million : Proton
5.0
4.0
3.0
2.0
1.0
X : parts per Million : 2H
S7
0
0.823
6.0
1.204
7.0
7.160
8.0
16.00
90.0
100.0
TP-7-106
1
70.0
80.0
H NMR (CDCl3)
CD3(CD2)34CD3
With 1,4-dioxane (0.25 mmol)
78
as the internal standard
86
78
3.0
2.0
3.0
2.0
1.0
0
0.877
0.834
4.0
1.249
1.186
5.0
3.705
3.689
6.0
7.260
7.0
-0.004
abundance
0
10.0
1.35
20.0
30.0
40.0
6.66
50.0
60.0
(Table 2, entry 3)
X : parts per Million : 1H
0.3
TP-7-106-2H
2
H NMR
(CHCl3 + slight CDCl3)
0.2
CD3(CD2)34CD3
78
86
78
abundance
0
0.1
(Table 2, entry 3)
5.0
4.0
1.0
X : parts per Million : 2H
S8
0
0.833
6.0
1.201
7.0
7.260
8.0
240.0
200.0
16.00
220.0
TP-9-36-dioxane (0.1 eq.)-CDCl3-eca500
160.0
180.0
1
H NMR (CDCl3)
With 1,4-dioxane (0.25 mmol)
CD3(CD2)34CD3
as the internal standard
140.0
87
86
87
0.68
abundance
0
20.0
40.0
60.0
80.0
100.0
8.26
120.0
(Table 2, entry 3c)
5.0
4.0
3.0
2.0
3.0
2.0
1.0
0
-0.004
4.0
1.281
1.248
1.223
1.209
1.186
0.890
0.880
0.877
0.862
0.854
0.839
0.818
5.0
3.705
6.0
7.260
7.0
TP-9-36-2H-eca500
2
H NMR
(CHCl3 + slight CDCl3)
CD3(CD2)34CD3
87
86
87
(Table 2, entry 3c)
6.0
1.0
X : parts per Million : 2H
S9
0
0.821
7.0
1.186
8.0
7.260
abundance
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 2.0 2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9 3.03.1
X : parts per Million : 1H
60.0
TP-7-77
10.21
H NMR (CDCl3)
8.00
50.0
1
40.0
CD 53; CD2 17; CD3 62
20.0
4.97
30.0
(Table 2, entry 4)
With 1,4-dioxane (0.25 mmol)
4.0
5.0
4.0
3.0
2.0
-0.014
5.0
3.0
2.0
0
3.685
6.0
7.260
7.0
1.589
1.268
1.242
1.232
1.114
1.083
1.061
1.034
0.965
0.942
0.919
0.890
0.868
0.852
abundance
0
0.47
10.0
as the internal standard
1.0
0
TP-7-77-2H
2
H NMR
(CHCl3 + slight CDCl3)
9.0
10.0 11.0 12.0 13.0 14.0 15.0 16.0
X : parts per Million : 1H
7.0
8.0
CD 53; CD2 17; CD3 62
abundance
-2.0 -1.0
0
1.0
2.0
3.0
4.0
5.0
6.0
(Table 2, entry 4)
X : parts per Million : 2H
S 10
0.942
0.873
1.0
1.220
6.0
1.572
7.0
7.260
8.0
240.0
H NMR (CDCl3)
160.0
180.0
7.03
1
8.00
200.0
220.0
TP-9-37-dioxane(0.25 mmol)-eca500
5.08
140.0
CD 43; CD2 15; CD3 74
as the internal standard
4.0
5.0
4.0
3.0
2.0
1.0
1.590
1.235
1.225
1.129
1.116
1.101
1.079
1.065
1.052
1.036
0.969
0.948
0.925
0.894
0.873
0.853
5.0
3.700
6.0
7.260
7.0
0
-0.006
abundance
0
20.0
0.56
60.0
With 1,4-dioxane (0.25 mmol)
40.0
80.0
100.0
120.0
(Table 2, entry 4c)
X : parts per Million : 1H
70.0
TP-9-37-2H-eca500
2
60.0
H NMR
40.0
50.0
(CHCl3 + slight CDCl3)
CD 43; CD2 15; CD3 74
abundance
0
10.0
20.0
30.0
(Table 2, entry 4c)
2.0
1.0
X : parts per Million : 2H
S 11
1.197
1.179
0.911
0.877
0.839
3.0
1.535
6.0
7.260
7.0
0
TP-8-127
1
8.00
H NMR (CDCl3)
With 1,4-dioxane (0.25 mmol)
as the internal standard
equatrial 75; axial 71
2.14
3.00
(Table 2, entry 5)
5.0
4.0
3.0
2.0
3.0
2.0
1.0
0
-0.014
4.0
1.241
1.118
1.031
0.881
5.0
3.687
3.685
6.0
7.260
7.0
1.644
1.618
abundance
0
10.0 20.0 30.0 40.0 50.0 60.0 70.0 80.0 90.0 100.0 110.0 120.0 130.0 140.0 150.0 160.0 170.0 180.0
TP-7-128
TP-7-127-2H
8.0
9.0
X : parts per Million : 1H
2
H NMR
6.0
7.0
(CHCl3 + slight CDCl3)
5.0
equatrial 75; axial 71
abundance
0
1.0
2.0
3.0
4.0
(Table 2, entry 5)
X : parts per Million : 2H
S 12
1.130
1.058
0.904
1.0
1.370
6.0
1.652
7.0
7.260
8.0
0
1
H NMR (CDCl3)
c
b
d
a
8.00
c
d
d
With 1,4-dioxane (0.25 mmol)
b
a
a
as the internal standard
a
c
d
b
b d
d
c
a 97; b 95; c 87; d 94
3.0
2.0
0.32
0.44
1.0
0
-0.020
2.0
0.860
3.0
1.234
1.087
4.0
1.410
5.0
3.684
3.664
6.0
7.260
7.0
0.18
0.12
(Table 2, entry 6)
1.657
190.0
abundance
0 10.0 20.0 30.0 40.0 50.0 60.0 70.0 80.0 90.0 100.0 110.0 120.0 130.0 140.0 150.0 160.0 170.0 180.0
TP-7-128
TP-7-128-2H
1.2
1.3
1.4
X : parts per Million : 1H
1.1
2
H NMR
0.9
1.0
(CHCl3 + slight CDCl3)
c
b
0.8
d
d
b
a
a
a
0.7
a
c
d
d
b d
d
c
a 97; b 95; c 87; d 94
(Table 2, entry 6)
abundance
0
0.1
0.2
0.3
0.5
b
0.4
0.6
c
4.0
1.0
X : parts per Million : 2H
S 13
0
0.867
5.0
1.168
6.0
1.613
1.494
7.0
7.260
8.0
1
8.00
80.0
70.0
TP-7-155
50.0
60.0
7.20
H NMR (CDCl3)
CD 35; CD2 39
20.0
2.60
30.0
40.0
(Table 2, entry 7)
With 1,4-dioxane (0.25 mmol)
abundance
0
10.0
as the internal standard
3.0
2.0
3.0
2.0
1.0
0
1.0
0
1.232
1.186
4.0
1.849
1.762
1.728
5.0
3.713
3.679
3.645
6.0
7.260
7.0
TP-7-155-2H
5.0
6.0
X : parts per Million : 1H
2
H NMR
4.0
(CHCl3 + slight CDCl3)
3.0
CD 35; CD2 39
CD 35; CD2 39
abundance
0
1.0
2.0
(Table 2, entry 7)
6.0
5.0
4.0
1.818
1.687
7.0
7.260
8.0
X : parts per Million : 2H
S 14
40.0
1
33.84
50.0
TP-9-41-dioxane(0.25 mmol)-eca500
H NMR (CDCl3)
30.0
H
H
H
H
16.00
ave. 14% D
20.0
(Table 2, entry 8c)
10.0
With 1,4-dioxane (0.25 mmol)
abundance
0
as the internal standard
3.0
2.0
1.0
0
-0.017
4.0
1.952
1.927
1.785
1.646
1.483
1.462
1.321
1.194
1.111
0.991
0.971
0.888
0.874
0.854
0.849
0.840
0.835
0.756
0.627
5.0
3.687
6.0
7.260
7.0
TP-9-42-2H-eca500
0.12
0.13
X : parts per Million : 1H
0.11
2
H NMR
0.08
0.09
0.1
(CHCl3 + slight CDCl3)
H
0.07
H
H
0.06
H
0.05
ave. 39% D
abundance
0
0.01
0.02
0.03
0.04
(Table 2, entry 8c)
5.0
4.0
3.0
2.0
1.0
X : parts per Million : 2H
S 15
0
0.915
6.0
1.164
7.0
7.260
8.0
TP-7-156
1
30.0
26.67
H NMR (CDCl3)
H
H
H
20.0
H
ave. 39% D
10.0
8.00
(Table 2, entry 8d)
With 1,4-dioxane (0.125 mmol)
abundance
0
as the internal standard
3.0
2.0
3.0
2.0
1.0
0
1.600
1.329
1.307
1.204
1.186
1.163
1.118
1.084
0.988
0.974
0.895
0.881
0.856
0.840
0.760
0.633
4.0
1.933
5.0
3.695
3.680
6.0
7.260
7.0
TP-7-156-2H
7.0
8.0
X : parts per Million : 1H
2
6.0
H NMR
5.0
(CHCl3 + slight CDCl3)
H
4.0
H
H
H
3.0
ave. 39% D
abundance
0
1.0
2.0
(Table 2, entry 8d)
1.0
X : parts per Million : 2H
S 16
0
0.823
4.0
1.186
1.092
5.0
1.455
6.0
1.778
7.0
7.260
8.0
0.17 0.18
8.00
0.16
TP-7-66
1
0.14 0.15
H NMR (CDCl3)
0.11 0.12 0.13
With 1,4-dioxane (0.25 mmol)
0.07 0.08 0.09
0.1
as the internal standard
CD2 96
0.91
abundance
0
0.01 0.02 0.03
0.04 0.05
0.06
(Table 2, entry 9)
4.0
3.0
2.0
3.0
2.0
1.0
0
0.055
-0.017
5.0
1.250
6.0
3.683
7.0
7.260
8.0
TP-8-66-2H
90.0
100.0
X : parts per Million : 1H
80.0
2
H NMR
50.0
60.0
70.0
(CHCl3 + slight CDCl3)
40.0
CD2 96
abundance
0
10.0
20.0
30.0
(Table 2, entry 9)
6.0
5.0
4.0
1.0
1.268
7.0
7.260
8.0
X : parts per Million : 2H
S 17
0