Supplementary Data
Synthetic procedures.
Oxidation of alcohol to aldehydes.
Decanal and its deuteriated analogs
Pyridiniumchlorochromate (72 mg, 0 .34 mmol) was added to a solution of decanol (20
mg, 0.12 mmol) (50 mg, 0.32 mmol), or a deuteriated decanol, in dichloromethane (2 mL), and
the mixture was stirred for 1 h and filtered. The filtrate was washed with 1 M NaOH (2 × 1 mL),
water (2 mL) and 1 M HCl (2 mL). The dichloromethane layer was separated, dried over
MgSO4, and the solvent was evaporated to afford the product (16 mg, 80 %).
Decanal: EI -MS: m/z (%), 156 (M+•, 2), 128 (5), 112 (20), 110 (10), 96 (20), 95 (20), 84 (15),
83 (25), 82 (30), 81 (20), 72 (5), 71 (35), 70 (20), 69 (30), 68 (35), 67 (25), 57 (100), 56
(40), 55 (60), 44 (50), 43 (50), 42 (25), 41 (80).
[1-2H]decanal: EI -MS: m/z (%), 157 (M+•, 3), 129 (5), 112 (15), 110 (15), 96 (15), 95 (20), 84
(250, 83 (20), 82 (25), 81 (15), 72 (15), 71 (35), 70 (25), 69 (30), 68 (35), 67 (25), 57
(100), 56 (40), 55 (55), 44 (50), 43 (50), 42 (25), 41 (75).
[2,2-2H2]decanal: EI -MS: m/z (%), 158 (M+•, 2), 130 (5), 112 (10), 110 (10), 97 (10), 96 (25) 95
(15), 85 (5), 84 ( 20), 83 (25), 82 (20), 81 (5), 72 (10), 71 (30), 70 (15), 69 (25), 68 (20),
67 (20), 57 (100), 56 (50), 55 (65), 44 (45), 43 (55), 42 (30), 41 (70).
[3,3-2H2]decanal: EI -MS: m/z (%), 158 (M+•, 1), 130 (5), 114 (15), 112 (10), 97 (15), 96 (25),
95 (10), 85 (10), 84 ( 20), 83 (25), 82 (20), 72 (15), 71 (30), 70 (25), 69 (20), 68 (30), 67
(15), 57 (100), 56 (50), 55 (65), 44 (45), 43 (55), 42 (30), 41 (85).
[4,4-2H2]decanal: EI -MS: m/z (%), 158 (M+•, 2), 130 (5), 114 (20), 112 (10), 97 (25), 96 (15),
95 (5), 85 (15), 84 ( 20), 83 (20), 82 (35), 72 (20), 71 (25), 70 (20), 69 (20), 68 (30), 67
(20), 57 (100), 56 (50), 55 (60), 44 (45), 43 (55), 42 (30), 41 (80).
[5,5-2H2]decanal: EI -MS: m/z (%), 158 (M+•, 2), 130 (5), 114 (20), 112 (10), 97 (20), 96 (15),
95 (10), 85 (12), 84 (15), 83 (30), 82 (25), 72 (25), 71 (25), 70 (15), 69 (25), 68 (20), 67
(15), 57 (100), 56 (50), 55 (50), 44 (60), 43 (60), 42 (20), 41 (85).
Decanal oxime and its deuteriated analogs
1
Decanal (15 mg, 0.1 mmol), or a deuteriated decanal, in ethanol (1 mL) was combined
with NH2OH•HCl (14 mg, 0.2 mmol) in water (1 mL). A solution of Na2CO3 (21 mg, 0.2 mmol)
in water (1 mL) was added dropwise, and the mixture was stirred overnight at 50 °C and
concentrated under reduced pressure. Water (2 mL) was added and the reconstituted mixture
was extracted with ether (2 x 1 mL). The combined ether layers were dried over Na2SO4 and
evaporated to give a clear oil (15 mg, 91%).
Decanal oxime: EI -MS: m/z (%), 171 (M+•, 1), 154 (5), 138 (2), 128 (2), 114 (2), 100 (5), 96
(15), 87 (10), 82 (10), 72 (20), 59 (100), 55 (20), 43 (30), 41 (50).
[1-2H]Decanal oxime: EI -MS: m/z (%), 172 (M+•, 2), 155 (5), 139 (2), 129 (3), 115 (3), 110
(10), 101 (25), 96 (20), 87 (25), 82 (20), 73 (30), 60 (100), 55 (20), 43 (60), 41 (90).
[2,2-2H2]Decanal oxime: EI -MS: m/z (%), 173 (M+•, 1), 156 (5), 140 (2), 130 (3), 112 (10), 98
(10), 87 (25), 84 (20), 73 (15), 61 (100), 57 (30), 55 (30), 43 (60), 41 (60).
[3,3-2H2]Decanal oxime: EI -MS: m/z (%),173 (M+•, 1), 156 (5), 140 (2), 130 (3), 116 (10), 102
(20), 98 (10), 88 (20), 84 (15), 74 (20), 59 (100), 55 (30), 43 (60), 41 (50).
[4,4-2H2]Decanal oxime: EI -MS: m/z (%),173 (M+•, 2), 156 (10), 140 (2), 130 (4), 116 (10), 102
(25), 98 (10), 87 (15), 84 (15), 72 (35), 60 (100), 56 (30), 43 (60), 41 (60).
[5,5-2H2]Decanal oxime: EI -MS: m/z (%),173 (M+•, 2), 156 (10), 140 (2), 130 (5), 116 (10), 102
(15), 98 (10), 87 (15), 84 (10), 72 (25), 59 (100), 56 (30), 43 (60), 41 (55).
Decylamine and its deuteriated analogs
Decanal oxime (15 mg, 0.1 mmol), or its deuteriated analogs, in dry THF (1 mL) was
added to lithium aluminum hydride (16 mg, 0.4 mmol), or lithium aluminum deuteride (18 mg,
0.4 mmol), in dry diethyl ether (1 mL). The reaction mixture was stirred at 40 °C overnight,
cooled to 0 °C, and quenched with water (0.2 mL). The cooled mixture was shaken with 2 M
HCl (5 mL) to dissolve the inorganic solids and the aqueous layer was discarded. The organic
layer was dried over MgSO4 and evaporated to yield the product as a clear liquid.
Decylamine: EI -MS: m/z (%), 157 (M+•, 5), 140 (2), 128 (3), 119 (2), 100 (10), 86 (20), 69 (10),
60 (10), 55 (20), 44 (80), 41 (100).
[1,1-2H2 ]Decylamine: EI -MS: m/z (%), 159 (M+•, 10), 142 (3), 130 (3), 121 (1), 102 (10), 88
(25), 71 (10), 61 (10), 55 (25), 46 (80), 41 (100).
2
[2,2-2H2]Decylamine: EI -MS: m/z (%), 159 (M+•, 10), 142 (3), 130 (5), 121 (2), 102 (10), 88
(30), 71 (15), 61 (15), 55 (25), 45 (80), 41 (100).
[3,3-2H2]Decylamine: EI -MS: m/z (%), 159 (M+•, 10), 142 (1), 130 (5), 121 (0), 102 (15), 88
(25), 71 (10), 61 (10), 55 (20), 44 (100), 41 (80).
[4,4-2H2]Decylamine: EI -MS: m/z (%), 159 (M+•, 10), 142 (1), 130 (2), 121 (1), 102 (15), 88
(25), 71 (15), 60 (10), 56 (50), 44 (90), 41 (100).
[5,5-2H2]Decylamine: EI -MS: m/z (%), 159 (M+•, 5), 142 (1), 130 (2), 119 (5), 100 (15), 88
(20), 71 (25), 60 (10), 56 (50), 45 (100), 41 (70).
N-Decyl-p-toluenesulfonamide (1) and its deuterated analogs
p-Toluenesulfonyl chloride (12 mg, 0.06 mmol) was dissolved in DCM (1 mL) and added
drop wise to a solution of decylamine (10 mg, 0.06 mmol), or other amines, DCM (1 mL) and
triethylamine (20 mg, 0.2 mmol) and stirred overnight. The reaction mixture was washed with
2M HCl (2 x 2 mL), followed by 2M NaOH (2 x 2 mL) dried over MgSO4, and evaporated to
give a white solid (16 mg, 85%).
N-Decyl-p-toluenesulfonamide (1): EI -MS: m/z (%), 311 (M+•, 3), 185 (5), 184 (90), 173 (5),
172 (40), 156 (60), 155 (100), 91 (90), 65 (20), 41 (20).
N-[1,1-2H2 ]decyl-p-toluenesulfonamide: EI -MS: m/z (%), 313 (M+•, 3), 187 (5), 186 (90), 173
(5), 172 (50), 158 (40), 155 (100), 91 (85), 65 (20), 43 (20), 41 (20).
N-[2,2-2H2]decyl-p-toluenesulfonamide: EI -MS: m/z (%), 313 (M+•, 5), 185 (5), 184 (90), 173
(5), 172 (30), 158 (70), 155 (100), 91 (95), 65 (20), 43 (20), 41 (15).
N-[3,3-2H2]decyl-p-toluenesulfonamide: EI -MS: m/z (%), 313 (M+•, 3), 185 (10), 184 (90), 173
(15), 172 (20), 158 (60), 155 (100), 91 (90), 65 (20), 43 (20), 41 (20).
N-[4,4-2H2]decyl-p-toluene sulfonamide: EI -MS: m/z (%), 313 (M+•, 3), 185 (40), 184 (90), 173
(20), 172 (15), 158 (60), 155 (100), 91 (95), 65 (20), 43 (25), 41 (20).
N-[5,5-2H2]decyl-p-toluenesulfonamide: EI -MS: m/z (%), 313 (M+•, 3), 185 20), 184 (80), 173
(15), 172 (20), 158 (55), 155 (100), 91 (100), 65 (25), 43 (20), 41 (20).
N-[2-octyl]-p-toluenesulfonamide: EI -MS: m/z (%), 283 (M+•, 2), 268 (5), 198 (100), 172 (5),
155 (50), 91 (40), 65 (10), 43 (10), 43 (10), 41 (10).
N-[t-butyl]-p-toluenesulfonamide: EI -MS: m/z (%), 227 (M+•, 2), 212 (100), 172 (1), 155 (70),
91 (80), 65 (15), 43 (10), 41 (10).
3
N-pentyl-p-toluenesulfonamide: EI -MS: m/z (%), 241 (M+•, 2), 184 (80), 173 (5), 172 (50), 155
(100), 91 (85), 86 (25), 65 (20), 43 (20), 41 (20).
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Supplementary Figures
.
.
O H
S N
O H
A
m/z 276
B
O
O
S NH2
S
O
O
H2N
Ion/Neutral Complex B
Ion/Neutral Complex A
m/z 276
O
S NH2
O
m/z 105
Supplementary Figure 1. Formation of m/z 105 ion upon collisional activation of prototonated
N-phenylethyl-p-toluenesulfonamide.
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Supplementary Figure 2. Proposed fragmentation of prototonated N- phenylethyl-ptoluenesulfonamide.
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