Formic Acid → 6-Dimethylamino hexanoic acid methyl ester

HRID 2090130

反応式

HRID 2090130 の反応式
[CH:1](O)=[O:2].CCN(C([C@@H]1C=[C:25]2[C@@H:14](CC3C4[C:21]2=[CH:22][CH:23]=[CH:24]C=4NC=3)[N:13]([CH3:27])[CH2:12]1)=O)CC.[OH2:28]>C(#N)C>[CH3:1][O:2][C:24](=[O:28])[CH2:23][CH2:22][CH2:21][CH2:25][CH2:14][N:13]([CH3:12])[CH3:27]

参加物

5

反応物 3

HCID 284Formic Acid2 回HCID 962WaterHCID 5761(+)-Lysergic acid diethylamide

生成物 1

HCID 540390256-Dimethylamino hexanoic acid methyl ester

試薬・触媒・溶媒 1

HCID 6342Acetonitrile溶媒

実験手順

[2-Diethoxy-phosphoryloxy)-ethyl]-(5-methoxycarbonyl-pentyl)-dimethylammonium trifluoroacetate. The methyl ester (1.73 g, 10 mmol) was dissolved in dry acetonitrile (15 mL) and K2CO3 (1.38 g, 10 mmol) was added. This suspension was refluxed under nitrogen gas for 36 h. After cooling to room temperature water was added and the pH was adjusted to 2 by adding TFA. The solution was purified by rp HPLC (Supelco Discovery C18, 21.2 mm×15 cm, 5 μm, A: 5% IPA, 95% H2O, 0.1% TFA, B: 90% IPA, 10% H2O, 0.1% TFA, 0 to 15% B over 14 min, tR=11.8 min) and lyophilized to give the TFA salt of the quaternary amine as light yellow oil (1.06 g, 3.0 mmol, 30%). LC-MS (Phenomenex Gemini, C18, 5 μm, 150×3.0 mm, A: 0.1% formic acid in water, B: 0.1% formic acid in acetonitrile, 10-50% B over 10 min) tR=6.4 min (LSD signal), m/z=354.2 for [M±H]+. 1NMR (CD3OD, 400 MHz) δ=1.41-1.50 (m, 8H, 2×OCH2CH3 and CH2); 1.77 (m, 2H, CH2); 1.90 (m, 2H, CH2); 2.44 (t, 2H, CH2, 3J=7.2 Hz); 3.25 (s, 6H, N(CH3)2); 3.48 (m, 2H, CH2); 3.72 (s, 3H, COOCH3) 3.82 (m, 2H, CH2); 4.26 (dq, 4H, 2×CH2CH3, 3J(H,H)=6.8 Hz, 3J(H,P)=8.0 Hz); 4.58 (brs, 2H, CH2). 13C NMR (CD3OD, 100.5 MHz) δ=16.4 (d, 2×OCH2CH3, 3J=6.1 Hz); 23.3 (CH2); 25.3 (CH2); 26.7 (CH2); 34.4 (CH2); 52.0 (CH3); 52.2 (CH3); 62.1 (d, CH2, 2J=5.3 Hz); 64.8 (CH2); 66.1 (d, CH2, 2J=6.1 Hz); 66.7 (CH2); 175.5 (CO).

出典と根拠

ORDレコード
ord-742f5e9d8e074f9bbb0319e421aaf101
出典データセット
uspto-grants-2013_05
特許番号
US08436138B2

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