2-adamantyl Chloroformate → Carbonate Ion

HRID 1198066ノート

反応式

HRID 1198066 の反応式
[CH3:1][C@:2]([C:14]([NH:16][C@H:17]([CH2:25][OH:26])[CH2:18][C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)=[O:15])([CH2:4][C:5]1[C:13]2[C:8](=[CH:9][CH:10]=[CH:11][CH:12]=2)[NH:7][CH:6]=1)[NH2:3].[CH:27]12[CH2:36][CH:31]3[CH2:32][CH:33]([CH2:35][CH:29]([CH2:30]3)[CH:28]1[O:37][C:38](Cl)=[O:39])[CH2:34]2>C1COCC1.C(OCC)(=O)C>[CH:29]12[CH2:35][CH:33]3[CH2:32][CH:31]([CH2:36][CH:27]([CH2:34]3)[CH:28]1[O:37][C:38](=[O:39])[NH:3][C:2]([CH2:4][C:5]1[C:13]3[C:8](=[CH:9][CH:10]=[CH:11][CH:12]=3)[NH:7][CH:6]=1)([CH3:1])[C:14]([NH:16][CH:17]([CH2:25][OH:26])[CH2:18][C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)=[O:15])[CH2:30]2.[C:38](=[O:39])([O-:15])[O-:37]

参加物

6

反応物 2

HCID 108785372-adamantyl ChloroformateHCID 54471265alpha-methyl-D-tryptophyl-L-phenylalaninol

生成物 2

HCID 19660Carbonate Ion収率 20%HCID 10165354Tricyclo[3.3,1.13,7]dec-2-yl-[2-[[1-(hydroxymethyl)-2-phenylethyl]amino]-1-(1H-indol-3-ylmethyl)-1-methyl-2-oxoethyl]carbamate

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒2 回HCID 8857Ethyl Acetate溶媒

実験手順

A solution of the α-methyl-D-tryptophyl-L-phenylalaninol (0.5 g, 1.42 mmol) and 4-N,N-dimethylaminopyridine (0.2 g,1.64 mmol), in anhydrous THF (20 mL) was treated dropwise with a solution of 2-adamantylchloroformate (1.4 mmol) in anhydrous THF (20 mL) at room temperature. The reaction was monitored by IR spectroscopy. Once complete, the reaction mixture was diluted with ethyl acetate and washed with 1M citric acid solution, then water. The dried (MgSO4) organic phase was evaporated to dryness and chromatographed over silica using 2% MeOH:98% CH2Cl2 as eluant. This gave the required compound (65% along with 20% carbonate impurity. NOTE: Some of the more acid labile urethanes required chromatography on neutral stationary phases. mp 96°-100° C. (EtOAc-hexane); IR (KBr) 3316, 1695 and 1658 cm-1 ; NMR (CD3OD) δ 1.28 (3H, s), 1.55 (2H, m), 1.68-2.06 (12H, m), 2.76 (2H, ABx, J 13.5 and 17 Hz), 3.31 (2H, Abq, J 14.5 Hz), 3.45 (2H, m), 4.12 (1H, m), 4.78 (1H, br.s) and 6.8-7.5 (10H, m); Anal. (C32H39N3O4), C, H, N.

後処理

  1. washwashed with 1M citric acid solution
  2. dry with materialThe dried (MgSO4) organic phase
  3. customwas evaporated to dryness
  4. customchromatographed over silica using 2% MeOH

出典と根拠

ORDレコード
ord-c128b85cee724710a92c51f4e92f55fe
出典データセット
uspto-grants-1994_01
特許番号
US05278316

反応ノート

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