N,N,N',N',N'',N''-Hexamethylmethanetriamine → 4,5,6,7-Tetrahydro-1-oxa-2,7-diaza-cyclopenta[e]azulene-9-carboxylic acid ethyl ester

HRID 497404ノート

反応式

HRID 497404 の反応式
[CH2:1]([O:3][C:4]([C:6]1[C:7]2[C:22](=[O:23])[CH2:21][CH2:20][CH2:19][CH2:18][C:8]=2[N:9](C(OC(C)(C)C)=O)[CH:10]=1)=[O:5])[CH3:2].[CH3:24][N:25](C(N(C)C)N(C)C)C.Cl.NO>CCO>[CH2:1]([O:3][C:4]([C:6]1[C:7]2[C:22]3[O:23][N:25]=[CH:24][C:21]=3[CH2:20][CH2:19][CH2:18][C:8]=2[NH:9][CH:10]=1)=[O:5])[CH3:2]

参加物

5

反応物 3

HCID 79831N,N,N',N',N'',N''-HexamethylmethanetriamineHCID 443297Hydroxyamine hydrochlorideHCID 206056554-oxo-5,6,7,8-tetrahydro-4H-cyclohepta[b]pyrrole-1,3-dicarboxylic acid 1-tert-butyl ester 3-ethyl ester

生成物 1

HCID 1360799654,5,6,7-Tetrahydro-1-oxa-2,7-diaza-cyclopenta[e]azulene-9-carboxylic acid ethyl ester収率 76%

試薬・触媒・溶媒 1

HCID 702Ethanol溶媒

反応条件

温度
60 °C

実験手順

In a sealed tube, 4-oxo-5,6,7,8-tetrahydro-4H-cyclohepta[b]pyrrole-1,3-dicarboxylic acid 1-tert-butyl ester 3-ethyl ester (2.6 mmol) and tris(dimethylamino)methane (5.2 mmol) are combined and heated at 60° C. for 3 hours. After cooling to RT the volatile material is removed in vacuo. To the residue were added hydroxylamine hydrochloride (7.8 mmol) and 7 mL EtOH. The mixture is heated at 100° C. for 16 hours. The solvent is evaporated in vacuo and the residue is taken up in CH2Cl2 and washed two times with NaHCO3 (aq). The organic layer is dried over Na2SO4 and evaporated in vacuo and the residue chromatographed using 10% MeOH in CH2Cl2 as mobile phase to yield 4,5,6,7-tetrahydro-1-oxa-2,7-diaza-cyclopenta[e]azulene-9-carboxylic acid ethyl ester as a white solid (76%). 1H NMR (CDCl3) 1.19 (t, 3H), 1.95-2.07 (m, 2H), 2.78 (t, 2H), 2.95 (t, 2H), 4.38 (q, 2H), 7.26 (s, 1H), 8.03 (s, 1H), 8.77 (s, 1H).

後処理

  1. temperatureAfter cooling to RT the volatile material
  2. customis removed in vacuo
  3. temperatureThe mixture is heated at 100° C. for 16 hours
  4. customThe solvent is evaporated in vacuo
  5. washwashed two times with NaHCO3 (aq)
  6. dry with materialThe organic layer is dried over Na2SO4
  7. customevaporated in vacuo
  8. customthe residue chromatographed

出典と根拠

ORDレコード
ord-078a799ba5c243a6846878e917dd4807
出典データセット
uspto-grants-2005_09
特許番号
US06949562B2

反応ノート

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