Acetic Anhydride → N,N'-bis-[2-acetyloxy-1-(acetyloxymethyl)ethyl]-5-[3-bromo-2-oxo-1-pyrrolidinyl]-2,4,6-triiodo-1,3-benzenedicarboxamide

HRID 977795

反応式

HRID 977795 の反応式
[C:1]([O:4][CH2:5][CH:6]([NH:12][C:13]([C:15]1[C:20]([I:21])=[C:19]([NH2:22])[C:18]([I:23])=[C:17]([C:24]([NH:26][CH:27]([CH2:33][O:34][C:35](=[O:37])[CH3:36])[CH2:28][O:29][C:30](=[O:32])[CH3:31])=[O:25])[C:16]=1[I:38])=[O:14])[CH2:7][O:8][C:9](=[O:11])[CH3:10])(=[O:3])[CH3:2].[Br:39][CH:40]([CH2:44][CH2:45]Br)[C:41](Br)=[O:42].C(=O)([O-])[O-].[K+].[K+].C(OC(=O)C)(=O)C>CN(C)C(=O)C.N1C=CC=CC=1>[C:30]([O:29][CH2:28][CH:27]([NH:26][C:24]([C:17]1[C:18]([I:23])=[C:19]([N:22]2[CH2:45][CH2:44][CH:40]([Br:39])[C:41]2=[O:42])[C:20]([I:21])=[C:15]([C:13]([NH:12][CH:6]([CH2:5][O:4][C:1](=[O:3])[CH3:2])[CH2:7][O:8][C:9](=[O:11])[CH3:10])=[O:14])[C:16]=1[I:38])=[O:25])[CH2:33][O:34][C:35](=[O:37])[CH3:36])(=[O:32])[CH3:31]

参加物

7

反応物 4

HCID 7918Acetic AnhydrideHCID 11430Potassium Carbonate2 回HCID 112898262,4-dibromobutanoyl BromideHCID 11766168N,N'-Bis[2-(acetyloxy)-1-[(acetyloxy)methyl]ethyl]-5-amino-2,4,6-triiodo-1,3-benzenedicarboxamide

生成物 1

HCID 19048411N,N'-bis-[2-acetyloxy-1-(acetyloxymethyl)ethyl]-5-[3-bromo-2-oxo-1-pyrrolidinyl]-2,4,6-triiodo-1,3-benzenedicarboxamide収率 45.8%

試薬・触媒・溶媒 2

HCID 1049Pyridine溶媒HCID 31374Dimethylacetamide溶媒

反応条件

温度
25 °C

実験手順

A solution of N,N'-bis-[2-acetyloxy-1-(acetyloxymethyl)ethyl]-5-[amino]-2,4,6-triiodo-1,3-benzenedicarboxamide, (8.73 g, 10 mmol) in dry N,N-dimethylacetamide (100 ml) was treated with 2,4-dibromobutyroyl bromide (4.017 g, 13 mmol) under nitrogen and the mixture was stirred for 13 hours at 25° C. The dimethylacetamide was removed by distillation at 55°-60° C. under high vacuum. The resulting thick paste was dissolved in dry N,N-dimethylacetamide (160 ml) and potassium carbonate (1.80 g, 13 mmol) was added. The mixture was stirred for 60 minutes. An additional portion of potassium carbonate (1.80 g, 13.0 mmol) was added and the mixture stirred for 80 minutes. The suspended salts were filtered off and the volume of the reaction mixture was reduced to about 80 ml by vacuum distillation at 0.05-0.10 mm/Hg. The residual solution was poured slowly with rapid stirring into ice-water (900 ml). The resulting mixture was stirred overnight at 0° C. and then filtered. The collected precipitate was dried in a vacuum desiccator (P2O5) and then crystallized from acetonitrile to give an off-white powder. This product was treated with acetic anhydride (30 ml) and pyridine (42 ml) for 32 hours at 25°, after which the volatile components were completely removed under high vacuum to obtain N,N'-bis-[2-acetyloxy-1-(acetyloxymethyl)ethyl]-5-[3-bromo-2-oxo-1-pyrrolidinyl]-2,4,6-triiodo-1,3-benzenedicarboxamide as a white powder (4.67 g, 45% yield), m.p. 232°-234°.

後処理

  1. customThe dimethylacetamide was removed by distillation at 55°-60° C. under high vacuum
  2. dissolutionThe resulting thick paste was dissolved in dry N,N-dimethylacetamide (160 ml)
  3. stirringThe mixture was stirred for 60 minutes
  4. stirringthe mixture stirred for 80 minutes
  5. filtrationThe suspended salts were filtered off
  6. distillationthe volume of the reaction mixture was reduced to about 80 ml by vacuum distillation at 0.05-0.10 mm/Hg
  7. additionThe residual solution was poured slowly
  8. stirringwith rapid stirring into ice-water (900 ml)
  9. stirringThe resulting mixture was stirred overnight at 0° C.
  10. filtrationfiltered
  11. dry with materialThe collected precipitate was dried in a vacuum desiccator (P2O5)
  12. customcrystallized from acetonitrile
  13. customto give an off-white powder
  14. customafter which the volatile components were completely removed under high vacuum

出典と根拠

ORDレコード
ord-2b04144917d443088544ff6b7a123a1e
出典データセット
uspto-grants-1997_03
特許番号
US05614638

関連ノート

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