1,8-Diazabicyclo(5.4.0)undec-7-ene → HCID 18001111、化合物

HRID 969276ノート

反応式

HRID 969276 の反応式
[CH:1]([C:3]1[CH:13]=[CH:12][C:6]([C:7]([O:9][CH2:10][CH3:11])=[O:8])=[CH:5][C:4]=1[N+:14]([O-])=O)=O.N12CCCN=C1CCCCC2.C1C=CC([P+](C2C=CC=CC=2)(C2C=CC=CC=2)[CH2:35][C:36]2[CH:41]=[C:40]([C:42]#[N:43])[CH:39]=[CH:38][CH:37]=2)=CC=1.[Br-]>C1(C)C=CC=CC=1>[NH2:14][C:4]1[CH:5]=[C:6]([CH:12]=[CH:13][C:3]=1[CH2:1][CH2:35][C:36]1[CH:37]=[CH:38][CH:39]=[C:40]([C:42]#[N:43])[CH:41]=1)[C:7]([O:9][CH2:10][CH3:11])=[O:8]

参加物

5

反応物 3

HCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 2778355(3-Cyanobenzyl)triphenylphosphonium bromideHCID 18001104Ethyl 4-formyl-3-nitrobenzoate

生成物 1

HCID 18001111HCID 18001111、化合物収率 136%

試薬・触媒・溶媒 1

HCID 1140Toluene溶媒

反応条件

温度
80 °C

実験手順

Ethyl 4-formyl-3-nitrobenzoate (5.81 g) was dissolved in 70 ml of toluene, then 2.1 ml of 1,8-diazabicyclo[5.4.0]-undec-7-ene and the mixture was stirred at 80° C. for one hour. To the reaction solution, 2.69 g of 3-[(1,1,1-triphenylphosphonio)methyl]benzonitrile bromide was added, and the mixture was stirred at 80° C. for 24 hours. Insoluble matters were filtered out and the filtrate was concentrated in vacuo. The resulting residue was purified by silica gel column chromatography using hexane-ethyl acetate (10:1) as an eluting solvent. The resulting intermediate (3.1 g) was dissolved in a mixed solvent of 50 ml of ethanol and 10 ml of tetrahydrofuran, then 1 g of a palladium oxide-barium sulfate complex was added and the mixture was stirred in a hydrogen atmosphere at room temperature for 3 days. The reaction solution was filtered through Celite and the filtrate was concentrated in vacuo. The resulting residue was purified by silica gel column chromatography using hexane-ethyl acetate (2:1) as an eluting solvent to give 2.35 g of ethyl 3-amino-4-[2-(3-cyanophenyl)ethyl]benzoate.

後処理

  1. filtrationInsoluble matters were filtered out
  2. concentrationthe filtrate was concentrated in vacuo
  3. customThe resulting residue was purified by silica gel column chromatography
  4. dissolutionThe resulting intermediate (3.1 g) was dissolved in a mixed solvent of 50 ml of ethanol and 10 ml of tetrahydrofuran
  5. addition1 g of a palladium oxide-barium sulfate complex was added
  6. stirringthe mixture was stirred in a hydrogen atmosphere at room temperature for 3 days
  7. filtrationThe reaction solution was filtered through Celite
  8. concentrationthe filtrate was concentrated in vacuo
  9. customThe resulting residue was purified by silica gel column chromatography

出典と根拠

ORDレコード
ord-b31f77fc53c9453585b6d15f3bcbf7a8
出典データセット
uspto-grants-2007_12
特許番号
US07307074B2

反応ノート

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