Diisopropylamine → GR 67330

HRID 621206

反応式

HRID 621206 の反応式
C([Li])CCC.C(NC(C)C)(C)C.[CH3:13][N:14]1[C:26]2[CH2:25][CH2:24][CH2:23][C:22](=[O:27])[C:21]=2[C:20]2[C:15]1=[CH:16][CH:17]=[CH:18][CH:19]=2.Cl[CH2:29][C:30]1[N:31]=[CH:32][N:33](C(C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[C:34]=1[CH3:35].C(=O)(O)[O-].[Na+].C(=O)([O-])[O-].[K+].[K+]>C1COCC1.O.C(O)(=O)C.CN(C)P(N(C)C)(N(C)C)=O>[CH3:13][N:14]1[C:26]2[CH2:25][CH2:24][CH:23]([CH2:29][C:30]3[N:31]=[CH:32][NH:33][C:34]=3[CH3:35])[C:22](=[O:27])[C:21]=2[C:20]2[C:15]1=[CH:16][CH:17]=[CH:18][CH:19]=2

参加物

11

反応物 6

HCID 7912DiisopropylamineHCID 11430Potassium CarbonateHCID 516892Sodium BicarbonateHCID 5988759-Methyl-1,2,3,9-tetrahydro-4H-carbazol-4-oneHCID 110469654-(Chloromethyl)-5-methyl-1-trityl-1H-imidazoleHCID 178418339Butyllithium

生成物 1

HCID 172316GR 67330収率 244.5%

試薬・触媒・溶媒 4

HCID 176Acetic Acid溶媒HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒4 回HCID 12679Hexamethylphosphoramide溶媒

実験手順

n-Butyllithium (1.45M in hexane; 2.07 ml) was added dropwise to a cold (-70°) stirred solution of diisopropylamine (0.42 ml) in dry THF (20 ml) under nitrogen. The solution was allowed to reach 0° over 30 min, cooled to -70° and added to a cold (-70°) stirred solution of ) 1,2,3,9-tetrahydro-9-methyl-4H-carbazol-4-one (500 mg) in dry THF (10 ml under nitrogen. Hexamethylphosphoramide (0.44 ml) was added and the mixture was allowed to reach 0° over 1 h. The solution was cooled to -70° and a suspension of 4-(chloromethyl)-5-methyl-1-(triphenylmethyl)-1H-imidazole (936 mg) in dry THF (15 ml) was added and the mixture was allowed to reach ca. 20° over 2.5 h. It was stirred for a further 18 h, poured into 8% sodium bicarbonate solution (100 ml) and extracted with dichloromethane (3×50 ml). The combined, dried organic extracts were evaporated to give a semi-solid which was treated with a mixture of acetic acid (10 ml), water (10 ml) and THF (10 ml) and heated at reflux for 1.5 h. The solution was poured into saturated potassium carbonate solution (100 mml) and extracted with dichloromethane (3×50 ml). The combined, dried organic extracts were evaporated to give a solid (ca. 1.8 g) which was purified by SPCC eluting with System A (200:10:1) to give the title compound (17 mg). The 1H-n.m.r. and t.l.c. of this material were consistent with those obtained from the product of Example 8.

後処理

  1. temperaturecooled to -70°
  2. additionadded to a cold (-70°)
  3. waitto reach 0° over 1 h
  4. temperatureThe solution was cooled to -70°
  5. additionwas added
  6. waitto reach ca. 20° over 2.5 h
  7. extractionextracted with dichloromethane (3×50 ml)
  8. customdried organic extracts were evaporated
  9. customto give a semi-solid which
  10. temperatureheated
  11. temperatureat reflux for 1.5 h
  12. extractionextracted with dichloromethane (3×50 ml)
  13. customdried organic extracts were evaporated

出典と根拠

ORDレコード
ord-fc2e5c44dcea4598abb18788b32d1ac0
出典データセット
uspto-grants-1989_04
特許番号
US04822881

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