Acetic Acid → HCID 178480946、化合物

HRID 51537

反応式

HRID 51537 の反応式
[Cl:1][C:2]1[C:3]2[C:10]([I:11])=[CH:9][N:8]([CH:12]3[CH2:17][CH2:16][C:15](=O)[CH2:14][CH2:13]3)[C:4]=2[N:5]=[CH:6][N:7]=1.[CH3:19][N:20]1[CH2:25][CH2:24][NH:23][CH2:22][CH2:21]1.C(O)(=O)C.COC(OC)OC.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+]>ClC(Cl)C>[Cl:1][C:2]1[C:3]2[C:10]([I:11])=[CH:9][N:8]([C@H:12]3[CH2:17][CH2:16][C@H:15]([N:23]4[CH2:24][CH2:25][N:20]([CH3:19])[CH2:21][CH2:22]4)[CH2:14][CH2:13]3)[C:4]=2[N:5]=[CH:6][N:7]=1

参加物

7

反応物 5

HCID 176Acetic AcidHCID 9005Trimethyl orthoformateHCID 531671-MethylpiperazineHCID 5049666Sodium triacetoxyborohydrideHCID 227364134-(4-Chloro-5-iodo-pyrrolo[2,3-d]pyrimidin-7-yl)-cyclohexanone

生成物 1

HCID 178480946HCID 178480946、化合物収率 24.8%

試薬・触媒・溶媒 1

HCID 63651,1-Dichloroethane溶媒

実験手順

A mixture of 4-(4-chloro-5-iodo-7H-pyrrolo[2,3-d]pyrimidin-7-yl)-1-cyclohexanone (5.6 g, 14.9 mmol), N-methylpiperazine (3.3 mL, 29.8 mmol), acetic acid (2.6 mL, 44.7 mmol), and trimethylorthoformate (9.9 mL, 89.4 mmol) in dichloroethane (100 mL) was stirred at ambient temperature under an atmosphere of nitrogen for 1 hr. Sodium triacetoxyborohydride (14.2 g, 67.05 mmol) was added into the mixture and stirred at ambient temperature under an atmosphere of nitrogen for 18 hours. The solvent was removed under reduced pressure. The residue was partitioned between saturated aqueous sodium bicarbonate solution and ethyl acetate. The water phase was further extracted with ethyl acetate and the combined organic extracts were dried over sodium sulfate. The solvent was removed under reduced pressure and the residue was purified by flash chromatography on silica gel using triethylamine/dichloromethane (2:98) followed by methanol/triethylamine/dichloromethane (2:3:95) as mobile phase to yield trans-4-chloro-5-iodo-7-[4-(4-methylpiperazino)cyclohexyl]-7H-pyrrolo[2,3-d]pyrimidine (1.7 g, 3.7 mmol). 1H NMR (DMSO-d6, 400 MHz) 8.63 (s, 1H), 8.12 (s, 1H), 4.63 (br, 1H), 2.15 (s, 3H), 1.94 (br, 6H), 1.45 (br, 2H) RP-20 HPLC (Hypersil C18, 5 μm, 250×4.6 mm; 25%-100% over 15 min with 0.05 M ammonium acetate, 1 mL/min) Rt 6.17 min.

後処理

  1. stirringstirred at ambient temperature under an atmosphere of nitrogen for 18 hours
  2. customThe solvent was removed under reduced pressure
  3. customThe residue was partitioned between saturated aqueous sodium bicarbonate solution and ethyl acetate
  4. extractionThe water phase was further extracted with ethyl acetate
  5. dry with materialthe combined organic extracts were dried over sodium sulfate
  6. customThe solvent was removed under reduced pressure
  7. customthe residue was purified by flash chromatography on silica gel

出典と根拠

ORDレコード
ord-77b7e1c130ff4c6882060a79fb95c1e7
出典データセット
uspto-grants-2004_03
特許番号
US06713474B2

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