Diisopropylamine → HCID 20146597, 화합물

HRID 569910노트

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HRID 569910 반응식
C([Li])CCC.C(NC(C)C)(C)C.[CH3:13][N:14]1[C:22]2[CH2:21][C:20]([CH3:24])([CH3:23])[CH2:19][C:18](=[O:25])[C:17]=2[CH:16]=[N:15]1.[CH:26](OCC)=[O:27]>CCCCCC.O1CCCC1.O>[CH3:13][N:14]1[C:22]2[CH2:21][C:20]([CH3:23])([CH3:24])[CH:19]([CH:26]=[O:27])[C:18](=[O:25])[C:17]=2[CH:16]=[N:15]1

참가 물질

8

반응물 4

HCID 7912DiisopropylamineHCID 8025Ethyl formateHCID 13070778HCID 13070778, 화합물HCID 178418339Butyllithium

생성물 1

HCID 20146597HCID 20146597, 화합물

시약·촉매·용매 3

HCID 962Water용매HCID 8028Tetrahydrofuran용매2회HCID 8058Hexane용매

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온도
0 °C

실험 절차

n-Butyllithium (23.8 ml of a 2.60 M solution in hexane) was added slowly to an ice-cold solution of 8.7 ml of N,N-diisopropylamine in 30 ml of anhydrous tetrahydrofuran. The solution was stirred at 0° C. for 15 minutes and treated with 10.8 ml of hexamethylphosporamide; it was then stirred at 0° C. for 15 minutes and cooled to -78° C. A solution of 5 g of 1,5,6,7-tetrahydro-1,6,6-trimethyl-4H-indazol-4-one in 150 ml of anhydrous tetrahydrofuran was added dropwise, followed by the dropwise addition of 8.9 ml of ethyl formate. The reaction was allowed to warm to room temperature and was stirred for 20 hours and 150 ml of water was added and the mixture was extracted with dichloromethane. The aqueous layer was acidified with aqueous hydrochloric acid and extracted exhaustively with dichloromethane. The combined extracts were dried over magnesium sulfate and concentrated in vacuo to provide a dark oil which crystallized upon standing. Flash chromatography of this material (10% acetone in dichloromethane) on silica gel provided product as light yellow crystals. Recrystallization from hexane/toluene gave 4,5,6,7-tetrahydro-1,6,6-trimethyl-4-oxo-1 H-indazole-5-carboxaldehyde melting at about 131°-132° C.

후처리

  1. additiontreated with 10.8 ml of hexamethylphosporamide
  2. stirringit was then stirred at 0° C. for 15 minutes
  3. temperaturecooled to -78° C
  4. temperatureto warm to room temperature
  5. stirringwas stirred for 20 hours
  6. extractionthe mixture was extracted with dichloromethane
  7. extractionextracted exhaustively with dichloromethane
  8. dry with materialThe combined extracts were dried over magnesium sulfate
  9. concentrationconcentrated in vacuo
  10. customto provide a dark oil which
  11. customcrystallized
  12. customRecrystallization from hexane/toluene

출처 및 근거

ORD 기록
ord-b301c9f651914e8790f3f530dbe29170
출처 데이터셋
uspto-grants-1988_03
특허 번호
US04734430

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