Diisopropylamine → HCID 178434197, compound

HRID 569909Notes

Reaction equation

HRID 569909 reaction equation
C(NC(C)C)(C)C.C([Li])CCC.[CH3:13][C:14]1[C:22]2[C:21](=[O:23])[CH2:20][CH2:19][CH2:18][C:17]=2[NH:16][N:15]=1.[CH:24](OCC)=[O:25]>O1CCCC1.CCCCCC>[OH:25][CH:24]=[C:20]1[CH2:19][CH2:18][C:17]2[NH:16][N:15]=[C:14]([CH3:13])[C:22]=2[C:21]1=[O:23]

Participants

7

Reactant 4

HCID 7912DiisopropylamineHCID 8025Ethyl formateHCID 178418339ButyllithiumHCID 178434195HCID 178434195, compound

Product 1

HCID 178434197HCID 178434197, compound

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Conditions

Temperature
-78 °C

Procedure

To an ice-cold solution of 13.9 ml of diisopropylamine in 50 ml of anhydrous tetrahydrofuran there was added, by syringe, 38 ml of 2.6 N butyllithium in hexane. The mixture was cooled to -78° C. and a solution of 4.5 grams of 1,5,6,7-tetrahydro-3-methyl-4H-indazol-4-one was added dropwise. The mixture was stirred at -78° C. for 30 minutes and a solution of 10 ml of ethyl formate in 30 ml of anhydrous tetrahydrofuran was added dropwise. When the addition was complete, the reaction was allowed to warm to 0° C. and it was quenched by the dropwise addition of water (200 ml). After the mixture was stirred vigorously for a few minutes, the two layers which formed were separated. The aqueous layer was washed with ethyl ether and then acidified to a pH of about 4 with 5 N hydrochloric acid. The slurry which formed was extracted several times with dichloromethane and the combined extracts were dried and concentrated under reduced pressure to give 1,5,6,7-tetrahydro-5-hydroxymethylene-3-methyl-4H-indazol-4-one as a clammy yellow semi-solid.

Workup

  1. additionWhen the addition
  2. temperatureto warm to 0° C.
  3. customit was quenched by the dropwise addition of water (200 ml)
  4. stirringAfter the mixture was stirred vigorously for a few minutes
  5. customthe two layers which formed
  6. customwere separated
  7. washThe aqueous layer was washed with ethyl ether
  8. customThe slurry which formed
  9. extractionwas extracted several times with dichloromethane
  10. customthe combined extracts were dried
  11. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-d18d9dccc92d46a7b26d759974d54b50
Source dataset
uspto-grants-1988_03
Patent number
US04734430

Reaction notes

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