Diisopropylamine → HCID 13655521, compound

HRID 1380786Notes

Reaction equation

HRID 1380786 reaction equation
C(NC(C)C)(C)C.C([Li])CCC.[C:13]([CH:15]([N:17]1[CH:21]=[N:20][CH:19]=[N:18]1)[CH3:16])#[N:14].[Cl:22][C:23]1[CH:30]=[C:29]([Cl:31])[CH:28]=[CH:27][C:24]=1[CH:25]=[O:26].[Cl-].[NH4+]>O1CCCC1>[C:13]([C:15]([CH3:16])([N:17]1[CH:21]=[N:20][CH:19]=[N:18]1)[CH:25]([OH:26])[C:24]1[CH:27]=[CH:28][C:29]([Cl:31])=[CH:30][C:23]=1[Cl:22])#[N:14]

Participants

7

Reactant 5

HCID 7912DiisopropylamineHCID 134042,4-DichlorobenzaldehydeHCID 25517Ammonium ChlorideHCID 13655520HCID 13655520, compoundHCID 178418339Butyllithium

Product 1

HCID 13655521HCID 13655521, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

To a 3-neck, 250-ml flask equipped with an addition funnel, argon inlet and a septum were added 25 mls of anhydrous tetrahydrofuran and 5.7 mls of diisopropylamine (passed through activity I neutral alumina) under an argon atmosphere. The system was cooled to about 0° C. and 33 mls of 1.6M butyl lithium solution (in hexane) were then added via a syringe. The system was stirred at 0° C. for 5 minutes and then further cooled to -68° C. After cooling, 6.1 gms of 1-cyano-1-(1,2,4-triazol-1-yl)ethane in tetrahydrofuran were added to the system. The system was stirred at -68° C. for 1 hour and then 8.8 gms of 2,4-dichlorobenzaldehyde were slowly added to the system. The system was allowed to warm to room temperature over 30 minutes. Saturated aqueous ammonium chloride was then added to the system and the product was extracted with methylene chloride. The organic solution was washed with water, dried over sodium sulfate and filtered. The solvent was removed by stripping to yield a yellow oil. This oil was then taken up in diethyl ether resulting in the precipitation of 4.1 gms of the erythio isomer of the title compound. The mother liquors were concentrated and again taken up in diethyl ether resulting in the precipitation of 2.60 gms of the threo isomer of the title compound, m.p. 164° -168° C.

Workup

  1. customTo a 3-neck, 250-ml flask equipped with an addition funnel, argon inlet
  2. temperaturefurther cooled to -68° C
  3. temperatureAfter cooling
  4. stirringThe system was stirred at -68° C. for 1 hour
  5. temperatureto warm to room temperature over 30 minutes
  6. extractionthe product was extracted with methylene chloride
  7. washThe organic solution was washed with water
  8. dry with materialdried over sodium sulfate
  9. filtrationfiltered
  10. customThe solvent was removed
  11. customto yield a yellow oil
  12. customThis oil was then taken up in diethyl ether resulting in the precipitation of 4.1 gms of the erythio isomer of the title compound
  13. concentrationThe mother liquors were concentrated
  14. customagain taken up in diethyl ether resulting in the precipitation of 2.60 gms of the threo isomer of the title compound, m.p. 164° -168° C.

Sources & evidence

ORD record
ord-c6da246f2da447b2bf503e16e3b3373f
Source dataset
uspto-grants-1986_04
Patent number
US04584008

Reaction notes

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