Diisopropylamine → HCID 19001401, compound

HRID 2259605Notes

Reaction equation

HRID 2259605 reaction equation
C([NH:4][CH:5](C)C)(C)C.C([Li])CCC.[Cl:13][C:14]1[CH:15]=[CH:16][C:17]2[C:25]3[CH:21]([CH2:22][N:23]([C:26]([NH:28][C:29]4[CH:34]=[CH:33][C:32]([C:35]([F:38])([F:37])[F:36])=[CH:31][CH:30]=4)=[O:27])[N:24]=3)[CH2:20]C[C:18]=2[CH:39]=1.C1(C)C=CC(S(C#N)(=O)=[O:47])=CC=1.[NH4+].[Cl-]>C1COCC1>[Cl:13][C:14]1[CH:15]=[CH:16][C:17]2[C:25]3[C:21]([C:5]#[N:4])([CH2:20][O:47][C:18]=2[CH:39]=1)[CH2:22][N:23]([C:26]([NH:28][C:29]1[CH:30]=[CH:31][C:32]([C:35]([F:37])([F:36])[F:38])=[CH:33][CH:34]=1)=[O:27])[N:24]=3

Participants

7

Reactant 5

HCID 7912DiisopropylamineHCID 25517Ammonium ChlorideHCID 87946p-Toluenesulphonyl cyanideHCID 23359466HCID 23359466, compoundHCID 178418339Butyllithium

Product 1

HCID 19001401HCID 19001401, compoundYield 66%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
-78 °C

Procedure

To a solution of diisopropylamine (0.42 mL, 3.0 mmoles) in 10 mL of THF was added, n-butyllithium (1.9 mL of 1.6M, 3.0 mmole) at -78° C. under N2. After 15 min, a solution of the product of Step D (0.5 g, 1.3 mmole) in 3 mL of THF was added dropwise and the dark red solution that formed was stirred at -78° C. for an additional 15 min. Then, p-toluene-sulfonyl cyanide (0.31 g, 1.7 mmole) in 2 mL of THF was added dropwise to the reaction mixture which decolorized near the end of the addition. Saturated aqueous NH4Cl was added and the reaction was allowed to warm to room temperature. The aqueous phase was extracted with ethyl acetate and the combined organic phases were dried (MgSO4) and concentrated (vacuum). The resulting solid was triturated with ether to afford the title compound (0.36 g, 66% yield) as a white solid, mp 227°- 229° C. 1H NMR (CDCl3): δ8.10 (s, 1H), 7.91 (d, 1H), 7.62 (ABq, 4H), 7.30 (m, 2H), 4.79 (d, 1H), 3.81 (d, 1H), 3.41 (m, 1H), 3.04 (m, 1H), 2.68 (m, 1H), 2.15 (td, 1H).

Workup

  1. customat -78° C.
  2. customthe dark red solution that formed
  3. additiondecolorized near the end of the addition
  4. temperatureto warm to room temperature
  5. extractionThe aqueous phase was extracted with ethyl acetate
  6. dry with materialthe combined organic phases were dried (MgSO4)
  7. concentrationconcentrated (vacuum)
  8. customThe resulting solid was triturated with ether

Sources & evidence

ORD record
ord-9ce93d33ac4e4093b63c034ae46e222f
Source dataset
uspto-grants-1995_12
Patent number
US05474998

Reaction notes

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