1-Naphthalenecarbonitrile → HCID 14839223, compound

HRID 2165875Notes

Reaction equation

HRID 2165875 reaction equation
[CH2:1]([Li:5])[CH2:2][CH2:3][CH3:4].[CH:6]([NH:9][CH:10]([CH3:12])[CH3:11])([CH3:8])[CH3:7].[Li+].[CH3:14]C([N-]C(C)C)C.[C:21]([C:23]1[C:32]2[C:27](=[CH:28][CH:29]=[CH:30][CH:31]=2)[CH:26]=[CH:25][CH:24]=1)#[N:22].[CH2:33]1[CH2:37][O:36][CH2:35][CH2:34]1>>[Li+:5].[CH3:7][CH:6]([N-:9][CH:10]([CH3:12])[CH3:11])[CH3:8].[CH3:4][C:3]1[CH:14]=[C:34]2[C:33]([CH:37]=[C:21]([C:23]3[C:32]4[C:27](=[CH:28][CH:29]=[CH:30][CH:31]=4)[CH:26]=[CH:25][CH:24]=3)[NH:22][C:35]2=[O:36])=[CH:1][CH:2]=1

Participants

7

Reactant 5

HCID 68461-NaphthalenecarbonitrileHCID 7912DiisopropylamineHCID 8028Tetrahydrofuran5×HCID 2724682Lithium diisopropylamideHCID 178418339Butyllithium

Product 2

HCID 2724682Lithium diisopropylamideHCID 14839223HCID 14839223, compoundYield 68%

Procedure

Part B. A solution of LDA in THF was prepared by the dropwise addition of 1.55M n-butyllithium in hexanes (111 mL, 166 mmol) to a solution of diisopropylamine (22.6 mL, 161 mmol) in THF (750 mL) at -78°. A solution of the product of Part A (29.13 g, 164.3 mmol) in THF (50 mL) was added dropwise to the LDA in THF solution at -78° and the reaction mixture was stirred for 1 hour at -78°. A solution of 1-cyanonaphthalene (25.2 g, 164.5 mmol) in THF (50 mL) was then added dropwise to the reaction mixture at -78°, and the reaction mixture was stirred at -78° for 1 hour after complete addition and then allowed to gradually warm with stirring to room temperature overnight. The reaction mixture was quenched with excess saturated aqueous NH4Cl, and then most of the THF was removed by distillation under nitrogen. The resulting precipitate was filtered, washed with water, dried, and recrystallized from hexane-ethyl acetate to afford the title compound (32.0 g, 112.1 mmol, 68% yield) as a solid: mp 221°-222°; MS m/e 286(M+ +H); IR(CHCl3) 1651 cm-1 ; 1H NMR(CDCl3) δ 8.70(s,1H), 8.23(s,1H), 7.83-8.13(m,3H), 7.40-7.73(m,6H), 6.67(s,1H), 2.53(s,3H). Anal. Calcd for C20H15NO: C,84.19; H,5.30; N,4.91. Found: C,83.93; H,5.03; N,4.79.

Workup

  1. stirringthe reaction mixture was stirred at -78° for 1 hour
  2. additionafter complete addition
  3. temperatureto gradually warm
  4. stirringwith stirring to room temperature overnight
  5. customThe reaction mixture was quenched with excess saturated aqueous NH4Cl
  6. custommost of the THF was removed by distillation under nitrogen
  7. filtrationThe resulting precipitate was filtered
  8. washwashed with water
  9. customdried
  10. customrecrystallized from hexane-ethyl acetate

Sources & evidence

ORD record
ord-ac25d4d5666647faaaf50f2e0ce0ff34
Source dataset
uspto-grants-1990_07
Patent number
US04942163

Reaction notes

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