Hydrochloric Acid → HCID 23311107, compound

HRID 745935Notes

Reaction equation

HRID 745935 reaction equation
[CH:1]([N-:4][CH:5]([CH3:7])[CH3:6])([CH3:3])C.[Li+].[Li][CH2:10]CCC.C(NC(C)C)(C)C.C[C:22]1[O:26][N:25]=[CH:24][CH:23]=1.NOC1CCCCC=1.[ClH:35]>C1COCC1.CO>[ClH:35].[NH2:25][C:24]1[N:4]2[C:5]([CH2:6][CH2:10][CH2:3][CH2:1]2)=[CH:7][C:22](=[O:26])[CH:23]=1

Participants

9

Reactant 6

HCID 313Hydrochloric Acid2×HCID 7912DiisopropylamineHCID 798335-MethylisoxazoleHCID 2724682Lithium diisopropylamideHCID 67709229HCID 67709229, compoundHCID 178418339Butyllithium

Product 1

HCID 23311107HCID 23311107, compoundYield 29%

Reagents, catalysts & solvents 2

HCID 887MethanolSolvent2×HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of lithium diisopropylamide (LDA), prepared from n-BuLi (64.5 ml, 0.1M) and diisopropylamine (10.1 g, 14 ml, 0.1M) in dry THF (100 ml) was added under N2 at -10° C. 5-methylisoxazole (4.2 g, 4.1 ml, 0.05M). The resultant yellow suspension was stirred (mechanical stirrer) at -10° C. for 1 hr before 1-aza-2-methoxy-1-cyclohexene (5.6 g, 0.05M) was added dropwise. A light yellow precipitate was immediately formed. The mixture was allowed to warm to ambient over a period of 20 hr. MeOH (40 ml) was slowly added and the resulting reddish solution was stirred at ambient for 2 hr. The solvents were evaporated in vacuo, and the residual oil was flash column chromatographed on silica gel (EM-60) with 30% MeOH in CH2Cl2 as the eluent to give the desired free base. The HCl salt was then prepared by adding conc HCl to a solution of the free base in methanol. Recrystallization from MeOH/ether gave the title compound (2.9 g, 29%). TLC (30% MeOH in CH2Cl2); Rf=0.53. IR (KBr), cm-1, 3330, 3180, 3030, 2950.

Workup

  1. additionwas added under N2 at -10° C
  2. additionwas added dropwise
  3. customA light yellow precipitate was immediately formed
  4. temperatureto warm
  5. customThe solvents were evaporated in vacuo
  6. customchromatographed on silica gel (EM-60) with 30% MeOH in CH2Cl2 as the eluent
  7. customto give the desired free base
  8. customRecrystallization from MeOH/ether

Sources & evidence

ORD record
ord-a985bc560616415d9907e3ed1a85ae40
Source dataset
uspto-grants-1986_07
Patent number
US04602013

Reaction notes

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