Quinone → Ammonium Hydroxide

HRID 623173

Reaction equation

HRID 623173 reaction equation
[C:1]1(=[O:8])[CH:6]=[CH:5][C:4](=[O:7])[CH:3]=[CH:2]1.[Li+].[C-:10]#[C:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.[Mg](C[CH2:21][CH2:22][N:23]([CH3:25])[CH3:24])Br.[NH4+].[Cl-].[CH2:28]1COCC1>CO.C(Cl)(Cl)Cl>[NH4+:23].[OH-:7].[CH3:24][N:23]([CH:22]([CH3:28])[CH2:21][CH:6]1[CH2:5][C:4](=[O:7])[CH:3]=[CH:2][C:1]1([OH:8])[C:10]#[C:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)[CH3:25]

Participants

8

Reactant 5

HCID 4650QuinoneHCID 8028Tetrahydrofuran3×HCID 25517Ammonium ChlorideHCID 3437284Lithium phenylacetylideHCID 178483493HCID 178483493, compound

Product 2

HCID 14923Ammonium HydroxideYield 0.1%HCID 212923575-[2-(N,N-Dimethylamino)propyl]-4-hydroxy-4-(phenylethynyl)-2-cyclohexen-1-one

Reagents, catalysts & solvents 1

HCID 21584188Chloroform methanolSolvent

Conditions

Temperature
0 °C

Procedure

To a 0° C. solution of p-benzoquinone (1.06 g, 9.79 mmol) in THF (50 mL), was added by cannula solution of lithium phenylacetylide (9.79 mmol; generated as described in Example 23a) in THF (25 mL). After stirring at 0° C. for 15 min, a solution of the Grignard BrMg(CH2)3N(CH3)2 (12.2 mL), 1.6M in THF) and N,N-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (13.5 mL, 112 mmol) was added by cannula. The ice bath was then removed and the reaction was allowed to warm to 23° C. and stir for 1 hr. At this time, TLC (30% EtOAc/hexane) showed no remaining dienone. The reaction was quenched by addition to H2O and Et2O. An emulsion formed which was broken up by addition of saturated NH4Cl. After back extracting the aqueous phase with Et2O (3 times), the combined organic phases were dried (MgSO4) and evaporated leaving a dark brown oil. Column chromatography (flash SiO2, 20% MeOH/CHCl3 and 0.1% NH4OH) of this oil gave 1.12 g of desired title product as a brown gum which crystallized on standing (39% yield).

Workup

  1. customThe ice bath was then removed
  2. temperatureto warm to 23° C.
  3. stirringstir for 1 hr
  4. customThe reaction was quenched by addition to H2O and Et2O
  5. customAn emulsion formed which
  6. extractionAfter back extracting the aqueous phase with Et2O (3 times)
  7. dry with materialthe combined organic phases were dried (MgSO4)
  8. customevaporated
  9. customleaving a dark brown oil

Sources & evidence

ORD record
ord-ef32839dd68944209e4d6293dfbac441
Source dataset
uspto-grants-1988_09
Patent number
US04772755

Linked notes

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