Quinone → Ammonium Hydroxide

HRID 623173

반응식

HRID 623173 반응식
[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]

참가 물질

8

반응물 5

HCID 4650QuinoneHCID 8028Tetrahydrofuran3회HCID 25517Ammonium ChlorideHCID 3437284Lithium phenylacetylideHCID 178483493HCID 178483493, 화합물

생성물 2

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

시약·촉매·용매 1

HCID 21584188Chloroform methanol용매

반응 조건

온도
0 °C

실험 절차

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).

후처리

  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

출처 및 근거

ORD 기록
ord-ef32839dd68944209e4d6293dfbac441
출처 데이터셋
uspto-grants-1988_09
특허 번호
US04772755

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