Quinone → Ammonium Hydroxide

HRID 623173

反応式

HRID 623173 の反応式
[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]

参加物

8

反応物 5

HCID 4650QuinoneHCID 8028Tetrahydrofuran3 回HCID 25517Ammonium ChlorideHCID 3437284Lithium phenylacetylideHCID 178483493HCID 178483493、化合物

生成物 2

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

試薬・触媒・溶媒 1

HCID 21584188Chloroform methanol溶媒

反応条件

温度
0 °C

実験手順

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).

後処理

  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

出典と根拠

ORDレコード
ord-ef32839dd68944209e4d6293dfbac441
出典データセット
uspto-grants-1988_09
特許番号
US04772755

関連ノート

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