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Triphenylphosphine → 1-(2,2-Dimethyl-4-oxotetralin-1-yl)-5-imidazolecarboxylic acid methyl ester

HRID 2089494
ノート
印刷プレビュー

反応式

HRID 2089494 の反応式
O[CH:2]1[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[C:5](=[O:12])[CH2:4][C:3]1([CH3:14])[CH3:13].[NH:15]1[CH:19]=[C:18]([C:20]([O:22][CH3:23])=[O:21])[N:17]=[CH:16]1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OC)=O)=NC(OC)=O>C1COCC1>[CH3:23][O:22][C:20]([C:18]1[N:17]([CH:2]2[C:11]3[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=3)[C:5](=[O:12])[CH2:4][C:3]2([CH3:14])[CH3:13])[CH:16]=[N:15][CH:19]=1)=[O:21]
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

6

反応物 4

HCID 11776TriphenylphosphineHCID 351621Azodicarboxylic acid dimethyl esterHCID 135275814-hydroxy-3,3-dimethyl-3,4-dihydro-2H-naphthalen-1-oneHCID 178418785HCID 178418785、化合物

生成物 1

HCID 249960101-(2,2-Dimethyl-4-oxotetralin-1-yl)-5-imidazolecarboxylic acid methyl ester

試薬・触媒・溶媒 1

HCID 8028
Tetrahydrofuran
溶媒

反応条件

温度
0 °C

実験手順

To a solution of 4-hydroxy-3,3-dimethyl-3,4-dihydro-2H-naphthalen-1-one (2.87 g, 13.88 mmol) and methyl 4-imidazolecarboxylate (CAS#17325-26-7, 1.25 g, 9.72 mmol) in THF (80 mL) at 0° C. is added triphenylphosphine (3.68 g, 13.88 mmol) and dimethyl azodicarboxylate (40% in toluene, 5.14 mL, 13.88 mmol) and the cooling bath is removed. After 15 hours, the mixture is concentrated and the resulting residue is dissolved in ethyl acetate (250 mL) and is extracted five times with 1M aqueous HCl (40 mL portions). The acidic aqueous phases are cooled to 0° C. and the pH is adjusted to ca. 12 with 4M aqueous NaOH at 0° C. The aqueous phase is then extracted three times with dichloromethane. The combined organic layers are dried over MgSO4 and filtered, and concentrated. The resulting residue is purified by silica gel flash chromatography (dichloromethane-methanol, 49:1) to give 3-(2,2-dimethyl-4-oxo-1,2,3,4-tetrahydro-naphthalen-1-yl)-3H-imidazole-4-carboxylic acid methyl ester; MS: (ESI) m/z 299.0 (M+H)+; 1H NMR (400 MHz, CDCl3) δ ppm 0.97 (s, 3 H), 1.15 (s, 3 H), 2.63 (d, J=16.8 Hz, 1 H), 2.74 (d, J=16.8 Hz, 1 H), 3.93 (s, 3 H), 6.79 (s, 1 H), 7.02 (d, J=7.6 Hz, 1 H), 7.35 (s, 1 H), 7.47 (t, J=7.6 Hz, 1 H), 7.55 (td, J=7.6, 1.5 Hz, 1 H), 7.86 (s, 1 H), 8.13 (dd, J=7.6, 1.5 Hz, 1 H);

後処理

  1. customthe cooling bath is removed
  2. concentrationthe mixture is concentrated
  3. dissolutionthe resulting residue is dissolved in ethyl acetate (250 mL)
  4. extractionis extracted five times with 1M aqueous HCl (40 mL portions)
  5. customat 0° C
  6. extractionThe aqueous phase is then extracted three times with dichloromethane
  7. dry with materialThe combined organic layers are dried over MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customThe resulting residue is purified by silica gel flash chromatography (dichloromethane-methanol, 49:1)

出典と根拠

ORDレコード
ord-f07e16d2b4044fd49a5db35b9248dd43
出典データセット
uspto-grants-2013_05
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US08436035B2

反応ノート

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