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

HRID 2089494
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HRID 2089494 반응식
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]
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참가 물질

6

반응물 4

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

생성물 1

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

시약·촉매·용매 1

HCID 8028
Tetrahydrofuran
용매

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온도
0 °C

실험 절차

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);

후처리

  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)

출처 및 근거

ORD 기록
ord-f07e16d2b4044fd49a5db35b9248dd43
출처 데이터셋
uspto-grants-2013_05
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US08436035B2

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