Hydrochloric Acid → Terphenyl scaffold, 16

HRID 25837

Reaktionsgleichung

Reaktionsgleichung von HRID 25837
[CH2:1]([C:8]1[CH:9]=[C:10]([C:28]2[CH:33]=[CH:32][C:31]([CH2:34]CC#N)=[CH:30][C:29]=2[CH2:38][CH:39]([CH3:41])[CH3:40])[CH:11]=[CH:12][C:13]=1[C:14]1[CH:19]=[CH:18][C:17]([O:20]CC#N)=[C:16]([CH2:24][CH:25]([CH3:27])[CH3:26])[CH:15]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C1COCC1.Cl.C(Cl)Cl.CO.CC[O:55][C:56]([CH3:58])=[O:57].[CH3:59][C:60]([OH:62])=[O:61]>CO>[CH2:1]([C:8]1[CH:9]=[C:10]([C:28]2[CH:33]=[CH:32][C:31]([CH2:34][CH2:58][C:56]([OH:55])=[O:57])=[CH:30][C:29]=2[CH2:38][CH:39]([CH3:41])[CH3:40])[CH:11]=[CH:12][C:13]=1[C:14]1[CH:19]=[CH:18][C:17]([O:20][CH2:59][C:60]([OH:62])=[O:61])=[C:16]([CH2:24][CH:25]([CH3:27])[CH3:26])[CH:15]=1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Komponenten

7

Edukt 5

HCID 313Hydrochloric AcidHCID 8028TetrahydrofuranHCID 21226129Dichloromethane methanolHCID 225652413-(3'-Benzyl-4''-(cyanomethoxy)-2,3''-diisobutyl-1,1': 4',1''-terphenyl-4-yl)propanenitrileHCID 22609514Ethyl acetate acetate

Produkt 1

HCID 10120948Terphenyl scaffold, 16Ausbeute 76,67 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 887MethanolLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

To a solution of 86.4 mg (159.78 μmol) 3-(3′-Benzyl-4″-(cyanomethoxy)-2,3″-diisobutyl-1,1′:4′,1″-terphenyl-4-yl)propanenitrile (57) in 6 ml methanol and 6 ml THF 3 ml (24.90 mmol, 155 eq.) 25% aq. NaOH-solution was added. The resulting mixture was refluxed for 24 h and then cooled to 0° C. After acidifying to pH 2 by adding 1 N aq. HCl-solution brine was added and the mixture was extracted with THF. The comb. org. fractions were washed twice with brine, dried over MgSO4 and evaporated. Column chromatography (first CH2Cl2/MeOH (4+1), then EtOAc/HOAc (95+5)) yielded 70.9 mg (122.5 μmol, 76.67%) 3-(3′-Benzyl-4″-(carboxymethoxy)-2,3″-diisobutyl-1,1′:4′,1″-terphenyl-4-yl)propanoic acid (58) as a white solid. Rf (EtOAc/HOAc (95+5))=0.76. 1H-NMR (500 MHz, d4-MeOH+1% d4-HOAc): δ=0.83 (d, 6H, J=6.62 Hz, 2*CH3), 1.02 (d, 6H, J=6.62 Hz, 2*CH3), 1.76 (m, 1H, CH), 2.07 (m, 1H, CH), 2.60 (d, 2H, J=7.25 Hz, CH2), 2.68 (d, 2H, J=7.25 Hz, CH2), 2.77 (t, 2H, J=7.57 Hz, CH2CH2CO2H), 3.06 (t, 2H, J=7.57 Hz, CH2CH2CO2H), 4.14 (s, 2H, CH2Ph), 4.79 (s, 2H, OCH2CO2H), 6.99 (d, 1H, J=8.36 Hz), 7.10 (m, 2H), 7.21-7.33 (m, 10H), 7.39 (d, 1H, J=7.72 Hz). 13C-NMR (125 MHz, d4-MeOH+1% d4-HOAc): δ =20.89, 22.85, 23.04, 29.82, 30.66, 30.92, 31.78, 35.38, 36, 89, 40.01, 40.52, 44.83, 112.38, 126.21, 126.74, 126.81, 128.36, 128.88, 129.30, 129.76, 131.08, 131.17, 131.31, 132.74, 133.18, 135.33, 139.16, 140.26, 140.92, 141.37, 141.81, 142.40, 143.14, 156.93, 160.58, 171.38, 178.30. MS (ESI): 580 (10), 579 (42), 578 (100), 326 (10), 312 (19), 289 (26), 260 (15), 186 (12), 173 (10). HR-MS (FAB): Calcd. for C38H42O5: 578.303225. Found: 578.303100.

Aufarbeitung

  1. temperatureThe resulting mixture was refluxed for 24 h
  2. additionwas added
  3. extractionthe mixture was extracted with THF
  4. washfractions were washed twice with brine
  5. dry with materialdried over MgSO4
  6. customevaporated

Quellen und Nachweise

ORD-Eintrag
ord-f26b02bf029e44a1a70f25c9ea777b1f
Quelldatensatz
uspto-grants-2005_02
Patentnummer
US06858600B2

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