Sodium Carbonate → 3-(2-Isobutyl-4'-methoxy-3'-naphthalen-1-ylmethyl-biphenyl-4-yl)propionitrile

HRID 971353

Reaktionsgleichung

Reaktionsgleichung von HRID 971353
FC(F)(F)S(O[C:7]1[CH:12]=[CH:11][C:10]([CH2:13][CH2:14][C:15]#[N:16])=[CH:9][C:8]=1[CH2:17][CH:18]([CH3:20])[CH3:19])(=O)=O.[CH3:23][O:24][C:25]1[CH:30]=[CH:29][C:28](B2OC(C)(C)C(C)(C)O2)=[CH:27][C:26]=1[CH2:40][C:41]1[C:50]2[C:45](=[CH:46][CH:47]=[CH:48][CH:49]=2)[CH:44]=[CH:43][CH:42]=1.C([O-])([O-])=O.[Na+].[Na+]>COCCOC.CCO.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH2:17]([C:8]1[CH:9]=[C:10]([CH2:13][CH2:14][C:15]#[N:16])[CH:11]=[CH:12][C:7]=1[C:28]1[CH:29]=[CH:30][C:25]([O:24][CH3:23])=[C:26]([CH2:40][C:41]2[C:50]3[C:45](=[CH:46][CH:47]=[CH:48][CH:49]=3)[CH:44]=[CH:43][CH:42]=2)[CH:27]=1)[CH:18]([CH3:20])[CH3:19]

Komponenten

6

Edukt 3

HCID 10340Sodium CarbonateHCID 121347033-Isobutyl-4-(trifluoromethylsulfonyloxy)benzenepropanenitrileHCID 225652322-(4-Methoxy-3-naphthalen-1-ylmethyl-phenyl)-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane

Produkt 1

HCID 225652733-(2-Isobutyl-4'-methoxy-3'-naphthalen-1-ylmethyl-biphenyl-4-yl)propionitrileAusbeute 88,1 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 178418397HCID 178418397, VerbindungKatalysatorHCID 20074477Dimethoxyethane ethanolLösungsmittel

Reaktionsbedingungen

Temperatur
80 °C

Versuchsvorschrift

452 mg (1.35 mmol) 4-(2-Cyanoethyl)-2-isobutylphenyl-trifluormethanesulfonate (6), 637.8 mg (1.70 mmol, 1.26 eq.) 2-(4-Methoxy-3-naphthalen-1-ylmethyl-phenyl)-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane (64) and 236.8 mg (205 μmol, 0.15 eq.) Pd(Ph3P)4 were dissolved in 20 ml DME/EtOH (9+1). To this yellow solution 1.35 ml (2.70 mmol, 2 eq.) of a 2 M aq. Na2CO3-solution was added and the resulting mixture was heated at 80° C. for 15 h. After concentrating the mixture in vacuo the residue was taken up in water and extracted with CH2Cl2. The comb. org. fractions were dried over MgSO4 and evaporated. Column chromatography (hexanes/EtOAc (3+1)) yielded 513.8 mg (1.19 mmol, 87.78%) 3-(2-Isobutyl-4′-methoxy-3′-naphthalen-1-ylmethyl-biphenyl-4-yl)propionitrile (65) as a clear oil. Rf (hexanes/EtOAc (3+1))=0.40. 1H-NMR (500 MHz, CDCl3): δ=0.51 (d, 6H, J=6.62 Hz, 2*CH3), 1.42 (m, 1H, CH), 2.17 (d, 2H, J=7.25 Hz, CH2), 2.56 (t, 2H, J=7.41 Hz, CH2CH2CN), 2.87 (t, 2H, J=7.41 Hz, CH2CH2CN), 3.91 (s, 3H, OCH3), 4.42 (s, 2H, CH2Naphthyl), 6.71 (d, 1H, J=2.21 Hz), 6.94 (m, 3H), 7.00 (d, 1H, J=7.72 Hz), 7.04 (dd, 1H, J1=8.36 Hz, J2=2.36 Hz), 7.22 (m, 1H), 7.35 (m, 1H), 7.41 (m, 2H), 7.69 (d, 1H, J=8.20 Hz), 7.81 (m, 1H), 7.97 (m, 1H). MS (EI): m/z=434 (16), 433 (48), 336 (9), 335 (56), 294 (11), 293 (83), 292 (17), 277 (9), 265 (20), 264 (100), 253 (29). HR-MS (EI): Calcd. for C31H31NO: 433.240564. Found: 433.241264.

Aufarbeitung

  1. concentrationAfter concentrating the mixture in vacuo the residue
  2. extractionextracted with CH2Cl2
  3. dry with materialfractions were dried over MgSO4
  4. customevaporated

Quellen und Nachweise

ORD-Eintrag
ord-32aaf0cca9d0421e8a9c777556c666f2
Quelldatensatz
uspto-grants-2007_12
Patentnummer
US07312246B2

Verknüpfte Notizen

Wird geladen…