Dichloromethane → 3-(2',2''-Diisobutyl-4-methoxy-3-naphthalen-1-ylmethyl-[1,1':4', 1'']-terphenyl-4''-yl)propionitrile

HRID 25846

Reaktionsgleichung

Reaktionsgleichung von HRID 25846
[C:1]([CH2:3][CH2:4][C:5]1[CH:10]=[CH:9][C:8]([C:11]2[CH:16]=[CH:15][C:14](OS(C(F)(F)F)(=O)=O)=[C:13]([CH2:25][CH:26]([CH3:28])[CH3:27])[CH:12]=2)=[C:7]([CH2:29][CH:30]([CH3:32])[CH3:31])[CH:6]=1)#[N:2].CO[C:35]1[CH:40]=[CH:39][C:38](B2OC(C)(C)C(C)(C)O2)=[CH:37][C:36]=1[CH2:50][C:51]1[C:60]2[C:55](=[CH:56][CH:57]=[CH:58][CH:59]=2)[CH:54]=[CH:53][CH:52]=1.[C:61]([O-:64])([O-])=O.[Na+].[Na+].C(Cl)Cl>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>[CH2:25]([C:13]1[CH:12]=[C:11]([C:8]2[CH:9]=[CH:10][C:5]([CH2:4][CH2:3][C:1]#[N:2])=[CH:6][C:7]=2[CH2:29][CH:30]([CH3:32])[CH3:31])[CH:16]=[CH:15][C:14]=1[C:38]1[CH:39]=[CH:40][C:35]([O:64][CH3:61])=[C:36]([CH2:50][C:51]2[C:60]3[C:55](=[CH:56][CH:57]=[CH:58][CH:59]=3)[CH:54]=[CH:53][CH:52]=2)[CH:37]=1)[CH:26]([CH3:28])[CH3:27]

Komponenten

7

Edukt 4

HCID 6344DichloromethaneHCID 10340Sodium CarbonateHCID 225652322-(4-Methoxy-3-naphthalen-1-ylmethyl-phenyl)-4,4,5,5-tetramethyl-[1,3,2]dioxaborolaneHCID 865871433-[2,3'-Diisobutyl-4'-(trifluoromethylsulfonyloxy)-4-biphenylyl]propanenitrile

Produkt 1

HCID 225652543-(2',2''-Diisobutyl-4-methoxy-3-naphthalen-1-ylmethyl-[1,1':4', 1'']-terphenyl-4''-yl)propionitrileAusbeute 79,86 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 178418397HCID 178418397, VerbindungKatalysatorHCID 20074477Dimethoxyethane ethanolLösungsmittel

Reaktionsbedingungen

Temperatur
80 °C

Versuchsvorschrift

202.8 mg (0.43 mmol) Trifluoro-methanesulfonic acid 4′-(2-cyano-ethyl)-3,2′-diisobutyl-biphenyl-4-yl-ester (75), 186.7 mg (0.50 mmol, 1.16 eq.) 2-(4-Methoxy-3-naphthalen-1-ylmethyl-phenyl)-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane (64) and 74.5 mg (64.4 μmol, 0.15 eq.) Pd(Ph3P)4 were dissolved in 10 ml DME/EtOH (9+1). To this yellow solution 0.43 ml (0.86 mmol, 2.00 eq.) of a 2 M aq. Na2CO3-solution was added and the resulting mixture was heated at 80° C. for 22 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 (CH2Cl2) yielded 194.3 mg (0.34 mmol, 79.86%) 3-(2′,2″-Diisobutyl-4-methoxy-3-naphthalen-1-ylmethyl-[1,1′:4′,1″]-terphenyl-4″-yl)propionitrile (76) as a clear oil. Rf (hexanes/EtOAc (6+1))=0.23. 1H-NMR (500 MHz, CDCl3): δ=0.52 (d, 6H, J=6.62 Hz, 2*CH3), 0.69 (d, 6H, J=6.62 Hz, 2*CH3), 1.46 (m, 1H, CH), 1.64 (m, 1H, CH), 2.23 (d, 2H, J=7.41 Hz, CH2), 2.45 (d, 2H, J=7.41 Hz, CH2), 2.61 (t, 2H, J=7.41 Hz, CH2CH2CN), 2.93 (t, 2H, J=7.41 Hz, CH2CH2CN), 3.91 (s, 3H, OCH3), 4.44 (s, 2H, CH2Naphthyl), 6.84 (d, 1H, J=2.21 Hz), 6.95 (d, 1H, J=8.67 Hz), 6.97-7.16 (m, 8H), 7.36 (m, 1H), 7.41-7.45 (m, 2H), 7.70 (m, 1H), 7.81 (m, 1H), 8.01 (m, 1H). MS (EI): m/z=565 (23), 468 (30), 467 (100), 425 (13), 374 (11), 368 (13), 335 (23), 334 (72), 327 (13), 324 (17), 319 (31), 293 (22), 292 (55), 279 (14), 278 (45), 277 (13), 276 (17), 264 (24), 263 (19), 251 (13), 250 (24), 249 (26), 248 (89), 237 (20), 236 (18), 235 (22), 234 (15), 233 (26), 221 (20), 220 (37), 217 (25), 215 (31), 179 (71), 178 (57), 165 (30), 160 (20), 142 (22), 141 (62), 115 (15), 91 (14), 57 (86), 55 (16). HR-MS (EI): Calcd. for C41H43NO: 565.334464. Found: 565.334507.

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-3e00186e5669411eae11bce3170ef762
Quelldatensatz
uspto-grants-2005_02
Patentnummer
US06858600B2

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