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

HRID 25842

Reaktionsgleichung

Reaktionsgleichung von HRID 25842
[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][C:26]3[C:35]4[C:30](=[CH:31][CH:32]=[CH:33][CH:34]=4)[CH:29]=[CH:28][CH:27]=3)[CH:12]=2)=[C:7]([CH2:36][CH:37]([CH3:39])[CH3:38])[CH:6]=1)#[N:2].[CH2:40]([C:44]1[CH:45]=[C:46](B2OC(C)(C)C(C)(C)O2)[CH:47]=[CH:48][C:49]=1[O:50][CH3:51])[CH:41]([CH3:43])[CH3:42].C([O-])([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>[CH2:40]([C:44]1[CH:45]=[C:46]([C:14]2[CH:15]=[CH:16][C:11]([C:8]3[CH:9]=[CH:10][C:5]([CH2:4][CH2:3][C:1]#[N:2])=[CH:6][C:7]=3[CH2:36][CH:37]([CH3:38])[CH3:39])=[CH:12][C:13]=2[CH2:25][C:26]2[C:35]3[C:30](=[CH:31][CH:32]=[CH:33][CH:34]=3)[CH:29]=[CH:28][CH:27]=2)[CH:47]=[CH:48][C:49]=1[O:50][CH3:51])[CH:41]([CH3:42])[CH3:43]

Komponenten

7

Edukt 4

HCID 6344DichloromethaneHCID 10340Sodium CarbonateHCID 121347052-(3-Isobutyl-4-methoxyphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneHCID 86587142Trifluoro-methanesulfonic acid 4'-(2-cyano-ethyl)-2'-isobutyl-3-naphthalen-1-ylmethyl-biphenyl-4-yl-ester

Produkt 1

HCID 225652343-(3,2''-Diisobutyl-4-methoxy-2'-naphthalen-1-ylmethyl-[1,1':4',1'']-terphenyl-4''-yl)propionitrileAusbeute 94,23 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 178418397HCID 178418397, VerbindungKatalysatorHCID 20074477Dimethoxyethane ethanolLösungsmittel

Reaktionsbedingungen

Temperatur
80 °C

Versuchsvorschrift

439.6 mg (0.80 mmol) Trifluoro-methanesulfonic acid 4′-(2-cyano-ethyl)-2′-isobutyl-3-naphthalen-1-ylmethyl-biphenyl-4-yl-ester (67), 266.2 mg (0.92 mmol, 1.15 eq.) 2-(3-isobutyl-4-methoxyphenyl)-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane (11, FIG. 6) and 140.4 mg (121.4 μmol, 0.15 eq.) Pd(Ph3P)4 were dissolved in 15 ml DME/EtOH (9+1). To this yellow solution 0.80 ml (1.60 mmol, 2.00 eq.) of a 2 M aq. Na2CO3-solution was added and the resulting mixture was heated at 80° C. for 9 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 426.5 mg (0.75 mmol, 94.23%) 3-(3,2″-Diisobutyl-4-methoxy-2′-naphthalen-1-ylmethyl-[1,1′:4′,1″]-terphenyl-4″-yl)propionitrile (68) as a clear oil. Rf (hexanes/EtOAc (6+1))=0.12. 1H-NMR (500 MHz, CDCl3): δ=0.52 (d, 6H, J=6.62 Hz, 2*CH3), 0.77 (d, 6H, J=6.62 Hz, 2*CH3), 1.47 (m, 1H, CH), 1.74 (m, 1H, CH), 2.24 (d, 2H, J=7.41 Hz, CH2), 2.41 (d, 2H, J=7.25 Hz, CH2), 2.58 (t, 2H, J=7.41 Hz, CH2CH2CN), 2.90 (t, 2H, J=7.41 Hz, CH2CH2CN), 3.79 (s, 3H, OCH3), 4.39 (s, 2H, CH2Naphthyl), 6.83 (d, 1H, J=8.36 Hz), 6.96 (m, 2H), 6.99 (dd, 1H, J1=7.88 Hz, J2=1.89 Hz), 7.08 (d, 1H, J=7.57 Hz), 7.11-7.17 (m, 3H), 7.22 (m, 1H), 7.30-7.35 (m, 3H), 7.38 (m, 1H), 7.67 (dm, 1H, J=7.88 Hz), 7.72 (dm, 1H, J=8.20 Hz), 7.78 (dm, 1H, J=8.20 Hz). MS (EI): m/z=565 (14), 452 (11), 410 (10), 404 (19), 403 (59), 349 (24), 306 (10), 290 (13), 247 (35), 191 (13), 142 (14), 141 (100). HR-MS (EI): Calcd. for C41H43NO: 565.334464. Found: 565.334575.

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-f29ebb2e557249cd848321619d229744
Quelldatensatz
uspto-grants-2005_02
Patentnummer
US06858600B2

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