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

HRID 25846

반응식

HRID 25846 반응식
[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]

참가 물질

7

반응물 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

생성물 1

HCID 225652543-(2',2''-Diisobutyl-4-methoxy-3-naphthalen-1-ylmethyl-[1,1':4', 1'']-terphenyl-4''-yl)propionitrile수율 79.86%

시약·촉매·용매 2

HCID 178418397HCID 178418397, 화합물촉매HCID 20074477Dimethoxyethane ethanol용매

반응 조건

온도
80 °C

실험 절차

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.

후처리

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

출처 및 근거

ORD 기록
ord-3e00186e5669411eae11bce3170ef762
출처 데이터셋
uspto-grants-2005_02
특허 번호
US06858600B2

연결된 노트

불러오는 중…