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

HRID 25842
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HRID 25842 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][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]
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참가 물질

7

반응물 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

생성물 1

HCID 225652343-(3,2''-Diisobutyl-4-methoxy-2'-naphthalen-1-ylmethyl-[1,1':4',1'']-terphenyl-4''-yl)propionitrile
수율 94.23%

시약·촉매·용매 2

HCID 178418397HCID 178418397, 화합물촉매HCID 20074477Dimethoxyethane ethanol용매

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온도
80 °C

실험 절차

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.

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-f29ebb2e557249cd848321619d229744
출처 데이터셋
uspto-grants-2005_02
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US06858600B2

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