4-Iodophenol → 3-(4-(Carboxymethoxy)-2,2''-diisobutyl-3-naphthalen-1-ylmethyl-[1,1':4',1'']-terphenyl-4''-yl)propionic acid

HRID 25848

Reaktionsgleichung

Reaktionsgleichung von HRID 25848
[Cl-].[Na+].O.O.Br[C:6]1[CH:7]=[CH:8][C:9]([OH:20])=[C:10]([C:12]([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)=O)[CH:11]=1.C(C1C=C(C2C=CC(CCC#N)=CC=2CC(C)C)C=CC=1C1C=CC(OCC#N)=C(CC2C=CC=CC=2)C=1)[C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1.C(C1C=C([C:86]2[CH:91]=[CH:90][C:89](CCC#N)=[CH:88][C:87]=2CC(C)C)C=CC=1OS(C(F)(F)F)(=O)=O)C1C=CC=CC=1.COC1C=CC=[CH:107][C:103]=1[C:104]([OH:106])=[O:105].C(C1C=C(C2C=CC(CCC#N)=CC=2[CH2:136][CH:137]([CH3:139])[CH3:138])C=CC=1OC)C1C=CC=CC=1.C(COC1C=CC(C2C=CC(C3C=CC(CCC#N)=CC=3CC(C)C)=CC=2CC2C3C(=CC=CC=3)C=CC=2)=CC=1[CH2:181][CH:182]([CH3:184])[CH3:183])#N.C(C1C=C(C2C=CC(CCC(O)=O)=CC=2CC(C)C)C=CC=1C1C=CC(O[CH2:205][C:206]([OH:208])=[O:207])=C(CC(C)C)C=1)C1C=CC=CC=1.I[C:229]1[CH:234]=CC(O)=[CH:231][CH:230]=1>CC(O)=O>[C:206]([CH2:205][O:20][C:9]1[CH:8]=[CH:7][C:6]([C:86]2[CH:87]=[CH:88][C:89]([C:27]3[CH:26]=[CH:25][C:24]([CH2:107][CH2:103][C:104]([OH:106])=[O:105])=[CH:23][C:22]=3[CH2:184][CH:182]([CH3:181])[CH3:183])=[CH:90][CH:91]=2)=[C:11]([CH2:139][CH:137]([CH3:136])[CH3:138])[C:10]=1[CH2:12][C:14]1[C:19]2[C:18](=[CH:234][CH:229]=[CH:230][CH:231]=2)[CH:17]=[CH:16][CH:15]=1)([OH:208])=[O:207]

Komponenten

11

Edukt 9

HCID 108944-IodophenolHCID 113702-Methoxybenzoic acidHCID 2290095-Bromo-2-hydroxybenzophenoneHCID 10120948Terphenyl scaffold, 16HCID 121347103-(3'-Benzyl-2-isobutyl-4'-methoxy-1,1'-biphenyl-4-yl)propanenitrile2×HCID 12134712Trifluoro-methanesulfonic acid 3-benzyl-4'-(2-Cyano-ethyl)-2'-isobutyl-biphenyl-4-yl esterHCID 121347153-(3',3''-Dibenzyl-4''-(cyanomethoxy)-2-isobutyl-1,1':4',1''-terphenyl-4-yl)propanenitrileHCID 225652383-(4-Cyanomethoxy-3,2''-diisobutyl-2'-naphthalen-1-ylmethyl-[1,1':4',1'']-terphenyl-4''-yl)propionitrileHCID 23713072Sodium chloride dihydrate

Produkt 1

HCID 225652143-(4-(Carboxymethoxy)-2,2''-diisobutyl-3-naphthalen-1-ylmethyl-[1,1':4',1'']-terphenyl-4''-yl)propionic acid

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 176Acetic AcidLösungsmittel

Versuchsvorschrift

To a solution of 36.3 mg (55.26 μmol) 3-(2′,2″-Diisobutyl-4-methoxycarbonylmethoxy-3-naphthalen-1-ylmethyl-[1,1′:4′,1″]-terphenyl-4″-yl)propionic acid methyl ester (79) in 8 ml 1.4-dioxane 2.0 ml (16.60 mmol, 301 eq.) 25% aq. NaOH-solution and 2.0 ml (3.08 mmol, 56 eq.) 40% aq. solution of Bu4NOH were added. The resulting mixture was refluxed for 24 h and then cooled to 0° C. Acidification to pH 1 by adding 1 N aq. HCl-solution led to a white precipitate which was obtained by filtration. A filtration over silica gel with EtOAc/HOAc (95+5)) as an eluent and a following lyophilization of the obtained oily product from a solution in CH3CN and aq. NH3-solution yielded 36.6 mg (55.2 μmol, 100%) of the bisammonia-salt of 3-(4-(Carboxymethoxy)-2,2″-diisobutyl-3-naphthalen-1-ylmethyl-[1,1′:4′,1″]-terphenyl-4″-yl)propionic acid (80) as a white solid. Rf (hexanes/EtOAc (1+1), sample dissolved in HOAc)=0.49. 1H-NMR (500 MHz, d4-MeOH): δ=0.43 (d, 6H, J=6.62 Hz, 2*CH3), 0.65 (d, 6H, J=6.62 Hz, 2*CH3), 1.35 (m, 1H, CH), 1.58 (m, 1H, CH), 2.14 (d, 2H, J=7.41 Hz, CH2), 2.44 (d, 2H, J=7.25 Hz, CH2), 2.56 (t, 2H, J=7.41 Hz, CH2CH2CO2NH4), 2.90 (t, 2H, J=7.57 Hz, CH2CH2NH4), 4.58 (s, 2H, CH2Naphthyl), 4.59 (s, 2H, OCH2CO2NH4), 6.62 (d, 1H, J=2.05 Hz), 6.89-7.08 (m, 8H), 7.38-7.45 (m, 4H), 7.73 (m, 1H), 7.83 (m, 1H), 8.08 (m, 1H). 13C-NMR (125 MHz, d4-MeOH): δ=22.97, 23.13, 30.75, 31.02, 32.69, 33.91, 38.49, 43.45, 43.73, 68.54, 112.71, 126.33, 126.85, 126.92, 126.99, 127.26, 128.00, 128.35, 129.01, 129.22, 129.90, 130.84, 131.09, 131.41, 131.49, 132.31, 132.42, 134.19, 135.91, 135.95, 138.60, 140.16, 140.53, 141.56, 141.86, 142.22, 142.28, 157.00, 177.34, 178.03. MS (FAB−): m/z=629 (18), 628 (29), 627 (54), 570 (42), 569 (100), 568 (16), 567 (24), 527 (24), 526 (30), 525 (70), 524 (30), 523 (58), 481 (30), 347 (14), 153 (96). HR-MS (FAB−): not possible.

Quellen und Nachweise

ORD-Eintrag
ord-2ef9bba2357243bcbd2780dc1a88b8b0
Quelldatensatz
uspto-grants-2005_02
Patentnummer
US06858600B2

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