Triphenylphosphine → HCID 68636110, Verbindung

HRID 130602

Reaktionsgleichung

Reaktionsgleichung von HRID 130602
CCOC(/N=N/C(OCC)=O)=O.[OH:13][C:14]1[CH:15]=[C:16]([C:24]([O:26][CH3:27])=[O:25])[CH:17]=[C:18]([CH:23]=1)[C:19]([O:21][CH3:22])=[O:20].[CH2:28](O)[CH2:29][O:30][CH2:31][CH2:32][O:33][CH2:34][CH2:35][O:36][CH2:37][CH2:38][O:39][CH2:40][CH2:41][O:42][CH2:43][CH2:44][OH:45].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C1COCC1>[OH:45][CH2:44][CH2:43][O:42][CH2:41][CH2:40][O:39][CH2:38][CH2:37][O:36][CH2:35][CH2:34][O:33][CH2:32][CH2:31][O:30][CH2:29][CH2:28][O:13][C:14]1[CH:23]=[C:18]([C:19]([O:21][CH3:22])=[O:20])[CH:17]=[C:16]([CH:15]=1)[C:24]([O:26][CH3:27])=[O:25]

Komponenten

6

Edukt 4

HCID 11776TriphenylphosphineHCID 17472Hexaethylene GlycolHCID 830651,3-Benzenedicarboxylic acid, 5-hydroxy-, 1,3-dimethyl esterHCID 5462977Diethyl azodicarboxylate

Produkt 1

HCID 68636110HCID 68636110, VerbindungAusbeute 31,2 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

Diethylazodicarboxylate (22.7 g, 130 mmol) was added over 3 min to a stirred solution of dimethyl 5-hydroxyisophthalate (21 g, 100 mmol), hexaethylene glycol (32 g, 113 mmol) and triphenylphosphine (34 g, 130 mmol) in 250 mL of anhydrous THF. After 2 h the reaction was concentrated and the residue suspended in 200 mL of ethyl ether. After being cooled at 0° C. for 30 min the precipitated triphenylphosphine oxide was removed by filtration and filtrate concentrated. The resultant mixture was chromatographed on silica eluting, first, with ethyl acetate to separate Ph3PO and symmetrical bis-substituted hexaethylene glycol by-product and, second, with 5% MeOH in ethyl acetate to elute desired mono-substituted hexaethylene glycol derivative. Evaporation of the solvent and drying under high vacuum afforded 14.8 g (31%) of the title compound as viscous oil. 1H NMR (DMSO-d6) δ 8.08 (s, 1H), 7.70 (s, 2H), 4.58 (t, J=5.5 Hz, 1H), 4.25 (m, 2H), 3.90 (s, 6H), 3.76 (m, 2H), 3.60 (m, 2H), 3.51 (m, 16H), 3.40 (m, 2H).

Aufarbeitung

  1. concentrationAfter 2 h the reaction was concentrated
  2. customwas removed by filtration and filtrate
  3. concentrationconcentrated
  4. customThe resultant mixture was chromatographed on silica eluting
  5. customfirst, with ethyl acetate to separate Ph3PO and symmetrical bis-substituted hexaethylene glycol by-product
  6. washsecond, with 5% MeOH in ethyl acetate to elute desired mono-substituted hexaethylene glycol derivative
  7. customEvaporation of the solvent
  8. customdrying under high vacuum

Quellen und Nachweise

ORD-Eintrag
ord-3d50f45aab6344f6ab51e11486138497
Quelldatensatz
uspto-grants-2008_06
Patentnummer
US07381818B2

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