Triethylamine → Diethyl[3-(1-tridecynyl)phenyl]phosphonate

HRID 1647965

Reaktionsgleichung

Reaktionsgleichung von HRID 1647965
C([C:3]1[CH:8]=[CH:7][C:6]([P:9](=[O:12])([O-:11])[O-:10])=[C:5](CC)[C:4]=1I)C.[CH:16]#[C:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH3:28].[C:29]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C[CH:30]=1.[CH2:48](N(CC)CC)[CH3:49]>C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH2:29]([O:11][P:9]([C:6]1[CH:7]=[CH:8][CH:3]=[C:4]([C:16]#[C:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH3:28])[CH:5]=1)(=[O:12])[O:10][CH2:48][CH3:49])[CH3:30]

Komponenten

6

Edukt 4

HCID 8471TriethylamineHCID 11776TriphenylphosphineHCID 1177541-TridecyneHCID 86748802Diethyl-3-iodophenylphosphonate

Produkt 1

HCID 9908538Diethyl[3-(1-tridecynyl)phenyl]phosphonateAusbeute 17,7 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 167845palladium(II) acetateKatalysator

Versuchsvorschrift

Diethyl-3-iodophenylphosphonate prepared according to Example 7 (2.0 g, 5.88 mmol) and 1-tridecyne (1.79 g, 9.97 mmol) were dissolved in triethyl amine (40 ml) in a two neck round bottom flask equipped with a condenser and a nitrogen dispersing tube. The flask was inerted. Triphenylphosphine (0.047 g, 0.179 mmol) and palladium acetate (0.015 g, 0.0668 mmol) were then added and the flask was heated in an oil bath to 100° to 105° C. for 40 hours. After cooling to room temperature and filtering, the triethylamine was removed on the rotary evaporator. The residue was extracted several times with acetonitrile, and the combined extracts were stripped down to a reddish brown liquid. Chromatography on silica eluting with 20% hexane in ethyl acetate gave the product as a pale yellow oil, 0.410 g, 1.045 mmol, 17.7% yield; 1H NMR (CDCl3) ∂ 0.88 (t, J=6.8 Hz, 3H), 1.18 to 1.50 (several m, 22H), 1.60 (quint, J=7.6 Hz, 2H), 2.40 (t, J=7.1 Hz, 2H), 4.11 (m, 4H), 7.38 (m, 1H), 7.55 (br d, J=7.8 Hz, 1H), 7.71 (dd, J=13.2, 7.6 Hz, 1H), 7.83 (d, J=14.1 Hz, 1H); FAB mass spectrum m/z 399 (M+Li)+.

Aufarbeitung

  1. customequipped with a condenser and a nitrogen dispersing tube
  2. temperaturethe flask was heated in an oil bath to 100° to 105° C. for 40 hours
  3. filtrationfiltering
  4. customthe triethylamine was removed on the rotary evaporator
  5. extractionThe residue was extracted several times with acetonitrile

Quellen und Nachweise

ORD-Eintrag
ord-3b0dd004643744b48019d6d26047b22c
Quelldatensatz
uspto-grants-1995_07
Patentnummer
US05434288

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