1-Iodo-4-(trifluoromethoxy)benzene → 2-Methyl-2-{2-methyl-4-[5-(4-trifluoromethoxy-phenyl)-pent-4-ynyloxy]-phenoxy}-propionic acid ethyl ester

HRID 852375Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 852375
I[C:2]1[CH:7]=[CH:6][C:5]([O:8][C:9]([F:12])([F:11])[F:10])=[CH:4][CH:3]=1.[CH2:13]([O:15][C:16](=[O:34])[C:17]([CH3:33])([O:19][C:20]1[CH:25]=[CH:24][C:23]([O:26][CH2:27][CH2:28][CH2:29][C:30]#[CH:31])=[CH:22][C:21]=1[CH3:32])[CH3:18])[CH3:14]>N1CCCCC1.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.[Cu]I>[CH2:13]([O:15][C:16](=[O:34])[C:17]([CH3:33])([O:19][C:20]1[CH:25]=[CH:24][C:23]([O:26][CH2:27][CH2:28][CH2:29][C:30]#[C:31][C:2]2[CH:7]=[CH:6][C:5]([O:8][C:9]([F:12])([F:11])[F:10])=[CH:4][CH:3]=2)=[CH:22][C:21]=1[CH3:32])[CH3:18])[CH3:14]

Komponenten

6

Edukt 2

HCID 27772941-Iodo-4-(trifluoromethoxy)benzeneHCID 866025402-Methyl-2-(2-methyl-4-pent-4-ynyloxy-phenoxy)-propionic acid ethyl ester

Produkt 1

HCID 694586952-Methyl-2-{2-methyl-4-[5-(4-trifluoromethoxy-phenyl)-pent-4-ynyloxy]-phenoxy}-propionic acid ethyl esterAusbeute 81,8 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 178418397HCID 178418397, VerbindungKatalysatorHCID 8082PiperidineLösungsmittel2×

Reaktionsbedingungen

Temperatur
50 °C

Versuchsvorschrift

The synthesis was performed following a procedure of Stara, Irena G.; Stary, Ivo; Kollarovic, Adrian; Teply, Filip; Saman, David; Fiedler, Pavel, Coupling reactions of halobenzenes with alkynes. The synthesis of phenylacetylenes and symmetrical or unsymmetrical 1,2-diphenylacetylenes, Collect. Czech. Chem. Commun. (1999), 64(4), 649-672. To a degassed (argon) solution of 178 mg (0.60 mmol) 1-iodo-4-trifluoromethoxy-benzene in 2 ml piperidine was added 29 mg (0.03 mmol) Pd(PPh3)4 and 5 mg (0.03 mmol) CuI. The reaction mixture was stirred at 50° C. for 10 min, then a solution of 152 mg (0.50 mmol) 2-methyl-2-(2-methyl-4-pent-4-ynyloxy-phenoxy)-propionic acid ethyl ester (example 13A]) in 2 ml piperidine was added dropwise within 1 h. During the addition the oil bath was slowly heated to 80° C. starting after 30 min. The reaction mixture was stirred at this temperature for 3 h and then extracted with chilled aqueous 10% KHSO4/Et2O (three times). The organic phases were washed with aqueous 10% NaCl, dried (Na2SO4) and evaporated. Purification by flash-chromatography on silica gel (n-heptane/EtOAc 95:5 to 9:1) yielded 190 mg of the title compound as a light yellow viscous oil.

Aufarbeitung

  1. customsymmetrical or unsymmetrical 1,2-diphenylacetylenes, Collect
  2. additionDuring the addition the oil bath
  3. temperaturewas slowly heated to 80° C.
  4. waitstarting after 30 min
  5. stirringThe reaction mixture was stirred at this temperature for 3 h
  6. extractionextracted with chilled aqueous 10% KHSO4/Et2O (three times)
  7. washThe organic phases were washed with aqueous 10% NaCl
  8. dry with materialdried (Na2SO4)
  9. customevaporated
  10. customPurification by flash-chromatography on silica gel (n-heptane/EtOAc 95:5 to 9:1)

Quellen und Nachweise

ORD-Eintrag
ord-576f61aa5f82429ab8100addd6edd3ec
Quelldatensatz
uspto-grants-2007_08
Patentnummer
US07253192B2

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