Triethylamine → ethyl 6-chloro-8-(5-chloro-1-pentynyl)-2-(trifluoromethyl)-2H-1-benzopyran-3-carboxylate

HRID 722323

Reaktionsgleichung

Reaktionsgleichung von HRID 722323
[Cl:1][C:2]1[CH:3]=[C:4](I)[C:5]2[O:10][CH:9]([C:11]([F:14])([F:13])[F:12])[C:8]([C:15]([O:17][CH2:18][CH3:19])=[O:16])=[CH:7][C:6]=2[CH:20]=1.C(N(CC)CC)C.[Cl:29][CH2:30][CH2:31][CH2:32][C:33]#[CH:34]>C1(C)C=CC=CC=1.C(OCC)C.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>[Cl:1][C:2]1[CH:3]=[C:4]([C:34]#[C:33][CH2:32][CH2:31][CH2:30][Cl:29])[C:5]2[O:10][CH:9]([C:11]([F:14])([F:13])[F:12])[C:8]([C:15]([O:17][CH2:18][CH3:19])=[O:16])=[CH:7][C:6]=2[CH:20]=1

Komponenten

8

Edukt 3

HCID 8471TriethylamineHCID 843081-Pentyne, 5-chloro-HCID 21883552ethyl 6-chloro-8-iodo-2-(trifluoromethyl)-2H-chromene-3-carboxylate

Produkt 1

HCID 21883733ethyl 6-chloro-8-(5-chloro-1-pentynyl)-2-(trifluoromethyl)-2H-1-benzopyran-3-carboxylateAusbeute 68 %

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 178418397HCID 178418397, VerbindungKatalysatorHCID 1140TolueneLösungsmittelHCID 3283Diethyl EtherLösungsmittel

Versuchsvorschrift

Ethyl 6-chloro-8-iodo-2-trifluoromethyl-2H-1-benzopyran-3-carboxylate (Example 73, Step 2) (1.50 g, 3.47 mmol), tetrakis(triphenylphosphine)palladium(0) (0.2 g, 0.174 mmol), copper(I)iodide (0.066 g, 0.347 mmol), and triethylamine (1.05 g, 10.4 mmol) were dissolved in toluene (50 mL). 5-Chloro-1-pentyne (0.53 g, 5.20 mmol) was added via syringe and the mixture stirred for 18 hours at room temperature. The reaction was diluted with diethyl ether (50 mL), extracted with 0.5 N HCl (2×25 mL), and water (2×25 mL). The organic phase was dried over MgSO4, filtered, and evaporated to yield an orange oil. The crude material was purified by flash chromatography in 2% ethyl acetate in hexane. Recrystallization from hexane afforded the ester as a white solid (0.96 g, 68%): mp 84.8–85.9° C. 1H NMR (CDCl3/300 MHz) 7.61 (s, 1H), 7.33 (d, 1H, J=2.6 Hz), 7.14 (d, 1H, J=2.6 Hz), 5.79 (q, 1H, J=6.7 Hz), 4.37−4.29 (m, 2H), 3.75 (t, 2H, J=6.7 Hz), 2.67 (t, 2H, J=6.7 Hz), 2.11–2.03 (m, 2H,), 1.35 (t, 3H, J=7.2 Hz). FABLRMS m/z 424.1 (M+NH4+). ESHRMS m/z 424.0694 (M+NH4+, Calc'd. 424.0694). Anal. Calc'd. for C18H15Cl2F3O3: C, 53.09; H,3.71;, Cl,17.41. Found: C, 53.02; H, 3.90; Cl, 17.63.

Aufarbeitung

  1. extractionextracted with 0.5 N HCl (2×25 mL), and water (2×25 mL)
  2. dry with materialThe organic phase was dried over MgSO4
  3. filtrationfiltered
  4. customevaporated
  5. customto yield an orange oil
  6. customThe crude material was purified by flash chromatography in 2% ethyl acetate in hexane
  7. customRecrystallization from hexane

Quellen und Nachweise

ORD-Eintrag
ord-980eda4c911a437487de89bbaa8769c0
Quelldatensatz
uspto-grants-2006_11
Patentnummer
US07138411B2

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