Ethyl 4-iodobenzoate → Ethyl 4-(3,3-dimethylcyclobutanecarbonyl)benzoate

HRID 537484Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 537484
I[C:2]1[CH:12]=[CH:11][C:5]([C:6]([O:8][CH2:9][CH3:10])=[O:7])=[CH:4][CH:3]=1.C([Mg]Cl)(C)C.[CH3:18][C:19]1([CH3:26])[CH2:22][CH:21]([C:23](Cl)=[O:24])[CH2:20]1>O1CCCC1.Cl.[Cu](I)I>[CH3:18][C:19]1([CH3:26])[CH2:22][CH:21]([C:23]([C:2]2[CH:12]=[CH:11][C:5]([C:6]([O:8][CH2:9][CH3:10])=[O:7])=[CH:4][CH:3]=2)=[O:24])[CH2:20]1

Komponenten

7

Edukt 3

HCID 142891Ethyl 4-iodobenzoateHCID 205352373,3-Dimethylcyclobutane-1-carbonyl chlorideHCID 178418918HCID 178418918, Verbindung

Produkt 1

HCID 68157422Ethyl 4-(3,3-dimethylcyclobutanecarbonyl)benzoateAusbeute 74,2 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 83717Copper iodideKatalysatorHCID 313Hydrochloric AcidLösungsmittelHCID 8028TetrahydrofuranLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

In a 3-neck flask at −30° C. (monitored with thermalcouple) containing ethyl 4-iodobenzoate (25.0 g, 89.0 mmol) in anhydrous tetrahydrofuran (148 mL) was added isopropylmagnesium chloride (51.0 mL, 20.4 mmol) dropwise over 30 min. and then stirred at the same temperature for another 105 min. Copper iodide (5.07 g, 26.6 mmol) was then added quickly in one portion. The mixture was brought to −20° C. for 25 min. to ensure the solid has dissolved. The reaction is then brought back to −40° C. 3,3-dimethylcyclobutane carbonyl chloride (15.6 g, 106 mmol) was then added over 5 min. the reaction was then warmed to 0° C. over 4 h. The mixture was then diluted with 1 N HCl and extracted three times with ethyl acetate. The combined organic layers were then washed two times with brine and then dried over sodium sulfate, filtered, and concentrated to provide 26.6 g of crude brown oil. Purification by silica gel flash chromatography twice (0-5% ethyl acetate in heptane) afforded ethyl 4-(3,3-dimethylcyclobutanecarbonyl)benzoate (17.2 g, 74% yield) as an oil. 1H NMR (400 MHz, CDCl3) δ 8.11 (d, J=8.2 Hz, 2H), 7.93 (d, J=8.2 Hz, 2H), 4.40 (q, J=7.2 Hz, 2H), 3.89 (quin, J=8.8 Hz, 1H), 2.27-2.14 (m, 2H), 2.12-2.02 (m, 2H), 1.41 (t, J=7.1 Hz, 3H), 1.27 (s, 3H), 1.08 (s, 3H). MS (M+1): 261.2.

Aufarbeitung

  1. waitThe mixture was brought to −20° C. for 25 min.
  2. dissolutionhas dissolved
  3. customis then brought back to −40° C
  4. extractionextracted three times with ethyl acetate
  5. washThe combined organic layers were then washed two times with brine
  6. dry with materialdried over sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customto provide 26.6 g of crude brown oil
  10. customPurification by silica gel flash chromatography twice (0-5% ethyl acetate in heptane)

Quellen und Nachweise

ORD-Eintrag
ord-502029a10f554724aa09d2e4b9ca88b3
Quelldatensatz
uspto-grants-2014_10
Patentnummer
US08859591B2

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