Hydrochloric Acid → 6-(3,4-Dimethoxy-benzoyl)-cyclohex-3-enecarboxylic acid

HRID 1919539Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1919539
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([Mg]Br)[CH:6]=[CH:7][C:8]=1[O:9][CH3:10].[C:13]1(=[O:23])[O:18][C:16](=[O:17])[C@H:15]2[CH2:19][CH:20]=[CH:21][CH2:22][C@@H:14]12.[NH4+].[Cl-].Cl>C1COCC1.C(Cl)Cl>[CH3:1][O:2][C:3]1[CH:4]=[C:5]([CH:6]=[CH:7][C:8]=1[O:9][CH3:10])[C:13]([CH:14]1[CH:15]([C:16]([OH:18])=[O:17])[CH2:19][CH:20]=[CH:21][CH2:22]1)=[O:23]

Komponenten

7

Edukt 4

HCID 313Hydrochloric AcidHCID 25517Ammonium ChlorideHCID 98495Tetrahydrophthalic anhydride, cis-HCID 178491916HCID 178491916, Verbindung

Produkt 1

HCID 222196226-(3,4-Dimethoxy-benzoyl)-cyclohex-3-enecarboxylic acidAusbeute 10 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 6344DichloromethaneLösungsmittelHCID 8028TetrahydrofuranLösungsmittel2×

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

A solution of 17 (59 mmol, 0.29 M) in THF was added dropwise to an ice-cooled solution of cis-1,2,3,6-tetrahydrophthalic anhydride in THF (120 mL) over a 1 hr period. After the addition was complete, the resulting mixture was stirred for another 30 min at 0° C. The reaction mixture was allowed to warm to rt and stirred overnight. The reaction was then stopped with sat. NH4Cl and the pH adjusted to 2 with concentrated HCl(aq) and then extracted with diethyl ether. The organic layer was washed with water and subsequently extracted with 1 M NaOH. The combined aqueous extract was acidified with concentrated HCl and extracted with EtOAc (3×100 mL). The organic layers were combined and dried over MgSO4, filtered, and concentrated under reduced pressure to afford oil. The oil was dissolved CH2Cl2 and filtered through silica gel to remove the dicarboxylic acid formed during workup. The product was recrystallized from diethyl ether to afford pure product (1.62 g, 10%) as a white solid; mp=109° C.; LRMS ESI [m−H]− cacld for C16H18O5 289, found m/z 289; 1H NMR (CDCl3, 500 MHz): δ 7.60-7.53 (m, 2 H), 6.92 (d, J=8.4 Hz, 1 H), 5.84-5.82 (m, 1 H), 5.71-5.68 (m, 1 H), 4.03-4.00 (m, 1 H), 3.98 (s, 3 H), 3.95 (s, 1 H), 3.10-3.07 (m, 1 H), 2.90-2.84 (m, 1 H), 2.54-2.44 (m, 3 H).

Aufarbeitung

  1. additionAfter the addition
  2. temperatureto warm to rt
  3. stirringstirred overnight
  4. extractionextracted with diethyl ether
  5. washThe organic layer was washed with water
  6. extractionsubsequently extracted with 1 M NaOH
  7. extractionThe combined aqueous extract
  8. extractionextracted with EtOAc (3×100 mL)
  9. dry with materialdried over MgSO4
  10. filtrationfiltered
  11. concentrationconcentrated under reduced pressure
  12. customto afford oil
  13. filtrationfiltered through silica gel
  14. customto remove the dicarboxylic acid
  15. customformed during workup
  16. customThe product was recrystallized from diethyl ether

Quellen und Nachweise

ORD-Eintrag
ord-b54483a602b14a86b664e289160fcc9a
Quelldatensatz
uspto-grants-2012_05
Patentnummer
US08168635B2

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