Potassium Hydroxide → 4-(5,8,8-Trimethyl-7,8-dihydro-naphthalen-2-yl-amino)-benzoic acid ethyl ester

HRID 1795600

Reaktionsgleichung

Reaktionsgleichung von HRID 1795600
CN(C1C=CC2C(C)=CCC(C)(C)C=2C=1)C1C=CC(C(O)=O)=CC=1.[CH2:25]([O:27][C:28](=[O:50])[C:29]1[CH:34]=[CH:33][C:32]([N:35](C)[C:36]2[CH:45]=[CH:44][C:43]3[C:42]([CH3:46])=[CH:41][CH2:40][C:39]([CH3:48])([CH3:47])[C:38]=3[CH:37]=2)=[CH:31][CH:30]=1)[CH3:26].[OH-].[K+]>C(O)C>[CH2:25]([O:27][C:28](=[O:50])[C:29]1[CH:30]=[CH:31][C:32]([NH:35][C:36]2[CH:45]=[CH:44][C:43]3[C:42]([CH3:46])=[CH:41][CH2:40][C:39]([CH3:48])([CH3:47])[C:38]=3[CH:37]=2)=[CH:33][CH:34]=1)[CH3:26]

Komponenten

5

Edukt 3

HCID 14797Potassium HydroxideHCID 21024369HCID 21024369, Verbindung2×HCID 22218212HCID 22218212, Verbindung2×

Produkt 1

HCID 210243674-(5,8,8-Trimethyl-7,8-dihydro-naphthalen-2-yl-amino)-benzoic acid ethyl ester

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 702EthanolLösungsmittel

Reaktionsbedingungen

Temperatur
40 °C

Versuchsvorschrift

PNMR (300 MHz, CDCl3) δ 1.28 (s, 6 H), 1.38 (t, 3 H, J=7.1 Hz), 2.06 (s, 3 H), 2.19 (d, 2 H, J=4.3 Hz), 4.35 (q, 2 H J=7.1 Hz), 5.68 (t, 1 H, J=4.3 Hz), 6.04 (s 1 H, NH), 6.98 (overlapping d & dd, 3 H), 7.11 (d, 1 H, J=2.3 Hz), 7.21 (d, 1 H, J=8.2 Hz), 7.93 (d, 2 H, J=8.8 Hz). 4-Methyl-(5,8,8-trimethyl-7,8-dihydro-naphthalen-2-yl)-amino]-benzoic acid ethyl ester (Compound 66) General Procedure M To a solution of4-(5,8,8-trimethyl-7,8-dihydro-naphthalen-2-ylamino)-benzoic acid ethyl ester (Compound 65, 31 mg, 0.09 mmol) in a 10% acetic acid in acetonitrile solution (1.0 mL) and 1.0 mL of ether were added formaldehyde (0.10 mL, 3.60 mmol) and then sodium cyanoborohydride (14 mg, 0.22 mmol) and the reaction stirred at room temperature for 1 h. 1 M aqueous NaOH was added until pH=6 and the resulting mixture was extracted twice with ethyl ether. The combined organic extracts were washed with brine, dried over Na2SO4, filtered, and the solvents were removed in vacuo. The crude product was purified by silica gel chromatography (10% ethyl acetate in hexanes) to give the title compound as yellow oil. PNMR (300 MHz, CDCl3) δ 1.24 (s, 6 H), 1.37 (t, 3 H, J=7.1 Hz), 2.08 (s, 3 H), 2.23 (d, 2 H, J=4.4 Hz), 3.38 (s, 3 H), 4.34 (q, 2 H, J=7.1 Hz), 5.78 (t, 1 H, J=4.4 Hz), 6.79 (d, 2 H, J=9.0 Hz), 7.03 (dd, 1 H, J=2.3 & 8.2 Hz), 7.16 (d, 1 H, J=2.3 Hz), 7.28 (d, 1 H, J=8.2 Hz), 7.88 (d, 2 H, J=9.0 Hz). 4-[Methyl-(5,8,8-trimethyl-7,8-dihydro-naphthalen-2-yl)-amino]-benzoic acid (Compound 67) General Procedure N A solution of 4-[methyl-(5,8,8-trimethyl-7,8-dihydro-naphthalen-2-yl)-amino]-benzoic acid ethyl ester (Compound 66, 12 mg, 0.03 mmol) in 3.0 mL of ethanol was treated with 0.55 M KOH (1.0 mL). The solution was heated to 40 ° C. and stirred for 20 h. The solution was cooled and concentrated under reduced pressure. The residue was diluted with water, acidified with 10% HCl, and extracted twice with ether. The combined organic extracts were washed with brine, dried over MgSO4, filtered, and the solvents were removed in vacuo to give the title compound as a solid. 4-[Ethyl-(5,8,8-trimethyl-7,8-dihydro-naphthalen-2-yl)-amino]-benzoic acid ethyl ester (Compound 68)

Aufarbeitung

  1. temperatureThe solution was cooled
  2. concentrationconcentrated under reduced pressure
  3. additionThe residue was diluted with water
  4. extractionextracted twice with ether
  5. washThe combined organic extracts were washed with brine
  6. dry with materialdried over MgSO4
  7. filtrationfiltered
  8. customthe solvents were removed in vacuo

Quellen und Nachweise

ORD-Eintrag
ord-f3e5e41732904c3ca44e87153b8aef09
Quelldatensatz
uspto-grants-2006_04
Patentnummer
US07026487B2

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