Hydrochloric Acid → Di-tert-butyl 5-methylisophthalate

HRID 843517

Reaktionsgleichung

Reaktionsgleichung von HRID 843517
[C:1](N1C=CN=C1)(N1C=CN=C1)=O.[C:13]1([CH3:25])[CH:18]=[C:17]([C:19]([OH:21])=[O:20])[CH:16]=[C:15]([C:22]([OH:24])=[O:23])[CH:14]=1.[CH2:26]1[CH2:36][CH2:35]N2C(=NCCC2)CC1.[CH3:37][C:38](O)([CH3:40])[CH3:39].Cl>CN(C=O)C.CCOCC>[C:13]1([CH3:25])[CH:18]=[C:17]([C:19]([O:21][C:38]([CH3:40])([CH3:39])[CH3:37])=[O:20])[CH:16]=[C:15]([C:22]([O:24][C:36]([CH3:35])([CH3:26])[CH3:1])=[O:23])[CH:14]=1

Komponenten

8

Edukt 5

HCID 313Hydrochloric AcidHCID 6386tert-ButanolHCID 681375-Methylisophthalic acidHCID 682631,1'-CarbonyldiimidazoleHCID 811841,8-Diazabicyclo(5.4.0)undec-7-ene

Produkt 1

HCID 22610876Di-tert-butyl 5-methylisophthalateAusbeute 84 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 3283Diethyl EtherLösungsmittelHCID 6228DimethylformamideLösungsmittel

Reaktionsbedingungen

Temperatur
40 °C

Versuchsvorschrift

1,1′-Carbonyldiimidazole (6.67 g, 0.0411 mol) was added to a solution of toluene-3,5-dicarboxylic acid (2) (3.364 g, 0.0187 mol) in DMF (30 mL) and the resulting mixture stirred at 40° C. under N2. After 1.5 h DBU (6.15 mL, 0.041 mol) and t-BuOH (7.7 mL, 0.0822 mol) were added. After 24 h the solution was cooled, ether (150 mL) added and the mixture acidified (HCl (aq.), 1.5 M). The ethereal layer was separated and the aqueous layer further extracted (ether, 150 mL). The organic fractions were combined, washed with water and 10% K2CO3 (aq.), dried (MgSO4), filtered and the solvent removed. The residue was purified by flash chromatography (EtOAc:hexane, 1:50) to afford a colorless oil which solidified upon standing to give di-tert-butyl toluene-3,5-dicarboxylate (4.58 g, 84%) as a white solid; mp 86.5-87.5° C. (hexane); IR (film) 1712 cm−1 (C═O), 1606, 1476 cm−1 (Ar C═C); 1H NMR (CDCl3) δ1.60 (s, 18H, C(CH3)3), 2.43 (s, 3H, CH3), 7.95 (br s, 2H, H-2, H-6), 8.38 (br s, 1H, H-4); 13C NMR (CDCl3) δ21.4 (CH3), 28.2 (C(CH3)3), 81.4 (C(CH3)3), 127.7, 132.1, 133.7, 138.1 (Ar), 165.2 (COO).

Aufarbeitung

  1. temperatureAfter 24 h the solution was cooled
  2. customThe ethereal layer was separated
  3. extractionthe aqueous layer further extracted (ether, 150 mL)
  4. washwashed with water and 10% K2CO3 (aq.)
  5. dry with materialdried (MgSO4)
  6. filtrationfiltered
  7. customthe solvent removed
  8. customThe residue was purified by flash chromatography (EtOAc:hexane, 1:50)
  9. customto afford a colorless oil which

Quellen und Nachweise

ORD-Eintrag
ord-e3cd9364f29e4a5d9f8038738659c9ae
Quelldatensatz
uspto-grants-2002_04
Patentnummer
US06379942B1

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