Hydrochloric Acid → Di-tert-butyl 5-methylisophthalate

HRID 2222063

반응식

HRID 2222063 반응식
[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

참가 물질

8

반응물 5

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

생성물 1

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

시약·촉매·용매 2

HCID 3283Diethyl Ether용매HCID 6228Dimethylformamide용매

반응 조건

온도
40 °C

실험 절차

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) δ 1.60 (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) δ 21.4 (CH3), 28.2 (C(CH3)3), 81.4 (C(CH3)3), 127.7, 132.1, 133.7, 138.1 (Ar), 165.2 (COO).

후처리

  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

출처 및 근거

ORD 기록
ord-f47ec98e60744e3291a422a27836be0f
출처 데이터셋
uspto-grants-2008_05
특허 번호
US07371553B2

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