tert-Butanol → HCID 86631944, compound

HRID 906135Notes

Reaction equation

HRID 906135 reaction equation
[CH3:1][O:2][C:3]([C:5]1[C:13]([CH3:14])=[CH:12][C:8]([C:9]([OH:11])=[O:10])=[C:7]([CH3:15])[C:6]=1[N+:16]([O-:18])=[O:17])=[O:4].Cl.CN(C)CCCN=C=NCC.[C:31](O)([CH3:34])([CH3:33])[CH3:32].C(N(CC)CC)C.C1(P(Cl)(C2C=CC=CC=2)=O)C=CC=CC=1>ClCCl.CN(C)C1C=CN=CC=1>[CH3:15][C:7]1[C:6]([N+:16]([O-:18])=[O:17])=[C:5]([C:3]([O:2][CH3:1])=[O:4])[C:13]([CH3:14])=[CH:12][C:8]=1[C:9]([O:11][C:31]([CH3:34])([CH3:33])[CH3:32])=[O:10]

Participants

8

Reactant 5

HCID 6386tert-Butanol2×HCID 8471TriethylamineHCID 73910Diphenylphosphinic chlorideHCID 27239391,3-Propanediamine, N'-(ethylcarbonimidoyl)-N,N-dimethyl-, monohydrochlorideHCID 86631943HCID 86631943, compound

Product 1

HCID 86631944HCID 86631944, compoundYield 68%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent

Procedure

4-(Methoxycarbonyl)-2,5-dimethyl-3-nitrobenzoic acid (9.5 mmol) was suspended in dichloromethane (30 mL) and N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride (1.82 g, 9.5 mmol) and 4-dimethylaminopyridine (1.16 g, 9.5 mmol) were added. The mixture was stirred at ambient temperature for 0.5 h. tert-Butanol (6 mL, 64 mmol) was added and the mixture was stirred for 15.5 h. tert-Butanol (20 mL, 213 mmol) was added and the mixture was stirred at reflux for 1 h. The dichloromethane was removed and the mixture was stirred at 75° C. for 21 h. Triethylamine (1.3 mL, 9.3 mmol) and diphenylphosphoryl chloride (1.96 mL, 9.5 mmol) were added and the mixture was stirred at 75° C. for 6 h. The mixture was cooled to ambient temperature and then was concentrated. The residue was partitioned between ethyl acetate and 1N hydrochloric acid. The organic portion was washed with 1N sodium hydroxide, brine, dried over sodium sulfate, then filtered and concentrated to afford an orange semi-solid which was purified by column chromatography (silica gel, 5-15% ethyl acetate in hexanes) to afford crude 1-tert-butyl 4-methyl 2,5-dimethyl-3-nitroterephthalate (1.98 g, 6.4 mmol, 68% yield) as a colorless oil. 1H NMR (400 MHz, CDCl3): δ 7.69 (s, 1H), 3.88 (s, 3H), 2.45 (s, 3H), 2.44 (s, 3H), 1.60 (s, 9H); GCMS for C15H19NO6: 309 (M+).

Workup

  1. additionwas added
  2. additionwas added
  3. temperatureat reflux for 1 h
  4. customThe dichloromethane was removed
  5. stirringthe mixture was stirred at 75° C. for 21 h
  6. stirringthe mixture was stirred at 75° C. for 6 h
  7. concentrationwas concentrated
  8. customThe residue was partitioned between ethyl acetate and 1N hydrochloric acid
  9. washThe organic portion was washed with 1N sodium hydroxide, brine
  10. dry with materialdried over sodium sulfate
  11. filtrationfiltered
  12. concentrationconcentrated
  13. customto afford an orange semi-solid which
  14. customwas purified by column chromatography (silica gel, 5-15% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-a91815c29a524af2be21260db2a6ffd6
Source dataset
uspto-grants-2011_09
Patent number
US08012956B2

Reaction notes

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