Dimethylformamide → Terephthalic acid monomethyl ester chloride diisopropylethylamine

HRID 41493

Reaction equation

HRID 41493 reaction equation
[CH3:1][O:2][C:3](=[O:13])[C:4]1[CH:12]=[CH:11][C:7]([C:8]([OH:10])=[O:9])=[CH:6][CH:5]=1.CN(C)C=O.S(Cl)([Cl:21])=O.[CH:23]([N:26]([CH2:30][CH3:31])[CH:27]([CH3:29])[CH3:28])([CH3:25])[CH3:24]>COCCOC>[Cl-:21].[CH3:1][O:2][C:3](=[O:13])[C:4]1[CH:12]=[CH:11][C:7]([C:8]([OH:10])=[O:9])=[CH:6][CH:5]=1.[CH:23]([N:26]([CH2:30][CH3:31])[CH:27]([CH3:29])[CH3:28])([CH3:25])[CH3:24]

Participants

6

Reactant 4

HCID 6228DimethylformamideHCID 15513Monomethyl terephthalateHCID 24386Thionyl ChlorideHCID 81531Diisopropylethylamine

Product 1

HCID 86628494Terephthalic acid monomethyl ester chloride diisopropylethylamine

Reagents, catalysts & solvents 1

HCID 80711,2-DimethoxyethaneSolvent

Conditions

Temperature
10 °C

Procedure

A suspension of 1.997 kg (11.08 mol) of terephthalic acid monomethyl ester in 15.60 kg of 1,2-dimethoxyethane was stirred in a nitrogen atmosphere while being cooled at 10° C. To the suspension was added 400 mL (5.17 mol) of N,N-dimethylformamide and 1.323 kg (10.56 mol) of thionyl chloride in this order, and then the container was washed with 1.00 L of 1,2-dimethoxyethane. The suspension was stirred under heating at 60 to 73° C. for 1 hour and 2 minutes and then stirred while being cooled. 1.36 kg (10.52 mol) of N,N-diisopropylethylamine was added dropwise to the solution while cooling at 0° C., and the container was washed with 1.00 L of 1,2-dimethoxyethane. Then the reaction solution was stirred at 25° C., and the stirring was stopped 38 minutes after the internal temperature had reached 20° C. The reaction mixture was transferred into a plastic container, and 22.00 kg of “monomethyl terephthalate chloride/N,N-diisopropylethylamine” solution (terephthalic acid monomethyl ester chloride content: 1.84 kg) was obtained as a slightly tannish solution.

Workup

  1. washthe container was washed with 1.00 L of 1,2-dimethoxyethane
  2. stirringThe suspension was stirred
  3. temperatureunder heating at 60 to 73° C. for 1 hour and 2 minutes
  4. stirringstirred
  5. temperaturewhile being cooled
  6. temperaturewhile cooling at 0° C.
  7. washthe container was washed with 1.00 L of 1,2-dimethoxyethane
  8. stirringThen the reaction solution was stirred at 25° C.
  9. customhad reached 20° C
  10. customwas obtained as a slightly tannish solution

Sources & evidence

ORD record
ord-373df78e44d04ba793a20f1da510e383
Source dataset
uspto-grants-2013_09
Patent number
US08530654B2

Linked notes

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