Dimethyl 2-chloroterephthalate → Dimethyl 2-chloro-cyclohexane-1,4-dicarboxylate

HRID 385200

Reaction equation

HRID 385200 reaction equation
C(OC)(=O)/C=C/C=C/C(OC)=O.[Cl:13][C:14]1[CH:23]=[C:22]([C:24]([O:26][CH3:27])=[O:25])[CH:21]=[CH:20][C:15]=1[C:16]([O:18][CH3:19])=[O:17]>CC(C)C(O)COC(CO)C.[Pd]>[Cl:13][CH:14]1[CH2:23][CH:22]([C:24]([O:26][CH3:27])=[O:25])[CH2:21][CH2:20][CH:15]1[C:16]([O:18][CH3:19])=[O:17]

Participants

5

Reactant 2

HCID 87740Dimethyl 2-chloroterephthalateHCID 5370244Dimethyl muconate, (E,E)-

Product 1

HCID 66809701Dimethyl 2-chloro-cyclohexane-1,4-dicarboxylate

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalyst2×HCID 86648893DimethyldipropyleneglycolSolvent

Conditions

Temperature
165 °C

Procedure

In a Parr pressure reactor, a stirred suspension of trans,trans dimethyl muconate (6.1 g, 36 mmol) in dimethyldipropyleneglycol (120 ml, 0.3 M) is heated under vinyl chloride pressure (18 psi (0.124 MPa) at 23° C.) to 165° C. for 48 hours. After cooling to room temperature, the reaction mixture is diluted using the same solvent to 200 ml in a volumetric flask, transferred into a round-bottom flask equipped with a magnetic stirring bar, and Pd/C catalyst is added (360 mg of Johnson-Matthey 5 percent Pd/C #6, 0.2 mol percent) at room temperature. The flask is equipped with a reflux condenser, flitted gas dispersion tube, and internal T probe. Under N2 flow (190 ml/min) and stirring (190 rpm) the mixture is heated to reflux while samples are taken at appropriate intervals (t=0.0, 0.25, 0.5, 1.0, 2.0, 4.0, 8.0 h) to monitor the progress of the reactions occurring. After 8 hour reaction time, dimethyl chloro-terephthalate is present. Some material also undergoes C—Cl bond cleavage and dimethyl 2-chloro-cyclohexane-1,4-dicarboxylate is also formed.

Workup

  1. temperatureAfter cooling to room temperature
  2. additionthe reaction mixture is diluted
  3. customtransferred into a round-bottom flask
  4. customequipped with a magnetic stirring bar
  5. customThe flask is equipped with a reflux condenser
  6. temperatureis heated
  7. temperatureto reflux while samples
  8. customare taken at appropriate intervals (t=0.0, 0.25, 0.5, 1.0, 2.0, 4.0, 8.0 h)

Sources & evidence

ORD record
ord-48293e6836224ac38b538d3c5b15e108
Source dataset
uspto-grants-2013_02
Patent number
US08367858B2

Linked notes

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