Acrylic Acid → 4-Cyclohexene-1,2-dicarboxylic acid, 1,2-dimethyl ester

HRID 2375130Notes

Reaction equation

HRID 2375130 reaction equation
CCCCCCCN1C(C)=CS/C/1=C/C1SC=C(C)[N+]=1CCCCCCC.[I-].[OH-:29].[Na+].[Na].[Na].[Na].[Na].[C:35](ON(OC(=O)C)CCN(OC(=O)C)OC(=O)C)(=[O:37])C.C=CC1C=CC=CC=1.[C:63]([OH:67])(=O)C=C.C[CH:69]([C:71]([C:74]([C:77](S)([CH3:79])C)([CH3:76])C)([CH3:73])C)[CH3:70].[OH-:81].[NH4+]>O>[CH3:35][O:37][C:76]([CH:74]1[CH:71]([C:73]([O:67][CH3:63])=[O:81])[CH2:69][CH:70]=[CH:79][CH2:77]1)=[O:29]

Participants

9

Reactant 7

HCID 6581Acrylic AcidHCID 7501StyreneHCID 14798Sodium Hydroxide2×HCID 14923Ammonium HydroxideHCID 32793Tert-dodecanethiolHCID 6444337PioninHCID 86664981Tetrasodium ethylenediamine tetraacetate

Product 1

HCID 241244-Cyclohexene-1,2-dicarboxylic acid, 1,2-dimethyl ester

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

To a polymerization vessel of a gas monomer reaction apparatus (manufactured by Taiatsu Techno Corporation, TAS-2J type) were charged 287 g of distilled water, 7.73 g of a surfactant (Pionin A-43-S (manufactured by TAKEMOTO OIL & FAT CO., LTD.): solid matter content of 48.5% by weight), 14.06 mL of 1 mol/L sodium hydroxide, 0.15 g of ethylenediamine tetraacetate tetrasodium salt, 255 g of styrene, 11.25 g of acrylic acid, and 3.0 g of tert-dodecyl mercaptan, followed by sealing of the reaction vessel and stirring at a stirring rate of 200 rpm. Degassing was conducted with a vacuum pump, followed by repeating nitrogen gas replacement several times. Thereto was injected 108.75 g of 1,3-butadiene, and the inner temperature is elevated to 60° C. Thereto was added a solution of 1.875 g of ammonium persulfate dissolved in 50 mL of water, and the mixture was stirred for 5 hours as it stands. The temperature was further elevated to 90° C., followed by stirring for 3 hours. After completing the reaction, the inner temperature was lowered to reach to the room temperature, and thereafter the mixture was treated by adding 1 mol/L sodium hydroxide and ammonium hydroxide to give the molar ratio of Na+ ion: NH4+ ion=1:5.3, and thus, the pH of the mixture was adjusted to 8.05. Thereafter, filtration with a polypropylene filter having the pore size of 1.0 μm was conducted to remove foreign substances such as dust followed by storage. Accordingly, Compound No. RP-1 was obtained in an amount of 774.7 g. Upon the measurement of halogen ion by ion chromatography, concentration of chloride ion was revealed to be 3 ppm. As a result of the measurement of the concentration of the chelating agent by high performance liquid chromatography, it was revealed to be 145 ppm.

Workup

  1. customTo a polymerization vessel of a gas monomer reaction apparatus (manufactured by Taiatsu Techno Corporation, TAS-2J type)
  2. customDegassing
  3. customis elevated to 60° C
  4. additionThereto was added a solution of 1.875 g of ammonium persulfate
  5. dissolutiondissolved in 50 mL of water
  6. stirringthe mixture was stirred for 5 hours as it
  7. customwas further elevated to 90° C.
  8. stirringby stirring for 3 hours
  9. customthe reaction
  10. customto reach to the room temperature
  11. additionthe mixture was treated
  12. customto give the molar ratio of Na+ ion
  13. filtrationThereafter, filtration with a polypropylene
  14. filtrationfilter
  15. customto remove foreign substances such as dust

Sources & evidence

ORD record
ord-f50df48a25aa41af8c15efa7bdd5c266
Source dataset
uspto-grants-2008_12
Patent number
US07465533B2

Reaction notes

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