p-Toluenesulfonic acid → HCID 86623178, compound

HRID 1753663Notes

Reaction equation

HRID 1753663 reaction equation
O[CH2:2][CH2:3][O:4][C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][C:6]=1[C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=1[OH:17].N(N([C:22]1C=CC=C[CH:23]=1)O)=O.[Al].[C:29]([OH:33])(=[O:32])[CH:30]=[CH2:31].C1(C)C=CC(S(O)(=O)=O)=CC=1.CS(O)(=O)=O>C([O-])(=O)C.[Mn+2].C([O-])(=O)C.C1(C)C=CC=CC=1>[C:29]([OH:33])(=[O:32])[CH:30]=[CH2:31].[C:29]([OH:33])(=[O:32])[CH:30]=[CH2:31].[CH2:22]([O:17][C:12]1[CH:13]=[CH:14][CH:15]=[CH:16][C:11]=1[C:6]1[CH:7]=[CH:8][CH:9]=[CH:10][C:5]=1[O:4][CH2:3][CH3:2])[CH3:23]

Participants

8

Reactant 5

HCID 6101p-Toluenesulfonic acid2×HCID 6395Methanesulfonic AcidHCID 6581Acrylic Acid3×HCID 19385115HCID 19385115, compoundHCID 178526393HCID 178526393, compound

Product 1

HCID 86623178HCID 86623178, compound

Reagents, catalysts & solvents 2

HCID 12525Manganous AcetateCatalystHCID 1140TolueneSolvent

Procedure

To a 2000 ml 3 neck round bottom equipped with an overhead stirrer, dean stark trap and temperature probe was added 2,2′-dihydroxyethoxy-biphenyl (368 g, 1.34 mole, 1.0 eq.), toluene (700 g), Prostab 5198 (0.023 g), aluminum N-nitrosophenylhydroxylamine (NPAL) (0.059 g), manganese acetate (0.023 g), acrylic acid (212.7 g, 2.95 mole, 2.2 eq), p-toluene sulfonic acid (pTSA, 23.1 g, 0.13 mole, 0.1 eq.) and heated to reflux. After 2.5 hours the reaction stalled with ˜45/45 product/intermediate and 10% starting material. The reaction was treated with acrylic acid (26 g) and pTSA (5 g) and continued refluxing. No additional conversion to product was observed. Acrylic acid (50 g) and methane sulfonic acid (5 g) were added. The Dean stark trap continued to collect water. Upon running the reaction overnight the product was ˜75% product and 7% mono acrylate. The reaction was washed 3 times with sodium chloride brine (200 ml), 3 times with brine with some 1N NaOH (200 ml), 3 times with sat. sodium carbonate (200 ml), dried over MgSO4 (5 g), filtered and concentrated in vacuo to recover the product. The product (500 g) was purified by series of 3 columns eluting with 50% hexane/chloroform to recover 220 g product at 92% purity (GC) and 3 other fractions of lesser purity. The refractive index of the (i.e. uncured) monomer was determined to be 1.559.

Workup

  1. temperatureheated to reflux
  2. temperaturecontinued refluxing
  3. customto collect water
  4. customthe reaction overnight the product
  5. washThe reaction was washed 3 times with sodium chloride brine (200 ml), 3 times with brine with some 1N NaOH (200 ml), 3 times with sat. sodium carbonate (200 ml)
  6. dry with materialdried over MgSO4 (5 g)
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customto recover the product
  10. customThe product (500 g) was purified by series of 3 columns
  11. washeluting with 50% hexane/chloroform
  12. customto recover 220 g product at 92% purity (GC) and 3 other fractions of lesser purity

Sources & evidence

ORD record
ord-954865fcc6584894a2035cebf9a237c5
Source dataset
uspto-grants-2015_10
Patent number
US09164195B2

Reaction notes

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