Toluene → HCID 91198503, compound

HRID 859811Notes

Reaction equation

HRID 859811 reaction equation
[C:1]([O:5][CH2:6][CH2:7][CH2:8][CH2:9][O:10][C:11]1[C:21]([O:22][CH2:23][CH2:24][CH2:25][CH2:26][O:27][C:28](=[O:31])[CH:29]=[CH2:30])=[C:20]([O:32][CH2:33][CH2:34][CH2:35][CH2:36][O:37][C:38](=[O:41])[CH:39]=[CH2:40])[CH:19]=[CH:18][C:12]=1[CH:13]=[CH:14][C:15]([OH:17])=[O:16])(=[O:4])[CH:2]=[CH2:3].S(Cl)(Cl)=O.[C:46]1([CH3:52])[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=1>CN(C)C=O.O>[C:1]([O:5][CH2:6][CH2:7][CH2:8][CH2:9][O:10][C:11]1[C:21]([O:22][CH2:23][CH2:24][CH2:25][CH2:26][O:27][C:28](=[O:31])[CH:29]=[CH2:30])=[C:20]([O:32][CH2:33][CH2:34][CH2:35][CH2:36][O:37][C:38](=[O:41])[CH:39]=[CH2:40])[CH:19]=[CH:18][C:12]=1[CH:13]=[CH:14][C:15]([O:17][C:49]1[CH:50]=[CH:51][C:46]([C:52]2[CH:20]=[CH:21][C:11]([O:16][C:15](=[O:17])[CH:14]=[CH:13][C:12]3[CH:18]=[CH:19][C:20]([O:32][CH2:33][CH2:34][CH2:35][CH2:36][O:37][C:38](=[O:41])[CH:39]=[CH2:40])=[C:21]([O:22][CH2:23][CH2:24][CH2:25][CH2:26][O:27][C:28](=[O:31])[CH:29]=[CH2:30])[C:11]=3[O:10][CH2:9][CH2:8][CH2:7][CH2:6][O:5][C:1](=[O:4])[CH:2]=[CH2:3])=[CH:12][CH:13]=2)=[CH:47][CH:48]=1)=[O:16])(=[O:4])[CH:2]=[CH2:3]

Participants

6

Reactant 3

HCID 1140TolueneHCID 24386Thionyl ChlorideHCID 69618850HCID 69618850, compound

Product 1

HCID 91198503HCID 91198503, compoundYield 85%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideCatalystHCID 962WaterSolvent

Conditions

Temperature
40 °C

Procedure

Into a three-neck flask, 2,3,4-tri(4-acryloyloxy-butyloxy)cinnamic acid (10.0 g), thionyl chloride (6.1 g), dimethylformamide (0.01 g) and 30 mL of toluene were added and stirred at 40° C. for 30 minutes. After cooling, toluene and excess thionyl chloride were removed by distillation and then 100 ml of tetrahydrofuran was added. To this reaction solution, 4,4′-dihydroxybiphenyl (1.6 g) was added and after cooling to 5° C., triethylamine (2.8 mL) was added dropwise. Subsequently, 4-dimethylaminopyridine (0.1 g) was added and after heating to 25° C., the solution was stirred for 5 hours. The resulting reaction solution was added to water (500 mL) and crystals precipitated were collected by filtration. The obtained crystals were dissolved in dimethylacetamide (20 mL), triethylamine (2.8 mL) was added thereto and the resulting solution was stirred at 60° C. for 1 hour. After cooling, the reaction solution was extracted with ethyl and washed with water. The extract was concentrated and then purified by column chromatography to obtain the titled compound (9.5 g). Yield: 85%. The NMR spectrum of m-40 obtained is shown below.

Workup

  1. temperatureAfter cooling
  2. customtoluene and excess thionyl chloride were removed by distillation
  3. addition100 ml of tetrahydrofuran was added
  4. additionTo this reaction solution, 4,4′-dihydroxybiphenyl (1.6 g) was added
  5. temperatureafter cooling to 5° C.
  6. additiontriethylamine (2.8 mL) was added dropwise
  7. additionSubsequently, 4-dimethylaminopyridine (0.1 g) was added
  8. temperatureafter heating to 25° C.
  9. stirringthe solution was stirred for 5 hours
  10. customThe resulting reaction solution
  11. customprecipitated
  12. filtrationwere collected by filtration
  13. dissolutionThe obtained crystals were dissolved in dimethylacetamide (20 mL)
  14. additiontriethylamine (2.8 mL) was added
  15. stirringthe resulting solution was stirred at 60° C. for 1 hour
  16. temperatureAfter cooling
  17. extractionthe reaction solution was extracted with ethyl
  18. washwashed with water
  19. concentrationThe extract was concentrated
  20. custompurified by column chromatography

Sources & evidence

ORD record
ord-eb8da2ef37944c1088b4d0479120bab9
Source dataset
uspto-grants-2006_12
Patent number
US07153548B2

Reaction notes

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