Acryloyl chloride → HCID 18649788, compound

HRID 2081828Notes

Reaction equation

HRID 2081828 reaction equation
[CH2:1]([NH:3][CH2:4][C@@H:5]([C@H:7]([C@H:9]([C@@H:11]([CH2:13][OH:14])[OH:12])[OH:10])[OH:8])[OH:6])[CH3:2].N([O-])=O.[Na+].[C:19](Cl)(=[O:22])[CH:20]=[CH2:21].[OH-].[K+]>O.C(Cl)Cl>[C:19]([N:3]([CH2:1][CH3:2])[CH2:4][C@@H:5]([C@H:7]([C@H:9]([C@@H:11]([CH2:13][OH:14])[OH:12])[OH:10])[OH:8])[OH:6])(=[O:22])[CH:20]=[CH2:21]

Participants

7

Reactant 4

HCID 13140Acryloyl chloride4×HCID 14797Potassium Hydroxide3×HCID 16739207HCID 16739207, compoundHCID 23668193Sodium Nitrite

Product 1

HCID 18649788HCID 18649788, compoundYield 72%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 6344DichloromethaneSolvent2×

Procedure

The N-ethyl-1-amino-1-deoxy-D-galacitol (63 g) is mixed with about 300 ml of water and 1 g of sodium nitrite. Then 100-150 ml of methylene chloride are added, and the solution is cooled in an ice bath. Acryloyl chloride (10% molar excess over the amine) is mixed with the same volume of methylene chloride. Potassium hydroxide, equal to twice the molar amount of acryloyl chloride, is dissolved in water and cooled. To the well stirred two-phase reaction mixture, portions of acryloyl chloride and KOH solutions were added in such a way that the pH remained between 7.5-9.5 (as checked frequently by a narrow range pH paper). After the last additions of acryloyl chloride and KOH solutions, the reaction mixture was further stirred for about one hour (the pH was periodically checked and corrected, if necessary). The two phases were allowed to separate in a separating funnel and the lower organic phase was discarded. The aqueous phase was treated with charcoal and filtered. The filtrate was treated with a combination of ion exchangers either in solution or by passing the filtrate through columns packed with ion exchangers. Thus, to the stirred solution, portions of Amberlite IR-120,H+ and IRA-68 (free base) were added (pH being kept neutral or slightly acid) until the silver reaction for chloride was negative. The resin was then removed, the filtrate treated with activated charcoal and the solution poured into crystallization dishes. Alternatively, the monomer solution was passed through 600 ml of IR-120 and 600 ml of IRA-68, preferentially packed in more than two columns. The solution passed always first through the cationic ion exchanger. A small quantity (several hundred mg) of p-methoxy phenol or sodium nitrite (polymerization inhibitors) were added to the monomer solution. The water evaporated within 1-2 weeks. The monomer appeared as a white solid. The yield was 72%. The monomer was recrystallized from ethanol-acetone, m.p. 80°-84° C. (polymerization).

Workup

  1. temperaturethe solution is cooled in an ice bath
  2. temperaturecooled
  3. additionwere added in such a way that the pH
  4. customto separate in a separating funnel
  5. additionThe aqueous phase was treated with charcoal
  6. filtrationfiltered
  7. additionThe filtrate was treated with a combination of ion exchangers either in solution
  8. additionThus, to the stirred solution, portions of Amberlite IR-120,H+ and IRA-68 (free base) were added (
  9. customslightly acid) until the silver reaction for chloride
  10. customThe resin was then removed
  11. additionthe filtrate treated with activated charcoal
  12. additionthe solution poured into crystallization dishes
  13. additionA small quantity (several hundred mg) of p-methoxy phenol or sodium nitrite (polymerization inhibitors) were added to the monomer solution
  14. customThe water evaporated within 1-2 weeks
  15. customThe monomer was recrystallized from ethanol-acetone, m.p. 80°-84° C. (polymerization)

Sources & evidence

ORD record
ord-16f819af875a4d18b9f5e0e1e30e0d81
Source dataset
uspto-grants-1993_02
Patent number
US05185466

Reaction notes

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