Water → HCID 12447823, compound

HRID 585028Notes

Reaction equation

HRID 585028 reaction equation
[H-].[Na+].[C:3]([O:11][CH2:12][CH3:13])(=[O:10])[CH2:4][C:5]([O:7][CH2:8][CH3:9])=[O:6].Cl[CH2:15][Si:16]([CH2:23]Cl)([CH3:22])[O:17][Si:18]([CH3:21])([CH3:20])[CH3:19].O>C(OCC)(=O)C>[C:3]([C:4]1([C:5]([O:7][CH2:8][CH3:9])=[O:6])[CH2:19][Si:18]([CH3:21])([CH3:20])[O:17][Si:16]([CH3:23])([CH3:22])[CH2:15]1)([O:11][CH2:12][CH3:13])=[O:10]

Participants

6

Reactant 4

HCID 962WaterHCID 7761Diethyl Malonate2×HCID 24758Sodium hydrideHCID 21904086HCID 21904086, compound2×

Product 1

HCID 12447823HCID 12447823, compound

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
5 °C

Procedure

Reaction method: To a dry 1 L 3-neck round bottom flask equipped with a reflex condenser, addition funnel and a N2 gas inlet was added di(ethyleneglycol) diethyl ether (diethyl carbitol) (650 mL, 590.85 g). To the solvent was added sodium hydride (28.80 g, 1.20 mol) under a N2 atmosphere, and the suspension was cooled to ˜5° C. in an ice/water bath. To the cooled suspension was added diethyl malonate (192.00 g, 1.20 mol) dropwise through the addition funnel. (CAUTION: A large quantity of H2 gas is evolved.) When the addition of the diethyl malonate was complete, the suspension had turned to a clear solution. The reaction mixture was heated to 50° C. and stirring was continued for 30 minutes at 50° C. To the solution at 50° C. was then added bis(chloromethyl)tetramethyldisiloxane (138.76 g, 0.6 mol) over a 5 minute period through the addition funnel. The reaction mixture was then heated to 112-115° C., and stirring was continued under a N2 atmosphere while the reaction was monitored by GC. After 20 hr, GC showed that a trace amount of bis(chloromethyl)-tetramethyldisiloxane remained (retention time: 11.5 min.). The mixture was cooled to room temperature and the mixture was transferred to a separatory funnel. Water (500 mL) and ethyl acetate were added, and the organic layer was separated. The aqueous layer was extracted with ethyl acetate (400 mL), and the combined organic layers were washed with water (2×500 mL) and saturated aqueous sodium chloride (500 mL). The organic layer was separated, and the ethyl acetate was removed using a rotary evaporator. The remaining solution was vacuum distilled to remove the di(ethyleneglycol) diethyl ether (b.p. 70° C. @ 8 mm Hg). The solution was concentrated to a final weight of 182 g of crude CDS_E. GC of the crude CDS_E solution was obtained (retention time: 15.2 min.). The solution of the crude product was used in the next reaction without further purification.

Workup

  1. customReaction method
  2. customTo a dry 1 L 3-neck round bottom flask equipped with a reflex condenser, addition funnel and a N2 gas inlet
  3. temperatureThe reaction mixture was heated to 50° C.
  4. customat 50° C.
  5. temperatureThe reaction mixture was then heated to 112-115° C.
  6. stirringstirring
  7. waitAfter 20 hr
  8. temperatureThe mixture was cooled to room temperature
  9. customthe mixture was transferred to a separatory funnel
  10. customthe organic layer was separated
  11. extractionThe aqueous layer was extracted with ethyl acetate (400 mL)
  12. washthe combined organic layers were washed with water (2×500 mL) and saturated aqueous sodium chloride (500 mL)
  13. customThe organic layer was separated
  14. customthe ethyl acetate was removed
  15. customa rotary evaporator
  16. distillationdistilled
  17. customto remove the di(ethyleneglycol) diethyl ether (b.p. 70° C. @ 8 mm Hg)
  18. concentrationThe solution was concentrated to a final weight of 182 g of crude CDS_E
  19. customGC of the crude CDS_E solution was obtained (retention time: 15.2 min.)

Sources & evidence

ORD record
ord-c7482021895f4fa08f001c41adf0bc97
Source dataset
uspto-grants-2005_08
Patent number
US06929897B2

Reaction notes

Loading…