Water → HCID 86732903, compound

HRID 1579934Notes

Reaction equation

HRID 1579934 reaction equation
O.[O:2]=[CH:3][C:4]([Cl:7])([Cl:6])[Cl:5].[C:8]1([N:14]=[C:15]=[O:16])[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1.CC(C)([O-])C.[Li+]>C1CCCCC1>[O:2]=[CH:3][C:4]([Cl:7])([Cl:6])[Cl:5].[C:8]1([N:14]=[C:15]=[O:16])[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1

Participants

6

Reactant 4

HCID 962Water4×HCID 6407ChloralHCID 7672Phenyl isocyanateHCID 236647642-Propanol, 2-methyl-, lithium salt (1:1)

Product 1

HCID 86732903HCID 86732903, compound

Reagents, catalysts & solvents 1

HCID 8078CyclohexaneSolvent

Conditions

Temperature
65 °C

Procedure

An open-ended glass tube about 300 mm. long and 75 mm. inside diameter was fitted with a rubber stopper at each end, each stopper having a central opening. A second, smaller glass tube about 300 mm. long but with an outside diameter of 45 mm. was positioned coaxially within the larger tube by insertion through the central openings in the rubber stoppers, and the assembly mounted vertically. The smaller inner tube was closed at its bottom end with a solid rubber stopper. The upper stopper of the outer tube was additionally provided with two smaller holes opening into the bore of the outer tube, one to admit nitrogen gas and the other, itself loosely stoppered, to admit monomer and initiator into the bore of the outer tube. Hot (65°C.) water was circulated through the smaller tube and a 65°C. water bath raised around the outer one. A mixture of chloral (625 ml.) and phenyl isocyanate (29 ml., 4 mole %) was heated to 65°C., mixed with 33 ml. of 3.2% lithium tertbutoxide in cyclohexane and used to fill the annular space between the concentric tubes and the resulting homogeneous mixture allowed to become motionless. Circulation of the hot water in the inner tube was continued but the hot water bath surrounding the outer tube was removed. A -20°C. cooling bath was then raised around the outer tube at the rate of 3 mm. per minute until the cooling bath reached the top level of the quiescent polymerization mixture and completely surrounded it. Cooling of the outer tube was continued for 30 minutes while the inner tube was still being kept warm. After 30 minutes of standing under these conditions, the flow of hot water into the inner tube was stopped and the hot water in the tube was removed by suction, the cooling bath still being in position around the outer tube. After another 30 minute period the stopper closing the bottom end of the inner tube was removed thus allowing the -20°C. bath liquid to enter and fill the center tube. After 30 minutes of thus cooling both the inside and outside tubes, the cold bath was removed and the resulting copolymer product allowed to warm to room temperature overnight before the glass was broken away. The resulting pipe section was void-free and had a smooth outer surface. The inner surface was relatively rough and uneven. Since the manner of cooling caused polymerization to occur from the outer wall inward, the shrinkage which occurred during polymerization caused the polymer to shrink away from the inner tube. The inner surface was machined smooth to give a strong pipe about 200 mm. long, 75 mm. OD, and 50 mm. ID.

Workup

  1. custominside diameter was fitted with a rubber stopper at each end
  2. customThe smaller inner tube was closed at its bottom end with a solid rubber stopper
  3. customThe upper stopper of the outer tube was additionally provided with two smaller holes
  4. customwas circulated through the smaller tube and a 65°C.
  5. temperatureraised around the outer one
  6. additionmixed with 33 ml
  7. customwas removed
  8. temperatureA -20°C. cooling bath
  9. temperaturewas then raised around the outer tube at the rate of 3 mm
  10. customthe top level of the quiescent polymerization mixture
  11. temperatureCooling of the outer tube
  12. temperaturewas still being kept warm
  13. waitAfter 30 minutes of standing under these conditions
  14. customthe hot water in the tube was removed by suction
  15. waitAfter another 30 minute period the stopper closing
  16. customthe bottom end of the inner tube was removed thus
  17. customthe -20°C. bath liquid
  18. temperatureAfter 30 minutes of thus cooling both the inside and outside tubes
  19. customthe cold bath was removed
  20. temperatureto warm to room temperature overnight before the glass
  21. temperatureSince the manner of cooling
  22. custompolymerization
  23. customoccurred during polymerization
  24. customto give a strong pipe about 200 mm

Sources & evidence

ORD record
ord-ba402d2508a34a999997947b46247826
Source dataset
uspto-grants-1976_01
Patent number
US03932318

Reaction notes

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