Dichloromethane → 26409-02-9

HRID 476922Notes

Reaction equation

HRID 476922 reaction equation
[C:1](Cl)(Cl)=[O:2].[OH:5][CH:6]1[CH2:11][CH2:10][N:9]([CH3:12])[CH2:8][CH2:7]1.C(N(CC)CC)C.C(Cl)[Cl:21]>C1(C)C=CC=CC=1>[Cl:21][CH2:10][CH2:11][CH:6]1[O:5][C:1](=[O:2])[N:9]([CH3:12])[CH2:8][CH2:7]1

Participants

6

Reactant 4

HCID 6344Dichloromethane2×HCID 6371PhosgeneHCID 8471TriethylamineHCID 660484-Piperidinol, 1-methyl-

Product 1

HCID 1983671426409-02-9Yield 22%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

To a cold (ice bath) solution of 85.8 g (0.868 mole) of phosgene in 500 ml of methylene chloride was added dropwise a solution of 100 g (0.868 mole) of 4-hydroxy-1-methylpiperidine in 250 ml of methylene chloride at such a rate that the internal temperature did not exceed 12° C. A crystalline solid precipitated during addition. The mixture was stirred in the cold for 1 hr after addition was complete and then 120.8 ml (87.7 g, 0.868 mole) of triethylamine was added dropwise at such a rate that the internal temperature did not exceed 25° C. The mixture was stirred at ambient temperature overnight and then diluted with 500 ml of toluene. The methylene chloride was removed by distillation and the resultant mixture was heated at reflux for 2 hr. The mixture was cooled and treated with 500 ml of 1N hydrochloric acid. The layers were separated and the organic layer was washed successively with 500 ml of 1N hydrochloric acid, 500 ml of a 4% sodium hydroxide solution and once with brine, dried over anhydrous sodium sulfate and concentrated to give an oil as residue. The oil was subjected to vacuum distillation to give 34.4 g (22%) of clear oil (b.p. 147°-150° C. at 0.4 mm).

Workup

  1. customdid not exceed 12° C
  2. customA crystalline solid precipitated during addition
  3. additionafter addition
  4. customdid not exceed 25° C
  5. stirringThe mixture was stirred at ambient temperature overnight
  6. customThe methylene chloride was removed by distillation
  7. temperaturethe resultant mixture was heated
  8. temperatureat reflux for 2 hr
  9. temperatureThe mixture was cooled
  10. additiontreated with 500 ml of 1N hydrochloric acid
  11. customThe layers were separated
  12. washthe organic layer was washed successively with 500 ml of 1N hydrochloric acid, 500 ml of a 4% sodium hydroxide solution and once with brine
  13. dry with materialdried over anhydrous sodium sulfate
  14. concentrationconcentrated
  15. customto give an oil as residue
  16. distillationThe oil was subjected to vacuum distillation

Sources & evidence

ORD record
ord-180b10f607ef43f6b0eae9e38430995b
Source dataset
uspto-grants-1989_12
Patent number
US04886794

Reaction notes

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