Dimethyl Sulfide → 1-(Diphenylmethyl)-2-azetidinecarboxaldehyde

HRID 2050194Notes

Reaction equation

HRID 2050194 reaction equation
ClN1C(=O)CCC1=O.CSC.[C:12]1([CH:18]([C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)[N:19]2[CH2:22][CH2:21][CH:20]2[CH2:23][OH:24])[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.C(N(CC)CC)C>C1(C)C=CC=CC=1.CCOCC>[C:12]1([CH:18]([C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)[N:19]2[CH2:22][CH2:21][CH:20]2[CH:23]=[O:24])[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=1

Participants

7

Reactant 4

HCID 1068Dimethyl SulfideHCID 8471TriethylamineHCID 31398ChlorosuccinimideHCID 427905(1-benzhydrylazetidin-2-yl)methanol

Product 1

HCID 127171451-(Diphenylmethyl)-2-azetidinecarboxaldehydeYield 67.4%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolvent3×HCID 3283Diethyl EtherSolvent

Procedure

To a solution of 2.36 g (17.7 mmoles) of N-chlorosuccinimide in 40 ml of dry toluene is added 1.77 ml (24.2 mmoles) of dimethyl sulfide, and the mixture is stirred at the same temperature for 25 minutes and cooled to -25° C. to -30° C. A solution of 3 g (11.8 mmoles) of 1-diphenylmethyl-2-hydroxymethylazetidine in 8 ml of toluene is dropwise added thereto in a period of 20 minutes and the mixture is stirred at the same temperature for 2 hours. A solution of 2.5 ml (11.8 mmoles) of triethylamine in 2 ml of toluene is dropwise added thereto in a period of 15 minutes. The reaction mixture is stirred at -25° C. for 30 minutes, mixed with 120 ml of ether, stirred at room temperature for 5 minutes, washed twice with 50 ml of water, dried over sodium sulfate and evaporated under reduced pressure. The resulting syrupy residue (3.2 g) is dissolved in 50 ml of methylene chloride and extracted four times with 20 (w/w) % aqueous sodium hydrogensulfite solution. The extract is washed with 20 ml of methylene chloride, adjusted to pH 10 with 20% aqueous sodium carbonate solution, and extracted four times with 50 ml of methylene chloride. The extract is washed with water, dried over sodium sulfate and evaporated under reduced pressure. The resulting syrupy residue (2.1 g) is recrystallized from a mixture of n-hexane and ether to yield 2 g of 1-diphenylmethyl-2-formylazetidine in 67% yield.

Workup

  1. temperaturecooled to -25° C. to -30° C
  2. waitin a period of 20 minutes
  3. stirringthe mixture is stirred at the same temperature for 2 hours
  4. waitin a period of 15 minutes
  5. stirringThe reaction mixture is stirred at -25° C. for 30 minutes
  6. stirringstirred at room temperature for 5 minutes
  7. washwashed twice with 50 ml of water
  8. dry with materialdried over sodium sulfate
  9. customevaporated under reduced pressure
  10. dissolutionThe resulting syrupy residue (3.2 g) is dissolved in 50 ml of methylene chloride
  11. extractionextracted four times with 20 (w/w) % aqueous sodium hydrogensulfite solution
  12. washThe extract is washed with 20 ml of methylene chloride
  13. extractionextracted four times with 50 ml of methylene chloride
  14. washThe extract is washed with water
  15. dry with materialdried over sodium sulfate
  16. customevaporated under reduced pressure
  17. customThe resulting syrupy residue (2.1 g) is recrystallized from a mixture of n-hexane and ether

Sources & evidence

ORD record
ord-f21eb105874b42a48a9ea924792d6085
Source dataset
uspto-grants-1980_04
Patent number
US04200628

Reaction notes

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