Methanesulfonyl chloride → HCID 21993950, compound

HRID 1978369Notes

Reaction equation

HRID 1978369 reaction equation
[C:1]([S:4][CH2:5][P:6]([O:11][CH2:12][CH3:13])([O:8][CH2:9][CH3:10])=[O:7])(=O)[CH3:2].C[O-].[Na+].CO.S(OCC1[CH2:30][CH2:29][N:28]([C:31]([O:33][C:34]([CH3:37])([CH3:36])[CH3:35])=[O:32])[CH2:27][CH2:26]1)(C)(=O)=O.CS(Cl)(=O)=O.OCSCC1CCN(C(OC(C)(C)C)=O)CC1>CO.O1CCCC1.O.C(N(CC)CC)C>[CH2:9]([O:8][P:6]([CH2:5][S:4][CH2:1][CH:2]1[CH2:30][CH2:29][N:28]([C:31]([O:33][C:34]([CH3:36])([CH3:35])[CH3:37])=[O:32])[CH2:27][CH2:26]1)([O:11][CH2:12][CH3:13])=[O:7])[CH3:10]

Participants

10

Reactant 5

HCID 31297Methanesulfonyl chlorideHCID 2765838Tert-butyl 4-(methylsulfonyloxymethyl)piperidine-1-carboxylateHCID 12536443S-[(Diethoxyphosphoryl)methyl] ethanethioateHCID 21993708HCID 21993708, compoundHCID 23694274Sodium methanolate methanol

Product 1

HCID 21993950HCID 21993950, compound

Reagents, catalysts & solvents 4

HCID 887MethanolSolventHCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 8471TriethylamineSolvent

Procedure

To a solution of 1.529 g (6.759 mM) of S-(diethoxyphosphorylmethyl) thioacetate in 30 ml of methanol was added 1.30 g (6.76 mM) of 28% sodium methoxide-methanol under ice-cooling and the mixture was stirred at the prevailing temperature for 20 minutes. To this reaction mixture was added crude tert-butyl 4-(mesyloxymethyl)piperidine-1-carboxylate [which was prepared by adding 0.73 ml (9.46 mM) of methanesulfonyl chloride to a solution of 1.75 g (8.11 mM) of tert-butyl 4-(hydroxymethylthiomethyl)piperidine-1-carboxylate and 1.51 ml (10.8 mM) of triethylamine in 30 ml of tetrahydrofuran with ice-cooling, stirring the mixture at the prevailing temperature for 0.5 hour, pouring the mixture in water, extracting it with 2 portions of ethyl acetate, drying the pooled organic layer over MgSO4, and concentrating it], and the mixture was refluxed for 3 hours. The solvent was distilled off under reduced pressure and the residue was diluted with water and extracted with 2 portions of ethyl acetate. The organic layers were pooled and dried over MgSO4 and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (hexane-ethyl acetate: 3/1 to ethyl acetate) to provide the title compound.

Workup

  1. temperaturecooling
  2. customwas prepared
  3. temperaturecooling
  4. stirringstirring the mixture at the prevailing temperature for 0.5 hour
  5. extractionextracting it with 2 portions of ethyl acetate
  6. dry with materialdrying the pooled organic layer over MgSO4
  7. concentrationconcentrating it], and the mixture
  8. temperaturewas refluxed for 3 hours
  9. distillationThe solvent was distilled off under reduced pressure
  10. additionthe residue was diluted with water
  11. extractionextracted with 2 portions of ethyl acetate
  12. dry with materialdried over MgSO4
  13. distillationthe solvent was distilled off under reduced pressure
  14. customThe residue was purified by silica gel column chromatography (hexane-ethyl acetate: 3/1 to ethyl acetate)

Sources & evidence

ORD record
ord-cec811c9c7bf4f8eb76c5cd3130d7d9f
Source dataset
uspto-grants-2001_05
Patent number
US06235731B1

Reaction notes

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