Sodium Hydroxide → 4-Tert-butylphenyldiphenyl sulfonium 3-(adamantane-1-carbonyloxy)-2,2-difluoro-3-phenyl propionate

HRID 58519Notes

Reaction equation

HRID 58519 reaction equation
C([O:3][C:4]([C:6]([F:28])([F:27])[CH:7]([O:14][C:15]([C:17]12[CH2:26][CH:21]3[CH2:22][CH:23]([CH2:25][CH:19]([CH2:20]3)[CH2:18]1)[CH2:24]2)=[O:16])[C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)=[O:5])C.O1CCOCC1.[OH-].[Na+].COS([O-])(=O)=O.[C:43]([C:47]1[CH:52]=[CH:51][C:50]([S+:53]([C:60]2[CH:65]=[CH:64][CH:63]=[CH:62][CH:61]=2)[C:54]2[CH:59]=[CH:58][CH:57]=[CH:56][CH:55]=2)=[CH:49][CH:48]=1)([CH3:46])([CH3:45])[CH3:44]>C(Cl)Cl.O>[C:17]12([C:15]([O:14][CH:7]([C:8]3[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=3)[C:6]([F:27])([F:28])[C:4]([O-:5])=[O:3])=[O:16])[CH2:24][CH:23]3[CH2:25][CH:19]([CH2:20][CH:21]([CH2:22]3)[CH2:26]1)[CH2:18]2.[C:43]([C:47]1[CH:52]=[CH:51][C:50]([S+:53]([C:60]2[CH:65]=[CH:64][CH:63]=[CH:62][CH:61]=2)[C:54]2[CH:55]=[CH:56][CH:57]=[CH:58][CH:59]=2)=[CH:49][CH:48]=1)([CH3:46])([CH3:44])[CH3:45]

Participants

7

Reactant 4

HCID 14798Sodium HydroxideHCID 312751,4-DioxaneHCID 1179666922-Ethoxycarbonyl-2,2-difluoro-1-phenylethyl 1-adamantanecarboxylateHCID 1317370174-Tert-butyl phenyldiphenylsulfonium methyl sulfate

Product 1

HCID 1317370164-Tert-butylphenyldiphenyl sulfonium 3-(adamantane-1-carbonyloxy)-2,2-difluoro-3-phenyl propionateYield 52%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

After stirring a mixed solution of 1-adamantane carboxylic acid 2-ethoxycarbonyl-2,2-difluoro-1-phenyl-ethyl ester (6.6 g) prepared in Synthesis Example 1-5, 1-4-dioxane (20 g) and 25% by mass of caustic soda (2.5 g) for 2 hours, water (30 g) was added to the reaction solution and washed with n-hexane to prepare an aqueous solution of sodium 3-(adamantane-1-carbonyloxy)-2,2-difluoro-3-phenyl propionate. An aqueous solution of 4-tert-butyl phenyldiphenylsulfonium methyl sulfate (95 g) and methylene chloride (100 g) were added to the product, stirred for 30 minutes, and then an organic layer was isolated and washed with water, and thereafter was concentrated under reduced pressure. Methylisobutyl ketone was added to the concentrated solution, and concentrated again. Diisopropyl ether was added to the concentrated solution for crystallization, and a solid obtained was dried under reduced pressure to obtain a target compound, or 4-tert-butylphenyldiphenyl sulfonium 3-(adamantane-1-carbonyloxy)-2,2-difluoro-3-phenyl propionate (5.4 g) as a white crystal (yield: 52%).

Workup

  1. washwashed with n-hexane
  2. customto prepare an aqueous solution of sodium 3-(adamantane-1-carbonyloxy)-2,2-difluoro-3-phenyl propionate
  3. customan organic layer was isolated
  4. washwashed with water
  5. concentrationwas concentrated under reduced pressure
  6. additionMethylisobutyl ketone was added to the concentrated solution
  7. concentrationconcentrated again
  8. additionDiisopropyl ether was added to the concentrated solution for crystallization
  9. customa solid obtained
  10. customwas dried under reduced pressure

Sources & evidence

ORD record
ord-1b48d87923584885ad5320c3ae2d22c0
Source dataset
uspto-grants-2016_09
Patent number
US09436083B2

Reaction notes

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