4-Chloro-2-nitrophenol → HCID 58056154, compound

HRID 1773490Notes

Reaction equation

HRID 1773490 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([OH:8])=[C:4]([N+:9]([O-:11])=[O:10])[CH:3]=1.[C:12]([Si:16]([CH3:26])([CH3:25])[O:17][CH:18]1[CH2:23][CH2:22][CH:21](O)[CH2:20][CH2:19]1)([CH3:15])([CH3:14])[CH3:13].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>O1CCCC1.C(OCC)(=O)C.CCCCCC>[C:12]([Si:16]([O:17][CH:18]1[CH2:19][CH2:20][CH:21]([O:8][C:5]2[CH:6]=[CH:7][C:2]([Cl:1])=[CH:3][C:4]=2[N+:9]([O-:11])=[O:10])[CH2:22][CH2:23]1)([CH3:26])[CH3:25])([CH3:15])([CH3:13])[CH3:14]

Participants

7

Reactant 3

HCID 69804-Chloro-2-nitrophenolHCID 11776TriphenylphosphineHCID 554539cis-4-((t-Butyldimethylsilyl)oxy)cyclohexan-1-ol

Product 1

HCID 58056154HCID 58056154, compoundYield 79%

Reagents, catalysts & solvents 3

HCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

A solution of diisopropylazadicarboxylate (1.65 g, 8.16 mmol) in anhydrous tetrahydrofuran (5 mL) was added, dropwise, at 0° C., to a solution of 4-chloro-2-nitrophenol (0.75 g, 4.32 mmol), 4-(tert-butyl-dimethyl-silanyloxy)-cyclohexanol (1.2 g, 5.21 mmol) and triphenylphosphine (2.27 g, 8.65 mmol) in anhydrous tetrahydrofuran (10 mL). The resulting mixture was stirred at 0° C. for 1 hour and at room temperature overnight. The reaction mixture was then sonicated for 20 minutes at room temperature and for 30 minutes at 40° C. and then was stirred at room temperature for 24 hours. The solvent was evaporated under reduced pressure and the residue was partitioned between ethyl acetate and an aqueous solution of sodium bicarbonate (5%), the organic layer was separated and the aqueous layer was extracted 3 times with ethyl acetate. The combined organic extracts were washed with brine, dried over anhydrous sodium sulfate, filtered and evaporated under reduced pressure. The yellow oily residue was purified on a silica gel plug (hexane/EtOAc, from 99/1 to 90/10) to give a yellow oil. This material was dissolved in a mixture of ethyl acetate and hexane (1/1) and the resulting solution was washed twice with an aqueous solution of sodium hydroxide (3 M) and once with brine, dried over anhydrous sodium sulfate, filtered and evaporated under reduced pressure to give 1.28 g (79% yield) of tert-butyl-[4-(4-chloro-2-nitro-phenoxy)-cyclohexyloxy]-dimethyl-silane as a light yellow oil.

Workup

  1. customat 0° C.
  2. customThe reaction mixture was then sonicated for 20 minutes at room temperature and for 30 minutes at 40° C.
  3. stirringwas stirred at room temperature for 24 hours
  4. customThe solvent was evaporated under reduced pressure
  5. customthe residue was partitioned between ethyl acetate
  6. customan aqueous solution of sodium bicarbonate (5%), the organic layer was separated
  7. extractionthe aqueous layer was extracted 3 times with ethyl acetate
  8. washThe combined organic extracts were washed with brine
  9. dry with materialdried over anhydrous sodium sulfate
  10. filtrationfiltered
  11. customevaporated under reduced pressure
  12. customThe yellow oily residue was purified on a silica gel plug (hexane/EtOAc, from 99/1 to 90/10)
  13. customto give a yellow oil
  14. washthe resulting solution was washed twice with an aqueous solution of sodium hydroxide (3 M) and once with brine
  15. dry with materialdried over anhydrous sodium sulfate
  16. filtrationfiltered
  17. customevaporated under reduced pressure

Sources & evidence

ORD record
ord-96f4964609d74284b45e0434f650a29c
Source dataset
uspto-grants-2016_02
Patent number
US09255110B2

Reaction notes

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