Sulfuric Acid → HCID 68750696, compound

HRID 624156Notes

Reaction equation

HRID 624156 reaction equation
[Mg].BrCCBr.Br[C:7]1[CH:12]=[CH:11][C:10]([N:13]([Si](C)(C)C)[Si](C)(C)C)=[CH:9][CH:8]=1.[C:22]1(=[O:32])[C:30]2[CH2:29][CH2:28][CH2:27][CH2:26][C:25]=2[C:24](=[O:31])[O:23]1.S(=O)(=O)(O)O>O1CCCC1>[NH2:13][C:10]1[CH:11]=[CH:12][C:7]([C:24]([C:25]2[CH2:26][CH2:27][CH2:28][CH2:29][C:30]=2[C:22]([OH:32])=[O:23])=[O:31])=[CH:8][CH:9]=1

Participants

7

Reactant 5

HCID 1118Sulfuric AcidHCID 78391,2-DibromoethaneHCID 124753,4,5,6-Tetrahydrophthalic anhydrideHCID 40926204-Bromo-N,N-bis(trimethylsilyl)anilineHCID 5462224Magnesium

Product 1

HCID 68750696HCID 68750696, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

To a suspension of 2.2 g magnesium turnings (83.5 mmol) in 15 ml tetrahydrofuran were added 0.1 mL 1,2-dibromethane to start the Grignard reaction followed by slow addition of 13.0 g 2-(4-bromphenyl)-1,1,1,3,3,3-hexamethyldisilazane (41 mmol) in 70 mL tetrahydrofuran over a period of 20 minutes at room temperature with subsequent stirring for further 30 minutes. The resulting mixture was added dropwise at −78° C. to a solution of 4,5,6,7-tetrahydro-isobenzofuran-1,3-dione (5.6 g) in 70 mL tetrahydrofuran. The reaction mixture was slowly warmed to room temperature. Sulfuric acid (2 mL, 1 M) was added and the solvent was removed under reduced pressure. The residue was added carefully to 20 mL of 0.5 M sulfuric acid solution and the desired product started to precipitate and was extracted with ethyl acetate. Acidification of the water phase and extraction with ethyl acetate was continued until pH˜4-5 (at least three times). The combined organic phases were washed with brine, dried over magnesium sulfate, filtered and the solvent was subsequently evaporated under reduced pressure. Purification of the raw material by column chromatography with ethyl acetate/hexane 1:1 and subsequently 100% ethyl acetate resulted in the desired product.

Workup

  1. customthe Grignard reaction
  2. customthe solvent was removed under reduced pressure
  3. additionThe residue was added carefully to 20 mL of 0.5 M sulfuric acid solution
  4. customto precipitate
  5. extractionwas extracted with ethyl acetate
  6. extractionAcidification of the water phase and extraction with ethyl acetate
  7. washThe combined organic phases were washed with brine
  8. dry with materialdried over magnesium sulfate
  9. filtrationfiltered
  10. customthe solvent was subsequently evaporated under reduced pressure
  11. customPurification of the raw material by column chromatography with ethyl acetate/hexane 1:1 and subsequently 100% ethyl acetate

Sources & evidence

ORD record
ord-5ff8ed1be43f4f35b3959d63a2dd2232
Source dataset
uspto-grants-2016_04
Patent number
US09302989B2

Reaction notes

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