Hydrochloric Acid → HCID 67148556, compound

HRID 2427472Notes

Reaction equation

HRID 2427472 reaction equation
[CH2:1]([O:3][C:4]([CH:6]1[CH2:11][CH2:10][CH:9]([O:12][Si:13]([C:26]([CH3:29])([CH3:28])[CH3:27])([C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)[C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)[CH2:8][CH2:7]1)=[O:5])[CH3:2].[CH:30]([N-:33]C(C)C)(C)[CH3:31].[Li+].CCCCCCC.C1COCC1.C(C1C=CC=CC=1)C.BrCC#N.Cl>C1COCC1.C(OCC)(=O)C>[CH2:1]([O:3][C:4]([C:6]1([CH2:31][C:30]#[N:33])[CH2:11][CH2:10][CH:9]([O:12][Si:13]([C:26]([CH3:28])([CH3:27])[CH3:29])([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)[C:20]2[CH:21]=[CH:22][CH:23]=[CH:24][CH:25]=2)[CH2:8][CH2:7]1)=[O:5])[CH3:2]

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 11534BromoacetonitrileHCID 2724682Lithium diisopropylamideHCID 22742125Tetrahydrofuran heptane ethylbenzolHCID 58018637HCID 58018637, compound

Product 1

HCID 67148556HCID 67148556, compoundYield 47%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-78 °C

Procedure

Treat a −78° C. solution of 4-(tert-butyl-diphenyl-silanyloxy)-cyclohexanecarboxylic acid ethyl ester (21.22 g, 51.7 mmol) in THF (200 mL) with a 2M solution of lithium diisopropylamide in heptane/THF/ethylbenzene (31 mL, 62.0 mmol) and stir at −78° C. for 15 minutes under N2. Warm the reaction to −20° C. and then re-cool to −78° C. Treat the reaction with bromoacetonitrile (9.30 g, 77.5 mmol) and stir at −78° C. for 1 hour. Warm the reaction to room temperature and stir 1 hour. Acidify the reaction with 1 N HCl, dilute with ethyl acetate, and wash with water. Dry the organic layer with Na2SO4 and remove the solvent in vacuo to afford crude product that is purified with a 0 to 20% ethyl acetate in hexanes gradient on silica gel to afford 10.96 g (47%) of the titled product. Rf=0.25 and 0.21 (5/1 hexanes/ethyl acetate). MS (m/z): 450 (M+).

Workup

  1. temperatureWarm
  2. customthe reaction to −20° C.
  3. temperaturere-cool to −78° C
  4. additionTreat
  5. stirringstir at −78° C. for 1 hour
  6. temperatureWarm
  7. customthe reaction to room temperature
  8. stirringstir 1 hour
  9. washwash with water
  10. dry with materialDry the organic layer with Na2SO4
  11. customremove the solvent in vacuo
  12. customto afford crude product that
  13. customis purified with a 0 to 20% ethyl acetate in hexanes gradient on silica gel

Sources & evidence

ORD record
ord-6a6c85a6b69d482691bece7d75b2d0c1
Source dataset
uspto-grants-2011_06
Patent number
US07968585B2

Reaction notes

Loading…