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Dimethylformamide → HCID 59504447, compound

HRID 418906
Notes
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Reaction equation

HRID 418906 reaction equation
[CH2:1]([O:3][C:4]([C:6]1[CH2:11][CH2:10][CH2:9][CH2:8][C:7]=1O)=[O:5])[CH3:2].[CH3:13][O:14][C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][C:16]=1B(O)O.CN(C=O)C.C(=O)([O-])[O-].[Na+].[Na+]>O.CC([O-])=O.CC([O-])=O.[Pd+2].C1(P(C2C=CC=CC=2)CCCCP(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(OCC)(=O)C.CO>[CH2:1]([O:3][C:4]([C:6]1[CH2:11][CH2:10][CH2:9][CH2:8][C:7]=1[C:16]1[CH:17]=[CH:18][CH:19]=[CH:20][C:15]=1[O:14][CH3:13])=[O:5])[CH3:2]
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

10

Reactant 4

HCID 6228DimethylformamideHCID 10340Sodium CarbonateHCID 27339582-Methoxyphenylboronic acidHCID 54695815Ethyl 2-hydroxycyclohex-1-ene-1-carboxylate

Product 1

HCID 59504447HCID 59504447, compoundYield 52%

Reagents, catalysts & solvents 5

HCID 82124
1,4-Bis(diphenylphosphino)butane
Catalyst
HCID 167845palladium(II) acetateCatalyst
HCID 887MethanolSolvent
HCID 962WaterSolvent
HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
70 °C

Procedure

Combine 2-hydroxy-cyclohex-1-enecarboxylic acid ethyl ester (8.92 g, 29.5 mmol), 2-methoxyphenylboronic acid (5.0 g, 32.4 mmol), DMF (60.0 mL), methanol (20.0 mL), and sodium carbonate in water (40.0 g in 40 mL) at room temperature. Purge several times with nitrogen then add Pd(OAc)2 (72.0 mg, 1 mmol %) and 1,4-bis(diphenyl phosphino)butane (170.0 mg) and purge again with nitrogen. Stir at 70° C. under nitrogen for 5 hours then filter reaction wash with Methanol and ethyl acetate. Concentrate reaction mixture on rotovap and add ethyl acetate. Wash 5 times with brine and dry over anhydrous sodium sulfate. Concentrate and flash chromatograph using 5 to 40% ethyl acetate/hexanes eluent to yield the titled compound (3.98 g, 52%). TLC Rf=0.25 in 10% ethyl acetate/hexanes. 1H NMR (CDCl3): 7.2 (t, 1H, J=6.0 Hz), 6.9 (m, 3H),), 3.8 (m, 5H), 2.5 (m, 4H), 1.8 (m, 4H), 0.8 (t, 3H, J=7 Hz).

Workup

  1. customat room temperature
  2. customPurge several times with nitrogen
  3. filtrationthen filter
  4. customreaction
  5. washwash with Methanol and ethyl acetate
  6. concentrationConcentrate
  7. customreaction mixture on rotovap
  8. washWash 5 times with brine
  9. dry with materialdry over anhydrous sodium sulfate
  10. concentrationConcentrate

Sources & evidence

ORD record
ord-7a098624b24b46a4ab473d98795a367a
Source dataset
uspto-grants-2012_01
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US08093302B2

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes