1,8-Diazabicyclo(5.4.0)undec-7-ene → HCID 57661613, compound

HRID 2400315Notes

Reaction equation

HRID 2400315 reaction equation
COC(=O)CCCCCCCCCCC=O.[Br-].C(OC(C1SC(C[P+](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1)=O)(C)(C)C.C1CCN2C(=NCCC2)CC1.[C:61]([O:65][C:66]([C:68]1[S:69][C:70]([CH:73]=[CH:74][CH2:75][CH2:76][CH2:77][CH2:78][CH2:79][CH2:80][CH2:81][CH2:82][CH2:83][CH2:84][C:85]([O:87][CH3:88])=[O:86])=[CH:71][CH:72]=1)=[O:67])([CH3:64])([CH3:63])[CH3:62]>CN(C=O)C.CO.[Pd]>[C:61]([O:65][C:66]([C:68]1[S:69][C:70]([CH2:73][CH2:74][CH2:75][CH2:76][CH2:77][CH2:78][CH2:79][CH2:80][CH2:81][CH2:82][CH2:83][CH2:84][C:85]([O:87][CH3:88])=[O:86])=[CH:71][CH:72]=1)=[O:67])([CH3:64])([CH3:63])[CH3:62]

Participants

8

Reactant 4

HCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 1042131712-Oxo-dodecanoic acid methyl esterHCID 69028200HCID 69028200, compoundHCID 86629717HCID 86629717, compound

Product 1

HCID 57661613HCID 57661613, compound

Reagents, catalysts & solvents 3

HCID 23938PalladiumCatalystHCID 887MethanolSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
80 °C

Procedure

12-Oxo-dodecanoic acid methyl ester (14.5 g, 63.4 mmol) and (5-tert-butoxycarbonyl-thiophen-2-ylmethyl)-triphenylphosphonium bromide (29.1 g, 63.4 mmol) were dissolved in DMF (350 mL). DBU was added and the mixture was heated to 80° C. for 35 minutes. The reaction mixture was allowed to cool to room temperature and separated between diethyl ether (3×500 mL) and water (2000 mL). The organic phases were collected and washed with water (1×500 mL). The organic phase was dried (MgSO4) and the solvent was removed in vacuo. The remaining crude material was added heptane (300 mL) and stirred for 30 minutes, filtered and the solvent was removed in vacuo to yield 13.6 g of crude material of an E/Z mixture of 5-(12-methoxycarbonyl-dodec-1-enyl)thiophene-2-carboxylic acid tert-butyl ester. This mixture was dissolved in methanol (200 mL). 2 g of 10% Palladium on carbon (50% wet with water) was added and the mixture was stirred under a hydrogen atmosphere with 10 bar pressure for 90 minutes, filtered and the solvent was removed in vacuo to yield 11.6 g of 5-(12-methoxycarbonyl-dodecyl)-thiophene-2-carboxylic acid tert-butyl ester.

Workup

  1. temperatureto cool to room temperature
  2. customseparated between diethyl ether (3×500 mL) and water (2000 mL)
  3. customThe organic phases were collected
  4. washwashed with water (1×500 mL)
  5. dry with materialThe organic phase was dried (MgSO4)
  6. customthe solvent was removed in vacuo
  7. additionThe remaining crude material was added heptane (300 mL)
  8. filtrationfiltered
  9. customthe solvent was removed in vacuo
  10. customto yield
  11. stirringthe mixture was stirred under a hydrogen atmosphere with 10 bar pressure for 90 minutes
  12. filtrationfiltered
  13. customthe solvent was removed in vacuo

Sources & evidence

ORD record
ord-ea42da1d83754a1981e8ff6a47140ed5
Source dataset
uspto-grants-2014_08
Patent number
US08796205B2

Reaction notes

Loading…