1,8-Diazabicyclo(5.4.0)undec-7-ene → HCID 86720226, compound

HRID 625157Notes

Reaction equation

HRID 625157 reaction equation
[Br:1][C:2]1[C:3]([CH3:22])=[C:4]([CH2:17][CH2:18][N+:19]([O-:21])=[O:20])[N:5]([S:7]([C:10]2[CH:16]=[CH:15][C:13]([CH3:14])=[CH:12][CH:11]=2)(=[O:9])=[O:8])[CH:6]=1.[CH3:23][O:24][CH:25]([O:32][CH3:33])[C:26](=[O:31])[CH:27]=[C:28]([CH3:30])[CH3:29].C1CCN2C(=NCCC2)CC1>[NH4+].[Cl-]>[Br:1][C:2]1[C:3]([CH3:22])=[C:4]([CH2:17][CH:18]([N+:19]([O-:21])=[O:20])[C:28]([CH3:30])([CH3:29])[CH2:27][C:26](=[O:31])[CH:25]([O:24][CH3:23])[O:32][CH3:33])[N:5]([S:7]([C:10]2[CH:11]=[CH:12][C:13]([CH3:14])=[CH:15][CH:16]=2)(=[O:8])=[O:9])[CH:6]=1

Participants

5

Reactant 3

HCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 14662915HCID 14662915, compoundHCID 71076701HCID 71076701, compound

Product 1

HCID 86720226HCID 86720226, compoundYield 86.6%

Reagents, catalysts & solvents 1

HCID 25517Ammonium ChlorideSolvent

Procedure

Following a general procedure,50 a mixture of 4-Ts (9.00 g, 23.3 mmol) and 1,1-dimethoxy-4-methyl-3-penten-2-one (11.1 g, 69.9 mmol, 3 equiv) was treated with DBU (10.5 mL, 69.9 mmol). The reaction mixture was stirred for 15 min under argon. A saturated solution of cold aqueous NH4Cl (50 mL, 0° C.) was added. The mixture was extracted with ethyl acetate (100 mL). The organic layer was washed with brine, dried (Na2SO4), concentrated and dried overnight under high vacuum. Addition of diethyl ether (50 mL) to the resulting solid, trituration, and filtration afforded a pale brown solid (11.0 g, 86%): mp 114-115° C.; 1H-NMR δ 1.22 (s, 3H), 1.27 (s, 3H), 1.85 (s, 3H), 2.42 (s, 3H), 2.64, 2.74 (AB, 2J=19.0 Hz, 2H), 3.15 (ABX, 2JAB=15.4 Hz, 3JBX=1.8 Hz, 1H), 3.32 (ABX, 2JAB=15.4 Hz, 3JAX=11.7 Hz, 1H), 3.41 (s, 3H), 3.43 (s, 3H), 4.37 (s, 1H), 5.19 (ABX, 3JAX=11.7 Hz, 3JBX=1.8 Hz, 1H), 7.28 (s, 1H), 7.31 (d, J=8.1 Hz, 2H), 7.59 (d, J=8.1 Hz, 2H); 13C NMR δ 0.7, 21.9, 23.8, 24.0, 25.9, 36.8, 44.2, 55.28, 55.29, 94.4, 104.9, 105.9, 122.6, 125.1, 125.9, 126.7, 130.5, 135.9, 145.6, 203.2; Anal. Calcd for C22H29BrN2O7S: C, 48.44; H, 5.36; N, 5.14. Found: C, 48.70; H, 5.30; N, 5.17.

Workup

  1. extractionThe mixture was extracted with ethyl acetate (100 mL)
  2. washThe organic layer was washed with brine
  3. dry with materialdried (Na2SO4)
  4. concentrationconcentrated
  5. customdried overnight under high vacuum
  6. additionAddition of diethyl ether (50 mL)
  7. filtrationto the resulting solid, trituration, and filtration

Sources & evidence

ORD record
ord-4bd98ae203164b9ca10ec0dce654c984
Source dataset
uspto-grants-2016_04
Patent number
US09303165B2

Reaction notes

Loading…