Nitrogen → Tert-butyl 6-allyl-2,3-di-p-tolyl-7,8-dihydropyrido[2,3-b]pyrazine-5(6H)-carboxylate

HRID 517877Notes

Reaction equation

HRID 517877 reaction equation
[C:1]1([CH3:31])[CH:6]=[CH:5][C:4]([C:7]2[N:8]=[C:9]3[CH2:23][CH2:22][CH2:21][N:20]([C:24]([O:26][C:27]([CH3:30])([CH3:29])[CH3:28])=[O:25])[C:10]3=[N:11][C:12]=2[C:13]2[CH:18]=[CH:17][C:16]([CH3:19])=[CH:15][CH:14]=2)=[CH:3][CH:2]=1.N#N.CN(C)CCN(C)C.[CH:42]([Li])([CH2:44]C)[CH3:43].C(Br)C=C>CCOCC.O>[CH2:44]([CH:21]1[N:20]([C:24]([O:26][C:27]([CH3:28])([CH3:30])[CH3:29])=[O:25])[C:10]2=[N:11][C:12]([C:13]3[CH:18]=[CH:17][C:16]([CH3:19])=[CH:15][CH:14]=3)=[C:7]([C:4]3[CH:3]=[CH:2][C:1]([CH3:31])=[CH:6][CH:5]=3)[N:8]=[C:9]2[CH2:23][CH2:22]1)[CH:42]=[CH2:43]

Participants

8

Reactant 5

HCID 947NitrogenHCID 7841Allyl bromideHCID 8037N,N,N',N'-TetramethylethylenediamineHCID 66666294Tert-butyl 2,3-di-p-tolyl-7,8-dihydropyrido[2,3-b]pyrazine-5(6H)-carboxylateHCID 178418400CID 53628100

Product 1

HCID 89690358Tert-butyl 6-allyl-2,3-di-p-tolyl-7,8-dihydropyrido[2,3-b]pyrazine-5(6H)-carboxylate

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 3283Diethyl EtherSolvent

Conditions

Temperature
-70 °C

Procedure

Tert-butyl 2,3-di-p-tolyl-7,8-dihydropyrido[2,3-b]pyrazine-5(6H)-carboxylate (step 1) (500 mg, 1.203 mmol) in Et2O (10 ml) degassed with N2 was treated with 1,2-di(dimethylamino) ethane (0.400 ml, 2.65 mmol). The mixture was cooled to −70° C. and treated with sec-butyllithium (1.4M in cyclohexane, 0.945 ml, 1.324 mmol) dropwise, maintaining the temperature at −70° C. After stirring at −70° C. for 2 hours allyl bromide (0.115 ml, 1.324 mmol) was added and the mixture was allowed to warm to room temperature and stirred for 16 hours. The resulting mixture was added dropwise to water (100 ml) and extracted with DCM (×3). The combined organic extracts were concentrated under reduced pressure and purification of the crude product by chromatography on silica eluting with 0-10% EtOAc in iso-hexane afforded the titled compound as a cream coloured solid;

Workup

  1. temperaturemaintaining the temperature at −70° C
  2. additionwas added
  3. temperatureto warm to room temperature
  4. extractionextracted with DCM (×3)
  5. concentrationThe combined organic extracts were concentrated under reduced pressure and purification of the crude product by chromatography on silica eluting with 0-10% EtOAc in iso-hexane

Sources & evidence

ORD record
ord-7905de4107d746da9c142bad8bab0110
Source dataset
uspto-grants-2015_08
Patent number
US09115129B2

Reaction notes

Loading…