Isobutylene → 2-(3-Bromophenyl)-4,4,8-trimethyl-1,2,3,4-tetrahydroquinoline-6-carbonitrile

HRID 1036868Notes

Reaction equation

[NH2:1][C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[CH:4][C:3]=1[CH3:10].[Br:11][C:12]1[CH:13]=[C:14]([CH:17]=[CH:18][CH:19]=1)[CH:15]=O.[CH2:20]=[C:21]([CH3:23])[CH3:22].FC(F)(F)S([O-])(=O)=O.[Yb+3].FC(F)(F)S([O-])(=O)=O.FC(F)(F)S([O-])(=O)=O>C(#N)C.C(OCC)(=O)C>[Br:11][C:12]1[CH:13]=[C:14]([CH:15]2[CH2:20][C:21]([CH3:23])([CH3:22])[C:9]3[C:2](=[C:3]([CH3:10])[CH:4]=[C:5]([C:6]#[N:7])[CH:8]=3)[NH:1]2)[CH:17]=[CH:18][CH:19]=1

Participants

Conditions

Temperature: 85 °C

Procedure

To a stirred solution of 4-amino-3-methyl-benzonitrile (10.3 g, 78.4 mmol) and 3-bromobenzaldehyde (9.2 mL, 78.4 mmol) in acetonitrile (150 mL) were added isobutene (21.0 mL, 313.5 mmol) and ytterbium(III) trifluoromethanesulfonate (Yb(OTf)3) (5.8 g, 9.5 mmol). The resulting mixture was stirred at 85° C. for 18 h in sealed tube. The mixture was diluted with ethyl acetate (300 mL) and washed with water (100 mL×2) and brine (100 mL×2) and then dried over anhydrous sodium sulfate. The solvent was removed in vacuo and the residue was purified by ISCO combi-flash chromatography (gradient elution, 10-30% ethyl acetate in petroleum ether) to afford 2-(3-bromo-phenyl)-4,4,8-trimethyl-1,2,3,4-tetrahydro-quinoline-6-carbonitrile (7.3 g, 26.1%) as a light yellow oil: LC/MS m/e obsd. (ESI+) [(M+H)+] 355.0 & 357.0.

Workup

washwashed with water (100 mL×2) and brine (100 mL×2)
dry with materialdried over anhydrous sodium sulfate
customThe solvent was removed in vacuo
customthe residue was purified by ISCO combi-flash chromatography (gradient elution, 10-30% ethyl acetate in petroleum ether)

Sources & evidence

ORD record: ord-1d2e55a5f4514e8b9eb0a1c1afb69f7f
Source dataset: uspto-grants-2013_10
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08546427B2

Reaction notes

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