Boron trifluoride etherate → Methyl 2-(4-cyanophenylamino)-2-(3-ethoxy-4-isopropoxyphenyl)acetate

HRID 1438184Notes

Reaction equation

[CH2:1]([O:3][C:4]1[CH:5]=[C:6]([CH:9]=[CH:10][C:11]=1[O:12][CH:13]([CH3:15])[CH3:14])[CH:7]=O)[CH3:2].[C:16]([C:18]1[CH:24]=[CH:23][C:21]([NH2:22])=[CH:20][CH:19]=1)#[N:17].C1(C)C=CC(S(C[N+]#[C-])(=O)=[O:32])=CC=1.B(F)(F)F.C[CH2:43][O:44][CH2:45]C>CO.O>[C:16]([C:18]1[CH:24]=[CH:23][C:21]([NH:22][CH:7]([C:6]2[CH:9]=[CH:10][C:11]([O:12][CH:13]([CH3:15])[CH3:14])=[C:4]([O:3][CH2:1][CH3:2])[CH:5]=2)[C:43]([O:44][CH3:45])=[O:32])=[CH:20][CH:19]=1)#[N:17]

Participants

Conditions

Temperature: 0 °C

Procedure

A solution of 141A (7.42 g, 35:6 mmol) and 4-cyanoaniline (4.21 g, 35.6 mmol) in methanol (120 mL) was stirred at 60° C. for 2 h. The reaction was cooled to 0° C. and p-toluenesulfonylmethyl isocyanide (6.95 g, 35.6 mmol) was added followed by dropwise addition of boron trifluoride etherate (13.5 mL, 107 mmol). After stirring for 30 min at 0° C., the reaction was allowed to warm to rt and stirring was continued for 2 h. Water (4 mL) was added and bright yellow precipitate was observed after stirring for 2 days. The solvent was removed and the residue was redissolved in ethyl acetate. The precipitate was filtered and dried to give 7.89 g of 141B as a white solid. 1H NMR (400 MHz, Methanol-d4) δ ppm 1.18-1.20 (m, 6H) 1.28 (t, J=6.98, 3H) 3.62 (s, 3H) 3.90-3.98 (m, 2H) 4.40-4.50 (m, 1H) 5.06 (s, 1H) 6.59 (d, J=8.90 Hz, 2H) 6.80-7.00 (m, 3H) 7.29 (d, J=8.90 Hz, 2H).

Workup

temperatureto warm to rt
stirringstirring
waitwas continued for 2 h
stirringafter stirring for 2 days
customThe solvent was removed
dissolutionthe residue was redissolved in ethyl acetate
filtrationThe precipitate was filtered
customdried

Sources & evidence

ORD record: ord-ec75ae4ee7e543689f4301fe7ad63f86
Source dataset: uspto-grants-2009_11
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07622585B2

Reaction notes

Loading…