Cesium carbonate → Tert-butyl N-[(4-cyanophenyl)methyl]-N-[(2-methylpropan-2-yl)oxycarbonyl]carbamate

HRID 1157384

Reaction equation

Br[CH2:2][C:3]1[CH:10]=[CH:9][C:6]([C:7]#[N:8])=[CH:5][CH:4]=1.[CH3:11][C:12]([O:15][C:16]([NH:18][C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])=[O:17])([CH3:14])[CH3:13].C(=O)([O-])[O-].[Cs+].[Cs+]>C1COCC1.[I-].[Li+]>[C:22]([O:21][C:19]([N:18]([CH2:2][C:3]1[CH:10]=[CH:9][C:6]([C:7]#[N:8])=[CH:5][CH:4]=1)[C:16]([O:15][C:12]([CH3:14])([CH3:13])[CH3:11])=[O:17])=[O:20])([CH3:25])([CH3:24])[CH3:23]

Participants

Conditions

Temperature: 70 °C

Procedure

4-(Bromomethyl)benzonitrile (5 g, 25.5 mmoles) and di-tert-butyliminodicarboxylate (5.54 g, 25.5 mmoles) were dissolved in anhydrous THF (50 mL) and cesium carbonate (16.62 g, 25.5 mmoles) and lithium iodide (170.5 mg, 1.275 mmoles) were added. The mixture was stirred at 70° C. for 23 h and the reaction was worked up as described in Preparative Example 244, Step B above. The residue was chromatographed on a silica gel column (50×5 cm) using 5% ethyl acetate in hexane as the eluant to give 4-(di-tert-butoxycarbonylaminomethyl)benzonitrile (7.07 g, 83%): FABMS: m/z 333.2 (MH+); HRFABMS: m/z 333.1816 (MH+). Calcd. for C18H25N2O4: m/z 333.1814; δH (CDCl3) 1.45 (18H, s, —COOC(CH3)3), 4.81 (2H, s, CH2), 7.37 (2H, d, Ar—H) and 7.62 ppm (2H, d, Ar—H); δC (CDCl3) CH3, 28.1, 28.1, 28.1, 28.1, 28.1, 28.1; CH2, 49.2; CH, 127.8, 127.8, 132.3, 132.3; C, 83.2, 83.2, 111.1, 118.9, 144.1, 152.4, 152.4.

Workup

customThe residue was chromatographed on a silica gel column (50×5 cm)

Sources & evidence

ORD record: ord-342e233134ed4d429609eaf3d2ee1b9f
Source dataset: uspto-grants-2010_10
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07807683B2

Linked notes

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