Ethyl Acetate → HCID 178440686, compound

HRID 1054530Notes

Reaction equation

[C:1]([C:5]1[CH:6]=[C:7]([NH2:12])[C:8]([NH2:11])=[CH:9][CH:10]=1)([CH3:4])([CH3:3])[CH3:2].[C:13]1(=O)[O:18][CH2:17][CH2:16][CH2:15][CH2:14]1.C([O-])([O-])=O.[Na+].[Na+].CCOC(C)=O>Cl>[C:1]([C:5]1[CH:10]=[CH:9][C:8]2[NH:11][C:13]([CH2:14][CH2:15][CH2:16][CH2:17][OH:18])=[N:12][C:7]=2[CH:6]=1)([CH3:4])([CH3:2])[CH3:3]

Participants

Conditions

Temperature: 100 °C

Procedure

A mixture of 4-tert-butyl-benzene-1,2-diamine (1 g, 6.09 mmol) and valerolactone (0.67 g, 6.70 mmol, 1.1 eq.) in 4N HCl aq (5 ml) was sealed and heated for 2 h at 100° C. LCMS analysis shows remaining diamine. Completion was achieved using excess of valerolactone (˜1.3 ml, 2 eq.) heating at 100° for 4 h. The reaction was cooled to RT and basified to pH 12 with a saturated solution of Na2CO3. EtOAc (100 ml) was added and organic separated, washed with saturated solution of Na2CO3, water, brine, dried over Na2SO4, filtered and concentrated. The residue was purified by flash column chromatography over silica gel, eluted with DCM-MeOH from 2% to 5% gradually to yield 1.19 g (79%) of a beige solid; MS (ESI+) for C15H22N2O m/z 1 [M+H]+, 247.15; HPLC purity 100% (ret. time, 1.42 min). 1H NMR (500 MHz, CHLOROFORM-d) δ ppm 1.38 (9H, s), 1.65-1.75 (2H, m), 2.00 (2H, quin, J=7.17 Hz), 2.98 (2H, t, J=7.09 Hz), 3.72 (2H, t, J=5.99 Hz), 7.31 (1H, dd, J=8.51, 1.58 Hz), 7.48 (1H, d, J=8.20 Hz), 7.56 (1H, d, J=1.26 Hz).

Workup

customwas sealed
temperatureheating at 100° for 4 h
washorganic separated, washed with saturated solution of Na2CO3, water, brine
dry with materialdried over Na2SO4
filtrationfiltered
concentrationconcentrated
customThe residue was purified by flash column chromatography over silica gel
washeluted with DCM-MeOH from 2% to 5% gradually

Sources & evidence

ORD record: ord-676c17d7857740589938541f661d67bc
Source dataset: uspto-grants-2016_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09394310B2

Reaction notes

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