Hydrochloric Acid → 4-Phenylbut-2-yn-1-amine

HRID 1781156Notes

Reaction equation

C([Li])CCC.CN1[CH2:12][CH2:11][CH2:10][N:9](C)C1=O.[CH2:15](Br)[C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1.Cl>C1COCC1>[CH:19]1[CH:20]=[CH:21][C:16]([CH2:15][C:12]#[C:11][CH2:10][NH2:9])=[CH:17][CH:18]=1

Participants

Conditions

Temperature: 0 °C

Procedure

The compound resulting from Example 60A (4.35 g of -75% pure material, -16.5 mmol) was dissolved in THF (87 mL), cooled to 0° C., then n-butyllithium (16.5 mL of 1.6M hexanes solution) was added dropwise, followed by 1,3-dimethyl-3,4,5,6-tetrahydro-2(1 H)-pyrimidinone (3.20 mL, 3.39 g, 26.5 mmol) and benzyl bromide (3.50 mL, 5.03 g, 29.4 mmol). The reaction was stirred at 0° C. for 3 hours, then 1N HCl was added. After washing with 3×Et2O, the pH was adjusted to 10 with 4N NaOH, then extracted with 4×Et2O. The second set of Et2O layers were combined, dried over Na2SO4, filtered and concentrated to give a residue which was purified by silica gel chromatography eluting with a gradient of 99:1, 98.75:1.25, and 98:2 CHCl3 -MeOH to afford 1.41 g (59%) of the title compound as a light brown oil. 1H NMR (CDCl3) δ 7.35,7.24 (both m, total 5H), 3.60 (t, 2H), 3.47 (t, 2H), 1.38 (br s, 2H). MS (DCl/NH3) m/e 146 (M+H)+, 163 (M+H+NH3)+.

Workup

washAfter washing with 3×Et2O
extractionextracted with 4×Et2O
dry with materialdried over Na2SO4
filtrationfiltered
concentrationconcentrated
customto give a residue which
customwas purified by silica gel chromatography
washeluting with a gradient of 99:1, 98.75:1.25, and 98:2 CHCl3 -MeOH

Sources & evidence

ORD record: ord-6e2150c708be4e9c8308fb78a619353c
Source dataset: uspto-grants-1997_05
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05631401

Reaction notes

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