Sodium prop-2-enolate → 6-allyloxy-N-((2-chlorothiazole-5-yl)methyl)-N-ethyl-nitropyridine-2-amine

HRID 1050716Notes

Reaction equation

Cl[C:2]1[N:7]=[C:6]([N:8]([CH2:11][C:12]2[S:16][C:15]([Cl:17])=[N:14][CH:13]=2)[CH2:9][CH3:10])[C:5]([N+:18]([O-:20])=[O:19])=[CH:4][CH:3]=1.[CH2:21]([O-:24])[CH:22]=[CH2:23].[Na+]>CN(C=O)C>[CH2:21]([O:24][C:2]1[N:7]=[C:6]([N:8]([CH2:11][C:12]2[S:16][C:15]([Cl:17])=[N:14][CH:13]=2)[CH2:9][CH3:10])[C:5]([N+:18]([O-:20])=[O:19])=[CH:4][CH:3]=1)[CH:22]=[CH2:23]

Participants

Conditions

Temperature: 7.5 °C

Procedure

1.10 g of 6-chloro-N-((2-chlorothiazole-5-yl)methyl)-N-ethyl-3-nitropyridine-2-amine, prepared according to the example 1, in 30 mL of DMF was added into a 100 mL three-necked flask equipped with a magnetic stirrer, a condenser and a drying tube, under stirring at 5-10° C., 1.02 g of sodium prop-2-en-1-olate (the content of 30.7%) in 20 mL of DMF was added dropwise, and the reaction was complete after further stirred for 4 to 6 hours. The reaction mixture was treated by the method according to the example 1 to obtain 0.25 g of 6-allyloxy-N-((2-chlorothiazole-5-yl)methyl)-N-ethyl-nitropyridine-2-amine, having the content of 91%, as a brown sticky solid in a yield of 19.4%. GC-MS (M+) (EI, 70 eV, m/z) calc: 354. found: 354. 1H NMR (CDCl3/TMS, 300 MHz) δ (ppm) 1.221 (t, J=7.2 Hz, 3H, CH3), 3.291 (q, J=7.2 Hz, 2H, CH2), 4.817 (s, 2H, CH2), 4.869 (d J=2.7 Hz, 2H, CH2), 5.464-5.267 (m, 2H, CH2), 6.086-5.957 (m, 1H, CH), 6.231 (d, J=8.7 Hz, 1H, Py H), 7.473 (s, 1H, Thiazole-H), 8.171 (d, J=8.7 Hz, 1H, Py H).

Workup

additionwas added into a 100 mL three-necked flask
customequipped with a magnetic stirrer, a condenser and a drying tube
stirringafter further stirred for 4 to 6 hours
additionThe reaction mixture was treated by the method

Sources & evidence

ORD record: ord-9742f559c04a4c379fe185bdedd32fe1
Source dataset: uspto-grants-2016_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09386769B2

Reaction notes

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