Ammonia → HCID 86746394, compound

HRID 1681060Notes

Reaction equation

HRID 1681060 reaction equation
[NH3:1].[CH2:2]([O:4][P:5]([CH2:10]/[CH:11]=[CH:12]/[CH2:13][NH:14][C:15]1[C:18](=[O:19])[C:17](=[O:20])[C:16]=1OCC)(=[O:9])[O:6][CH2:7][CH3:8])[CH3:3]>>[CH2:2]([O:4][P:5]([CH2:10]/[CH:11]=[CH:12]/[CH2:13][NH:14][C:15]1[C:18](=[O:19])[C:17](=[O:20])[C:16]=1[NH2:1])(=[O:9])[O:6][CH2:7][CH3:8])[CH3:3]

Participants

3

Reactant 2

HCID 222AmmoniaHCID 23175398HCID 23175398, compound

Product 1

HCID 86746394HCID 86746394, compoundYield 68%

Procedure

Ethanolic ammonia (235 mL) was combined with [(E)-4[(2-ethoxy-3,4-dioxo-1-cyclobuten-1-yl)amino]-2-butenyl]phosphonic acid diethyl ester (7.15 g, 21.6 mmol) and the solution was left stirring for 3 days and then evaporated. Recrystallization from methanol in ethyl acetate removed a yellow impurity, but flash chromatography (7.5 cm diameter, elution with 5% methanol in dichloromethane) was required to eliminate a more polar contaminant. Recrystallization of this material with methanol in ethyl acetate (final volume=200 mL) afforded [(E)-4-[(2-amino-3,4-dioxo-1-cyclobuten-1-yl)amino]-2-butenyl]phosphonic acid diethyl ester as a flocculant white solid (4.43 g, 68%, mp 145°-147° C.); IR (KBr, cm-1): 3280, 3100, 1800, 1640; MS (+FAB): 303 (MH+, 100), 135 (62); 1H NMR (DMSO, 400 MHz): δ 7.5 (br s, 3NH), 5.74-5.68 (m, 1H), 5.57-5.48 (m, 1H), 4.09 (br s, 2H), 4.02-3.91 (m, 4H), 2.64 (d of d, J=21.5 and 7 Hz, 2H), 1.19 (t, J=7 Hz, 6H).

Workup

  1. waitthe solution was left
  2. customevaporated
  3. customRecrystallization from methanol in ethyl acetate
  4. customremoved
  5. washa yellow impurity, but flash chromatography (7.5 cm diameter, elution with 5% methanol in dichloromethane)
  6. customRecrystallization of this material with methanol in ethyl acetate (final volume=200 mL)

Sources & evidence

ORD record
ord-5e0a11d3273a490b9d285ecbc44ce6aa
Source dataset
uspto-grants-1992_12
Patent number
US05168103

Reaction notes

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