Hydroxylamine → HCID 57904851, compound

HRID 1093065Notes

Reaction equation

HRID 1093065 reaction equation
[C:1]([C:3]1([NH:13][C:14](=[O:23])[O:15][CH2:16][C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[CH2:12][CH2:11][C:6]2([O:10][CH2:9][CH2:8][O:7]2)[CH2:5][CH2:4]1)#[N:2].[NH2:24][OH:25].[C:26]([C:33]([O:35][CH2:36][CH3:37])=[O:34])#[C:27][C:28]([O:30][CH2:31][CH3:32])=[O:29]>CCO>[CH2:16]([O:15][C:14]([NH:13][C:3]1([C:1]2[NH:24][O:25][C:27]([CH2:26][C:33]([O:35][CH2:36][CH3:37])=[O:34])([C:28]([O:30][CH2:31][CH3:32])=[O:29])[N:2]=2)[CH2:12][CH2:11][C:6]2([O:10][CH2:9][CH2:8][O:7]2)[CH2:5][CH2:4]1)=[O:23])[C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1

Participants

5

Reactant 3

HCID 787HydroxylamineHCID 69803Diethyl acetylenedicarboxylateHCID 57905043HCID 57905043, compound

Product 1

HCID 57904851HCID 57904851, compoundYield 82%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Conditions

Temperature
70 °C

Procedure

A mixture of benzyl 8-cyano-1,4-dioxaspiro[4.5]decan-8-ylcarbamate (37.4 g, 118.33 mmol), hydroxylamine (7.98 mL, 130 mmol, 50 wt % in water) in EtOH (750 mL) was heated at 70° C. for 48 h. The mixture was then cooled to room temperature and treated with diethyl acetylenedicarboxylate (22.73 mL, 142 mmol). After 48 h at room temperature, the reaction mixture was concentrated and the resulting yellow residue was taken up in ethyl acetate (500 mL), washed with water (2×100 mL) followed by brine (100 mL), then dried (Na2SO4), filtered and concentrated to give a yellow oil. Flash chromatography on silica gel (using 5% to 50% ethyl acetate-hexane gradient) afforded the title compound as a yellow oil (50 g, 82% yield). 1H NMR (500 MHz, CDCl3) δ: 7.33-7.37 (m, 5H), 5.80 (s, 1H), 5.07 (s, 2H), 4.84 (d, 1H, J=23.8 Hz), 4.33 (q, 1H, J=7.02 Hz), 4.27 (q, 1H, J=7.22 Hz), 4.09-4.20 (m, 3H), 3.93 (s, 2H), 3.90-3.92 (m, 2H), 2.16-2.23 (m, 4H), 2.03 (s, 1H), 1.62-1.74 (m, 4H), 1.24-1.37 (m, 6H). LCMS (M+H)=336.14.

Workup

  1. temperatureThe mixture was then cooled to room temperature
  2. concentrationthe reaction mixture was concentrated
  3. washwashed with water (2×100 mL)
  4. dry with materialdried (Na2SO4)
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customto give a yellow oil

Sources & evidence

ORD record
ord-8de7ed0f7e9a4246a46298cd6fe52585
Source dataset
uspto-grants-2012_03
Patent number
US08129398B2

Reaction notes

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