Hydroxylamine → HCID 178472245, compound

HRID 1093074Notes

Reaction equation

HRID 1093074 reaction equation
[C:1]([C:3]1([NH:11][C:12](=[O:14])[O-:13])[CH2:8][CH2:7][CH:6]([CH2:9][OH:10])[CH2:5][CH2:4]1)#[N:2].[NH2:15][OH:16].[C:17]([C:24]([O:26][CH2:27][CH3:28])=[O:25])#[C:18][C:19]([O:21][CH2:22][CH3:23])=[O:20]>CCO>[CH2:1]([O:14][C:12]([NH:11][C:3]1([C:1]([NH:15][O:16]/[C:18](=[CH:17]\[C:24]([O:26][CH2:27][CH3:28])=[O:25])/[C:19]([O:21][CH2:22][CH3:23])=[O:20])=[NH:2])[CH2:4][CH2:5][CH:6]([CH2:9][OH:10])[CH2:7][CH2:8]1)=[O:13])[C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1

Participants

5

Reactant 3

HCID 787HydroxylamineHCID 69803Diethyl acetylenedicarboxylateHCID 86634935HCID 86634935, compound

Product 1

HCID 178472245HCID 178472245, compound

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Conditions

Temperature
70 °C

Procedure

A mixture of 1-cyano-4-(hydroxymethyl)cyclohexylcarbamate (6.5 g, 22.54 mmol), 50% aq. hydroxylamine (1.66 mL, 27.05 mmol) in EtOH (150 mL) was heated at 70° C. for 18 h. The mixture was then cooled to room temperature and treated with diethyl acetylenedicarboxylate (4.33 mL, 27.1 mmol). After 18 h at room temperature, the reaction mixture was concentrated and the resulting yellow residue was taken up in ethyl acetate (250 mL), washed with water (2×100 mL) followed by brine (100 mL), then dried (Na2SO4), filtered and concentrated to give yellow oil. Flash column chromatography on silica gel (using 5% to 50% ethyl acetate-hexane gradient) afforded the title compound as a mixture of isomers and as a yellow oil (8 g, 72% yield). 1H NMR (500 MHz, CDCl3) δ: 7.30-7.36 (m, 6H), 5.59 (s, 0.5 H), 5.75 (s, 0.5 H), 5.13 (s, 1H), 5.04 (s, 2H), 4.32-4.36 (m, 1H), 4.24-4.29 (m, 1H), 4.09-4.17 (m, 4H), 3.46-3.51 (m, 2H), 2.54-2.58 (m, 2H), 1.45-1.57 (m, 5H), 1.23-1.26 (m, 6H). LCMS (M+H)=492.36.

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 yellow oil

Sources & evidence

ORD record
ord-d342ab2033cf4db381059b74951ae0ba
Source dataset
uspto-grants-2012_03
Patent number
US08129398B2

Reaction notes

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