Diethyl Oxalate → HCID 178470406, compound

HRID 1432801Notes

Reaction equation

HRID 1432801 reaction equation
CC1(C)C2C1CCC2=O.C(OCC)(=O)C(OCC)=O.CC(C)([O-])C.[K+].[CH2:26]([O:28][C:29](=[O:41])[C:30]([CH:32]1[CH2:37][CH:36]2[CH:34]([C:35]2([CH3:39])[CH3:38])[C:33]1=O)=O)[CH3:27].Cl.[NH2:43][NH2:44]>C(O)C.O>[CH2:26]([O:28][C:29]([C:30]1[NH:44][N:43]=[C:33]2[C:32]=1[CH2:37][CH:36]1[C:35]([CH3:39])([CH3:38])[CH:34]12)=[O:41])[CH3:27]

Participants

8

Reactant 5

HCID 7268Diethyl OxalateHCID 115031Hydrazinium chlorideHCID 127403286,6-Dimethylbicyclo[3.1.0]hexan-2-oneHCID 23665647Potassium tert-butoxideHCID 69062930(6,6-Dimethyl-2-oxo-bicyclo[3.1.0]hex-3-yl)-oxo-acetic acid ethyl ester

Product 1

HCID 178470406HCID 178470406, compound

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 962WaterSolvent

Conditions

Temperature
80 °C

Procedure

(±)-6,6-Dimethyl-bicyclo[3.1.0]hexan-2-one (1.49 g, 12.0 mmol), diethyl oxalate (2.46 g, 16.8 mmol) and potassium t-butoxide (18.0 mL, 1M in THF, 18.0 mmol) were stirred in ethanol (40 mL) at room temperature for 2 hours. The desired (6,6-dimethyl-2-oxo-bicyclo[3.1.0]hex-3-yl)-oxo-acetic acid ethyl ester was observed by LCMS (m/z (ES+): 247 [M+Na]+, 225 [M+H]+)but not isolated. Hydrazine monohydrochloride (0.168 g, 24.4 mmol) in water (2.0 mL) was added and the solution heated to 80° C. for 18 hours. Solvent was removed under reduced pressure and the resulting oil poured into 0.1M aqueous hydrochloric acid (30 mL) and extracted into DCM (200 mL). Solvent was removed under reduced pressure and the residue purified by column chromatography (0-50% EtOAc/n-hexane, silica) to give (±)-1,1-dimethyl-1a,3,5,5a-tetrahydro-1H-2,3-diaza-cyclopropa[a]pentalene-4-carboxylic acid ethyl ester as a pale yellow oil which solidified upon standing. m/z (ES+): 243 [M+Na]+, 221 [M+H]+, 175 [M−OEt]+; 1H NMR (CD3OD): δ 4.4-4.3 (m, 2H, OCH2), 2.90 (dd, 1H, J1=17.5, J2=6.9), 2.65 (d, 1H, J=17.5), 2.1-2.0 (m, 1H), 1.95 (t, 1H, J=12.9), 1.37 (td, J1=7.1, J2=2.0), 1.13 (s, 3H, exo-CH3), 0.74 (d, 3H, J=2.0, endo-CH3).

Workup

  1. custom247 [M+Na]+, 225 [M+H]+)but not isolated
  2. customSolvent was removed under reduced pressure
  3. additionthe resulting oil poured into 0.1M aqueous hydrochloric acid (30 mL)
  4. extractionextracted into DCM (200 mL)
  5. customSolvent was removed under reduced pressure
  6. customthe residue purified by column chromatography (0-50% EtOAc/n-hexane, silica)

Sources & evidence

ORD record
ord-c9a6691eb3484a0c851eb87760110373
Source dataset
uspto-grants-2009_11
Patent number
US07612106B2

Reaction notes

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