Participants
| Role | Name | HCID | Charge |
|---|
| Reactant | Hydrochloric Acid | HCID 313 | — |
| Reactant | Ethyl Bromide | HCID 6332 | — |
| Reactant | Trimethylpyruvic acid | HCID 13150 | — |
| Reactant | tert-Butyl methyl ether | HCID 15413 | — |
| Reactant | 1,8-Diazabicyclo(5.4.0)undec-7-ene | HCID 81184 | — |
| Reactant | Cyclohexylhydrazine hydrochloride | HCID 207836 | — |
| Reactant | Sodium Bicarbonate | HCID 516892 | — |
| Reactant | HCID 86623017 | HCID 86623017 | — |
| Solvent | Water | HCID 962 | — |
| Solvent | Ethyl Acetate | HCID 8857 | — |
| Product | HCID 54739191 | HCID 54739191 | 57% |
Reaction Steps
Ethyl-2-(cyclohexylhydrazono)-3,3-dimethylbutanoate. To a solution of trimethylpyruvic acid (0.6 g, 2.77 mmol) in MTBE (4.0 ml) was added DBU (0.58 ml, 3.85 mmol) followed by bromoethane (0.5 ml, 6.70 mmol) at room temperature. The reaction was heated in the microwave at 120° C. for 20 minutes. The reaction was cooled and 10% NaHCO3 (aq) added. The layers were separated and the organic layer was washed again with 10% NaHCO3 (aq). The aqueous layer backextracted with Et2O several times. The combined organic layers were washed with Brine, dried (MgSO4), filtered and concentrated. The resulting oil was redissolved in Ethanol (5.0 mL) and cyclohexylhydrazine hydrochloride (0.500 g, 3.32 mmol) and DBU (0.500 ml, 3.32 mmol) were added. The reaction was heated in the microwave at 150° C. for 25 minutes. The reaction was cooled to room temperature and 1N HCl added. The solution was diluted with H2O and EtOAc and the layers separated. The aqueous layer was backextracted with EtOAc several times. The combined organic layers were washed with Brine, dried (MgSO4), filtered and concentrated. The product was purified by column chromatography (SiO2, 5-15% EtOAc/Hexanes) to give the title compound as a colorless oil (0.403 g, 57%). 1H NMR (400 MHz, DMSO-d6) d ppm 9.32 (d, J=4.80 Hz, 1H) 4.20 (q, J=7.07 Hz, 2H) 3.08-3.26 (m, 1H) 1.79-1.94 (m, 2H) 1.48-1.74 (m, 3H) 1.26 (t, J=7.07 Hz, 3H) 1.22-1.37 (m, 5H) 1.15 (s, 9H).
Provenance & Evidence
| DOI | 10.6084/m9.figshare.5104873.v1 |
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| Patent number | USRE044613E1 |
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| Source dataset | uspto-grants-2013_11 |
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| ORD ID | ord-8d0772a6a0444420b063103210a5b156 |
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| Source note | uspto-grants-2013_11 |
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