HCID 18938446, compound → Ethyl 3-amino-5-(trimethylsilyl)-4-pentynoate

HRID 1735631Notes

Reaction equation

HRID 1735631 reaction equation
C1(C)C=CC(S(O)(=O)=O)=CC=1.[NH2:12][CH:13]([C:22]#[C:23][Si:24]([CH3:27])([CH3:26])[CH3:25])[CH2:14][C:15]([O:17][C:18](C)(C)[CH3:19])=[O:16]>C(O)C>[NH2:12][CH:13]([C:22]#[C:23][Si:24]([CH3:27])([CH3:25])[CH3:26])[CH2:14][C:15]([O:17][CH2:18][CH3:19])=[O:16]

Participants

3

Reactant 1

HCID 18938446HCID 18938446, compound

Product 1

HCID 10353172Ethyl 3-amino-5-(trimethylsilyl)-4-pentynoate

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

The p-toluenesulfonic acid salt of (±)1,1-dimethylethyl 3-amino-5-(trimethylsilyl)-4-pentynoate is prepared by treating p-toluenesulfonic acid with (±)1,1-dimethylethyl 3-amino-5-(trimethylsilyl)-4-pentynoate, the product of step 2, in the presence of MTBE/heptane. The resulting reaction mixture is then heated to 55°-60° C. for one hour, cooled, filtered and dried to give (±) 1,1,-dimethylethyl 3-amino-5-(trimethylsilyl)-4-pentynoate, mono p-toluenesulfonic acid salt. The (±)1,1-dimethylethyl 3-amino-5-(trimethylsilyl)-4-pentynoate mono p-toluenesulfonic acid salt is treated with ethanol in the presence an organic acid or an inorganic acid at reflux temperature. The reaction mixture is then cooled to ambient temperature, concentrated and treated with methyl t-butyl ether and a suitable aqueous base to give ethyl 3-amino-5-(trimethylsilyl)-4-pentynoate. Suitable inorganic acid agents are exemplified by sulfuric acid and hydrochloric acid and suitable organic acid agents are exemplified by camphorsulfonic acid and p-toluenesulfonic acid with p-toluenesulfonic acid being preferred. Suitable aqueous bases are exemplified by sodium bicarbonate, sodium carbonate, sodium hydroxide with sodium bicarbonate being preferred. Other alkanol solvents such as methanol, isopropanol, butanol and pentanol would also be suitable for the practice of this invention. However, it is to be understood that the use of a different alkanol solvent would give a different ester i.e. use of methanol for ethanol would give the corresponding methyl ester.

Workup

  1. temperaturean inorganic acid at reflux temperature
  2. concentrationconcentrated
  3. additiontreated with methyl t-butyl ether

Sources & evidence

ORD record
ord-e49dae5800304f16bc7aa58f7f24aefe
Source dataset
uspto-grants-1996_07
Patent number
US05536869

Reaction notes

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