1,4-Dioxane hydrochloride → Ethyl 1-amino-2-vinylcyclopropane-1-carboxylate hydrochloride

HRID 1818766Notes

Reaction equation

HRID 1818766 reaction equation
[CH2:1]([O:3][C:4]([C:6]1([NH2:18])[CH2:8][C:7]1(C(OC(C)(C)C)=O)[CH:9]=[CH2:10])=[O:5])[CH3:2].[ClH:19].O1CCOCC1>>[ClH:19].[CH2:1]([O:3][C:4]([C:6]1([NH2:18])[CH2:8][CH:7]1[CH:9]=[CH2:10])=[O:5])[CH3:2]

Participants

3

Reactant 2

HCID 204431481,4-Dioxane hydrochlorideHCID 68818551Boc-1-amino-2-vinylcyclopropane carboxylic acid ethyl ester

Product 1

HCID 53419329Ethyl 1-amino-2-vinylcyclopropane-1-carboxylate hydrochloride

Procedure

Boc-1-amino-2-vinylcyclopropane carboxylic acid ethyl ester (1.50 g, 5.88 mmol) was dissolved in 4N HCl/dioxane (10 mL, 40 mmol) and was stirred overnight at room temperature. The reaction mixture was concentrated to supply racemic 1-amino-2-vinylcyclopropane carboxylic acid ethyl ester hydrochloride as a brownish oil (1.04 g, 92%). The two enantiomers were then separated by chiral HPLC. Conditions: Chiralpak AD column, 50×500 mm, 20 μM; 95% 0.01% DEA/hexane:5% ethanol as solvent; flow rate:75 mL/min; stop time:45 min; abs=207 nm; maximum load: 300 mg. After separation, 210 mg of enantiomer 50177-020A (retention time=25 min) and 235 mg of enantiomer 50177-020B (retention time=32 min) were collected. 50177-020: 1H NMR(DMSO-d6, 500 MHz) δ 8.80(s, br, 3H), 5.64 (m, 1H), 5.38 (d, J=17.1 Hz, 1H), 5.21(d, J=10.4 Hz, 1H), 4.21 (m, 2H), 2.34 (m, 1H), 1.68(m, 2H), 1.23 (t, J=7.2 Hz, 3H).; LC-MS (retention time 0.64 min), MS m/z 156(MH+).

Workup

  1. concentrationThe reaction mixture was concentrated to supply racemic 1-amino-2-vinylcyclopropane carboxylic acid ethyl ester hydrochloride as a brownish oil (1.04 g, 92%)
  2. customThe two enantiomers were then separated by chiral HPLC
  3. custom45 min
  4. customAfter separation, 210 mg of enantiomer 50177-020A (retention time=25 min) and 235 mg of enantiomer 50177-020B (retention time=32 min)
  5. customwere collected

Sources & evidence

ORD record
ord-9978ceb0e41d40b9af851951434cb268
Source dataset
uspto-grants-2009_10
Patent number
US07601686B2

Reaction notes

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