Lithium hydroxide, monohydrate → 2-Vinyl-morpholine-2,4-dicarboxylic acid 4-tert-butyl ester

HRID 2176239Notes

Reaction equation

HRID 2176239 reaction equation
C[O:2][C:3]([C:5]1([CH:18]=[CH2:19])[O:10][CH2:9][CH2:8][N:7]([C:11]([O:13][C:14]([CH3:17])([CH3:16])[CH3:15])=[O:12])[CH2:6]1)=[O:4].O.[OH-].[Li+]>O1CCCC1.CO.O>[C:14]([O:13][C:11]([N:7]1[CH2:8][CH2:9][O:10][C:5]([CH:18]=[CH2:19])([C:3]([OH:4])=[O:2])[CH2:6]1)=[O:12])([CH3:17])([CH3:16])[CH3:15]

Participants

4

Reactant 2

HCID 168937Lithium hydroxide, monohydrateHCID 867060762-Vinyl-morpholine-2,4-dicarboxylic acid 4-tert-butyl ester 2-methyl ester

Product 1

HCID 867060782-Vinyl-morpholine-2,4-dicarboxylic acid 4-tert-butyl esterYield 90.1%

Reagents, catalysts & solvents 1

HCID 21892291Methanol tetrahydrofuran waterSolvent

Procedure

A solution of crude 2-vinyl-morpholine-2,4-dicarboxylic acid 4-tert-butyl ester 2-methyl ester (3.284 mmol) in tetrahydrofuran/methanol/water (50 mL, 2:2:1) was treated with lithium hydroxide monohydrate (413.3 mg, 9.852 mmol). After stirring at room temperature for 2 h, the volatiles were removed in vacuo and the residue was cooled to 0° C. and quenched with hydrochloric acid (1 M). The aqueous layer was extracted with dichloromethane (2×). The combined organics were filtered through a phase separator and the volatiles were removed in vacuo to provide the title compound (761.4 mg, 90% over 2 steps) as colorless needles. 1H NMR (300 MHz, CDCl3) δ 1.48 (s, 9H), 3.31-3.42 (m, 1H), 3.45-3.61 (m, 2H), 3.87-3.94 (m, 2H), 4.02 (d, J=13.6 Hz, 1H), 5.44 (d, J=10.7 Hz, 1H), 5.60 (d, J=17.4 Hz, 1H), 5.85 (dd, J=17.4, 10.7 Hz, 1H).

Workup

  1. customthe volatiles were removed in vacuo
  2. temperaturethe residue was cooled to 0° C.
  3. customquenched with hydrochloric acid (1 M)
  4. extractionThe aqueous layer was extracted with dichloromethane (2×)
  5. filtrationThe combined organics were filtered through a phase separator
  6. customthe volatiles were removed in vacuo

Sources & evidence

ORD record
ord-fecd5168fbce42c4a952a02bcf2509ef
Source dataset
uspto-grants-2015_06
Patent number
US09062092B2

Reaction notes

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