Glutamic acid diethyl ester hydrochloride → diethyl(S)-2-(4-nitrophthalimido)glutarate

HRID 381582

Reaction equation

HRID 381582 reaction equation
C(N(C(C)C)CC)(C)C.[N+:10]([C:13]1[CH:14]=[C:15]2[C:20](=[O:21])[O:19][C:17](=O)[C:16]2=[CH:22][CH:23]=1)([O-:12])=[O:11].Cl.[CH2:25]([O:27][C:28](=[O:38])[C@H:29]([CH2:31][CH2:32][C:33]([O:35][CH2:36][CH3:37])=[O:34])[NH2:30])[CH3:26]>C1(C)C=CC=CC=1.C(OCC)C>[N+:10]([C:13]1[CH:14]=[C:15]2[C:20](=[O:21])[N:30]([C@@H:29]([CH2:31][CH2:32][C:33]([O:35][CH2:36][CH3:37])=[O:34])[C:28]([O:27][CH2:25][CH3:26])=[O:38])[C:17](=[O:19])[C:16]2=[CH:22][CH:23]=1)([O-:12])=[O:11]

Participants

6

Reactant 3

HCID 73960Glutamic acid diethyl ester hydrochlorideHCID 81531DiisopropylethylamineHCID 2309764-Nitrophthalic acid anhydride

Product 1

HCID 10429715diethyl(S)-2-(4-nitrophthalimido)glutarate

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 3283Diethyl EtherSolvent

Procedure

Diisopropylethylamine (24 ml, 0.138 mole) (Aldrich) was added to a suspension of 4-nitrophthalic anhydride (25 g, 0.13 mole) (Tokyo Kasei) and L-glutamic acid diethyl ester hydrochloride (35 g, 0.146 mole) (Aldrich) in toluene (130 ml). The reaction mixture was stirred at reflux utilizing a Dean-Stark trap for 2.5 hours. After cooling, the solution was diluted with diethyl ether (300 ml), washed with water (75 ml), saturated NaHCO3 solution (50 ml), dried (MgSO4), and concentrated in vacuo at 70° C. to give diethyl(S)-2-(4-nitrophthalimido)glutarate as an oil that solidified to a white solid on standing (35.8 g). M.P.=65.5-66.5° C. 1H NMR (DMSO-d6, 300 MHz) δ: 1.12 (t, J=7 Hz, 3H, ester CH3), 1.14 (t, J=7 Hz, 3H, ester CH3), 2.2-2.5 (m, 4H, glu CH2CH2), 3.96 (q, J=7 Hz, 2H, ester CH2), 4.08-4.19 (m, 2H, ester CH2), 4.97-5.04 (m, 1H, glu CH), 8.19 (dd, J=8,0.5 Hz, 1H, Ar), 8.56 (dd,=2,0.5 Hz, 1H, Ar), 8.68 (dd, J=8,2 Hz, 1H, Ar). Mass spectrum (CI—CH4); 379 (M+1, 28.8%), 333 (71.6%), 305 (100%). Anal. Calculated for C17H18N2O8: C, 53.97; H, 4.80; N, 7.40. Found: C, 53.89; H, 4.82; N, 7.42.

Workup

  1. temperatureat reflux
  2. customfor 2.5 hours
  3. temperatureAfter cooling
  4. washwashed with water (75 ml), saturated NaHCO3 solution (50 ml)
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated in vacuo at 70° C.

Sources & evidence

ORD record
ord-c511e394a895437eac28589c1e4caa66
Source dataset
uspto-grants-2001_10
Patent number
US06306865B1

Linked notes

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