Triethylamine → HCID 14986744, compound

HRID 2051563Notes

Reaction equation

HRID 2051563 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([CH:9]=[CH:10][C:11]=1[N+:12]([O-:14])=[O:13])[C:6]([OH:8])=O.Cl.[CH2:16]([O:18][C:19](=[O:29])[C@H:20]([CH2:22][CH2:23][C:24]([O:26][CH2:27][CH3:28])=[O:25])[NH2:21])[CH3:17].C(N(CC)CC)C.C1(N=C=NC2CCCCC2)CCCCC1>CN(C)C=O.CO.ClCCl.CCCCCC.C(OCC)(=O)C>[CH3:1][O:2][C:3]1[CH:4]=[C:5]([CH:9]=[CH:10][C:11]=1[N+:12]([O-:14])=[O:13])[C:6]([NH:21][C@H:20]([C:19]([O:18][CH2:16][CH3:17])=[O:29])[CH2:22][CH2:23][C:24]([O:26][CH2:27][CH3:28])=[O:25])=[O:8]

Participants

9

Reactant 4

HCID 8471TriethylamineHCID 10868DicyclohexylcarbodiimideHCID 73960Glutamic acid diethyl ester hydrochlorideHCID 787643-Methoxy-4-nitrobenzoic acid

Product 1

HCID 14986744HCID 14986744, compound

Reagents, catalysts & solvents 4

HCID 887MethanolSolventHCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolventHCID 21226206Ethyl acetate hexaneSolvent

Procedure

A solution of 3-methoxy-4-nitrobenzoic acid (10.0 g, 50.7 mmoles), (L)-glutamate diethyl ester hydrochloride (12.2 g, 50.7 mmoles), and 1-hydroxyenzotriazole (6.85 g, 50.7 mmoles) in dry dimethylformamide (250 mL) was stirred under nitrogen while triethylamine (5.13 g, 7.07 mL, 50.7 mmol) was added dropwise during 1 minute. After 15 minutes, 1,3-dicyclohexylcarbodiimide (11.5 g, 55.8 mmoles) was added in portions during 2 minutes. The reaction mixture was filtered after 18 hours and the solids were rinsed with dichloromethane (2×50 mL). The filtrate was spin evaporated and dried to an amber residue that was dissolved in dichloromethane (300 mL). The organic phase was washed successively with saturated bicarbonate solution, 5% citric acid, and 1:1 brine/water (1×300 mL each). The organic phase was then dried (MgSO4) and filtered to give a brown-orange solution that showed a major spot on tlc (silica, 2:1 hexane/ethyl acetate, Rf = 0.2). The solution was poured onto a silica gel column (500 g, pre-wet with dichloromethane) and rinsed with dichloromethane (500 mL). The product was removed by gradient elution using 10% and 15% added ethyl acetate (8×250 mL fractions each). Like fractions were combined by spin evaporation and dried (high vacuum) to give a clear yellow oil; yield, 11.5 g (59%); 1H-NMR (DMSO-d6) δ 1.15 and 1.18 (2t overlapped, 6H), 1.9-2.2 (m, 2H), 2.45 (t obscured by DMSO, 2H), 3.98 (s, 3H), 3.9-4.2 (2q overlapped, 4H), 4.46 (m, 1H), 7.58 (dxd, Jo =8 Hz, Jm =2 Hz, 1H), 7.71 (d, Jm =2 Hz, 1H), 7.97 (d, Jo =8 Hz, 1H), 9.00 (d, 1H); uv (MeOH) 327 nm max (2940), 295 min (2090), 257 sh (6640), 235 sh (9140), 203 max (29700); mass spec (CI) m/e 383 (100%). Anal. Calcd. for C17H22N2O8 (Mr 382.37): C, 53.40; H, 5.80; N, 7.33. Found: C, b 53.29; H, 5.85; N, 7.29.

Workup

  1. additionwas added dropwise during 1 minute
  2. filtrationThe reaction mixture was filtered after 18 hours
  3. washthe solids were rinsed with dichloromethane (2×50 mL)
  4. customevaporated
  5. customdried to an amber residue that
  6. dissolutionwas dissolved in dichloromethane (300 mL)
  7. washThe organic phase was washed successively with saturated bicarbonate solution, 5% citric acid, and 1:1 brine/water (1×300 mL each)
  8. dry with materialThe organic phase was then dried (MgSO4)
  9. filtrationfiltered
  10. customto give a brown-orange solution that
  11. washrinsed with dichloromethane (500 mL)
  12. customThe product was removed by gradient elution
  13. additionadded ethyl acetate (8×250 mL fractions each)
  14. customLike fractions were combined by spin evaporation
  15. customdried (high vacuum)
  16. customto give a clear yellow oil
  17. customyield

Sources & evidence

ORD record
ord-386a90e7e4bc4c0d82ea37258e8796cb
Source dataset
uspto-grants-1991_05
Patent number
US05019577

Reaction notes

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