L-Phenylalanine → Ninhydrin

HRID 882684Notes

Reaction equation

HRID 882684 reaction equation
N[C@H:2]([C:11]([O:13]CC=C)=[O:12])[CH2:3][CH2:4][C:5]([O:7]CC=C)=O.ClC(Cl)([O:20]C(=O)OC(Cl)(Cl)Cl)Cl.CCN(CC)CC.N[C@H:37]([C:45](O)=O)[CH2:38][C:39]1C=CC=CC=1>C(Cl)Cl>[CH:37]1[CH:45]=[C:4]2[C:5]([C:11]([OH:12])([OH:13])[C:2](=[O:20])[C:3]2=[CH:39][CH:38]=1)=[O:7]

Participants

6

Reactant 4

HCID 6140L-PhenylalanineHCID 8471Triethylamine2×HCID 94429TriphosgeneHCID 11053369diallyl L-glutamate

Product 1

HCID 10236Ninhydrin

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent4×

Procedure

To a stirred solution of diallyl glutamate (110 mg, 0.42 mmol) and triphosgene (43 mg, 0.14 mmol) in CH2Cl2 (4 mL) at −78° C. was added Et3N (180 μL, 1.3 mmol) in CH2Cl2 (0.8 mL). The reaction mixture was allowed to warm to room temperature and stirred for 1.5 h. The phenylalanine derivative (140 mg, 0.251 mmol) in a solution of CH2Cl2 (1 mL) and Et3N (70 μL, 0.5 mmol) was then added at −78° C. and the reaction was stirred at room temperature for 12 h. The solution was diluted with CH2Cl2, washed twice with H2O, dried over MgSO4 (anh.) and purified by column chromatography (Hexane:AcOEt 3:1) to give 100 mg (57%) (TLC in CH2Cl2:MeOH 20:1 Rf=0.3, revealed with ninhydrin and uv light). 1H-NMR (CDCl3, 300 MHz) δ 7.80-6.95 (13H, aromatics, NHFmoc), 5.98-5.82 (m, 3H, 3-CH2CHCH2), 5.54 (bd, 1H, NHurea), 5.43-5.19 (m, 7H, 3-CH2CHCH2, NHurea), 4.85-4.78 (m, 1H, CH(pheala.)), 4.67-4.50 (m, 9H, 3-CH2CHCH2, CH2(Fmoc), CH(glu.)), 4.28 (t, 1H, CH(Fmoc)), 3.05 (d, 2H, CH2(pheala.)), 2.53-2.33 (m, 2H, CH2(glu.)), 2.25-2.11 and 1.98-1.80 (2m, 2H, CH2(glu.)).

Workup

  1. stirringthe reaction was stirred at room temperature for 12 h
  2. washwashed twice with H2O
  3. dry with materialdried over MgSO4 (anh.)
  4. custompurified by column chromatography (Hexane:AcOEt 3:1)

Sources & evidence

ORD record
ord-4e6dfa49d09c46758c07019c71996148
Source dataset
uspto-grants-2012_08
Patent number
US08236330B2

Reaction notes

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