L-Valine → 3-[4-(4-Dimethylamino-phenylazo)-phenyl]-5-isopropyl-1-methyl-2-thioxo-imidazolidin-4-one

HRID 2237404

Reaction equation

HRID 2237404 reaction equation
[NH:1]([CH3:9])[C@H:2]([C:6]([OH:8])=O)[CH:3]([CH3:5])[CH3:4].[CH3:10][N:11]([C:13]1[CH:18]=[CH:17][C:16]([N:19]=[N:20][C:21]2[CH:26]=[CH:25][C:24]([N:27]=[C:28]=[S:29])=[CH:23][CH:22]=2)=[CH:15][CH:14]=1)[CH3:12].N[C@H](C(O)=O)C(C)C.CC1OC(C)CN(C(CN2C(=O)SC3C2=CC=CC=3)=O)C1.N(C)[C@H](C(O)=O)C(C)C>O1CCOCC1.O>[CH3:10][N:11]([CH3:12])[C:13]1[CH:14]=[CH:15][C:16]([N:19]=[N:20][C:21]2[CH:26]=[CH:25][C:24]([N:27]3[C:6](=[O:8])[CH:2]([CH:3]([CH3:4])[CH3:5])[N:1]([CH3:9])[C:28]3=[S:29])=[CH:23][CH:22]=2)=[CH:17][CH:18]=1

Participants

7

Reactant 4

HCID 6287L-ValineHCID 820844-((4-Isothiocyanatophenyl)azo)-N,N-dimethylanilineHCID 444080N-Methyl-L-valineHCID 131728121DABTH MeVal

Product 1

HCID 875057463-[4-(4-Dimethylamino-phenylazo)-phenyl]-5-isopropyl-1-methyl-2-thioxo-imidazolidin-4-oneYield 99.5%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 312751,4-DioxaneSolvent2×

Procedure

From a stock solution of 0.500 M N-(Me)-D,L-valine (20 mmol in 40 mL 0.25 M KOH), a 5.0-mL aliquot (2.5 mmol MeVal) was heated to 60° C. and mixed with 0.100M DABITC (5.0 mL, 0.5 mmol) in dioxane. In order to obtain a homogeneous solution another 3.5 mL dioxane and 2.5 mL water were added. This reaction mixture became inhomogeneous in contrast to the mixture containing Val, indicating that the DABTH-MeVal formed precipitated. The reaction was monitored by TLC (SiO2 Tol/EtOAc, 2:1; spots developed with both UV and long wavelength light) and after 30 min all the DABITC had been consumed. The subsequent extraction was performed as described above. The product crystallized from DCM:hexane (1:4, v/v) to yield 189.0 mg (99.5%) of the desired product. Analysis: m.p. 164.5-169° C., Rf-TLC 0.73 (SiO2; EtOAc:MeOH, 4:1). UV (acetonitrile:water 1:1) λmax=265 nm, ε265=26000 (see also FIG. 12). Fluorescence measurements: see FIGS. 9 and 10. 1H NMR(CDCl3, 25° C.) δ1.05, 1.25[d+d, 3+3H, J=6.9, 7.1 Hz, CH3(γ,γ′)], 2.47 [m, 1H, J=3.3, 6.9, 7.1 Hz, CH(β)], 3.09 [s, 6H, N(CH3)2] 3.4[s, 3H, N—CH3], 4.4 [d, 1H, J=3.3 Hz, CH(α)], 6.74, 6.77 [d+d, 2H, azobenzene C6—H, C7—H] 7.37, 7.40 [d+d, 2H, azobenzene C5—H, C8—H] 7.87, 7.90, 7.92, 7.95 [4d, 4H, azobenzene C1—H—C4—H].

Workup

  1. additionwere added
  2. customformed
  3. customprecipitated
  4. customafter 30 min
  5. customhad been consumed
  6. extractionThe subsequent extraction
  7. customThe product crystallized from DCM:hexane (1:4, v/v)

Sources & evidence

ORD record
ord-fc9bcb650ff940d68fd6288b1c6678d5
Source dataset
uspto-grants-2010_05
Patent number
US07718437B2

Linked notes

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