Methylglyoxal → HCID 10759808, compound

HRID 1871086Notes

Reaction equation

HRID 1871086 reaction equation
[CH:1](=O)[C:2]([CH3:4])=[O:3].[CH3:6][C:7]1([CH3:16])[CH2:12][CH:11]([NH2:13])[CH2:10][C:9]([CH3:15])([CH3:14])[NH:8]1.C1(C)C=CC(S([CH:26]([N+:34]#[C-:35])[C:27]2[CH:32]=[CH:31][C:30]([F:33])=[CH:29][CH:28]=2)(=O)=O)=CC=1.C([O-])([O-])=O.[K+].[K+]>CS(C)=O.CCOC(C)=O>[CH3:6][C:7]1([CH3:16])[CH2:12][CH:11]([N:13]2[C:1]([C:2](=[O:3])[CH3:4])=[C:26]([C:27]3[CH:28]=[CH:29][C:30]([F:33])=[CH:31][CH:32]=3)[N:34]=[CH:35]2)[CH2:10][C:9]([CH3:15])([CH3:14])[NH:8]1

Participants

7

Reactant 4

HCID 880MethylglyoxalHCID 11430Potassium CarbonateHCID 375244-Amino-2,2,6,6-tetramethylpiperidineHCID 10827289a-Tosyl-(4-fluorobenzyl) isocyanide

Product 1

HCID 10759808HCID 10759808, compoundYield 75.1%

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of pyruvaldehyde (40% w/w solution in water, 7.56 mL, 8.91 g, 49.5 mmol) in 90 mL of DMSO at room temperature was added dropwise 2,2,6,6-tetramethyl-4-amino-piperidine (9.24 mL, 8.43 g, 65.4 mmol). After 10 min α-(p-toluenesulfonyl)-4-fluorobenzylisonitrile (13.0 g, 44.95 mmol) and K2CO3 (7.46 g, 53.95 mmol) were added. After 23 h, the solution was diluted with 250 mL of EtOAc and washed with 2×200 mL of 3N HCl. The aqueous layers were combined and basified with excess solid K2CO3 until the bubbling ceased. The aqueous layer was transferred to a separatory funnel and extracted 2×250 mL of EtOAc. The combined organics were washed with 3×100 mL of water and concentrated in vacuo to yield the title compound (11.6 g, 75%) as a brown oil, which could be recrystallized from CHCl3 /hexanes: mp=134-36° C.; IR (KBr) 3430, 3144, 1659, 1653, 1219 cm-1 ; 1H NMR (CDCl3) δ 7.76 (1H, s), 7.43 (2H, m), 7.12 (2H, t, J=8.7 Hz), 5.39 (1H, tt, J=3.1, 12.5 Hz), 2.11 (3H, s), 2.10 (2H, m), 1.50 (2H, t, J=12.2 Hz), 1.37 (6H, s), 1.22 (6H, s); 13C NMR (CDCl3) δ 190.77, 164.69, 161.41, 149.79, 137.42, 131.47, 131.36, 127.03, 115.57, 115.29, 52.02, 50.57, 46.20, 34.61, 30.45, 28.06.

Workup

  1. washwashed with 2×200 mL of 3N HCl
  2. customThe aqueous layer was transferred to a separatory funnel
  3. extractionextracted 2×250 mL of EtOAc
  4. washThe combined organics were washed with 3×100 mL of water
  5. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-0b28c7fe82ba46ea8fd5e6e7163aed50
Source dataset
uspto-grants-2000_08
Patent number
US06100399

Reaction notes

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