Sulfuric acid magnesium salt (1:1) → HCID 86754511, compound

HRID 618784Notes

Reaction equation

HRID 618784 reaction equation
[C:1]([O:5][C:6](=[O:27])[CH:7]([C:25]#[N:26])[C:8](=S)[NH:9][C:10]1[CH:15]=[C:14]([C:16]([F:19])([F:18])[F:17])[CH:13]=[C:12]([C:20]([F:23])([F:22])[F:21])[CH:11]=1)([CH3:4])([CH3:3])[CH3:2].S([O-])([O-])(=O)=O.[Mg+2]>C(Cl)Cl.[Hg]=O>[C:1]([O:5][C:6](=[O:27])[C:7]([C:25]#[N:26])=[C:8]([NH:9][C:10]1[CH:15]=[C:14]([C:16]([F:19])([F:18])[F:17])[CH:13]=[C:12]([C:20]([F:23])([F:22])[F:21])[CH:11]=1)[NH:9][CH2:10][CH2:11][CH:12]([CH3:20])[CH3:13])([CH3:4])([CH3:3])[CH3:2]

Participants

5

Reactant 2

HCID 24083Sulfuric acid magnesium salt (1:1)HCID 54499127HCID 54499127, compound

Product 1

HCID 86754511HCID 86754511, compoundYield 46.2%

Reagents, catalysts & solvents 2

HCID 30856Mercuric oxideCatalystHCID 6344DichloromethaneSolvent2×

Procedure

To a solution of 2-{N-[3,5-bis(trifluoromethyl)phenyl]thiocarbamoyl}cyanoacetic acid tert-butylester (1.12 g, 2.7 mmol, prepared from cyanoacetic acid tert-butyl ester and 3,5-bis(trifluoromethyl)phenylisothiocyanate) in DCM (15 mL) 3-methylbutylamine (1.0 mL, 8.60 mmol), magnesium sulfate (0.5 g) and mercury(II) oxide (2.0 g) were added. The resulting mixture was stirred at room temperature for 14 h, diluted with DCM (30 mL), filtered over Celite, washed with ice-cold diluted hydrochloric acid, with brine (2×20 mL), dried (magnesium sulfate) and concentrated. The residue was crystallized from heptane. 0.29 g (23%) of the title compound was obtained as colourless crystals, mp. 128-129° C. From the mother liquor additional 0.25 g (20%) of product were obtained. 1H NMR (400 MHz, DMSO-d6): δ=0.82 (d, J=7 Hz, 6H), 1.41 (s, 9H), 1.43 (q, J=7 Hz, 2H), 1.57 (nonett, J=7 Hz, 1H), 3.18 (q, br, J=7 Hz, 2H), 7.63 (s, 2H), 7.70 (s, 1H), 8.91 (s, br, 1H), 9.52 (s, 1H); 13C NMR (100 MHz, DMSO-d6): δ=21.96, 24.95, 28.02, 37.50, 41.84, 61.55, 79.66, 115.53, 118.67, 119.87, 123.05 (q, J=282 Hz), 130.44 (q, J=33 Hz), 142,11, 160.46, 167.93. Anal. Calcd. for C21H25F6N3O2 (465.44): C, 54.19; H, 5.41; N, 9.03. Found: C, 54.27; H, 5.57; N, 8.84.

Workup

  1. filtrationfiltered over Celite
  2. washwashed with ice-cold diluted hydrochloric acid, with brine (2×20 mL)
  3. dry with materialdried (magnesium sulfate)
  4. concentrationconcentrated
  5. customThe residue was crystallized from heptane

Sources & evidence

ORD record
ord-8c78172d02bb44be993ec3cde2f20aa4
Source dataset
uspto-grants-1999_09
Patent number
US05955548

Reaction notes

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