Iodine → HCID 178469221, compound

HRID 76309Notes

Reaction equation

HRID 76309 reaction equation
O=[C:2]([CH3:9])[CH2:3][C:4]([O:6][CH2:7][CH3:8])=[O:5].[CH3:10][C:11]([NH2:14])([CH3:13])[CH3:12].S([O-])([O-])(=O)=O.[Mg+2].O.[O-2].[O-2].[O-2].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.[Al+3].[Al+3].[Cl:39][C:40]1[CH:41]=[CH:42][C:43]([O:51][CH3:52])=[C:44]([CH:50]=1)[C:45]([N:47]=[C:48]=[S:49])=[O:46].II.C(=O)(O)[O-].[Na+]>C1(C)C=CC=CC=1.C(OCC)C.C(OCC)(=O)C.N1C=CC=CC=1.CO>[C:11]([N:14]1[C:2]([CH3:9])=[C:3]([C:4]([O:6][CH2:7][CH3:8])=[O:5])/[C:48](=[N:47]/[C:45]([C:44]2[CH:50]=[C:40]([Cl:39])[CH:41]=[CH:42][C:43]=2[O:51][CH3:52])=[O:46])/[S:49]1)([CH3:13])([CH3:12])[CH3:10]

Participants

13

Reactant 7

HCID 807IodineHCID 6385Tert-ButylamineHCID 8868Ethyl AcetoacetateHCID 24083Sulfuric acid magnesium salt (1:1)HCID 516892Sodium BicarbonateHCID 167716985-Chloro-2-methoxybenzoyl isothiocyanateHCID 71586775Bentonite

Product 1

HCID 178469221HCID 178469221, compoundYield 71.7%

Reagents, catalysts & solvents 5

HCID 887MethanolSolventHCID 1049PyridineSolventHCID 1140TolueneSolventHCID 3283Diethyl EtherSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
45 °C

Procedure

To a solution of ethyl 3-oxobutanoate (1.3 g, 10 mmol) and 2-methylpropan-2-amine (0.73 g, 10 mmol) in toluene (15 mL) were added anhydrous magnesium sulfate (3.0 g, 25 mmol) and Montmorillonite K10 (3.0 g, 10 mmol). The resulting mixture was stirred at 45° C. for 14 h and then cooled to room temperature. The mixture was diluted with anhydrous ethyl ether, filtered and washed with ethyl ether. The filtrate and washings were combined and concentrated under reduced pressure. The residue was dissolved in THF (60 mL), 5-chloro-2-methoxybenzoyl isothiocyanate (2.16 g, 9.5 mmol) was added and the mixture was stirred at ambient temperature for 2 h. Iodine (2.4 g, 9.5 mmol) was added followed by addition of MeOH (100 mL) and pyridine (10 mL). The mixture was left overnight at room temperature and then treated with ethyl acetate and a saturated solution of sodium bicarbonate for additional 1 h. The layers were separated and the aqueous layer was extracted with ethyl acetate. The extracts were combined, washed with brine, dried with MgSO4 and concentrated under reduced pressure. The solid was triturated with hexane-ethyl ether (1:1) to provide 2.8 g of the title compound. 1H NMR (300 MHz, DMSO-d6) δ ppm 1.37 (t, 3 H), 1.74 (s, 9 H), 2.76 (s, 3 H), 3.82 (s, 3 H), 4.32 (q, J=6.9 Hz, 2 H), 7.16 (d, J=8.7 Hz, 1 H), 7.52 (dd, J=8.7, 2.8 Hz, 1 H), 8.01 (d, J=3.2 Hz, 1 H); MS (DCI/NH3) m/z 411 (M+H)+.

Workup

  1. temperaturecooled to room temperature
  2. filtrationfiltered
  3. washwashed with ethyl ether
  4. concentrationconcentrated under reduced pressure
  5. dissolutionThe residue was dissolved in THF (60 mL)
  6. stirringthe mixture was stirred at ambient temperature for 2 h
  7. waitThe mixture was left overnight at room temperature
  8. customThe layers were separated
  9. extractionthe aqueous layer was extracted with ethyl acetate
  10. washwashed with brine
  11. dry with materialdried with MgSO4
  12. concentrationconcentrated under reduced pressure
  13. customThe solid was triturated with hexane-ethyl ether (1:1)

Sources & evidence

ORD record
ord-3f5caf4cdadf427f82fca23c6e8a673f
Source dataset
uspto-grants-2014_09
Patent number
US08835475B2

Reaction notes

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