Iodine → HCID 178441286, compound

HRID 76247Notes

Reaction equation

HRID 76247 reaction equation
[C:1]([N:5]=[CH:6][CH2:7][CH2:8][CH2:9][CH2:10][CH3:11])([CH3:4])([CH3:3])[CH3:2].[Cl:12][C:13]1[CH:14]=[CH:15][C:16]([O:24][CH3:25])=[C:17]([CH:23]=1)[C:18]([N:20]=[C:21]=[S:22])=[O:19].II.CO>O1CCCC1.N1C=CC=CC=1>[CH2:8]([C:7]1=[CH:6][N:5]([C:1]([CH3:2])([CH3:3])[CH3:4])[S:22]/[C:21]/1=[N:20]\[C:18](=[O:19])[C:17]1[CH:23]=[C:13]([Cl:12])[CH:14]=[CH:15][C:16]=1[O:24][CH3:25])[CH2:9][CH2:10][CH3:11]

Participants

7

Reactant 4

HCID 807IodineHCID 887MethanolHCID 11829679N-(tert-butyl)-N-hexylideneamineHCID 167716985-Chloro-2-methoxybenzoyl isothiocyanate

Product 1

HCID 178441286HCID 178441286, compoundYield 69.7%

Reagents, catalysts & solvents 2

HCID 1049PyridineSolventHCID 8028TetrahydrofuranSolvent

Procedure

To the product of Example 1A (1.90 g, 12.2 mmol) in tetrahydrofuran (10 mL) at room temperature under N2 was added the product of Example 1C (2.30 g, 10.1 mmol). After 1 h at room temperature, the reaction was treated with I2 (2.59 g, 10.2 mmol), methanol (30 mL) and pyridine (3 mL) and stirred for 1 hour. The reaction was then partitioned between saturated NaHCO3/diethyl ether with continued stirring overnight. The reaction was diluted further with saturated NaHCO3/diethyl ether, the layers separated and the aqueous phase extracted again with diethyl ether (2×). The organics were combined, dried (MgSO4), filtered and solvent evaporated. Toluene/acetonitrile was added and evaporated 2× to remove excess pyridine and H2O. The crude was flash chromatographed, eluting with diethyl ether:CH2Cl2:hexane (7:3:3) to provide 2.68 g of the desired product with impurities running above and below. This material was dissolved in a minimum of CH2Cl2, hexane added until slightly cloudy and allowed to sit for 4 hours. A white crystalline solid was collected and washed with cold 1:1 CH2Cl2:hexane to provide 962.78 mg of the title compound. The mother liquor was recrystallized from methanol to provide 555 mg additional title compound. The second mother liquor was concentrated to dryness, dissolved in a minimum of CH2Cl2 and flash chromatographed on silica gel, eluting with diethyl ether:CH2Cl2:hexane (7:1:3) to provide an additional 600 mg of the title compound. 1H NMR (300 MHz, CDCl3) δ 0.98 (t, 3H), 1.37-1.49 (m, 2H), 1.65 (s, 9H), 1.67-1.77 (m, 2H), 2.83 (t, 2H), 3.92 (s, 3H), 6.91 (d, 1H), 7.34 (dd, 1H), 7.95 (s, 1H), 8.11 (d, 1H). MS (DCI/NH4+) m/z 381 (M+H)+. Anal. calcd for C19H25ClN2O2S: C, 59.91; H, 6.61; N, 7.35. Found: C, 59.88; H, 6.67; N, 7.42.

Workup

  1. customThe reaction was then partitioned between saturated NaHCO3/diethyl ether
  2. stirringwith continued stirring overnight
  3. additionThe reaction was diluted further with saturated NaHCO3/diethyl ether
  4. customthe layers separated
  5. extractionthe aqueous phase extracted again with diethyl ether (2×)
  6. dry with materialdried (MgSO4)
  7. filtrationfiltered
  8. customsolvent evaporated
  9. additionToluene/acetonitrile was added
  10. customevaporated 2×
  11. customto remove excess pyridine and H2O
  12. customchromatographed
  13. washeluting with diethyl ether:CH2Cl2:hexane (7:3:3)

Sources & evidence

ORD record
ord-3835bdcb2e984db8803f97a15648dfd5
Source dataset
uspto-grants-2014_09
Patent number
US08835475B2

Reaction notes

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