Trichloroacetyl isocyanate → HCID 86587924, compound

HRID 459068Notes

Reaction equation

HRID 459068 reaction equation
[CH3:1][C:2]([Si:5]([CH3:50])([CH3:49])[O:6][C@H:7]([C@@H:22]([CH3:48])/[CH:23]=[C:24](/[CH3:47])\[CH2:25][C@H:26]([CH3:46])[C@@H:27]([O:38][Si:39]([C:42]([CH3:45])([CH3:44])[CH3:43])([CH3:41])[CH3:40])[C@H:28]([CH3:37])[C@@H:29]([OH:36])[C@@H:30]([CH3:35])/[CH:31]=[CH:32]\[CH:33]=[CH2:34])[C@@H:8]([CH3:21])/[CH:9]=[CH:10]\[C:11]([N:13]([CH3:20])[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)=[O:12])([CH3:4])[CH3:3].ClC(Cl)(Cl)[C:53]([N:55]=C=O)=[O:54]>C(Cl)Cl>[NH2:55][C:53]([O:36][C@@H:29]([C@@H:30]([CH3:35])/[CH:31]=[CH:32]\[CH:33]=[CH2:34])[C@@H:28]([CH3:37])[C@H:27]([O:38][Si:39]([C:42]([CH3:45])([CH3:44])[CH3:43])([CH3:40])[CH3:41])[C@@H:26]([CH3:46])[CH2:25]/[C:24](/[CH3:47])=[CH:23]\[C@H:22]([CH3:48])[C@@H:7]([O:6][Si:5]([C:2]([CH3:4])([CH3:3])[CH3:1])([CH3:49])[CH3:50])[C@@H:8]([CH3:21])/[CH:9]=[CH:10]\[C:11]([N:13]([CH3:20])[C:14]1[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=1)=[O:12])=[O:54]

Participants

4

Reactant 2

HCID 76400Trichloroacetyl isocyanateHCID 86760453HCID 86760453, compound

Product 1

HCID 86587924HCID 86587924, compoundYield 60%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
23 °C

Procedure

To a solution of (2Z,4S,5S,6S,7Z,10S,11R,12R,13S,14S,15Z)-5,11-bis[[(1,1-dimethylethyl) dimethylsilyl]oxy]-13-hydroxy-N,4,6,8,10,12,14-heptamethyl-N-phenyl-2,7,15,17-octadecatetraenamide (110 mg, 0.152 mmol, 1 eq) in CH2Cl2 (2 mL) is treated with trichloroacetyl isocyanate (43 mg, 0.228 mmol, 1.5 eq) at 23° C. (20 minutes). The solution is concentrated, and the residue dissolved in CH3OH (2 mL). To this solution is added K2CO3 (0.1 g) and the mixture is stirred at 23° C. (2 hours). The reaction mixture is concentrated and the residue dissolved in Et2O (5 mL). The organic solution is washed with H2O (1×20 mL) and brine (1×20 mL). The aqueous layer is extracted with Et2O (3×5 mL) and the combined extracts are dried (Na2SO4) and concentrated. Chromatography (SiO2, 30–50% EtOAc-hexanes gradient elution) provided the desired compound (70 mg, 60%).

Workup

  1. concentrationThe solution is concentrated
  2. dissolutionthe residue dissolved in CH3OH (2 mL)
  3. additionTo this solution is added K2CO3 (0.1 g)
  4. concentrationThe reaction mixture is concentrated
  5. dissolutionthe residue dissolved in Et2O (5 mL)
  6. washThe organic solution is washed with H2O (1×20 mL) and brine (1×20 mL)
  7. extractionThe aqueous layer is extracted with Et2O (3×5 mL)
  8. dry with materialthe combined extracts are dried (Na2SO4)
  9. concentrationconcentrated
  10. washChromatography (SiO2, 30–50% EtOAc-hexanes gradient elution)

Sources & evidence

ORD record
ord-6b8b20c1b05d45b29908c9f21358cdba
Source dataset
uspto-grants-2007_03
Patent number
US07192980B2

Reaction notes

Loading…