Trichloroacetonitrile → HCID 68502400, compound

HRID 1712617Notes

Reaction equation

HRID 1712617 reaction equation
[OH:1][CH2:2][C:3]1[CH:8]=[CH:7][C:6]([CH:9]2[CH2:14][CH2:13][N:12]([C:15]([O:17][CH2:18][C:19]3[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=3)=[O:16])[CH2:11][CH:10]2[O:25][CH2:26][C:27]2[CH:28]=[CH:29][C:30]3[O:35][CH2:34][CH2:33][N:32]([CH2:36][CH2:37][CH2:38][O:39][CH3:40])[C:31]=3[CH:41]=2)=[CH:5][CH:4]=1.[H-].[Na+].Cl[C:45](Cl)(Cl)[C:46]#N.F[C:51](F)(F)S(O)(=O)=O.C(=O)([O-])O.[Na+]>C(Cl)(Cl)(Cl)Cl.ClCCl.CC(O)C>[CH:46]([O:1][CH2:2][C:3]1[CH:4]=[CH:5][C:6]([CH:9]2[CH2:14][CH2:13][N:12]([C:15]([O:17][CH2:18][C:19]3[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=3)=[O:16])[CH2:11][CH:10]2[O:25][CH2:26][C:27]2[CH:28]=[CH:29][C:30]3[O:35][CH2:34][CH2:33][N:32]([CH2:36][CH2:37][CH2:38][O:39][CH3:40])[C:31]=3[CH:41]=2)=[CH:7][CH:8]=1)([CH3:45])[CH3:51]

Participants

9

Reactant 5

HCID 11011TrichloroacetonitrileHCID 24758Sodium hydrideHCID 62406Trifluoromethanesulfonic acidHCID 516892Sodium BicarbonateHCID 68501539HCID 68501539, compound

Product 1

HCID 68502400HCID 68502400, compound

Reagents, catalysts & solvents 3

HCID 3776IsopropanolSolventHCID 5943Carbon TetrachlorideSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
-30 °C

Procedure

The solution of 0.200 g of benzyl 4-(4-hydroxymethylphenyl)-3-[4-(3-methoxypropyl)-3,4-dihydro-2H-benzo[1,4]oxazin-6-ylmethoxy]piperidine-1-carboxylate (Example 270c) in 8 ml of carbon tetrachloride at 0° C. is admixed with 0.019 g of sodium hydride and then stirred for 20 minutes. The reaction mixture is admixed with 0.326 g of trichloroacetonitrile and stirred at 0° C. for 3 hours. Afterwards, a solution of 0.0322 g of 2-propanol in 5 ml of dichloromethane is added and the reaction mixture is cooled to −30° C. and admixed slowly with 0.108 g of trifluoromethanesulphonic acid. The reaction solution is stirred at −20° C. for 19 hours and subsequently poured onto 25 ml of aqueous saturated sodium hydrogencarbonate solution. The mixture is extracted twice with 50 ml of tert-butyl methyl ether. The combined organic phases are washed with 30 ml of brine, dried over sodium sulphate, filtered and concentrated by evaporation. The title compound is obtained as a yellowish oil from the residue by means of flash chromatography (SiO2 60F). Rf=0.15 (1:2 EtOAc-heptane); Rt=5.92.

Workup

  1. customat 0° C.
  2. stirringstirred at 0° C. for 3 hours
  3. stirringThe reaction solution is stirred at −20° C. for 19 hours
  4. extractionThe mixture is extracted twice with 50 ml of tert-butyl methyl ether
  5. washThe combined organic phases are washed with 30 ml of brine
  6. dry with materialdried over sodium sulphate
  7. filtrationfiltered
  8. concentrationconcentrated by evaporation

Sources & evidence

ORD record
ord-5f5dc1e415ab465ba5d78e3affb7271f
Source dataset
uspto-grants-2010_09
Patent number
US07790715B2

Reaction notes

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