2-Chlorophenothiazine → 2-Chloro-10-propargylphenothiazine

HRID 462079Notes

Reaction equation

HRID 462079 reaction equation
[CH2:1]([Li])[CH2:2][CH2:3]C.[Cl:6][C:7]1[CH:20]=[CH:19][C:18]2[S:17][C:16]3[C:11](=[CH:12][CH:13]=[CH:14][CH:15]=3)[NH:10][C:9]=2[CH:8]=1.ClC1C=CC2SC3C(=CC=CC=3)N([Li])C=2C=1.C(Br)C#C>CCOCC>[Cl:6][C:7]1[CH:20]=[CH:19][C:18]2[S:17][C:16]3[C:11](=[CH:12][CH:13]=[CH:14][CH:15]=3)[N:10]([CH2:3][C:2]#[CH:1])[C:9]=2[CH:8]=1

Participants

6

Reactant 4

HCID 70882-ChlorophenothiazineHCID 7842Propargyl bromideHCID 178418339ButyllithiumHCID 178506919HCID 178506919, compound

Product 1

HCID 149596962-Chloro-10-propargylphenothiazine

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Conditions

Temperature
0 °C

Procedure

To a solution containing 0.2 mole of butyllithium in 350 ml. of absolute ether (prepared in situ under nitrogen) were added 46.5 g. (0.2 mole) of 2-chlorophenothiazine while the mixture was maintained at -10° C. The reaction mixture was then allowed to stir for forty-five minutes at 0° C. To the resulting solution of 2-chloro-10-phenothiazinyllithium were added 30 g. (0.25 mole) of propargyl bromide in 30 ml. of absolute ether. This reaction mixture was allowed to stir at room temperature overnight. After quenching with dilute hydrochloric acid, the ethereal phase of the reaction mixture was washed with water and dried over anhydrous calcium sulfate. Upon removal of the solvent a semi-solid mass of crude 2-chloro-10-propargylphenothiazine remained. Recrystallized from methanol and from ether-hexane, pure 2-chloro-10-propargylphenothiazine melted at 112.0°-115.0° C. The structure was confirmed by nuclear magnetic resonance spectroscopy.

Workup

  1. stirringto stir at room temperature overnight
  2. customAfter quenching with dilute hydrochloric acid
  3. washthe ethereal phase of the reaction mixture was washed with water
  4. dry with materialdried over anhydrous calcium sulfate
  5. customUpon removal of the solvent a semi-solid mass of crude 2-chloro-10-propargylphenothiazine
  6. customRecrystallized from methanol and from ether-hexane, pure 2-chloro-10-propargylphenothiazine melted at 112.0°-115.0° C

Sources & evidence

ORD record
ord-b3a745db87544f81be1cbaee1a99296f
Source dataset
uspto-grants-1977_12
Patent number
US04065471

Reaction notes

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