Sodium Hydroxide → 3-Demethylthiocolchicine

HRID 2308993Notes

Reaction equation

HRID 2308993 reaction equation
[CH3:1][C:2]([NH:4][CH:5]1[C:21]2[C:14](=[CH:15][CH:16]=[C:17]([S:22][CH3:23])[C:18]([CH:20]=2)=[O:19])[C:13]2[C:12]([O:24][CH3:25])=[C:11]([O:26][CH3:27])[C:10]([O:28][C@@H]3O[C@H](CO)[C@@H](O)[C@H](O)[C@H]3O)=[CH:9][C:8]=2[CH2:7][CH2:6]1)=[O:3].[OH-].[Na+]>P(=O)(O)(O)O.CO>[CH3:1][C:2]([NH:4][C@@H:5]1[C:21]2[C:14](=[CH:15][CH:16]=[C:17]([S:22][CH3:23])[C:18]([CH:20]=2)=[O:19])[C:13]2[C:8](=[CH:9][C:10]([OH:28])=[C:11]([O:26][CH3:27])[C:12]=2[O:24][CH3:25])[CH2:7][CH2:6]1)=[O:3]

Participants

5

Reactant 2

HCID 14798Sodium HydroxideHCID 72067HCID 72067, compound2×

Product 1

HCID 840763-DemethylthiocolchicineYield 94.3%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 1004Phosphoric AcidSolvent

Procedure

A solution of thiocolchicoside (2.3 g, 3.96 mmol) in phosphoric acid (85-88%, 65 ml) after dissolving by heating, was stirred at room temperature for overnight. The TLC analysis showed the absence of thiocolchicoside in the reaction mixture, (one small drop of reaction mixture was diluted with MeOH (0.5 ml) and applied to a TLC plate and run in solvent system A). The reaction mixture was poured on ice, adjusted to pH 5 by the addition of 15% aqueous NaOH solution, followed by several extractions with CH2Cl2 (4×25 ml). The combined organic layers were dried (Na2SO4) and evaporated to afford a residue, which was crystallized with acetone to afford 3-demethylthiocolchicine as a yellow solid (1.5 g, 93%), mp 316° C.; [α]D25 =-251° (c 0.21, CHCl3); IR (CHCl3) cm-1 ; 3440 (OH); CIMS: m/e 402 (M+ +1); Anal. Calcd. for C21H23NO5S: C, 62.82; H, 5.77; N, 3.48; S, 7.98. Found C, 63.09; H, 5.86; N, 3.26; S, 8.25%.

Workup

  1. temperatureby heating
  2. custom(one small drop of reaction mixture
  3. additionThe reaction mixture was poured on ice
  4. extractionfollowed by several extractions with CH2Cl2 (4×25 ml)
  5. dry with materialThe combined organic layers were dried (Na2SO4)
  6. customevaporated
  7. customto afford a residue, which
  8. customwas crystallized with acetone

Sources & evidence

ORD record
ord-8df3cf768a864b6e8908d14f76e524e0
Source dataset
uspto-grants-1987_09
Patent number
US04692463

Reaction notes

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