(-)-Mandelic acid → HCID 11729384, compound

HRID 2258360Notes

Reaction equation

HRID 2258360 reaction equation
C(O)(=O)[C@@H](C1C=CC=CC=1)O.[CH2:12]([N:15]1[C@@H:20]([CH3:21])[CH2:19][N:18]([C@H:22]([C:30]2[CH:31]=[C:32]([OH:36])[CH:33]=[CH:34][CH:35]=2)[C:23]2[CH:28]=[CH:27][CH:26]=[C:25]([Br:29])[CH:24]=2)[C@H:17]([CH3:37])[CH2:16]1)[CH:13]=[CH2:14]>C(O)C>[CH2:12]([N:15]1[C@H:20]([CH3:21])[CH2:19][N:18]([C@@H:22]([C:30]2[CH:31]=[C:32]([OH:36])[CH:33]=[CH:34][CH:35]=2)[C:23]2[CH:28]=[CH:27][CH:26]=[C:25]([Br:29])[CH:24]=2)[C@@H:17]([CH3:37])[CH2:16]1)[CH:13]=[CH2:14]

Participants

4

Reactant 2

HCID 11914(-)-Mandelic acidHCID 57114127HCID 57114127, compound

Product 1

HCID 11729384HCID 11729384, compoundYield 44%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

(R)-(-)-Mandelic acid (11.50g, 75.6 mmol) was added to a suspension of 28.55 g (68.7 mmol) of (±)-3-((αR*)-α-((2R*,5S*)-4-allyl-2,5-dimethyl-1-piperazinyl)-3-bromobenzyl)phenol (Example 84, infra) in 450 mL of absolute ethanol. The mixture was heated to complete solution and then allowed to crystallize at room temperature. Crystals were collected and recrystallized from absolute ethanol. The crystalline mandelate salt was treated with excess 1N aqueous sodium hydroxide and then titrated to pH 8 with 6N hydrochloric acid. The precipitated free amine was recrystallized from absolute ethanol to give 6.25 g (44% of theoretical for one enantiomer) of (+)-3-((αS)-α-((2S,5R)-4-allyl-2,5-dimethyl-1-piperazinyl)-3-bromobenzyl)-phenol as a white solid, mp 205°-206° C. [α]D20 =+20° (methanol, c=2). Calc. for C22H27BrN2O: C, 63.62; H, 6.55; N, 6.74; Br, 19.24. Found: C, 63.63; H, 6.57; N, 6.68; Br, 19.16.

Workup

  1. temperatureThe mixture was heated to complete solution
  2. customto crystallize at room temperature
  3. customCrystals were collected
  4. customrecrystallized from absolute ethanol
  5. additionThe crystalline mandelate salt was treated with excess 1N aqueous sodium hydroxide
  6. customThe precipitated free amine was recrystallized from absolute ethanol

Sources & evidence

ORD record
ord-3ae9520ba82344fd9ce8cf36994cdc3a
Source dataset
uspto-grants-1997_08
Patent number
US05658908

Reaction notes

Loading…