D-Tartaric acid → HCID 13825850, compound

HRID 1493745Notes

Reaction equation

HRID 1493745 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([CH:8]([C:14]2([OH:24])[CH:21]3[CH2:22][CH:17]4[CH2:18][CH:19]([CH2:23][CH:15]2[CH2:16]4)[CH2:20]3)[N:9]2[CH:13]=[CH:12][N:11]=[CH:10]2)[CH:5]=[CH:6][CH:7]=1.[C:25]([OH:34])(=[O:33])[C@H:26]([C@@H:28]([C:30]([OH:32])=[O:31])[OH:29])[OH:27]>CO.C(#N)C>[C:30]([CH:28]([CH:26]([C:25]([OH:34])=[O:33])[OH:27])[OH:29])([OH:32])=[O:31].[Cl:1][C:2]1[CH:3]=[C:4]([CH:8]([C:14]2([OH:24])[CH:15]3[CH2:23][CH:19]4[CH2:18][CH:17]([CH2:22][CH:21]2[CH2:20]4)[CH2:16]3)[N:9]2[CH:13]=[CH:12][N:11]=[CH:10]2)[CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 2

HCID 439655D-Tartaric acidHCID 9862895HCID 9862895, compound

Product 1

HCID 13825850HCID 13825850, compoundYield 38%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 6342AcetonitrileSolvent

Procedure

43.0 g (125.4 mmol) of (3-chlorophenyl)-(2-hydroxy-2-adamantyl)-(1-imidazolyl)-methane and 18.83 g (125.4 mmol) of D(-)-tartaric acid were dissolved in a mixture of 67 ml of methanol and 440 ml of acetonitrile at the boiling point. When the solution was slowly cooled to room temperature, crystallization occurred. After 2 days, the crystals were filtered off under suction and washed with acetonitrile and ether and dried for 3 hours at 98° C./3-6 mbar. 23.50 g of (3-chlorophenyl)-(2-hydroxy-2-adamantyl)-(1-imidazolyl)-methane hydrogen tartrate ([α]D : (+) 4.26° (c=1.0, CH3OH)) were obtained. This product was dissolved in a boiling mixture of 33 ml of methanol and 193 ml of acetonitrile and allowed to crystallize out at room temperature. After isolation as described above, 18.00 g of product [α]D22 : (+) 5.30° (c=1.0, CH3OH)) were obtained. These 18.00 g were recrystallized in an analogous manner from 26 ml of methanol and 151 ml of acetonitrile. 14.2 g of product [α]D22 : (+) 5.53° (c=1.0, CH3OH)) were obtained. A further recrystallization from 20 ml of methanol and 116 ml of acetonitrile gave 11.7 g of product ([α]D22 : (+) 5.90° (c=1.0, CH3OH)). Further recrystallization of this substance from 16 ml of methanol and 95 ml of acetonitrile in 9.60 g of (3-chlorophenyl)-(2-hydroxy-2-adamantyl)-(1-imidazolyl)-methane hydrogen tartrate ([α]D22 : (+) 6.18° (c=1.0, CH 3 OH)) as a pure diastereomeric salt of melting point 112°-113° C. (decomposition). The mother liquors from the 3rd, 4th and 5th recrystallizations were combined and evaporated down in vacuo, and the remaining residue (8.20 g) was recrystallized from 11.5 ml of methanol and 66.5 ml of acetonitrile in a manner analogous to that described above. 5.4 g of product ([α]D22 : (+) 5.81° (c=1.0, CH3OH)) were obtained, and this product was recrystallized twice more from appropriate methanol/acetonitrile mixtures in an analogous manner. Thereafter, a further 3.60 g of pure diastereomeric hydrogen tartrate ([α]D22 : (+) 6.20° (c=1.0, CH3OH)) were obtained at this point. A total of 13.20 g (=42.7% of theory) of pure (+)-(3-chlorophenyl)-(2-hydroxy-2-adamantyl)-(1-imidazolyl)-methane hydrogen tartrate were obtained in this manner (starting from D(-)-tartaric acid).

Workup

  1. customcrystallization
  2. filtrationthe crystals were filtered off under suction
  3. washwashed with acetonitrile and ether
  4. customdried for 3 hours at 98° C./3-6 mbar

Sources & evidence

ORD record
ord-920973a0236e465ea886322dc413dedd
Source dataset
uspto-grants-1991_06
Patent number
US05023357

Reaction notes

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