Water → HCID 13825835, compound

HRID 1493738Notes

Reaction equation

HRID 1493738 reaction equation
[CH2:1]([Li])[CH2:2][CH2:3][CH3:4].[Cl:6][C:7]1[CH:8]=[C:9]([CH:13]([N:15]2[CH:19]=[CH:18][N:17]=[CH:16]2)[CH3:14])[CH:10]=[CH:11][CH:12]=1.[CH3:20]N(CCN(C)C)C.[OH2:28].C[CH2:30][CH2:31][CH2:32][CH2:33][CH3:34]>C1COCC1.CC#N>[Cl:6][C:7]1[CH:8]=[C:9]([C:13]([C:1]2([OH:28])[CH:33]3[CH2:34][CH:4]4[CH2:20][CH:31]([CH2:30][CH:2]2[CH2:3]4)[CH2:32]3)([N:15]2[CH:19]=[CH:18][N:17]=[CH:16]2)[CH3:14])[CH:10]=[CH:11][CH:12]=1

Participants

8

Reactant 5

HCID 962WaterHCID 8037N,N,N',N'-TetramethylethylenediamineHCID 8058HexaneHCID 199020911-[1-(3-Chlorophenyl)ethyl]-1H-imidazoleHCID 178418339Butyllithium

Product 1

HCID 13825835HCID 13825835, compoundYield 6.3%

Reagents, catalysts & solvents 2

HCID 6342AcetonitrileSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-70 °C

Procedure

36 ml (54 mmol) of a 1.5 molar solution of n-butyllithium in hexane were added dropwise to a solution of 5.37 g (26 mmol) of 1-(3-chlorophenyl)-1-(1-imidazolyl)-ethane and 3.14 g (27 mmol) of TMEDA in 60 ml of absolute THF at -70° C. The mixture was stirred for 20 minutes at -70° C., after which a solution of 3.91 g of adamantone in 20 ml of absolute THF was added dropwise at -70° C. Stirring was continued for 1 hour at -70° C. and for 1.5 hours at -70° C. to room temperature, 100 ml of water were added at about 10° C., while cooling, and the mixture was extracted with CH2Cl2. The combined CH2Cl2 extracts were dried and filtered and then evaporated down in vacuo. The residue (10.1 g) was chromatographed with elution with CH2Cl2 /C2H5OH mixtures having an increasing C2H5O content (up to a maximum of 2% by volume), over a silica gel S/CH2Cl2 column (diameter 2.0 cm, height 41 cm). After elution of 3.3 g of unchanged adamantone (=84% of the amount used), a fraction (about 1.0 g) enriched with the desired compound was obtained during elution with CH2Cl2. This fraction was chromatographed again over the silica gel S column (diameter 2.0 cm, height 34 cm) using 4:1 petroleum ether/CH2Cl2, elution being carried out with petroleum ether/CH2Cl2 mixtures having an increasing CH2Cl2 content and then with CH2Cl2. After elution of preliminary zones (content 0.25 g), fractions shown to be pure by linear chromatography were combined and evaporated down in vacuo. 0.58 g (=6.3% yield) of pure 1-(3-chlorophenyl)-1-(2-hydroxy-2-adamantyl)-1-(1-imidazolyl)-ethane of melting point 121° C. (from CH3CN) was obtained.

Workup

  1. stirringStirring
  2. waitwas continued for 1 hour at -70° C. and for 1.5 hours at -70° C. to room temperature
  3. temperaturewhile cooling
  4. extractionthe mixture was extracted with CH2Cl2
  5. dry with materialThe combined CH2Cl2 extracts were dried
  6. filtrationfiltered
  7. customevaporated down in vacuo
  8. customThe residue (10.1 g) was chromatographed with elution with CH2Cl2 /C2H5OH
  9. washAfter elution of 3.3 g of unchanged adamantone (=84% of the amount
  10. customwas obtained during elution with CH2Cl2
  11. customThis fraction was chromatographed again over the silica gel S column (diameter 2.0 cm, height 34 cm)
  12. wash4:1 petroleum ether/CH2Cl2, elution
  13. washAfter elution of preliminary zones (content 0.25 g), fractions
  14. customevaporated down in vacuo

Sources & evidence

ORD record
ord-a9681f90edc940a2beef85c205aa0351
Source dataset
uspto-grants-1991_06
Patent number
US05023357

Reaction notes

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