Ethyl Acetate → HCID 69019332, compound

HRID 860818Notes

Reaction equation

HRID 860818 reaction equation
[Li]CCCC.Br[C:7]1[CH:8]=[N:9][CH:10]=[CH:11][CH:12]=1.[Cl:13][C:14]1[CH:19]=[CH:18][C:17]([C:20]([C:22]2[CH:23]=[CH:24][C:25]3[N:31]4[N:32]=[N:33][N:34]=[C:30]4[CH2:29][S:28][CH:27]([C:35]4[CH:40]=[CH:39][CH:38]=[C:37]([Cl:41])[CH:36]=4)[C:26]=3[CH:42]=2)=[O:21])=[CH:16][CH:15]=1.CCOC(C)=O>C(OCC)C.C1COCC1>[Cl:41][C:37]1[CH:36]=[C:35]([CH:27]2[C:26]3[CH:42]=[C:22]([C:20]([C:17]4[CH:18]=[CH:19][C:14]([Cl:13])=[CH:15][CH:16]=4)([C:7]4[CH:8]=[N:9][CH:10]=[CH:11][CH:12]=4)[OH:21])[CH:23]=[CH:24][C:25]=3[N:31]3[N:32]=[N:33][N:34]=[C:30]3[CH2:29][S:28]2)[CH:40]=[CH:39][CH:38]=1

Participants

7

Reactant 4

HCID 8857Ethyl AcetateHCID 122863-BromopyridineHCID 69021592HCID 69021592, compoundHCID 178418339Butyllithium

Product 1

HCID 69019332HCID 69019332, compoundYield 6.3%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolvent2×HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-70 °C

Procedure

nBuLi (0.009 mol) was added dropwise at −70° C. to a mixture of 3-bromo-pyridine (0.009 mol) in diethyl ether (10 ml) under N2 flow. The mixture was stirred at −70° C. for 15 minutes. A suspension of intermediate (31) (0.003 mol) in THF (30 ml) was added dropwise at −70° C. The mixture was stirred at −70° C. for 1 hour, then brought slowly to room temperature, stirred overnight and poured out into ice water. EtOAc was added. The mixture was extracted with EtOAc. The organic layer was separated, dried (MgSO4), filtered, and the solvent was evaporated. The residue was purified by column chromatography over silica gel (eluent: CH2Cl2/CH3OH/NH4OH 95/5/0.2; 15–40 μm). The pure fractions were collected and the solvent was evaporated, yielding 0.12 g (7%). This fraction was taken up in diethyl ether. The precipitate was filtered off and dried in a vacuum, yielding 0.1 g (6%) of 6-(3-chlorophenyl)-α-(4-chlorophenyl)-α-(3-pyridinyl)-4H,6H-tetrazolo[1,5-a][4,1]benzothiazepine-8-methanol, MS (MH+) m/e: 532, 534, 536.

Workup

  1. additionwas added dropwise at −70° C
  2. stirringThe mixture was stirred at −70° C. for 1 hour
  3. custombrought slowly to room temperature
  4. stirringstirred overnight
  5. extractionThe mixture was extracted with EtOAc
  6. customThe organic layer was separated
  7. dry with materialdried (MgSO4)
  8. filtrationfiltered
  9. customthe solvent was evaporated
  10. customThe residue was purified by column chromatography over silica gel (eluent: CH2Cl2/CH3OH/NH4OH 95/5/0.2; 15–40 μm)
  11. customThe pure fractions were collected
  12. customthe solvent was evaporated
  13. customyielding 0.12 g (7%)
  14. filtrationThe precipitate was filtered off
  15. customdried in a vacuum

Sources & evidence

ORD record
ord-c861ead7ead046df8a57d292067d55ac
Source dataset
uspto-grants-2006_12
Patent number
US07153958B2

Reaction notes

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