Acetic Acid → HCID 69337530, compound

HRID 1179086Notes

Reaction equation

HRID 1179086 reaction equation
[ClH:1].[CH3:2][O:3][C:4](=[O:17])[C@H:5]([CH2:7][C:8]1[C:16]2[C:11](=[CH:12][CH:13]=[CH:14][CH:15]=2)[NH:10][CH:9]=1)[NH2:6].C([O-])(O)=O.[Na+].[CH3:23][N:24]([CH3:38])[C:25]1([C:32]2C=C[CH:35]=[CH:34][CH:33]=2)[CH2:30][CH2:29][C:28](=O)[CH2:27][CH2:26]1.C(O)(=O)C.[O-][S:44]([O-])(=O)=O.[Na+].[Na+].[BH-](OC(C)=O)(OC(C)=O)OC(C)=O.[Na+]>ClCCCl>[ClH:1].[ClH:1].[CH3:2][O:3][C:4](=[O:17])[CH:5]([NH:6][CH:28]1[CH2:29][CH2:30][C:25]([N:24]([CH3:38])[CH3:23])([C:32]2[S:44][CH:35]=[CH:34][CH:33]=2)[CH2:26][CH2:27]1)[CH2:7][C:8]1[C:16]2[C:11](=[CH:12][CH:13]=[CH:14][CH:15]=2)[NH:10][CH:9]=1

Participants

9

Reactant 7

HCID 176Acetic AcidHCID 313Hydrochloric AcidHCID 24436Sodium SulfateHCID 77980L-Tryptophan, methyl esterHCID 516892Sodium Bicarbonate2×HCID 5049666Sodium triacetoxyborohydrideHCID 114244924-(Dimethylamino)-4-phenylcyclohexan-1-one

Product 1

HCID 69337530HCID 69337530, compound

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent

Procedure

The hydrochloride of L-tryptophan methyl ester (1.01 g) was stirred vigorously for 15 minutes with 1,2-dichloroethane (20 ml) and saturated NaHCO3 solution (20 ml) and the aqueous phase was immediately extracted with 1,2-dichloroethane (2×20 ml). After drying with Na2SO4, the organic phase was concentrated to 40 ml, and 4-dimethylamino-4-phenylcyclohexanone (893 mg, 4 mmol.) was added thereto under argon. Glacial acetic acid (0.228 ml, 4 mmol.) and Na2SO4 (2 g) were added to the clear solution. After a reaction time of 15 minutes, NaBH(OAc)3 (1.2 g) was added to the reaction mixture, and stirring was carried out for 4 days at room temperature. For working up, saturated NaHCO3 solution (40 ml) was added and stirring was carried out for 15 minutes. The aqueous phase was extracted with dichloromethane (2×20 ml). The combined organic phases were dried and then concentrated, yielding a light-brown oil. Purification by column chromatography was carried out with ethyl acetate and methanol. The nonpolar diastereomer (918 mg; m.p. 108-112° C.) was dissolved in 2-butanone (15 ml) and converted with chlorotrimethylsilane (0.4 ml) into the corresponding dihydrochloride (white solid; 326 mg; m.p. 197-202° C.).

Workup

  1. extractionthe aqueous phase was immediately extracted with 1,2-dichloroethane (2×20 ml)
  2. dry with materialAfter drying with Na2SO4
  3. additionwas added
  4. stirringstirring
  5. waitwas carried out for 15 minutes
  6. extractionThe aqueous phase was extracted with dichloromethane (2×20 ml)
  7. customThe combined organic phases were dried
  8. concentrationconcentrated
  9. customyielding a light-brown oil
  10. customPurification by column chromatography
  11. dissolutionThe nonpolar diastereomer (918 mg; m.p. 108-112° C.) was dissolved in 2-butanone (15 ml)

Sources & evidence

ORD record
ord-a9e8a77ef15e40a88a90419bc7c731b6
Source dataset
uspto-grants-2007_10
Patent number
US07276518B2

Reaction notes

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