Potassium Carbonate → (R)-1-(2-(6,11-dihydrodibenzo[b,e]thiepin-11-ylidene)-1-ethyl)-3-piperidinecarboxylic acid ethyl ester hydrogen oxalate

HRID 612446Notes

Reaction equation

HRID 612446 reaction equation
Br[CH2:2][CH:3]=[C:4]1[C:10]2[CH:11]=[CH:12][CH:13]=[CH:14][C:9]=2[CH2:8][S:7][C:6]2[CH:15]=[CH:16][CH:17]=[CH:18][C:5]1=2.[C:19](=[O:22])([O-:21])[O-].[K+].[K+].[C:25](C(C(C(O)=O)O)O)([OH:27])=[O:26].[CH2:35]([O:37][C:38]([C@@H:40]1[CH2:45][CH2:44][CH2:43][NH:42][CH2:41]1)=[O:39])[CH3:36]>CN(C)C=O.C1C=CC=CC=1>[C:25]([OH:27])(=[O:26])[C:19]([OH:21])=[O:22].[CH2:35]([O:37][C:38]([C@@H:40]1[CH2:45][CH2:44][CH2:43][N:42]([CH2:2][CH:3]=[C:4]2[C:10]3[CH:11]=[CH:12][CH:13]=[CH:14][C:9]=3[CH2:8][S:7][C:6]3[CH:15]=[CH:16][CH:17]=[CH:18][C:5]2=3)[CH2:41]1)=[O:39])[CH3:36]

Participants

6

Reactant 3

HCID 11430Potassium CarbonateHCID 2733695(R)-(-)-Ethyl Nipecotate TartrateHCID 5396280411-(2-Bromoethylidene)-6,11-dihydrodibenzo[b,e]thiepine

Product 1

HCID 69947848(R)-1-(2-(6,11-dihydrodibenzo[b,e]thiepin-11-ylidene)-1-ethyl)-3-piperidinecarboxylic acid ethyl ester hydrogen oxalateYield 86%

Reagents, catalysts & solvents 2

HCID 241BenzeneSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
70 °C

Procedure

To a solution of 11-(2-bromoethylidene)-6,11-dihydrodibenzo[b,e]thiepine (4.43 g, 0.014 mol, Coll.Czech.Chem.Comm. 52, 1566 (1987)) in N,N-dimethylformamide (75 ml), potassium carbonate (19.3 g, 0.14 mol) and (R)-3-piperidinecarboxylic acid ethyl ester tartrate (6.43 g, 0.0209 mol) were added and the mixture was stirred at 70° C. for 6 h. The reaction mixture was diluted with benzene (300 ml), the solid was filtered off and the filtrate was washed with water (5×80 ml). The benzene solution was dried (MgSO4) and the solvent removed in vacuo. The oily residue (6.83 g) was dissolved in acetone and treated with a solution of oxalic acid in ethanol. The solid was isolated and the crude hydrogen oxalate (5.8 g) was recrystallised from a mixture of 96% ethanol and ether to yield 5.81 g (86%) of (R)-1-(2-(6,11-dihydrodibenzo[b,e]thiepin-11-ylidene)-1-ethyl)-3-piperidinecarboxylic acid ethyl ester hydrogen oxalate.

Workup

  1. filtrationthe solid was filtered off
  2. washthe filtrate was washed with water (5×80 ml)
  3. dry with materialThe benzene solution was dried (MgSO4)
  4. customthe solvent removed in vacuo
  5. dissolutionThe oily residue (6.83 g) was dissolved in acetone
  6. additiontreated with a solution of oxalic acid in ethanol
  7. customThe solid was isolated
  8. customthe crude hydrogen oxalate (5.8 g) was recrystallised from a mixture of 96% ethanol and ether

Sources & evidence

ORD record
ord-f9a4d39ae7a342798ae46dd0db2e2d0a
Source dataset
uspto-grants-1999_12
Patent number
US06004983

Reaction notes

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