Potassium Carbonate → 1-(2-(6,11-Dihydrodibenzo[b,e]thiepin-11-ylidene)-1-ethyl)-4-piperidinecarboxylic acid ethyl ester hydrogen oxalate

HRID 612443Notes

Reaction equation

HRID 612443 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+].[CH2:25]([O:27][C:28]([CH:30]1[CH2:35][CH2:34][NH:33][CH2:32][CH2:31]1)=[O:29])[CH3:26]>CS(C)=O.C1C=CC=CC=1.[I-].[Na+]>[C:28]([OH:29])(=[O:27])[C:19]([OH:21])=[O:22].[CH2:25]([O:27][C:28]([CH:30]1[CH2:35][CH2:34][N:33]([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)[CH2:32][CH2:31]1)=[O:29])[CH3:26]

Participants

7

Reactant 3

HCID 11430Potassium CarbonateHCID 70770Ethyl 4-piperidinecarboxylateHCID 5396280411-(2-Bromoethylidene)-6,11-dihydrodibenzo[b,e]thiepine

Product 1

HCID 699489471-(2-(6,11-Dihydrodibenzo[b,e]thiepin-11-ylidene)-1-ethyl)-4-piperidinecarboxylic acid ethyl ester hydrogen oxalateYield 72%

Reagents, catalysts & solvents 3

HCID 5238Sodium IodideCatalystHCID 241BenzeneSolventHCID 679Dimethyl SulfoxideSolvent

Conditions

Temperature
100 °C

Procedure

To a solution of 11-(2-bromoethylidene)-6,11-dihydrodibenzo[b,e]thiepine (4.76 g, 0.015 mol, prepared similarly as described in Coll. Czech. Chem. Comm. 52, 1566, 1987) in dimethylsulfoxide (90 ml), potassium carbonate (3.1 g, 0.0225 mol), 4-piperidinecarboxylic acid ethyl ester (2.36 g, 0.015 mol) and sodium iodide (50 mg) were added and the mixture was stirred at 100° C. for 4 h. The reaction mixture was diluted with benzene (100 ml), the solid was filtered off and the filtrate was washed with water (4×60 ml). The benzene solution was dried (MgSO4) and the solvent removed in vacuo. The oily residue (6.34 g) was dissolved in acetone and treated with an ethanolic solution of oxalic acid. The resulting precipitate was filtered off and washed with a hot mixture of ethanol and acetone, affording 5.2 g (72%) of 1-(2-(6,11-dihydrodibenzo[b,e]thiepin-11-ylidene)-1-ethyl)-4-piperidinecarboxylic acid ethyl ester hydrogen oxalate.

Workup

  1. filtrationthe solid was filtered off
  2. washthe filtrate was washed with water (4×60 ml)
  3. dry with materialThe benzene solution was dried (MgSO4)
  4. customthe solvent removed in vacuo
  5. dissolutionThe oily residue (6.34 g) was dissolved in acetone
  6. additiontreated with an ethanolic solution of oxalic acid
  7. filtrationThe resulting precipitate was filtered off
  8. washwashed with a hot mixture of ethanol and acetone

Sources & evidence

ORD record
ord-a01a8f87d24b4cfcbd7c568aee95928f
Source dataset
uspto-grants-1999_12
Patent number
US06004983

Reaction notes

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