Thionyl Chloride → HCID 19698672, compound

HRID 1078627Notes

Reaction equation

HRID 1078627 reaction equation
[CH:1]1[C:14]2[C:13]3([C:16](O)=O)[CH2:15][CH:6]([C:7]4[C:12]3=[CH:11][CH:10]=[CH:9][CH:8]=4)[C:5]=2[CH:4]=[CH:3][CH:2]=1.S(Cl)(Cl)=O.[NH:23]1[CH2:33][CH2:32][CH:26]([C:27]([O:29]CC)=O)[CH2:25][CH2:24]1>C1(C)C=CC=CC=1.CN(C)C=O>[CH:1]1[C:14]2[C:13]3([CH2:16][N:23]4[CH2:24][CH2:25][CH:26]([CH:27]([C:25]5[CH:24]=[N:23][CH:33]=[CH:32][CH:26]=5)[OH:29])[CH2:32][CH2:33]4)[CH2:15][CH:6]([C:7]4[C:12]3=[CH:11][CH:10]=[CH:9][CH:8]=4)[C:5]=2[CH:4]=[CH:3][CH:2]=1

Participants

6

Reactant 3

HCID 24386Thionyl ChlorideHCID 70770Ethyl 4-piperidinecarboxylateHCID 125071199,10-Dihydro-9,10-methano-9-anthracenecarboxylic acid

Product 1

HCID 19698672HCID 19698672, compoundYield 92.2%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideCatalystHCID 1140TolueneSolvent2×

Procedure

A solution of 9,10-dihydro-9,10-methano-9-anthracenecarboxylic acid (21.8 g, 92.4 mmol) in toluene (160 mL) was treated with thionyl chloride (11.7 g, 99 mmol) and N,N-dimethylformamide (0.1 g). The resulting solution was heated to reflux temperature for 2 h, then was cooled to room temperature. The mixture was then treated dropwise with a solution of ethyl isonipecotate (31.1 g, 198 mmol) in toluene (20 mL), using an ice/water bath to keep the reaction temperature <35° C. Upon complete addition, the mixture was stirred for 1 h at room temperature, then was washed sequentially with 10% hydrochloric acid (40 mL), water (40 mL), 1N aqueous sodium hydroxide (40 mL), water (40 mL) and brine (40 mL). The aqueous washes were extracted with toluene (100 mL). The organic extracts were combined, dried (MgSO4), filtered and concentrated to afford the title compound (33.0 g, 85.2 mmol, 92%) as an off-white solid. 1H NMR (d6-DMSO): δ 7.33-7.14 (m, 4H), 6.99 (m, 4H), 4.54 (br, 1H), 4.38 (s, 1H, H-C(10)), 4.09 (q, J=6.5 Hz, 2H, CH2CH3), 3.8 (br, 1H), 3.0-2.5 (br, 6H), 2.05-1.45 (br, 5H), 1.19 (t, J=6.5 Hz, 3H, CH2CH3).

Workup

  1. temperatureThe resulting solution was heated
  2. temperatureto reflux temperature for 2 h
  3. customthe reaction temperature <35° C
  4. additionUpon complete addition
  5. washwas washed sequentially with 10% hydrochloric acid (40 mL), water (40 mL), 1N aqueous sodium hydroxide (40 mL), water (40 mL) and brine (40 mL)
  6. extractionThe aqueous washes were extracted with toluene (100 mL)
  7. dry with materialdried (MgSO4)
  8. filtrationfiltered
  9. concentrationconcentrated

Sources & evidence

ORD record
ord-9a679d216dce48fdbbcff57531dad59e
Source dataset
uspto-grants-1996_08
Patent number
US05550136

Reaction notes

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