Benzoyl chloride → 10-(2-dimethylaminoethyl)-10,11-dihydro-5-phenylthiomethyl-5H-dibenzo[a,d]cyclohepten-5-benzoate

HRID 2083172Notes

Reaction equation

HRID 2083172 reaction equation
[C:1]1([S:7][CH3:8])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.C1([Li])C=CC=CC=1.[CH3:16][N:17]([CH3:36])[CH2:18][CH2:19][CH:20]1[C:26]2[CH:27]=[CH:28][CH:29]=[CH:30][C:25]=2[C:24](=O)[C:23]2[CH:32]=[CH:33][CH:34]=[CH:35][C:22]=2[CH2:21]1.[C:37]1([S:43][CH2:44][Li:45])[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=1.CN(C)CCC1[C:56]2[CH:57]=[CH:58][CH:59]=[CH:60][C:55]=2[C:54](CSC2C=CC=CC=2)([OH:61])C2C=CC=CC=2C1.C(Cl)(=[O:82])C1C=CC=CC=1>CCOCC.O1CCCC1>[C:37]1([S:43][CH2:44][Li:45])[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=1.[CH3:16][N:17]([CH3:36])[CH2:18][CH2:19][CH:20]1[C:26]2[CH:27]=[CH:28][CH:29]=[CH:30][C:25]=2[C:24]([CH2:8][S:7][C:1]2[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=2)([C:56]2[C:55]([C:54]([O-:61])=[O:82])=[CH:60][CH:59]=[CH:58][CH:57]=2)[C:23]2[CH:32]=[CH:33][CH:34]=[CH:35][C:22]=2[CH2:21]1

Participants

10

Reactant 6

HCID 7412Benzoyl chlorideHCID 7520ThioanisoleHCID 2035929910-(2-dimethylaminoethyl)-10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-oneHCID 2035931810-(2-dimethylaminoethyl)-10,11-dihydro-5-phenylthiomethyl-5H-dibenzo[a,d]cycloheptene-5-olHCID 178506676HCID 178506676, compoundHCID 178506884HCID 178506884, compound

Product 2

HCID 8673422810-(2-dimethylaminoethyl)-10,11-dihydro-5-phenylthiomethyl-5H-dibenzo[a,d]cyclohepten-5-benzoateHCID 178506884HCID 178506884, compound

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolvent2×HCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of phenylthiomethyllithium (~0.5 m) is prepared by reacting 6.22 g. (0.05 mole) of thioanisole in 72 ml. of dry tetrahydrofuran with 22.0 ml. of 2.3M solution of phenyllithium for 15 hours at room temperature under nitrogen. A solution of 1.94 g. (0.007 mole) of 10-(2-dimethylaminoethyl)-10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-one in 40 ml. of tetrahydrofuran is then added to a 42 ml. (~0.021 mole) portion of the phenylthiomethyllithium with ice-cooling. Stirring is initiated at room temperature for 24 hours. The resulting 10-(2-dimethylaminoethyl)-10,11-dihydro-5-phenylthiomethyl-5H-dibenzo[a,d]cycloheptene-5-ol is then poured onto a saturated salt solution and extracted with ether and the ether solution dried over anhydrous magnesium sulfate. The ether solution is cooled in ice and treated with 4.5 ml. of n-butyllithium in hexane (1.54 M solution 0.007 ice and 0.96 ml. (0.008 mole) of benzoyl chloride in 10 ml. ether is then added. The mixture is stirred for 3 hours at room temperature, diluted with ether and washed with water, saturated with sodium bicarbonate and then washed again with water. The ether is dried over anhydrous magnesium sulfate, filtered and evaporated and the residue purified to give 10-(2-dimethylaminoethyl)-10,11-dihydro-5-phenylthiomethyl-5H-dibenzo[a,d]cyclohepten-5-benzoate.

Workup

  1. extractionextracted with ether
  2. dry with materialthe ether solution dried over anhydrous magnesium sulfate
  3. temperatureThe ether solution is cooled in ice
  4. additiontreated with 4.5 ml
  5. stirringThe mixture is stirred for 3 hours at room temperature
  6. washwashed with water, saturated with sodium bicarbonate
  7. washwashed again with water
  8. dry with materialThe ether is dried over anhydrous magnesium sulfate
  9. filtrationfiltered
  10. customevaporated
  11. customthe residue purified

Sources & evidence

ORD record
ord-6a42ec544b984d6bb44258f5e3b75c52
Source dataset
uspto-grants-1978_04
Patent number
US04083997

Reaction notes

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