2-Trimethylsilyl-1,3-dithiane → [2-(5-[1,3]dithian-2-ylidenemethyl-10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-yl)-ethyl]-dimethylamine

HRID 1935326Notes

Reaction equation

HRID 1935326 reaction equation
C[Si](C)(C)[CH:3]1[S:8][CH2:7][CH2:6][CH2:5][S:4]1.C([Li])CCC.[CH3:16][N:17]([CH3:37])[CH2:18][CH2:19][C:20]1([CH:35]=O)[C:26]2[CH:27]=[CH:28][CH:29]=[CH:30][C:25]=2[CH2:24][CH2:23][C:22]2[CH:31]=[CH:32][CH:33]=[CH:34][C:21]1=2>C1COCC1.CCCCCC.C(OCC)C>[S:4]1[CH2:5][CH2:6][CH2:7][S:8][C:3]1=[CH:35][C:20]1([CH2:19][CH2:18][N:17]([CH3:37])[CH3:16])[C:21]2[CH:34]=[CH:33][CH:32]=[CH:31][C:22]=2[CH2:23][CH2:24][C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][C:26]1=2

Participants

7

Reactant 3

HCID 834132-Trimethylsilyl-1,3-dithianeHCID 224639665-(2-dimethylaminoethyl)-10,11-dihydro-5H-dibenzo[a,d]cycloheptene-5-carbaldehydeHCID 178418339Butyllithium

Product 1

HCID 22463995[2-(5-[1,3]dithian-2-ylidenemethyl-10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-yl)-ethyl]-dimethylamine

Reagents, catalysts & solvents 3

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Procedure

To a solution of 2-trimethylsilyl-1,3-dithiane (2.5 mL, 12.8 mmol) in 10 mL of THF stirred at −78° C. and maintained under a nitrogen atmosphere was added butyllithium (5.1 mL of a 2.5M solution in hexane; 12.8 mmol) dropwise. The mixture was stirred in the cold for 20 minutes and then treated with 5-(2-dimethylamino-ethyl)-10,11-dihydro-5H-dibenzo[a,d]cycloheptene-5-carbaldehyde (102), 3.1 g in 20 mL of THF; 10.6 mmol) added dropwise. The solution was stirred for 1.5 hours at −78° C., warmed to ambient temperature and stirred an additional 1.5 hours. The solution was diluted with ethyl ether and quenched with saturated aqueous ammonium chloride. The organic layer was washed with saturated aqueous ammonium chloride (1×), saturated aqueous sodium bicarbonate (1×), and brine (1×), dried the over sodium sulfate, filtered, and evaporated to dryness. The resulting oil was purified by chromatography on silica gel (95:5 of methylene chloride:methanol). The product fractions were evaporated to dryness to yield the title product as an oil.

Workup

  1. temperaturemaintained under a nitrogen atmosphere
  2. addition10.6 mmol) added dropwise
  3. stirringThe solution was stirred for 1.5 hours at −78° C.
  4. stirringstirred an additional 1.5 hours
  5. customquenched with saturated aqueous ammonium chloride
  6. washThe organic layer was washed with saturated aqueous ammonium chloride (1×), saturated aqueous sodium bicarbonate (1×), and brine (1×)
  7. dry with materialdried the over sodium sulfate
  8. filtrationfiltered
  9. customevaporated to dryness
  10. customThe resulting oil was purified by chromatography on silica gel (95:5 of methylene chloride:methanol)
  11. customThe product fractions were evaporated to dryness

Sources & evidence

ORD record
ord-7e188ad5765349daa747ccfd1ee065ba
Source dataset
uspto-grants-2002_05
Patent number
US06387893B1

Reaction notes

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