Dimethyl Disulfide → 1-methylthiomethyl-3,4,5,5a,6,7-hexahydro-9-methoxy-2H-naphth[1,2-d]azepin-2-one

HRID 1105547Notes

Reaction equation

HRID 1105547 reaction equation
C([Li])CCC.[CH3:6][C:7]1[C:8](=[O:24])[NH:9][CH2:10][CH2:11][CH:12]2[CH2:21][CH2:20][C:19]3[C:14](=[CH:15][CH:16]=[C:17]([O:22][CH3:23])[CH:18]=3)[C:13]=12.[CH3:25][S:26]SC>CCCCCC.O1CCCC1>[CH3:25][S:26][CH2:6][C:7]1[C:8](=[O:24])[NH:9][CH2:10][CH2:11][CH:12]2[CH2:21][CH2:20][C:19]3[C:14](=[CH:15][CH:16]=[C:17]([O:22][CH3:23])[CH:18]=3)[C:13]=12

Participants

6

Reactant 3

HCID 12232Dimethyl DisulfideHCID 205556141-methyl-9-methoxy-3,4,5,5a,6,7-hexahydro-2H-naphth[1,2-d]azepin-2oneHCID 178418339Butyllithium

Product 1

HCID 205555951-methylthiomethyl-3,4,5,5a,6,7-hexahydro-9-methoxy-2H-naphth[1,2-d]azepin-2-one

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Procedure

The starting material is prepared as follows: 36.4 ml of 2.5 M n-butyl lithium in hexane are added dropwise under nitrogen and at room temperature to the stirred suspension of 7.8 g of 1-methyl-9-methoxy-3,4,5,5a,6,7-hexahydro-2H-naphth[1,2-d]azepin-2one in 70 ml of anhydrous tetrahydrofuran. The mixture is stirred at room temperature for 45 minutes and cooled in a dry ice-acetone bath. The solution of 5.45 ml of dimethyl disulfide in 60 ml of tetrahydrofuran is added dropwise and the mixture stirred with said cooling for 2 hours. It is quenched by the slow addition of 150 ml of water, the mixture is extracted with chloroform, the extract is dried and evaporated. The residue is crystallized from diethylether and recrystallized from ethyl acetate, to give the 1-methylthiomethyl-3,4,5,5a,6,7-hexahydro-9-methoxy-2H-naphth[1,2-d]azepin-2-one melting at 182°-182°.

Workup

  1. customThe starting material is prepared
  2. temperaturecooled in a dry ice-acetone bath
  3. stirringthe mixture stirred
  4. temperaturewith said cooling for 2 hours
  5. customIt is quenched by the slow addition of 150 ml of water
  6. extractionthe mixture is extracted with chloroform
  7. customthe extract is dried
  8. customevaporated
  9. customThe residue is crystallized from diethylether
  10. customrecrystallized from ethyl acetate

Sources & evidence

ORD record
ord-73dbf69a66d24002b0d9ffb0d16bf09b
Source dataset
uspto-grants-1982_01
Patent number
US04309345

Reaction notes

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