Ethanethiol → Hydrochloric Acid

HRID 979159Notes

Reaction equation

HRID 979159 reaction equation
[CH2:1]([SH:3])[CH3:2].C([Li])CCC.[Br:9][C:10]1[C:15]2[O:16][CH2:17][C@@H:18]3[C@@H:23]([CH2:24]OS(C)(=O)=O)[CH2:22][N:21]([CH3:30])[CH2:20][C@H:19]3[C:14]=2[CH:13]=[C:12]([O:31][CH3:32])[CH:11]=1.[ClH:33].C(OCC)(=O)C>O1CCCC1.C(O)(C)C.O>[Br:9][C:10]1[C:15]2[O:16][CH2:17][C@@H:18]3[C@@H:23]([CH2:24][S:3][CH2:1][CH3:2])[CH2:22][N:21]([CH3:30])[CH2:20][C@H:19]3[C:14]=2[CH:13]=[C:12]([O:31][CH3:32])[CH:11]=1.[ClH:33]

Participants

9

Reactant 4

HCID 6343EthanethiolHCID 21866389Hydrogen chloride-ethyl acetateHCID 53720630HCID 53720630, compoundHCID 178418339Butyllithium

Product 2

HCID 313Hydrochloric AcidHCID 54148598HCID 54148598, compound

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 3776IsopropanolSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

To a stirred solution of 0.46 ml ethanethiol in 40 ml dry tetrahydrofuran (THF) under nitrogen at -10° is added dropwise 2.3 ml n-butyllithium (2.28M in hexane). This solution is added to a solution of 1.91 g (±)-[4R*,4aS*,10bR*]-7-bromo-4-(methylsulfonyloxymethyl)-1,3,4,4a,5,10b-hexahydro-9-methoxy-2-methyl-2H-[1]benzopyrano[4,3-c]pyridine in 25 ml THF. After stirring 2 h at 25°, 5 ml H2O is added and the reaction mixture concentrated under reduced pressure. The residue is partitioned between 25 ml H2O and 50 ml CH2Cl2. The CH2Cl2 phase is washed with 20 ml H2O, dried over Na2SO4, filtered and concentrated. Flash chromatography with CH2Cl2 /MeOH (40:1) yields an oil which is dissolved in 40 ml isopropyl alcohol. The solution is warmed at 50° and 1 ml 3.4N HCl/ethyl acetate is added. After cooling overnight the product is filtered, washed with isopropyl alcohol/ether (1:1) and dried to afford the title compound, m.p. 268°-269° dec (HCl salt).

Workup

  1. concentrationthe reaction mixture concentrated under reduced pressure
  2. customThe residue is partitioned between 25 ml H2O and 50 ml CH2Cl2
  3. washThe CH2Cl2 phase is washed with 20 ml H2O
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customFlash chromatography with CH2Cl2 /MeOH (40:1) yields an oil which
  8. temperatureThe solution is warmed at 50°
  9. temperatureAfter cooling overnight the product
  10. filtrationis filtered
  11. washwashed with isopropyl alcohol/ether (1:1)
  12. customdried

Sources & evidence

ORD record
ord-5d3611958357433ca346310fd1c77203
Source dataset
uspto-grants-1987_05
Patent number
US04666916

Reaction notes

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