Borane → HCID 70045205, compound

HRID 280656Notes

Reaction equation

HRID 280656 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([CH:8]=[CH:9][C:10]=1[S:11][C:12]1[CH:17]=[CH:16][C:15]([Cl:18])=[CH:14][CH:13]=1)[C:5]([NH2:7])=O.B>O1CCCC1>[ClH:1].[Cl:1][C:2]1[CH:3]=[C:4]([CH:8]=[CH:9][C:10]=1[S:11][C:12]1[CH:17]=[CH:16][C:15]([Cl:18])=[CH:14][CH:13]=1)[CH2:5][NH2:7]

Participants

4

Reactant 2

HCID 6331BoraneHCID 23320963HCID 23320963, compound

Product 1

HCID 70045205HCID 70045205, compoundYield 114.3%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

A solution of 3-chloro-4-(4-chlorophenylthio)benzamide (44.7 g, 150 mmol) in tetrahydrofuran (300 ml) was added dropwise over 30 minutes to a stirred 1.0M solution of borane in tetrahydrofuran (450 ml) under a nitrogen atmosphere at ambient temperature. The mixture was refluxed for 16 hours, cooled to 0° C., and quenched by addition of 2.0N hydrochloric acid. The solvent was evaporated under vacuum and the solid residue was slurried in water, filtered, and washed with water (4×300 ml). The solid was partially dried in the air, washed with diethyl ether (3×200 ml), and dried under vacuum at 50° C. for 3 hours and at ambient temperature for 16 hours. The crude product was suspended in diethyl ether (700 ml), vigorously stirred for 30 minutes, filtered, washed with diethyl ether, and dried to provide 27.5 g (57%) 3-chloro-4-(4-chlorophenylthio) benzylamine hydrochloride, m.p. 237°-240° C. The free base was liberated by slurrying the salt (6.77 g) in water (100 ml), basifying with 2.5N aqueous sodium hydroxide, adding diethyl ether (100 ml), and filtering. The biphasic filtrate was separated and the aqueous phase was extracted with diethyl ether. The combined diethyl ether phases were washed with water and brine, dried over anhydrous magnesium sulfate, and evaporated under vacuum. The oily residue was kept under vacuum at ambient temperature for 16 hours to provide 5.80 g (97%) of 3-chloro-4-(4-chlorophenylthio)benzylamine as a colorless oil, 60 MHz 'H NMR (DMSO-d6): 2.22 broad s (2H), 3.37 s (2H), 7.1-7.5 complex m (7H); (DMSO-d6 /D2O/DCl) 4.05 s (2H), 7.03 d (J=9Hz, 1H), 7.3-7.6 broad m (6H).

Workup

  1. temperatureThe mixture was refluxed for 16 hours
  2. customquenched by addition of 2.0N hydrochloric acid
  3. customThe solvent was evaporated under vacuum
  4. filtrationfiltered
  5. washwashed with water (4×300 ml)
  6. customThe solid was partially dried in the air
  7. washwashed with diethyl ether (3×200 ml)
  8. customdried under vacuum at 50° C. for 3 hours and at ambient temperature for 16 hours
  9. filtrationfiltered
  10. washwashed with diethyl ether
  11. customdried

Sources & evidence

ORD record
ord-c9c8bf626a9245ce92b163fef8c22054
Source dataset
uspto-grants-1986_05
Patent number
US04590201

Reaction notes

Loading…