Dichloromethane → HCID 178484053, compound

HRID 967186Notes

Reaction equation

HRID 967186 reaction equation
[OH:1][CH2:2][C@H:3]1[CH2:8][CH2:7][C@H:6]([CH2:9][N:10]([CH3:24])[S:11]([C:14]2[CH:19]=[CH:18][C:17]([C:20]([F:23])([F:22])[F:21])=[CH:16][CH:15]=2)(=[O:13])=[O:12])[CH2:5][CH2:4]1.ClCCl.[Br:28][CH2:29]/[CH:30]=[CH:31]/[CH2:32]Br.[OH-].[Na+]>S([O-])(O)(=O)=O.C([N+](CCCC)(CCCC)CCCC)CCC.O>[Br:28][CH2:29]/[CH:30]=[CH:31]/[CH2:32][O:1][CH2:2][C@H:3]1[CH2:8][CH2:7][C@H:6]([CH2:9][N:10]([CH3:24])[S:11]([C:14]2[CH:19]=[CH:18][C:17]([C:20]([F:23])([F:21])[F:22])=[CH:16][CH:15]=2)(=[O:13])=[O:12])[CH2:5][CH2:4]1

Participants

7

Reactant 4

HCID 6344DichloromethaneHCID 14798Sodium HydroxideHCID 641245trans-1,4-Dibromo-2-buteneHCID 178484051HCID 178484051, compound

Product 1

HCID 178484053HCID 178484053, compoundYield 69.6%

Reagents, catalysts & solvents 2

HCID 94433Tetrabutylammonium hydrogen sulfateCatalystHCID 962WaterSolvent

Procedure

A heterogenous mixture of 1.59 g (4.35 mmol) of trans-N-(4-hydroxymethyl-cyclohexylmethyl)-N-methyl-4-trifluoromethyl-benzenesulfonamide (example 5.1), 5.0 ml of dichloromethane , 37.2 g (174 mmol) of (E)-1,4-dibromo-2-butene, 15.0 ml of 50% w/w sodium hydroxide solution and 0.44 g (1.3 mmol) of tetrabutylammonium hydrogensulfate was stirred vigorously at room temperature for 3 days. Afterwards, 30 ml of deionized water were added and the reaction mixture was extracted with 3 portions of n-hexane. The combined organic phases were then washed with water (3 times), 1 N aqueous hydrochloric acid solution, saturated aqueous sodium bicarbonate solution, brine and were finally dried over magnesium sulfate and evaporated under reduced pressure. The excess of the (E)-1,4-dibromo-2-butene was distilled off under reduced pressure (0.5 torr) at 100° C. The residue thus obtained was chromatographed on silicagel with a 3:1 v/v mixture of dichloromethane and hexane as the eluent giving 1.51 g (69.6%) of trans-N-[4-(4-bromo-(E)-but-2-enyloxymethyl)-cyclohexylmethyl]-N-methyl-4-trifluoromethyl-benzenesulfonamide as pale yellow solid, MS: 515 (MNH4+, 1Br).

Workup

  1. extractionthe reaction mixture was extracted with 3 portions of n-hexane
  2. washThe combined organic phases were then washed with water (3 times), 1 N aqueous hydrochloric acid solution, saturated aqueous sodium bicarbonate solution, brine
  3. dry with materialwere finally dried over magnesium sulfate
  4. customevaporated under reduced pressure
  5. distillationThe excess of the (E)-1,4-dibromo-2-butene was distilled off under reduced pressure (0.5 torr) at 100° C
  6. customThe residue thus obtained
  7. customwas chromatographed on silicagel with a 3:1 v/v mixture of dichloromethane and hexane as the eluent

Sources & evidence

ORD record
ord-05dbd08d95164312918581da33076caa
Source dataset
uspto-grants-2005_10
Patent number
US06953806B2

Reaction notes

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