Benzyl Bromide → HCID 86624487, compound

HRID 1961496Notes

Reaction equation

HRID 1961496 reaction equation
[OH-].[Na+:2].[OH:3][C:4]1[CH:9]=[CH:8][C:7]([S:10]([OH:13])(=[O:12])=[O:11])=[CH:6][C:5]=1[I:14].[CH2:15](Br)[C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1.O.S(=O)(=O)(O)O>C(O)(C)C>[CH2:15]([O:3][C:4]1[CH:9]=[CH:8][C:7]([S:10]([O-:13])(=[O:11])=[O:12])=[CH:6][C:5]=1[I:14])[C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1.[Na+:2]

Participants

6

Reactant 4

HCID 7498Benzyl Bromide3×HCID 14798Sodium Hydroxide2×HCID 405125HCID 405125, compoundHCID 21910475Sulfuric acid hydrate (1:1)

Product 1

HCID 86624487HCID 86624487, compound

Reagents, catalysts & solvents 1

HCID 3776IsopropanolSolvent

Conditions

Temperature
84 °C

Procedure

Sodium hydroxide (pellets, 110 g, 2.75 mol, 3.00 eq) was added portionwise to the vigorously stirring aqueous solution of the 4-hydroxy-3-iodo-benzenesulfonic acid. After addition was complete, 10-15 min., isopropyl alcohol (150 mL) was added to the resulting white suspension. The dropping-funnel was charged with benzyl bromide (Aldrich; 164.9 g, 0.964 mol, 1.05 eq.) and added to the reaction mixture over a period of approx. 5 mins. and the reaction mixture was heated to 80°≦Tint≦84° C. After approx. 25 min. it was determined that the reaction was not proceeding further and therefore additional sodium hydroxide (3.67 g, 91.8 mmol, 0.1 eq.) and then benzyl bromide (15.7 g, 91.8 mmol, 0.1 eq.) were added to the reaction mixture to give a homogenous solution. After 70 min. from the original benzyl bromide addition, the heating was stopped and the reaction was allowed to cool slowly in the oil-bath with stirring. At 7.5 h, the reaction mixture appeared as a suspension of fine-reflective precipitate in brown liquid. The reaction mixture was acidified with 3:1 water-sulfuric acid from about pH 13 to between pH 7.5 and 8 (approx. 70 mL is required). The reaction mixture was then cooled gradually to about 5° C. and stirred at that temperature for ˜1 h. The waxy white plaques were collected by filtration, washed with dichloromethane and dried under high vacuum (lyophilizer, 100-200 mTorr) for ˜24 h to give sodium 4-benzyloxy-3-iodo-benzenesulfonate as a brilliant white, crystalline solid, (267.7 g, 71%).

Workup

  1. additionAfter addition
  2. additionadded to the reaction mixture over a period of approx. 5 mins
  3. waitAfter approx. 25 min. it was determined that the reaction
  4. customto give a homogenous solution
  5. temperatureto cool slowly in the oil-bath
  6. waitAt 7.5 h
  7. additionthe reaction mixture appeared as a suspension of fine-reflective precipitate in brown liquid
  8. temperatureThe reaction mixture was then cooled gradually to about 5° C.
  9. stirringstirred at that temperature for ˜1 h
  10. filtrationThe waxy white plaques were collected by filtration
  11. washwashed with dichloromethane
  12. customdried under high vacuum (lyophilizer, 100-200 mTorr) for ˜24 h

Sources & evidence

ORD record
ord-3885d4039c5c497b998b8ee6c5d96de2
Source dataset
uspto-grants-2013_04
Patent number
US08415328B2

Reaction notes

Loading…