1,2-Dibromo-1,1,2,2-tetrachloroethane → HCID 10811304, compound

HRID 1953041Notes

Reaction equation

HRID 1953041 reaction equation
[C:1]([O:5][C:6]([N:8]1[C:12](=[O:13])[CH2:11][CH2:10][CH:9]1[CH2:14][O:15][Si:16]([C:19]([CH3:22])([CH3:21])[CH3:20])([CH3:18])[CH3:17])=[O:7])([CH3:4])([CH3:3])[CH3:2].C[Si]([N-][Si](C)(C)C)(C)C.[Li+].C1([Se][Br:40])C=CC=CC=1.BrC(Cl)(Cl)C(Cl)(Cl)Br>O1CCCC1>[C:1]([O:5][C:6]([N:8]1[C@@H:9]([CH2:14][O:15][Si:16]([C:19]([CH3:22])([CH3:21])[CH3:20])([CH3:17])[CH3:18])[CH:10]=[C:11]([Br:40])[C:12]1=[O:13])=[O:7])([CH3:4])([CH3:3])[CH3:2]

Participants

6

Reactant 4

HCID 694261,2-Dibromo-1,1,2,2-tetrachloroethaneHCID 123446BromoselenobenzeneHCID 2733832Lithium HexamethyldisilazideHCID 13195228HCID 13195228, compound

Product 1

HCID 10811304HCID 10811304, compoundYield 59.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent4×

Procedure

A solution of 2-(tert-butyldimethylsilanyloxymethyl)-5-oxopyrrolidine-l-carboxylic acid tert-butyl ester (16.5 grams, 50 mmol) in tetrahydrofuran (800 mL) was cooled in bath at -78° C. A 1M solution of lithium bis(trimethylsilyl)amide in tetrahydrofuran (100 mL, 100 mmol) was added slowly. After stirring for 2 hours, a solution of phenylselenylbromide (14.16 grams, 60 mmol) in tetrahydrofuran (100 mL) was added and, after 15 minutes, a solution of 1,2-dibromotetrachloroethane (19.5 grams, 60 mmol) in tetrahydrofuran (100 mL) was added. The reaction mixture was stirred for an additional 1.5 hours while cooling at -78° and was quenched by addition of saturated ammonium chloride solution. Water and diethyl ether were added. The aqueous phase was separated and extracted with diethyl ether. The combined organic layers were concentrated to an orange oil which was dissolved in methylene chloride (1000 mL). A 30% w/v aqueous solution of hydrogen peroxide (20 mL) was added and the mixture was stirred vigorously overnight. Water (50 mL) was added. The aqueous layer was separated and extracted with methylene chloride. The combined organic layers were dried over magnesium sulfate and concentrated to an orange oil. The title compound (12.0 grams, 59%) was isolated by flash chromatography on silica gel eluting first with a 1:1 mixture of hexane and methylene chloride and then with methylene chloride alone.

Workup

  1. stirringThe reaction mixture was stirred for an additional 1.5 hours
  2. temperaturewhile cooling at -78°
  3. customwas quenched by addition of saturated ammonium chloride solution
  4. additionWater and diethyl ether were added
  5. customThe aqueous phase was separated
  6. extractionextracted with diethyl ether
  7. concentrationThe combined organic layers were concentrated to an orange oil which
  8. dissolutionwas dissolved in methylene chloride (1000 mL)
  9. additionwas added
  10. stirringthe mixture was stirred vigorously overnight
  11. additionWater (50 mL) was added
  12. customThe aqueous layer was separated
  13. extractionextracted with methylene chloride
  14. dry with materialThe combined organic layers were dried over magnesium sulfate
  15. concentrationconcentrated to an orange oil

Sources & evidence

ORD record
ord-0cb812aa4c2f47ae94e8e0ddfbbf40d1
Source dataset
uspto-grants-2000_09
Patent number
US06114361

Reaction notes

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