Triphenylphosphine → HCID 13650342, compound

HRID 745335Notes

Reaction equation

HRID 745335 reaction equation
[CH3:1][CH:2]([CH2:7][CH2:8][CH2:9][CH:10]([CH3:17])[CH2:11][CH2:12][CH2:13][CH:14]([CH3:16])[CH3:15])[CH2:3][CH2:4][CH2:5]O.S([O-])([O-])(=O)=O.[Ca+2].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Br:43]Br>O.CCCCCC.CN(C)C=O>[Br:43][CH2:5][CH2:4][CH2:3][CH:2]([CH3:1])[CH2:7][CH2:8][CH2:9][CH:10]([CH3:17])[CH2:11][CH2:12][CH2:13][CH:14]([CH3:16])[CH3:15]

Participants

8

Reactant 4

HCID 11776TriphenylphosphineHCID 24408BromineHCID 24497Calcium SulfateHCID 136503404,8,12-Trimethyltridecan-1-ol

Product 1

HCID 13650342HCID 13650342, compound

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8058HexaneSolvent

Procedure

Into a 250 ml, three-necked, round-bottom flask equipped with a thermometer, serum cap, argon blubber and a magnetic stir bar was added 10 g (40 mmol) of 4,8,12-trimethyltridecanol, 30 ml of purified dimethylformamide (DMF) (stored over calcium sulfate prior to distillation) and 11.2 g (43 mmol) of triphenylphosphine. The solution was cooled to 0° C. before 2.19 ml (43 mmol) of bromine was added via syringe at such a rate that the temperature remained below 30° C. At the end of the addition a persistent orange color remained. The reaction was poured into 200 ml of hexane and 200 ml of water. The aqueous layer was extracted 3×200 ml of hexane. The combined organic layers were rinsed with 300 ml of saturated sodium bicarbonate, 100 ml brine, and were dried with 80 cc of sodium sulfate. The solvent was removed at reduced pressure with a rotary evaporator to afford a mixture of oil and solid. The mixture was triturated with hexane and filtered over a short plug of 40 g of silica gel eluting with hexane. Removal of the solvent left 10.7 g of colorless oil. Distillation through a 10 cm, vacuum jacqueted vigreaux afforded 9.7 g of colorless product, i.e. 1-bromo-4,8,12-trimethyltridecane, bp 119°-20° C. at 0.15 mm Hg.

Workup

  1. customInto a 250 ml, three-necked, round-bottom flask equipped with a thermometer, serum
  2. customcap
  3. additionwas added via syringe at such a rate that the temperature
  4. customremained below 30° C
  5. additionAt the end of the addition a persistent orange color
  6. extractionThe aqueous layer was extracted 3×200 ml of hexane
  7. washThe combined organic layers were rinsed with 300 ml of saturated sodium bicarbonate, 100 ml brine
  8. dry with materialwere dried with 80 cc of sodium sulfate
  9. customThe solvent was removed at reduced pressure with a rotary evaporator
  10. customto afford
  11. additiona mixture of oil and solid
  12. customThe mixture was triturated with hexane
  13. filtrationfiltered over a short plug of 40 g of silica gel eluting with hexane
  14. customRemoval of the solvent
  15. waitleft 10.7 g of colorless oil
  16. distillationDistillation through a 10 cm, vacuum

Sources & evidence

ORD record
ord-f00aebefa1aa4e41af11f3d7424d94e1
Source dataset
uspto-grants-1986_07
Patent number
US04598160

Reaction notes

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