1,2-Dibromoethane → HCID 67085016, compound

HRID 1047463Notes

Reaction equation

HRID 1047463 reaction equation
[Mg].BrCCBr.Cl[CH2:7][Si:8]([CH3:11])([CH3:10])[CH3:9].[C:12]([Si:16]([C:58]1[CH:63]=[CH:62][CH:61]=[CH:60][CH:59]=1)([C:52]1[CH:57]=[CH:56][CH:55]=[CH:54][CH:53]=1)[O:17][CH:18]1[CH:22]([CH2:23][O:24][C:25]([C:38]2[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=2)([C:32]2[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=2)[C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[C:21](OS(C(F)(F)F)(=O)=O)=[CH:20][CH2:19]1)([CH3:15])([CH3:14])[CH3:13].[Na]>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.CCCCCCC.O1CCCC1>[C:12]([Si:16]([C:52]1[CH:53]=[CH:54][CH:55]=[CH:56][CH:57]=1)([C:58]1[CH:59]=[CH:60][CH:61]=[CH:62][CH:63]=1)[O:17][C:18]1([CH2:7][Si:8]([CH3:11])([CH3:10])[CH3:9])[CH2:19][CH2:20][CH:21]=[C:22]1[CH2:23][O:24][C:25]([C:26]1[CH:27]=[CH:28][CH:29]=[CH:30][CH:31]=1)([C:38]1[CH:39]=[CH:40][CH:41]=[CH:42][CH:43]=1)[C:32]1[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1)([CH3:15])([CH3:13])[CH3:14]

Participants

9

Reactant 5

HCID 78391,2-DibromoethaneHCID 75361Silane, (chloromethyl)trimethyl-HCID 5360545SodiumHCID 5462224MagnesiumHCID 86669102HCID 86669102, compound

Product 1

HCID 67085016HCID 67085016, compoundYield 96.1%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 8028TetrahydrofuranSolvent3×HCID 8900HeptaneSolvent

Conditions

Temperature
40 °C

Procedure

Magnesium (turning) (33 g, 5.22 mol) was mixed with anhydrous tetrahydrofuran (2 L). 1,2-Dibromoethane (8 ml) was added thereto and stirred for 15 min. To the resulting solution, a mixture of chloromethyltrimethylsilane (364 ml, 2.61 mol) and anhydrous tetrahydrofuran (0.6 L) was added dropwise for 10 min. The mixture solution thus obtained was heated to 40° C. and cooled slowly to precipitate trimethylsilylmethyl magnesium chloride. A mixture of the compound of formula (X) obtained in Example 2-3 (892 g), tetrakis(triphenylphosphine)palladium (37.7 g, 0.033 mmol) and anhydrous tetrahydrofuran (4.5 L) were added to the resulting solution for 20 min dropwise and stirred at room temperature for 1 to 2 hrs. After completion of the reaction, the resulting solution was cooled to 0° C. and 3% aqueous sodium bisulfonate (8 L) was added thereto. The resulting mixture was filtered through Celite, washed with ethyl acetate (4 L). The organic layer thus separated was condensed under a reduced pressure. The residue thus obtained was mixed with heptane (6 L) and Celite (400 g), stirred for 2 hrs, filtered and washed with heptane (2 L). The organic layer thus separated was washed with a mixture of methanol and water mixed in a weight ratio of 6:1 (5.6 L) twice, dried over anhydrous sodium sulfate, filtered, and condensed under a reduced pressure. The residue was crystallized with a mixture of isopropyl alcohol and water to obtain the title compound as a crystalline solid (786 g).

Workup

  1. additionwas added dropwise for 10 min
  2. customThe mixture solution thus obtained
  3. temperaturecooled slowly
  4. customto precipitate trimethylsilylmethyl magnesium chloride
  5. additionwere added to the resulting solution for 20 min dropwise
  6. stirringstirred at room temperature for 1 to 2 hrs
  7. customAfter completion of the reaction
  8. temperaturethe resulting solution was cooled to 0° C.
  9. filtrationThe resulting mixture was filtered through Celite
  10. washwashed with ethyl acetate (4 L)
  11. customThe organic layer thus separated
  12. customcondensed under a reduced pressure
  13. customThe residue thus obtained
  14. stirringstirred for 2 hrs
  15. filtrationfiltered
  16. washwashed with heptane (2 L)
  17. customThe organic layer thus separated
  18. washwas washed with a mixture of methanol and water
  19. additionmixed in a weight ratio of 6:1 (5.6 L) twice
  20. dry with materialdried over anhydrous sodium sulfate
  21. filtrationfiltered
  22. customcondensed under a reduced pressure
  23. customThe residue was crystallized with a mixture of isopropyl alcohol and water

Sources & evidence

ORD record
ord-e13acdf330f9466bb3aa8365a9a12636
Source dataset
uspto-grants-2013_10
Patent number
US08569491B2

Reaction notes

Loading…