Isopropylamine → HCID 53724790, compound

HRID 1680945Notes

Reaction equation

HRID 1680945 reaction equation
[C:1]1([CH:7]([C:14]2C=[CH:18][CH:17]=[CH:16][CH:15]=2)[C:8]2C=CC=CC=2)C=[CH:5][CH:4]=[CH:3][CH:2]=1.C(N)(C)C.C([Li])CCC.CCCCCC.CC(CCCCC)=CCCC(=O)C.C([N-]C(C)C)(C)C.[Li+].[CH3:56][Si:57](Cl)([CH3:59])[CH3:58].C(N(CC)CC)C.C(=O)(O)[O-:69].[Na+]>O1CCCC1>[CH3:8][C:7]([CH2:14][CH2:15][CH2:16][CH2:17][CH3:18])=[CH:1][CH2:2][CH2:3][C:4]([O:69][Si:57]([CH3:59])([CH3:58])[CH3:56])=[CH2:5]

Participants

11

Reactant 9

HCID 6363IsopropylamineHCID 6397ChlorotrimethylsilaneHCID 8058HexaneHCID 8471TriethylamineHCID 10614TriphenylmethaneHCID 516892Sodium Bicarbonate2×HCID 2724682Lithium diisopropylamideHCID 54035825HCID 54035825, compoundHCID 178418339Butyllithium

Product 1

HCID 53724790HCID 53724790, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent4×

Conditions

Temperature
0 °C

Procedure

Triphenylmethane indicator (50 mg) is added to isopropylamine (9.15 ml, 0.065 moles) in anhydrous tetrahydrofuran (80 ml). The solution is cooled to 0° C. and a solution of n-butyllithium (2.34 m) in hexane (28.5 ml, 0.065 moles) is added carefully while stirring at 0°-5° C. The mixture is kept at 0° C. for 20 minutes and then cooled to -70° C. 6-Methyl-2-oxo-5-undecene (9.1 g, 0.05 moles, 60:40 E:Z mixture) is dissolved in anhydrous tetrahydrofuran (9.0 ml.) and added to the above solution of lithium diisopropylamide in tetrahydrofuran while stirring at -70° C. within 15 minutes (-70°-65° C.). To the resultant enolate solution is added immediately at -70° C. while stirring a freshly prepared and centrifuged solution of trimethylsilyl chloride (15 ml, ~0.12 moles) and triethylamine (4.0 ml, ~0.029 moles) in tetrahydrofuran (25 ml). The solution is kept at -70° C. for 1.5 hours. Solid sodium bicarbonate (10 g) is added. The solution is then allowed to come to -10° C., and a saturated aqueous sodium bicarbonate solution (60 ml) is added. The solution is then allowed to come to room temperature, the tetrahydrofuran layer is separated, and the aqueous layer is re-extracted with ether. The combined organic extract is washed with saturated aqueous chloride solution, dried with sodium sulfate, filtered, and evaporated in vacuo. Drying in high vacuo gives crude 6-methyl-2-trimethylsiloxy-undec-1,5-diene (13.75 g).

Workup

  1. temperaturecooled to -70° C
  2. stirringwhile stirring at -70° C. within 15 minutes (-70°-65° C.)
  3. stirringwhile stirring
  4. customa freshly prepared
  5. waitThe solution is kept at -70° C. for 1.5 hours
  6. customto come to -10° C.
  7. customto come to room temperature
  8. customthe tetrahydrofuran layer is separated
  9. extractionthe aqueous layer is re-extracted with ether
  10. extractionThe combined organic extract
  11. washis washed with saturated aqueous chloride solution
  12. dry with materialdried with sodium sulfate
  13. filtrationfiltered
  14. customevaporated in vacuo
  15. customDrying in high vacuo

Sources & evidence

ORD record
ord-b02deb555bfa48f49d43c4f1428999cb
Source dataset
uspto-grants-1981_06
Patent number
US04276216

Reaction notes

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