Benzaldehyde → HCID 68502098, compound

HRID 1983550Notes

Reaction equation

HRID 1983550 reaction equation
C[Si](C)(C)[NH:3][Si](C)(C)C.C([Li])CCC.[CH:15](=O)[C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1.C[Si](C)(C)OC(O[Si](C)(C)C)(O[Si](C)(C)C)C.C=C.[CH3:42][Si:43](Cl)([CH3:45])[CH3:44].CO.[CH2:49]([CH2:52][O:53]C)[O:50]C>C(OCC)(=O)C.C(O)(=O)C.C(N(CC)CC)C>[CH3:42][Si:43]([CH3:45])([CH3:44])[O:50][C@H:49]1[C@@H:15]([C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)[NH:3][C:52]1=[O:53]

Participants

12

Reactant 8

HCID 240BenzaldehydeHCID 887MethanolHCID 6325EthyleneHCID 6397ChlorotrimethylsilaneHCID 80711,2-DimethoxyethaneHCID 13838HexamethyldisilazaneHCID 86609623HCID 86609623, compoundHCID 178418339Butyllithium

Product 1

HCID 68502098HCID 68502098, compound

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 8471TriethylamineSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of hexamethyldisilazane (HMDS, 460 mL, 2.2 mol) in anhydrous dimethoxyethane (200 mL) at 0° C. was added a 2.5 M solution of n-butyllithium (nBuLi, 800 mL, 2.0 mol) over 45 min to maintain the reaction temperature at less than 40° C. After the addition, benzaldehyde was added to the reaction mixture over 1 h to maintain the reaction temperature at less than 40° C. After the addition was complete the mixture was cooled to 0° C. and tris(trimethylsiloxy)ethane (643 g, 2.2 mol) was added and the mixture was stirred until reaction was complete (12 h); reaction completion was determined by the disappearance of the starting ethene material. The reaction mixture was quenched with trimethylsilylchloride (TMSCl, 217.28 g, 1.0 eq), triethylamine (50 mL) and acetic acid (20 mL) and diluted with ethyl acetate (1.0 L). The lithium salt was filtered off via a sintered funnel. The filtrate was concentrated to dryness. The solid was taken up in heptane (1.0 L) and treated with methanol (96 g, 1.5 eq) at 20 to 40° C. to give crystals of the product. The solid product was collected via vacuum filtration through a Buchner funnel and washed with cold 15% ethyl acetate in heptane. The solid was taken up in ethyl acetate (1.5 L) and washed with brine, dried over sodium sulfate (200 g) and concentrated to give a white powder. Mp: 118 to 120°° C., 1H NMR (400 MHz, CDCl3) δ (ppm): −0.08 (s, 9H), 4.79 (d, J=4.4 Hz, 1H), 5.09 (dd, J=4.4, 2.7 Hz, 1H), 6.16 (bm, 1H), 7.3 to 7.4 (m, 5H).

Workup

  1. temperatureto maintain the reaction temperature at less than 40° C
  2. additionwas added to the reaction mixture over 1 h
  3. temperatureto maintain the reaction temperature at less than 40° C
  4. additionAfter the addition
  5. custom(12 h)
  6. customreaction completion
  7. filtrationThe lithium salt was filtered off via a sintered funnel
  8. concentrationThe filtrate was concentrated to dryness
  9. customto give crystals of the product
  10. filtrationThe solid product was collected via vacuum filtration through a Buchner funnel
  11. washwashed with cold 15% ethyl acetate in heptane
  12. washwashed with brine
  13. dry with materialdried over sodium sulfate (200 g)
  14. concentrationconcentrated
  15. customto give a white powder

Sources & evidence

ORD record
ord-7275f80f80ac4e78904ac53fef7a4474
Source dataset
uspto-grants-2009_06
Patent number
US07541458B2

Reaction notes

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