4-Bromobenzaldehyde → HCID 86725944, compound

HRID 2169299Notes

Reaction equation

HRID 2169299 reaction equation
[C:1]1([Li])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[CH2:8]([O:10][C:11](=[O:25])[C:12]([C:23]#[N:24])=[C:13]1[CH2:22][CH2:21][C:16]2([O:20][CH2:19][CH2:18][O:17]2)[CH2:15][CH2:14]1)[CH3:9].C1C(C=O)=CC=C(Br)C=1>O1CCCC1.[Cu]I>[CH2:8]([O:10][C:11](=[O:25])[CH:12]([C:23]#[N:24])[C:13]1([C:1]2[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=2)[CH2:14][CH2:15][C:16]2([O:17][CH2:18][CH2:19][O:20]2)[CH2:21][CH2:22]1)[CH3:9]

Participants

6

Reactant 3

HCID 707414-BromobenzaldehydeHCID 5114445ST51003188HCID 178506676HCID 178506676, compound

Product 1

HCID 86725944HCID 86725944, compoundYield 57.91%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-30 °C

Procedure

To a stirred suspension of CuI (5.67 g, 29.88 mmol) in tetrahydrofuran (70 mL) was added phenyl lithium (1.8M dibutyl ether) (33.2 mL, 59.76 mmol) at −78° C. and the resulting mixture was allowed to stir at −30° C. for 2 h. To the resulting reaction mixture at −78° c. was added the pre-cooled solution of cyano-(1,4-dioxa-spiro[4.5]dec-8-ylidene)-acetic acid ethyl ester (262) in tetrahydrofuran (30 mL) and the resulting mixture was allowed to stir at −30° C. for 1 h. The reaction was monitored by silica TLC (P-anisaldehyde active). The reaction mixture was quenched with saturated NH4Cl-solution and the reaction mixture was diluted with ethyl acetate and the organic layer was separated. The organic part was dried over Na2SO4 and concentrated under reduced pressure, The resulting crude product was purified over silica gel (normal, 100-200 mesh) column chromatography using a gradient eluent 2% to 10% ethyl acetate in hexane to get cyano-(8-phenyl-1,4-dioxa-spiro[4.5]dec-8-yl)-acetic acid ethyl ester (263) (3.8 g, 57.91%), as colorless gummy liquid.

Workup

  1. customTo the resulting reaction mixture at −78° c
  2. stirringto stir at −30° C. for 1 h
  3. customThe reaction mixture was quenched with saturated NH4Cl-solution
  4. additionthe reaction mixture was diluted with ethyl acetate
  5. customthe organic layer was separated
  6. dry with materialThe organic part was dried over Na2SO4
  7. concentrationconcentrated under reduced pressure
  8. customThe resulting crude product was purified over silica gel (normal, 100-200 mesh) column chromatography

Sources & evidence

ORD record
ord-80875419983e45ab9d0d4f51d745a1c1
Source dataset
uspto-grants-2015_06
Patent number
US09045486B2

Reaction notes

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