Carbon Dioxide → HCID 58950766, compound

HRID 556157Notes

Reaction equation

HRID 556157 reaction equation
[CH2:1]1[C:10](=[O:11])[CH2:9][C:8]2[C:3](=[CH:4][CH:5]=[CH:6][CH:7]=2)[CH2:2]1.P(C(C)(C)C)(C(C)(C)C)C(C)(C)C.C(=O)=O.[Li+].C[Si]([N-][Si](C)(C)C)(C)C.Br[C:39]1[CH:44]=[CH:43][C:42]([Cl:45])=[C:41]([Cl:46])[CH:40]=1>C1(C)C=CC=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd]>[Cl:45][C:42]1[CH:43]=[C:44]([CH:9]2[C:8]3[C:3](=[CH:4][CH:5]=[CH:6][CH:7]=3)[CH2:2][CH2:1][C:10]2=[O:11])[CH:39]=[CH:40][C:41]=1[Cl:46]

Participants

8

Reactant 5

HCID 280Carbon DioxideHCID 290134-Bromo-1,2-dichlorobenzeneHCID 682662-TetraloneHCID 83681Tris(1,1-dimethylethyl)phosphineHCID 2733832Lithium Hexamethyldisilazide

Product 1

HCID 58950766HCID 58950766, compoundYield 73%

Reagents, catalysts & solvents 2

HCID 6505921(1E,4E)-1,5-diphenylpenta-1,4-dien-3-one; palladiumCatalystHCID 1140TolueneSolvent

Procedure

To a stirring solution of β-tetralone (34) (1.00 g, 6.84 mmol) and pd(dba)2 (39 mg, 1 mol%) in toluene was added t-Bu3P (228 uL, 10 wt % in hexanes, 1.1%). The solution was chilled (dry-ice bath) before adding LiHMDS (7.5 mL, 1M in hexanes, 1.1 eq) followed by 1-bromo-3,4-dichlorobenzene (1 mL, 1.1 eq). The solution was then allowed to warm to ambient temperature and heated under microwave radiation for 5 minutes (maximum temperature 140° C.). After cooling, the reaction was quenched with aqueous ammonium chloride and extracted with MTBE. The organic layer was dried with sodium sulfate, filtered through celite, and evaporated. The crude oil was separated on silic gel to give the title compound (1.45 g, 73%) as a slight brown oil. This material was assayed as 90% pure. TLC Rf (25% EA/Hex)=0.42. GCMS Rt=13.21 min m/z=290 (M+). 1H NMR (CDCl3, δ): 7.37 (d, J=8.3 Hz, 1H), 7.3-7.2 (m, 3H), 7.17 (d, J=2.1 Hz, 1H), 6.9 (m, 2H), 4.68 (s, 1H), 3.1 (m, 2H), 2.7 (m, 2H). 13C NMR (CDCl3, δ): 208.4, 137.7, 136.7, 135.3, 132.7, 131.5, 130.7, 130.5, 129.2, 128.2, 128.1, 127.7, 127.3, 58.6, 37.1, 28.0.

Workup

  1. temperatureheated under microwave radiation for 5 minutes (maximum temperature 140° C.)
  2. temperatureAfter cooling
  3. customthe reaction was quenched with aqueous ammonium chloride
  4. extractionextracted with MTBE
  5. dry with materialThe organic layer was dried with sodium sulfate
  6. filtrationfiltered through celite
  7. customevaporated
  8. customThe crude oil was separated on silic gel

Sources & evidence

ORD record
ord-2dab74e3eb014d228d9708b5122d33c3
Source dataset
uspto-grants-2011_11
Patent number
US08053603B2

Reaction notes

Loading…