Ammonia → HCID 57474451, compound

HRID 552926Notes

Reaction equation

HRID 552926 reaction equation
Br[C:2]1[CH:3]=[C:4]2[C:8](=[CH:9][CH:10]=1)[NH:7][CH:6]=[C:5]2[CH2:11][CH2:12][CH2:13][N:14]([CH3:16])[CH3:15].C(P(C(C)(C)C)C(C)(C)C)(C)(C)C.C[Si](C)(C)[Si](C)(C)C.[Li].[NH3:39]>C1COCC1.CO.ClCCl.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.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[CH3:15][N:14]([CH3:16])[CH2:13][CH2:12][CH2:11][C:5]1[C:4]2[C:8](=[CH:9][CH:10]=[C:2]([NH2:39])[CH:3]=2)[NH:7][CH:6]=1

Participants

9

Reactant 4

HCID 222AmmoniaHCID 83681Tris(1,1-dimethylethyl)phosphineHCID 11426012HCID 11426012, compoundHCID 57425481Lithium hexamethyldisilane

Product 1

HCID 57474451HCID 57474451, compound

Reagents, catalysts & solvents 4

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 887MethanolSolventHCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

To an argon purged vial fitted with a magnetic stirbar and containing 54 (324 mg, 1.15 mmol) was cannulated a solution of Pd2(dba)3 (53 mg, 0.058 mmol), and Tri-t-butyl phosphine solution (0.34 mL, 10%, 0.11 mmol) in dry THF (8 mL). The flask was fitted with a condenser and a 1M solution of lithium hexamethyldisilane in THF (3.45 mL, 3.45 mmol) was added. The reaction was placed in a metal heating block and heated to reflux. The reaction was stirred at this temperature for 16 hours. TLC (10% 2M ammonia in methanol, 90% dichloromethane) revealed all starting material had reacted. The reaction was cooled to room temperature and quenched with 1M aqueous hydrogen chloride (15 mL). The acidic reaction was extracted with ethyl acetate (3×10 mL). The aqueous phase was basified with 3N sodium hydroxide (8 mL) and partitioned into ethyl acetate (3×10 mL). The organics were washed with brine, dried over magnesium sulfate, and treated with charcoal. Filtration through celite, concentration and further drying under high vacuum afforded a dark yellow oil. Purification of the product was performed using silica gel column chromatography (5-10% 2M ammonia in methanol, 95-90% dichloromethane) Yield: 162 mg of brown oil, compound 55 (65%). 1H NMR (CDCl3) δ 7.76 (br s, NH), 7.17-7.14 (d, 1H, J=8.4 Hz), 6.92-6.90 (dd, 2H, J=2.1, 4.5 Hz), 6.67-6.64 (dd, 1H, J=2.1, 8.4 Hz), 2.73-2.68 (t, J=7.5, 2H), 2.41-2.36 (t, J=7.5 Hz, 2H), 2.26 (s, 8 H).

Workup

  1. customTo an argon purged vial fitted with a magnetic stirbar
  2. customThe flask was fitted with a condenser
  3. temperatureheating block
  4. temperatureheated to reflux
  5. customhad reacted
  6. customquenched with 1M aqueous hydrogen chloride (15 mL)
  7. customThe acidic reaction
  8. extractionwas extracted with ethyl acetate (3×10 mL)
  9. custompartitioned into ethyl acetate (3×10 mL)
  10. washThe organics were washed with brine
  11. dry with materialdried over magnesium sulfate
  12. additiontreated with charcoal
  13. filtrationFiltration
  14. concentrationthrough celite, concentration
  15. customfurther drying under high vacuum
  16. customafforded a dark yellow oil
  17. customPurification of the product

Sources & evidence

ORD record
ord-c753d86038784ee8805bd6ca026e7cf6
Source dataset
uspto-grants-2011_05
Patent number
US07951940B2

Reaction notes

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