Ammonium Chloride → HCID 90060223, compound

HRID 1779231Notes

Reaction equation

HRID 1779231 reaction equation
[C:1]([O:13][CH3:14])(=[O:12])[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][C:9]([O-:11])=O.C(Cl)(=O)C(Cl)=O.[C:21]1([CH2:27][CH2:28][CH2:29][CH2:30]Br)[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1.[Mg].C1(CCCCBr)C=CC=CC=1.[Mg].[Cl-].[NH4+]>C1(C)C=CC=CC=1.O1CCCC1.CN(C)C=O.C(OCC)(=O)C>[O:11]=[C:9]([CH2:30][CH2:29][CH2:28][CH2:27][C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)[CH2:8][CH2:7][CH2:6][CH2:5][CH2:4][CH2:3][CH2:2][C:1]([O:13][CH3:14])=[O:12]

Participants

11

Reactant 6

HCID 25517Ammonium ChlorideHCID 65578Oxalyl chlorideHCID 2596681-Bromo-4-phenylbutaneHCID 5462224MagnesiumHCID 69942819-Methoxy-9-oxo-nonanoateHCID 67856166HCID 67856166, compound2×

Product 1

HCID 90060223HCID 90060223, compoundYield 42%

Reagents, catalysts & solvents 4

HCID 6228DimethylformamideCatalystHCID 1140TolueneSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
60 °C

Procedure

A commercially available reagent of monomethyl azelate (2.73 g, 13.5 mmol) was dissolved in toluene (21 mL), and N,N-dimethylformamide (0.00085 mL, 0.110 mmol) and oxalyl chloride (1.5 mL, 11.8 mmol) were then added. The reaction mixture was stirred at 60° C. for 2 hours, and then concentrated under reduced pressure. The residue was dissolved in tetrahydrofuran (27 mL), and the solution was then cooled to −40° C. Iron (III) tris(acetylacetonate) (200 mg, 0.566 mmol) was added. Magnesium 4-phenylbutyl bromide, prepared beforehand, was then added dropwise over 10 minutes [Magnesium 4-phenylbutyl bromide was prepared as follows: 4-phenylbutyl bromide (2.96 g, 13.9 mmol) was dissolved in tetrahydrofuran (11 mL), and magnesium (337 mg, 13.9 mmol) was then added, and subsequently dissolved by stirring the mixture for 30 minutes with occasional warming by a dryer]. After 1.5 hours, ethyl acetate (100 mL) and a saturated aqueous solution (100 mL) of ammonium chloride were added. The outer temperature was then cooled to room temperature. After separation, the organic layer was washed with a saturated aqueous solution (100 mL) of sodium chloride. The solvent was then distilled off under reduced pressure. The residue was purified on Biotage (silica gel, n-hexane/ethyl acetate) to obtain 1.81 g (5.68 mmol, 42% yield) of methyl 9-oxo-13-phenyl-tridecanoate.

Workup

  1. concentrationconcentrated under reduced pressure
  2. dissolutionThe residue was dissolved in tetrahydrofuran (27 mL)
  3. temperaturethe solution was then cooled to −40° C
  4. customwas prepared
  5. dissolutionsubsequently dissolved
  6. stirringby stirring the mixture for 30 minutes
  7. temperaturewith occasional warming by a dryer]
  8. waitAfter 1.5 hours
  9. temperatureThe outer temperature was then cooled to room temperature
  10. customAfter separation
  11. washthe organic layer was washed with a saturated aqueous solution (100 mL) of sodium chloride
  12. distillationThe solvent was then distilled off under reduced pressure
  13. customThe residue was purified on Biotage (silica gel, n-hexane/ethyl acetate)

Sources & evidence

ORD record
ord-66e8d9ce360847dea5b9b26cfeffa233
Source dataset
uspto-grants-2016_02
Patent number
US09266853B2

Reaction notes

Loading…