Ammonium Chloride → HCID 59504645, compound

HRID 1260183Notes

Reaction equation

HRID 1260183 reaction equation
C([Mg]Cl)(C)C.I[C:7]1[CH:14]=[CH:13][C:10]([C:11]#[N:12])=[CH:9][CH:8]=1.[O:15]=[C:16]1[CH2:19][O:18][CH2:17]1.[Cl-].[NH4+]>C(OCC)C.C1COCC1.O>[OH:15][C:16]1([C:7]2[CH:14]=[CH:13][C:10]([C:11]#[N:12])=[CH:9][CH:8]=2)[CH2:19][O:18][CH2:17]1

Participants

8

Reactant 4

HCID 25517Ammonium ChlorideHCID 764674-IodobenzonitrileHCID 150242543-OxetanoneHCID 178418918HCID 178418918, compound

Product 1

HCID 59504645HCID 59504645, compound

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

Under inert conditions, 11 ml (21.8 mmol) of a 2 M solution of isopropylmagnesium chloride in diethyl ether were added dropwise at −40° C. to a solution of 5.0 g (21.8 mmol) of 4-iodobenzonitrile in 100 ml of anhydrous THF. After the mixture had been stirred at the same temperature for 1.5 h, it was cooled down to −78° C. and, with the aid of a cannula, was slowly added to a solution, likewise cooled to −78° C., of 2.95 g (32.7 mmol, 80% in dichloromethane) of 3-oxooxetane [G. Wuitschik et al., Angew. Chem. Int. Ed. Engl. 2006, 45 (46), 7736-7739] in 100 ml of anhydrous THF. After the addition had ended, the reaction mixture was stirred first at −78° C. for 10 min, then at 0° C. for 2 h and finally at RT for 30 min. Then a few ml of saturated aqueous ammonium chloride solution were added. Subsequently, the solvent was substantially removed on a rotary evaporator. The residue obtained was diluted with 200 ml of water and extracted three times with approx. 200 ml each time of ethyl acetate. The combined organic extracts were washed successively with water and saturated sodium chloride solution. After drying over anhydrous magnesium sulphate, the mixture was filtered and the solvent was removed on a rotary evaporator. The resulting crude product was purified by crystallization from 10:1 cyclohexane/ethyl acetate. 2.42 g (63% of theory) of the title compound were obtained.

Workup

  1. additionwas slowly added to a solution
  2. additionAfter the addition
  3. stirringthe reaction mixture was stirred first at −78° C. for 10 min
  4. waitat 0° C. for 2 h
  5. waitfinally at RT for 30 min
  6. customSubsequently, the solvent was substantially removed on a rotary evaporator
  7. customThe residue obtained
  8. extractionextracted three times with approx. 200 ml each time of ethyl acetate
  9. washThe combined organic extracts were washed successively with water and saturated sodium chloride solution
  10. dry with materialAfter drying over anhydrous magnesium sulphate
  11. filtrationthe mixture was filtered
  12. customthe solvent was removed on a rotary evaporator
  13. customThe resulting crude product was purified by crystallization from 10:1 cyclohexane/ethyl acetate

Sources & evidence

ORD record
ord-9bf8d6bf29174f15a8ec61cb98c69120
Source dataset
uspto-grants-2013_06
Patent number
US08470811B2

Reaction notes

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