Dichloromethane → HCID 21949596, compound

HRID 2215212Notes

Reaction equation

HRID 2215212 reaction equation
[CH:1]1([C:4]2[O:5][C:6]([CH3:11])=[C:7]([CH3:10])[N+:8]=2[O-])[CH2:3][CH2:2]1.O=P(Cl)(Cl)[Cl:14].[CH2:17]([Cl:19])[Cl:18]>>[Cl:14][CH:1]([C:4]1[O:5][C:6]([CH3:11])=[C:7]([CH3:10])[N:8]=1)[CH2:2][CH2:17][Cl:19].[Cl:18][CH2:10][C:7]1[N:8]=[C:4]([CH:1]2[CH2:3][CH2:2]2)[O:5][C:6]=1[CH3:11]

Participants

5

Reactant 3

HCID 6344DichloromethaneHCID 24813Phosphorus oxychlorideHCID 21949613HCID 21949613, compound

Product 2

HCID 21949596HCID 21949596, compoundHCID 21949671HCID 21949671, compound

Procedure

In step b], both products were isolated and characterized as follows: 36.27 g of 2-cyclopropyl-4,5-dimethyl-oxazole 3-oxide (152 mmol, prepared from cyclohexanecarboxaldehyde and diacetyl monooxime as described above) was dissolved in 555 ml of CH2Cl2 and treated dropwise with 16.75 ml of POCl3 (1.2 eq.). The reaction mixture was refluxed over night and then quenched by carefully pouring onto crashed ice/3N NaOH. Separation of the layers, additional extraction of the aqueous phase with CH2Cl2, washing with Na2CO3 and water, drying of the combined organic phase over sodium sulfate, evaporation of the solvents, and, finally, flash chromatography (SiO2, hexane/AcOEt=9/1) yielded in the less polar fractions 6.53 g of 2-(1,3-dichloro-propyl)-4,5-dimethyl-oxazole (MS: 207.1, 209.1 (M+)) and in the more polar ones 10.33 g of 4-chloromethyl-2-cyclopropyl-5-methyl-oxazole as colorless liquid, exhibiting in the 1H-NMR the typical signals at 4.42 ppm (s, 2H), 2.27 (s, 3H), 1.97–2.03 ppm (m, 1H), 0.98–1.04 ppm (m, 4H).

Workup

  1. customIn step b], both products were isolated
  2. temperatureThe reaction mixture was refluxed over night
  3. customquenched
  4. additionby carefully pouring
  5. customSeparation of the layers, additional extraction of the aqueous phase with CH2Cl2
  6. washwashing with Na2CO3 and water
  7. dry with materialdrying of the combined organic phase over sodium sulfate, evaporation of the solvents

Sources & evidence

ORD record
ord-c3d5400dcdd64b57a32db5f1ac6f07c6
Source dataset
uspto-grants-2006_09
Patent number
US07109225B2

Reaction notes

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