Ammonia → 1-(2,6,6-Trimethyl-1-cyclohexen-1-yl)-2-buten-1-one

HRID 1579752Notes

Reaction equation

HRID 1579752 reaction equation
N.[CH3:2][C:3]1[CH:7]=[C:6]([C:8]2[C:13]([CH3:15])([CH3:14])[CH2:12][CH2:11][CH2:10][C:9]=2[CH3:16])[O:5]N=1.[Na].[Cl-].[NH4+]>C(O)(C)(C)C.O1CCCC1>[CH3:16][C:9]1[CH2:10][CH2:11][CH2:12][C:13]([CH3:14])([CH3:15])[C:8]=1[C:6](=[O:5])[CH:7]=[CH:3][CH3:2]

Participants

7

Reactant 4

HCID 222AmmoniaHCID 25517Ammonium ChlorideHCID 30160553-Methyl-5-(2,6,6-trimethyl-1-cyclohexen-1-yl)isoxazoleHCID 5360545Sodium

Product 1

HCID 320521-(2,6,6-Trimethyl-1-cyclohexen-1-yl)-2-buten-1-oneYield 85.3%

Reagents, catalysts & solvents 2

HCID 6386tert-ButanolSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a mixture of liquid ammonia (500 ml), tetrahydrofuran (30 ml), tert-butanol (2.796 g) and 3-methyl-5-[2,6,6-trimethyl-cyclohex-1-en-1-yl]-isoxazole (2.593 g; 12.65 millimoles), kept under stirring, there was added sodium metal until the solution acquired a steady blue colour. The reaction mixture was stirred for 15 more minutes, solid ammonium chloride was added thereto until complete discolouration, and the ammonia was then evaporated under a stream of argon. After having added 50 ml of ether and 300 ml of a concentrated ammonium chloride solution in water, the mixture was extracted with two fractions of 300 ml of ether and 150 ml of chloroform, respectively. The combined organic extracts were dried over magnesium sulphate, concentrated under reduced pressure and dissolved in 50 ml of toluene containing traces of p-toluene-sulphonic acid. The thus obtained mixture was refluxed for 24 hours, concentrated in vacuo and then distilled to yield 2.074 g (yield 84%) of 2,6,6-trimethyl-1-[but-2-enoyl]-cyclohex-1-ene; b.p. 55°/0.04 Torr. The analytical data of the obtained product were identical with those of a pure sample prepared by one of the known methods.

Workup

  1. additionwas added
  2. customuntil complete discolouration, and the ammonia was then evaporated under a stream of argon
  3. additionAfter having added 50 ml of ether and 300 ml of a concentrated ammonium chloride solution in water
  4. extractionthe mixture was extracted with two fractions of 300 ml of ether and 150 ml of chloroform
  5. dry with materialThe combined organic extracts were dried over magnesium sulphate
  6. concentrationconcentrated under reduced pressure
  7. dissolutiondissolved in 50 ml of toluene containing traces of p-toluene-sulphonic acid
  8. temperatureThe thus obtained mixture was refluxed for 24 hours
  9. concentrationconcentrated in vacuo
  10. distillationdistilled

Sources & evidence

ORD record
ord-1132f3059315406191ee2db2877a56e3
Source dataset
uspto-grants-1976_01
Patent number
US03931323

Reaction notes

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