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

HRID 1579751Notes

Reaction equation

HRID 1579751 reaction equation
N.[CH3:2][C:3]1[CH2:8][CH2:7][CH2:6][C:5]([CH3:10])([CH3:9])[C:4]=1[C:11](=[O:16])[CH2:12][C:13](N)=[CH2:14].[Na].[Cl-].[NH4+]>C(O)(C)(C)C.O1CCCC1>[CH3:2][C:3]1[CH2:8][CH2:7][CH2:6][C:5]([CH3:9])([CH3:10])[C:4]=1[C:11](=[O:16])[CH:12]=[CH:13][CH3:14]

Participants

7

Reactant 4

HCID 222AmmoniaHCID 25517Ammonium ChlorideHCID 5360545SodiumHCID 215694802,6,6-Trimethyl-1-[3-amino-but-3-enoyl]-cyclohex-1-ene

Product 1

HCID 320521-(2,6,6-Trimethyl-1-cyclohexen-1-yl)-2-buten-1-oneYield 19%

Reagents, catalysts & solvents 2

HCID 6386tert-ButanolSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a mixture of liquid ammonia (250 ml), anhydrous tetrahydrofuran (15 ml), tert-butanol (0.358 g) and 1.002 g (4.84 millimoles) of 2,6,6-trimethyl-1-[3-amino-but-3-enoyl]-cyclohex-1-ene, 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 and solid ammonium chloride was added thereto until complete discolouration and the ammonia was then evaporated under a stream of argon. After having added to the mixture 25 ml of ether and 75 ml of a concentrated ammonium chloride solution in water, the mixture was extracted with two fractions of 200 ml of ether and 100 ml of chloroform, respectively. The combined organic extracts were dried over anhydrous sodium sulphate, concentrated under reduced pressure and the thus obtained residue (1.038 g) was dissolved in 10 ml of toluene. The said solution was then refluxed overnight, then concentrated under reduced pressure. The thus obtained residue was subjected to a fractional distillation to yield 0.177 g of 2,6,6-trimethyl-1-[but-2-enoyl]-cyclohex-1-ene. The analytical data of the obtained product were identical with those of a pure sample prepared by one of the known methods (cf. Swiss Pat. No. 505,773).

Workup

  1. additionwas added
  2. customuntil complete discolouration and the ammonia was then evaporated under a stream of argon
  3. additionAfter having added to the mixture 25 ml of ether and 75 ml of a concentrated ammonium chloride solution in water
  4. extractionthe mixture was extracted with two fractions of 200 ml of ether and 100 ml of chloroform
  5. dry with materialThe combined organic extracts were dried over anhydrous sodium sulphate
  6. concentrationconcentrated under reduced pressure
  7. dissolutionthe thus obtained residue (1.038 g) was dissolved in 10 ml of toluene
  8. temperatureThe said solution was then refluxed overnight
  9. concentrationconcentrated under reduced pressure
  10. distillationThe thus obtained residue was subjected to a fractional distillation

Sources & evidence

ORD record
ord-157593b7a29a411da68f22a7f96da507
Source dataset
uspto-grants-1976_01
Patent number
US03931323

Reaction notes

Loading…