Toluene → 3,3-Dimethyl-12-isopropyl-1-aza-1,5,9-cyclododecatriene

HRID 1155796

Reaction equation

HRID 1155796 reaction equation
P(OCC)(OCC)O[CH2:3]C.C=CC=C.C(O[Al](CC)CC)C.[CH:23](=[N:27][CH:28]=[C:29]([CH3:31])[CH3:30])[CH:24]([CH3:26])[CH3:25].[S].[C:33]1([CH3:39])[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1>C/C(/[O-])=C/C(C)=O.C/C(/[O-])=C/C(C)=O.[Ni+2]>[CH3:30][C:29]1([CH3:3])[CH2:31][CH:38]=[CH:37][CH2:36][CH2:35][CH:34]=[CH:33][CH2:39][CH:23]([CH:24]([CH3:26])[CH3:25])[N:27]=[CH:28]1

Participants

8

Reactant 6

HCID 1140TolueneHCID 78451,3-Butadiene4×HCID 31215Triethyl phosphiteHCID 220593Propenylamine, N-isobutylidene-2-methyl-HCID 5362487SulfurHCID 16683109Ethoxydiethylaluminium

Product 1

HCID 5575123,3-Dimethyl-12-isopropyl-1-aza-1,5,9-cyclododecatrieneYield 9,120%

Reagents, catalysts & solvents 1

HCID 9834912Nickel(II) acetylacetonateCatalyst

Conditions

Temperature
60 °C

Procedure

Under a blanketing gas (argon), 2.57 g (0.01 mol) of nickel acetylacetonate and 1.66 g (0.01 mol) of triethyl phosphite are dissolved in 120 g of absolute toluene, after which the solution is saturated at 20°-25° C. with 1,3-butadiene. 3.9 g (0.03 mol) of ethoxydiethylaluminium are then slowly added dropwise, whilst passing in a gentle stream of 1,3-butadiene, and during the addition the original green colour changes in the course of 5 minutes to light red. The reaction mixture is heated to 60° C. and 122.5 g (0.98 mol) of N-isobutylidene-2-methylpropenylamine [prepared by reacting isobutyraldehyde with ammonia in accordance with J. Org. Chem., 26, 1822-25 (1961); boiling point 139°-141° C./760 mm Hg] are added dropwise in the course of 45 minutes, whilst passing in a vigorous stream of 1,3-butadiene, at such a rate that the butadiene passed in is just consumed. After the dropwise addition has ended, the mixture is stirred for a further 1 hour at 60° C. whilst continuously passing in 1,3-butadiene, and is then cooled to 20°-25° C. In order to deactivate the catalyst, 0.32 g (0.01 mol) of sulphur is added to the reaction solution and the solution is distilled. A first fraction, which in addition to 120 g of toluene also contains traces of triethyl phosphite and butadiene dimers (gas chromatogram), is obtained at a bath temperature of up to 50° C./1 mm Hg. Subsequent fine distillation yields 212.5 g (0.912 mol) of 3,3-dimethyl-12-isopropyl-1-aza-1,5,9-cyclododecatriene; yield 93% of theory, based on converted N-isobutylidene-2-methylpropenylamine (conversion 100%); boiling point 54°-55° C./0.01 mm Hg; nD20 =1.4832.

Workup

  1. additionduring the addition the original green colour changes in the course of 5 minutes to light red
  2. customin is just consumed
  3. additionAfter the dropwise addition
  4. temperatureis then cooled to 20°-25° C
  5. additionis added to the reaction solution
  6. distillationthe solution is distilled
  7. additionA first fraction, which in addition to 120 g of toluene also contains traces of triethyl phosphite and butadiene dimers (gas chromatogram)
  8. customis obtained at a bath temperature of up to 50° C./1 mm Hg
  9. distillationSubsequent fine distillation

Sources & evidence

ORD record
ord-ea6f6f535a8b4e1fa87e1739e29789bb
Source dataset
uspto-grants-1982_06
Patent number
US04332969

Linked notes

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