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

HRID 1980014

반응식

HRID 1980014 반응식
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

참가 물질

8

반응물 6

HCID 1140TolueneHCID 78451,3-Butadiene5회HCID 31215Triethyl phosphiteHCID 220593Propenylamine, N-isobutylidene-2-methyl-HCID 5362487SulfurHCID 16683109Ethoxydiethylaluminium

생성물 1

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

시약·촉매·용매 1

HCID 9834912Nickel(II) acetylacetonate촉매

실험 절차

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 under protective gas (argon), whereupon the solution is saturated at 20°-25° C. with 1,3-butadiene. There is subsequently slowly added dropwise, whilst a gentle flow of 1,3-butadiene is being introduced, 3.9 g (0.03 mol) of ethoxy-diethylaluminum. The mixture is heated to 60° C. and, as a strong stream of 1,3-butadiene is being fed in, 122.5 g (0.98 mol) of N-isobutylidene-2-methylpropenylamine [produced by reaction of isobutyraldehyde with ammonia according to J. Org. Chem., 26, 1822-25 (1961)] is added dropwise, within 45 minutes, in such a manner that the introduced butadiene is exactly used up. After completion of the dropwise addition, stirring is maintained for one further hour at 60° C., with the continuous feeding in of 1,3-butadiene, and the temperature is then lowered to 20°-25° C. The catalyst is inactivated by the addition of 0.32 g (0.01 mol) of sulfur, and the reaction solution is distilled. Subsequent fine distillation yields 212.5 g (0.912 mol) of 3,3-dimethyl-12-isopropyl-1-aza-1,5,9-cyclododecatriene; b.p. 54°-55° C./1.33 Pa; nD20 =1.4832.

후처리

  1. additionis being introduced
  2. additionis added dropwise, within 45 minutes
  3. additionAfter completion of the dropwise addition
  4. customis then lowered to 20°-25° C
  5. distillationthe reaction solution is distilled
  6. distillationSubsequent fine distillation

출처 및 근거

ORD 기록
ord-ff0138aa7a004e2887cbb8875f391ebc
출처 데이터셋
uspto-grants-1984_11
특허 번호
US04484004

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