N,N,N',N'-Tetramethylethylenediamine → alpha,alpha-Bis(2,4-dichlorophenyl)-1-(methoxymethyl)imidazole-2-methanol

HRID 261959

반응식

HRID 261959 반응식
[CH3:1][O:2][CH2:3][N:4]1[CH:8]=[CH:7][N:6]=[CH:5]1.CN(C)CCN(C)C.C([Li])CCC.[Cl:22][C:23]1[CH:38]=[C:37]([Cl:39])[CH:36]=[CH:35][C:24]=1[C:25]([C:27]1[CH:32]=[CH:31][C:30]([Cl:33])=[CH:29][C:28]=1[Cl:34])=[O:26]>O1CCCC1>[Cl:22][C:23]1[CH:38]=[C:37]([Cl:39])[CH:36]=[CH:35][C:24]=1[C:25]([C:27]1[CH:32]=[CH:31][C:30]([Cl:33])=[CH:29][C:28]=1[Cl:34])([C:5]1[N:4]([CH2:3][O:2][CH3:1])[CH:8]=[CH:7][N:6]=1)[OH:26]

참가 물질

6

반응물 4

HCID 8037N,N,N',N'-TetramethylethylenediamineHCID 883591-(methoxymethyl)-1H-imidazoleHCID 22352856Bis(2,4-dichlorophenyl)methanoneHCID 178418339Butyllithium

생성물 1

HCID 12433909alpha,alpha-Bis(2,4-dichlorophenyl)-1-(methoxymethyl)imidazole-2-methanol

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매2회

반응 조건

온도
-60 °C

실험 절차

To a solution of 7.6 g (0.0676 mol) of 1-(methoxymethyl)imidazole and 8.1 g (0.0676 mol) of N,N,N',N'-tetramethylethylenediamine in 150 ml of anhydrous tetrahydrofuran were added dropwise under a nitrogen atmosphere at -60° C., 43 ml. (0.070 mol) of n-butyl lithium solution (15% in n-hexane). The solution was stirred at -60° C. for one hour. Then 23 g (0.0676 mol) of 2,2',4,4'-tetrachlorobenzophenone (prepared as described by S. D. Wilson and Yuan Ying Cheng, J. Org. Chem. 5, 223-6 (1940)) in 150 ml. of anhydrous tetrahydrofuran were added dropwise. The solution was stirred another hour at -60° C. and one night at room temperature. The reaction mixture was decomposed with 100 ml. of water and extracted with diethyl ether. The organic phase was dried over sodium sulphate and concentrated and the residue was extracted with a mixture of 2N hydrochloric acid and diethyl ether on which a solid substance was formed, which was crystallised from a mixture of isopropyl alcohol and diethyl ether. The product appeared to be the hydrochloride of the desired compound, contaminated with the compound without methoxymethyl group. Ammonia and diethyl ether were added to liberate the free base. The ethereal phase was concentrated and the residue was four times crystallised from a mixture of isopropyl alcohol and petroleum ether (boiling range 60°-80° C.). α,α-Bis-(2,4-dichlorophenyl)-1-(methoxymethyl)imidazole-2-methanol was obtained. Melting point 145.5°-146° C.

후처리

  1. stirringThe solution was stirred another hour at -60° C. and one night at room temperature
  2. extractionof water and extracted with diethyl ether
  3. dry with materialThe organic phase was dried over sodium sulphate
  4. concentrationconcentrated
  5. extractionthe residue was extracted with a mixture of 2N hydrochloric acid and diethyl ether on which a solid substance
  6. customwas formed
  7. customwhich was crystallised from a mixture of isopropyl alcohol and diethyl ether
  8. additionAmmonia and diethyl ether were added
  9. concentrationThe ethereal phase was concentrated
  10. customcrystallised from a mixture of isopropyl alcohol and petroleum ether (boiling range 60°-80° C.)

출처 및 근거

ORD 기록
ord-b73baf68f2ab4960870eef7494f9fc7b
출처 데이터셋
uspto-grants-1979_05
특허 번호
US04152441

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