Hydrochloric Acid → 4,4-Dimethyl-6-hydroxymethyl-2-cyclohexen-1-one

HRID 1699433

반응식

HRID 1699433 반응식
C(NC(C)C)(C)C.C([Li])CCC.[Li].[CH3:14][C:15]1([CH3:22])[CH2:20][CH2:19][C:18](=[O:21])[CH:17]=[CH:16]1.[CH2:23]=[O:24].Cl>O1CCCC1.CCCCCC>[CH3:14][C:15]1([CH3:22])[CH2:20][CH:19]([CH2:23][OH:24])[C:18](=[O:21])[CH:17]=[CH:16]1

참가 물질

9

반응물 6

HCID 313Hydrochloric AcidHCID 712Formaldehyde2회HCID 7912DiisopropylamineHCID 1368392-Cyclohexen-1-one, 4,4-dimethyl-HCID 3028194LithiumHCID 178418339Butyllithium

생성물 1

HCID 183201824,4-Dimethyl-6-hydroxymethyl-2-cyclohexen-1-one수율 68%

시약·촉매·용매 2

HCID 8028Tetrahydrofuran용매HCID 8058Hexane용매

반응 조건

온도
0 °C

실험 절차

To a solution of diisopropylamine (7.27 g, 7 mmol) in anhydrous tetrahydrofuran (THF) was added drop wise a hexane solution (1.62 mol/l) of n-butyllithium (44.4 ml, 70 mmol) at −78° C. The solution was warmed to 0° C. and stirred for 1 hr at this temperature. After thus prepared lithium diisopopylamide solution was again cooled to −78° C., 4,4-dimethyl-2-cyclohexen-1-one (7.5 g, 60 mmol) was added dropwise and stirring was continued for 1 hr. Then, gaseous formaldehyde, generated by a thermal decomposition of paraformaldehyde (5 g) over an oil bath, was blown through the solution with a gentle stream of dry nitrogen gas and the reaction mixture was stirred for 2 hr. After standing over night at room temperature, 1N hydrochloric acid was added until the solution became weak acid. The solvent was removed and the residue was extracted with ether. After drying over anhydrous sodium sulfate and removal of the solvent, a mixture of 4,4-dimethyl-6-methylene-2-cyclohexen-1-one and 4,4-dimethyl-6-hydroxymethyl-2-cyclohexen-1-one was obtained (7.03 g). This mixture (3.0 g) was treated in refixing benzene for 2 hr in the presence of catalytic amount of anhydrous p-toluenegulfonic acid and molecular sieve 3A (4 g). The solution was neutralized with 1N sodium bicarbonate and washed with brine. After drying over anhydrous sodium sulfate and removal of the solvent, crude 4,4-dimethyl-6-methylene-2-cyclohexen-1-one (Yoshixol) was obtained (2.35 g, overall yield 68%). The analytical sample was available. 2-cyclohexen-1-one was obtained (2.35 g, overall yield 68%). The analytical sample was available after purification by column chromatography or kugelrohr distillation but yield was much lowered. This NMR analysis of Yoshixol is following: IR(neat): 1670(C═O), 1620(C═C) cm-1. 1H NMR (60 MHZ, CCL4), d1.15 (s,6H,C(CH3)2), 2.57 (bs,2H,CH2), 5.20, 5.93 (2 m,2H,CH2═), 5.87 (d,J=10,1H,2-H), 6.63 (d,J=10 Hz,3-H).

후처리

  1. stirringstirring
  2. waitwas continued for 1 hr
  3. stirringthe reaction mixture was stirred for 2 hr
  4. waitAfter standing over night at room temperature
  5. customThe solvent was removed
  6. extractionthe residue was extracted with ether
  7. dry with materialAfter drying over anhydrous sodium sulfate and removal of the solvent
  8. additiona mixture of 4,4-dimethyl-6-methylene-2-cyclohexen-1-one

출처 및 근거

ORD 기록
ord-4814b785ab2c419daa6f47b177011b8b
출처 데이터셋
uspto-grants-2002_02
특허 번호
US06346551B1

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