Acetic Acid → Tert-butyl 4-hydroxy-4-(4-methoxycarbonyl-6-nitrophenyl)-2-butynoate

HRID 357644

반응식

HRID 357644 반응식
[C:1]([O:5][C:6]([CH3:9])([CH3:8])[CH3:7])(=[O:4])[C:2]#[CH:3].C([N-]C(C)C)(C)C.[Li+].CCCCCCC.O1CCCC1.C(C1C=CC=CC=1)C.[CH3:38][O:39][C:40]([C:42]1[CH:49]=[CH:48][C:45]([CH:46]=[O:47])=[C:44]([N+:50]([O-:52])=[O:51])[CH:43]=1)=[O:41].C(O)(=O)C>O1CCCC1.O>[OH:47][CH:46]([C:45]1[C:44]([N+:50]([O-:52])=[O:51])=[CH:43][C:42]([C:40]([O:39][CH3:38])=[O:41])=[CH:49][CH:48]=1)[C:3]#[C:2][C:1]([O:5][C:6]([CH3:9])([CH3:8])[CH3:7])=[O:4]

참가 물질

8

반응물 5

HCID 176Acetic AcidHCID 543038tert-Butyl propiolateHCID 2724682Lithium diisopropylamideHCID 3457222Methyl 4-formyl-3-nitrobenzoateHCID 22742125Tetrahydrofuran heptane ethylbenzol

생성물 1

HCID 18937575Tert-butyl 4-hydroxy-4-(4-methoxycarbonyl-6-nitrophenyl)-2-butynoate수율 106.2%

시약·촉매·용매 2

HCID 962Water용매HCID 8028Tetrahydrofuran용매3회

실험 절차

To a solution of tert-butyl propiolate (3.54 ml, 25.81 mmole) in tetrahydrofuran (60 ml) was added at -70° C. under the argon atmosphere a solution of 2.0M lithium diisopropylamide in a heptane-tetrahydrofuran-ethylbenzene mixture (13.0 ml, 26 mmole), and the mixture was stirred for 30 minutes. The reaction mixture was then added to a solution of 4-methoxycarbonyl-2-nitrobenzaldehyde (4.5 g, 21.5 mmole) in tetrahydrofuran (100 ml), and the mixture was further stirred at -75° C. for 5 minutes. After a solution of acetic acid (3.2 ml, 53.3 mmole) in tetrahydrofuran (10 ml) and water were added, the reaction mixture was extracted with ethyl acetate (400 ml). The organic layer was washed with dilute hydrochloric acid, a saturated aqueous sodium hydrogen carbonate solution and a saturated aqueous saline in this sequence. After the organic layer was dried over anhydrous magnesium sulfate, the solvent was removed under reduced pressure to give the crude product of tert-butyl 4-hydroxy-4-(4-methoxycarbonyl-6-nitrophenyl)-2-butynoate as a brown oil (7.655 g).

후처리

  1. stirringthe mixture was further stirred at -75° C. for 5 minutes
  2. extractionthe reaction mixture was extracted with ethyl acetate (400 ml)
  3. washThe organic layer was washed with dilute hydrochloric acid
  4. dry with materialAfter the organic layer was dried over anhydrous magnesium sulfate
  5. customthe solvent was removed under reduced pressure

출처 및 근거

ORD 기록
ord-152cc7b5fab546ad89babf657ef4fcae
출처 데이터셋
uspto-grants-1998_11
특허 번호
US05840895

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