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

HRID 357644

反応式

HRID 357644 の反応式
[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]

参加物

8

反応物 5

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

生成物 1

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

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒3 回

実験手順

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).

後処理

  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

出典と根拠

ORDレコード
ord-152cc7b5fab546ad89babf657ef4fcae
出典データセット
uspto-grants-1998_11
特許番号
US05840895

関連ノート

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