3-Methyl-2-nitrobenzoic acid → (1Z)-3-imino-3-(3-methyl-4-nitrophenyl)-1-[2-(propyloxy)phenyl]prop-1-en-1-amine

HRID 422045ノート

反応式

HRID 422045 の反応式
[CH3:1][C:2]1[CH:3]=[C:4]([C:11]([N:13]2C=CN=C2)=O)[CH:5]=[CH:6][C:7]=1[N+:8]([O-:10])=[O:9].C(N1C=CN=C1)([N:20]1C=CN=C1)=O.CC1C([N+]([O-])=O)=C(C=CC=1)C(O)=O.[Li].[CH2:44]([O:47][C:48]1[CH:53]=[CH:52][CH:51]=[CH:50][C:49]=1[C:54](=O)[CH3:55])[CH2:45][CH3:46]>O1CCCC1>[NH:13]=[C:11]([C:4]1[CH:5]=[CH:6][C:7]([N+:8]([O-:10])=[O:9])=[C:2]([CH3:1])[CH:3]=1)/[CH:55]=[C:54](/[C:49]1[CH:50]=[CH:51][CH:52]=[CH:53][C:48]=1[O:47][CH2:44][CH2:45][CH3:46])\[NH2:20]

参加物

6

反応物 4

HCID 215753-Methyl-2-nitrobenzoic acidHCID 682631,1'-CarbonyldiimidazoleHCID 574454481-[2-(Propyloxy)phenyl]ethanone lithium saltHCID 574454491-[(3-methyl-4-nitrophenyl)carbonyl]-1H-imidazole2 回

生成物 1

HCID 86633656(1Z)-3-imino-3-(3-methyl-4-nitrophenyl)-1-[2-(propyloxy)phenyl]prop-1-en-1-amine収率 46%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

実験手順

A solution of 1,1,1-trimethyl-N-(trimethylsilyl)silanamine (2.70 g, 16.8 mmol) in dry tetrahydrofuran (40 mL) was cooled to −78° C., at which time was added n-butyllithium 1.6 N (10.5 mL, 16.8 mmol) followed by commercially available acetophenone (5.50 g, 31 mmol). The reaction mixture was stirred for 1 h at −78° C. to give the 1-[2-(propyloxy)phenyl]ethanone lithium salt. Concurrent with the above was prepared a solution of 1-[(3-methyl-4-nitrophenyl)carbonyl]-1H-imidazole by adding 1,1′-carbonylbis(1H-imidazole) (2.70 g, 16.8 mmol) to 3-methyl-2-nitrobenzoic acid (2.50 g, 14.0 mmol) in tetrahydrofuran (40 mL) at room temperature. To the 1-[2-(propyloxy)phenyl]ethanone lithium salt solution was slowly added the 1-[(3-methyl-4-nitrophenyl)carbonyl]-1H-imidazole solution at −78° C. and the mixture was allowed to warm to room temperature. The reaction mixture was quenched with hydrochloric acid 1.0 N (100 mL) and the product was extracted with ethyl acetate (150 mL). The organic phase was washed with brine (80 mL), dried over anhydrous sodium sulfate, filtered and concentrated in vacuo. The residue was purified by flash chomatography (SiO2, ethyl acetate/hexanes 1:2), followed by re-crystallization from diethyl ether and hexanes (1:5) to afford (1Z)-3-imino-3-(3-methyl-4-nitrophenyl)-1-[2-(propyloxy)phenyl]prop-1-en-1-amine (2.20 g, 46%).

後処理

  1. customThe reaction mixture was quenched with hydrochloric acid 1.0 N (100 mL)
  2. extractionthe product was extracted with ethyl acetate (150 mL)
  3. washThe organic phase was washed with brine (80 mL)
  4. dry with materialdried over anhydrous sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customThe residue was purified by flash chomatography (SiO2, ethyl acetate/hexanes 1:2)
  8. customfollowed by re-crystallization from diethyl ether and hexanes (1:5)

出典と根拠

ORDレコード
ord-c7136c1339e7475783f0c97485affc18
出典データセット
uspto-grants-2012_01
特許番号
US08101625B2

反応ノート

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