Hydrochloric Acid → (Z)-2-(2-hydroxymethyl-10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-ylidene)propiononitrile

HRID 452178

反応式

HRID 452178 の反応式
[H-].[Na+].[C:3]([CH:5](P(=O)(OCC)OCC)[CH3:6])#[N:4].O=[C:16]1[C:22]2[CH:23]=[CH:24][C:25]([C:27](OCC)=[O:28])=[CH:26][C:21]=2[CH2:20][CH2:19][C:18]2[CH:32]=[CH:33][CH:34]=[CH:35][C:17]1=2.[BH4-].[Li+].Cl>CN(C=O)C.C1COCC1.O>[OH:28][CH2:27][C:25]1[CH:24]=[CH:23][C:22]2/[C:16](=[C:5](\[CH3:6])/[C:3]#[N:4])/[C:17]3[CH:35]=[CH:34][CH:33]=[CH:32][C:18]=3[CH2:19][CH2:20][C:21]=2[CH:26]=1.[OH:28][CH2:27][C:25]1[CH:24]=[CH:23][C:22]2/[C:16](=[C:5](/[CH3:6])\[C:3]#[N:4])/[C:17]3[CH:35]=[CH:34][CH:33]=[CH:32][C:18]=3[CH2:19][CH2:20][C:21]=2[CH:26]=1

参加物

10

反応物 5

HCID 313Hydrochloric AcidHCID 24758Sodium hydrideHCID 282103Diethyl (1-cyanoethyl)phosphonateHCID 4148881Lithium borohydrideHCID 67211051ethyl 10,11-dihydro-5-oxo-5H-dibenzo[a,d]cycloheptene-2-carboxylate

生成物 2

HCID 67210308(Z)-2-(2-hydroxymethyl-10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-ylidene)propiononitrile収率 27%HCID 67210474(E)-2-(2-hydroxymethyl-10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-ylidene)propiononitrile収率 27%

試薬・触媒・溶媒 3

HCID 962Water溶媒HCID 6228Dimethylformamide溶媒2 回HCID 8028Tetrahydrofuran溶媒

反応条件

温度
80 °C

実験手順

[step 2] To a solution of sodium hydride (60%, 0.856 g, 21.4 mmol) and diethyl 1-cyanoethylphosphonate (4.09 g, 21.4 mmol) in DMF (35 mL) was added a solution of ethyl 10,11-dihydro-5-oxo-5H-dibenzo[a,d]cycloheptene-2-carboxylate (3.0 g, 10.7 mmol) obtained in step 1 in DMF (10 mL) under ice-cooling, and the mixture was stirred at 80° C. for 3 hr. Water was added to the mixture, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give a residue. The obtained residue was dissolved in THF (50 mL), lithium borohydride (1.11 g, 50.9 mmol) was added, and the mixture was stirred at 50° C. for 5 hr. The mixture was neutralized with 2 mol/L hydrochloric acid, and extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (chloroform/ethyl acetate=98/2) to give (E)-2-(2-hydroxymethyl-10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-ylidene)propiononitrile (0.730 g, 27%) and (Z)-2-(2-hydroxymethyl-10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-ylidene)propiononitrile (0.728 g, 27%).

後処理

  1. temperaturecooling
  2. extractionthe mixture was extracted with ethyl acetate
  3. dry with materialThe organic layer was dried over anhydrous magnesium sulfate
  4. concentrationconcentrated under reduced pressure
  5. customto give a residue
  6. stirringthe mixture was stirred at 50° C. for 5 hr
  7. extractionextracted with ethyl acetate
  8. dry with materialThe organic layer was dried over anhydrous magnesium sulfate
  9. concentrationconcentrated under reduced pressure
  10. customThe residue was purified by silica gel column chromatography (chloroform/ethyl acetate=98/2)

出典と根拠

ORDレコード
ord-98bb4fba1536491a84161ca2f5714aaa
出典データセット
uspto-grants-2013_07
特許番号
US08486980B2

関連ノート

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