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

HRID 452178

반응식

HRID 452178 반응식
[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

참가 물질

10

반응물 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

생성물 2

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

시약·촉매·용매 3

HCID 962Water용매HCID 6228Dimethylformamide용매2회HCID 8028Tetrahydrofuran용매

반응 조건

온도
80 °C

실험 절차

[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%).

후처리

  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)

출처 및 근거

ORD 기록
ord-98bb4fba1536491a84161ca2f5714aaa
출처 데이터셋
uspto-grants-2013_07
특허 번호
US08486980B2

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