Water → (4-Diethoxythiophosphoryloxyimino-cyclohexa-2,5-dienylidene)-phenyl-acetonitrile

HRID 1018886

反応式

HRID 1018886 の反応式
[OH:1][N:2]=[C:3]1[CH:8]=[CH:7][C:6](=[C:9]([C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)[C:10]#[N:11])[CH:5]=[CH:4]1.[P:18](Cl)([O:23][CH2:24][CH3:25])([O:20][CH2:21][CH3:22])=[S:19].C(N(CC)CC)C.O>O1CCCC1>[CH2:21]([O:20][P:18]([O:1][N:2]=[C:3]1[CH:8]=[CH:7][C:6](=[C:9]([C:12]2[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=2)[C:10]#[N:11])[CH:5]=[CH:4]1)([O:23][CH2:24][CH3:25])=[S:19])[CH3:22]

参加物

6

反応物 4

HCID 962WaterHCID 8471TriethylamineHCID 17305O,O-diethyl phosphorochloridothioateHCID 3468332-(4-(Hydroxyimino)cyclohexa-2,5-dien-1-ylidene)-2-phenylacetonitrile

生成物 1

HCID 53671907(4-Diethoxythiophosphoryloxyimino-cyclohexa-2,5-dienylidene)-phenyl-acetonitrile

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

実験手順

8 g (36 mmol) of (4-Hydroxyimino-cyclohexa-2,5-dienylidene)-phenyl-acetonitrile, prepared as described in example 1.1, are dissolved in 90 ml of tetrahydrofuran (THF) and cooled in an ice bath. After adding 7.5 g (39 mmol) of diethyl chlorothiophosphate to the solution, 5.4 g (54 mmol) of triethylamine are added dropwise, keeping the temperature below 5° C. The reaction mixture is gradually warmed to room temperature, and stirred overnight. The reaction mixture is poured into 100 ml of water, and extracted with ethyl acetate. The organic phase is washed with 0.1N hydrochloric acid solution, water, and sodium chloride solution. The organic phase is dried over MgSO4, the solvent is distilled off, and the residue is purified by flash chromatography on silica gel with ethyl acetate—hexane (1:3) as eluent. The product is a yellow solid, with mp 66-82° C. The structure is confirmed by the 1H-NMR spectrum (CDCl3); δ [ppm]: 1.32-1.42 (m, 6H), 4.21-4.37 (m, 4H), 6.87(Z)/6.98(E) (dd, 1H), 7.17(Z)/-7.19(E) (dd, 1H), 7.26(E)17.37(Z) (dd, 1H), 7.43-7.54 (m, 6H). 1H-NMR reveals that the product is a 56:44 mixture of Z and E isomers. The signals are tentatively assigned to Z and E isomers.

後処理

  1. temperaturecooled in an ice bath
  2. additionare added dropwise
  3. customthe temperature below 5° C
  4. extractionextracted with ethyl acetate
  5. washThe organic phase is washed with 0.1N hydrochloric acid solution, water, and sodium chloride solution
  6. dry with materialThe organic phase is dried over MgSO4
  7. distillationthe solvent is distilled off
  8. customthe residue is purified by flash chromatography on silica gel with ethyl acetate—hexane (1:3) as eluent
  9. additiona 56:44 mixture of Z and E isomers

出典と根拠

ORDレコード
ord-614d88f86e0d4711a627a27850ba58bc
出典データセット
uspto-grants-2002_11
特許番号
US06485886B1

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