Methanol → [(E)-3-(4-formyl-3,5-dimethylphenyl)-allyl]-phosphonic acid diethyl ester

HRID 1360783

反応式

HRID 1360783 の反応式
CO[C:3](=O)[CH2:4][CH2:5][C:6]1[CH:11]=[C:10]([CH3:12])[C:9]([C:13]2NC3C=C(C4OC(NC5C=CC(OC)=CC=5)=NN=4)C=CC=3N=2)=[C:8]([CH3:36])[CH:7]=1.N([O-])=O.[Na+].C[OH:43].C([P:47](=[O:54])([O:51][CH2:52][CH3:53])[O:48][CH2:49][CH3:50])C=C>[H+].[B-](F)(F)(F)F.O.CC([O-])=O.CC([O-])=O.[Pd+2]>[CH2:49]([O:48][P:47]([CH2:3]/[CH:4]=[CH:5]/[C:6]1[CH:7]=[C:8]([CH3:36])[C:9]([CH:13]=[O:43])=[C:10]([CH3:12])[CH:11]=1)(=[O:54])[O:51][CH2:52][CH3:53])[CH3:50]

参加物

8

反応物 4

HCID 887MethanolHCID 573014Diethyl allylphosphonateHCID 23668193Sodium NitriteHCID 669668163-(4-{6-[5-(4-Methoxy-phenylamino)-[1,3,4]oxadiazol-2-yl]-1H-benzoimidazol-2-yl}-3,5-dimethyl-phenyl)-propionic acid methyl ester

生成物 1

HCID 86632823[(E)-3-(4-formyl-3,5-dimethylphenyl)-allyl]-phosphonic acid diethyl ester

試薬・触媒・溶媒 3

HCID 167845palladium(II) acetate触媒HCID 962Water溶媒HCID 28118Tetrafluoroboric acid溶媒

反応条件

温度
0 °C

実験手順

To a suspension of 4-amino-2,6-dimethylbenzaldehyde (3.0 g, 20.1 mmol) (Example 1-60, step B) in enough 42% HBF4 to be stirred at 0° C. was added a solution of NaNO2 (1.39 g, 20.1 mmol) in water (10 ml) slowly. After 30 min at 0° C., MeOH (50 mL) was added and followed by Pd(OAc)2 (677 mg) and diethyl allylphosphonate (5.38 g, 30.2 mmol). The reaction mixture was heated at 80° C. for 30 min and the suspension was filtered through Celite, washed with CH2Cl2. The filtrate was extracted with CH2Cl2 and the combined organic layers were washed with water, brine, dried with MgSO4, and filtered. The solvent was removed under reduced pressure and the residue was purified by flash chromatography using a gradient of heptane/EtOAc (10:1 to 5:1 then followed by 100% EtOAc) to give the title compound as a light yellow oil. MS: m/z 311 (M+1).

後処理

  1. temperatureThe reaction mixture was heated at 80° C. for 30 min
  2. filtrationthe suspension was filtered through Celite
  3. washwashed with CH2Cl2
  4. extractionThe filtrate was extracted with CH2Cl2
  5. washthe combined organic layers were washed with water, brine
  6. dry with materialdried with MgSO4
  7. filtrationfiltered
  8. customThe solvent was removed under reduced pressure
  9. customthe residue was purified by flash chromatography

出典と根拠

ORDレコード
ord-66bd870ee3284d83b6b1ff5d37893e27
出典データセット
uspto-grants-2011_02
特許番号
US07879850B2

関連ノート

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