海萝胶 → Methyl 4-cyano-2-cyclopropyl-7-fluoro-5-methyl-1,3-benzoxazole-6-carboxylate

HRID 17464

反应方程式

HRID 17464 反应方程式
[CH:1]1([C:4]2[O:5][C:6]3[C:7](=[C:9]([C:17]#[N:18])[C:10]([CH3:16])=[C:11]([CH:14]=[O:15])[C:12]=3[F:13])[N:8]=2)[CH2:3][CH2:2]1.O.O.P([O-])(O)(O)=O.[Na+].CC(=CC)C.Cl([O-])=O.[Na+].Cl.C[Si](C=[N+]=[N-])(C)C.[CH2:44]([O:46]CC)C.C(=O)([O-])O.[Na+]>C(O)(C)(C)C.C(OCC)(=O)C.O.O1CCCC1>[C:17]([C:9]1[C:7]2[N:8]=[C:4]([CH:1]3[CH2:2][CH2:3]3)[O:5][C:6]=2[C:12]([F:13])=[C:11]([C:14]([O:46][CH3:44])=[O:15])[C:10]=1[CH3:16])#[N:18]

参与物

12

反应物 7

HCID 313海萝胶HCID 105532-甲基-2-丁烯HCID 516892碳酸氢钠HCID 23159941trimethylsilyldiazomethane Et2OHCID 23668197亚氯酸钠HCID 23673460二水合磷酸二氢钠HCID 860975112-Cyclopropyl-7-fluoro-6-formyl-5-methyl-1,3-benzoxazole-4-carbonitrile

产物 1

HCID 68584578Methyl 4-cyano-2-cyclopropyl-7-fluoro-5-methyl-1,3-benzoxazole-6-carboxylate

试剂、催化剂与溶剂 4

HCID 962聚[6-[4-(4-氰基苯基)苯氧基]己基甲基丙烯酸酯]溶剂HCID 6386叔丁醇溶剂HCID 8028四氢呋喃溶剂HCID 8857乙酸乙酯溶剂

实验过程

2-Cyclopropyl-7-fluoro-6-formyl-5-methyl-1,3-benzoxazole-4-carbonitrile (I-182) (280 mg, 1.15 mmol) was dissolved in tert-butanol (8 ml), tetrahydrofuran (6 ml) and water (6 ml), then at 0° C., sodium dihydrogenphosphate dihydrate (268 mg, 1.72 mmol), 2-methyl-2-butene (515 μl, 4.59 mmol), then sodium chlorite (purity 80%, 389 mg, 3.44 mmol) were added. After stirring at room temperature for 6 hours, the solvent was evaporated away under reduced pressure. The residue was fractionated with ethyl acetate and aqueous 1 mol hydrochloric acid solution. The aqueous layer was further extracted twice with ethyl acetate. The organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. The insoluble matter was separated by filtration, then the solvent was evaporated away under reduced pressure. Benzene (6 ml) and methanol (2 ml) were added to it, then at 0° C., 2 M trimethylsilyldiazomethane/diethyl ether solution (1.15 ml, 2.29 mmol) was added. After stirring at room temperature for 18 hours, an aqueous saturated sodium hydrogencarbonate solution was added at 0° C. The solution was extracted three times with ethyl acetate. The organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate.

后处理

  1. customthe solvent was evaporated away under reduced pressure
  2. extractionThe aqueous layer was further extracted twice with ethyl acetate
  3. washwashed with saturated brine
  4. dry with materialdried over anhydrous sodium sulfate
  5. customThe insoluble matter was separated by filtration
  6. customthe solvent was evaporated away under reduced pressure
  7. additionBenzene (6 ml) and methanol (2 ml) were added to it
  8. stirringAfter stirring at room temperature for 18 hours
  9. extractionThe solution was extracted three times with ethyl acetate
  10. washwashed with saturated brine
  11. dry with materialdried over anhydrous sodium sulfate

来源与证据

ORD记录
ord-fa7d282936834f32bfd058f39b21932c
来源数据集
uspto-grants-2010_06
专利号
US07737166B2

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