抗氧剂264 → Tert-butyl [3-(2-tert-butyl-4-cyano-5-methyl-6-phenyl-1,3-benzoxazol-7-yl)-2-cyclopentenyl]carbamate

HRID 17268

反应方程式

HRID 17268 反应方程式
Br[C:2]1[C:3]([C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)=[C:4]([CH3:17])[C:5]([C:15]#[N:16])=[C:6]2[C:10]=1[O:9][C:8]([C:11]([CH3:14])([CH3:13])[CH3:12])=[N:7]2.[C:24]([O:28][C:29]([NH:31][CH:32]1[CH2:36][CH2:35][C:34]([Sn](CCCC)(CCCC)CCCC)=[CH:33]1)=[O:30])([CH3:27])([CH3:26])[CH3:25].C(C1C(O)=C(C(C)(C)C)C=C(C)C=1)(C)(C)C>Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.O1CCOCC1>[C:11]([C:8]1[O:9][C:10]2[C:2]([C:34]3[CH2:35][CH2:36][CH:32]([NH:31][C:29](=[O:30])[O:28][C:24]([CH3:26])([CH3:25])[CH3:27])[CH:33]=3)=[C:3]([C:18]3[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=3)[C:4]([CH3:17])=[C:5]([C:15]#[N:16])[C:6]=2[N:7]=1)([CH3:12])([CH3:13])[CH3:14]

参与物

6

反应物 3

HCID 31404抗氧剂264HCID 15630117Tert-butyl (3-tri-n-butylstannylcyclopent-2-enyl)carbamateHCID 685849237-Bromo-2-tert-butyl-5-methyl-6-phenyl-1,3-benzoxazole-4-carbonitrile

产物 1

HCID 86630798Tert-butyl [3-(2-tert-butyl-4-cyano-5-methyl-6-phenyl-1,3-benzoxazol-7-yl)-2-cyclopentenyl]carbamate收率 61%

试剂、催化剂与溶剂 2

HCID 178418476HCID 178418476，化合物催化剂HCID 312751,4-二氧六环溶剂

实验过程

A 1,4-dioxane (20 ml) solution of 7-bromo-2-tert-butyl-5-methyl-6-phenyl-1,3-benzoxazole-4-carbonitrile (I-9) (414 mg, 1.12 mmol), 1-(N-tert-butoxycarbonylamino)-3-tri-n-butylstannyl-2-cyclopentene (530 mg, 1.12 mmol), bis(triphenylphosphine)palladium(II) chloride (39.3 mg, 56.1 μmol), 2,6-di-tert-butyl-p-cresol (28 mg, 127 μmol) was refluxed overnight. After cooling, the reaction liquid was concentrated under reduced pressure, the residue was purified by silica gel column chromatography (n-hexane:ethyl acetate=10:1→8:1) to obtain tert-butyl [3-(2-tert-butyl-4-cyano-5-methyl-6-phenyl-1,3-benzoxazol-7-yl)-2-cyclopentenyl]carbamate (322 mg, 61%) as a yellow white solid. A part of it (270 mg) was stirred in hydrochloric acid/1,4-dioxane solution, followed by purifying by silica gel column chromatography to obtain 7-(3-amino-cyclopent-1-enyl)-2-tert-butyl-5-methyl-6-phenyl-1,3-benzoxazole-4-carbonitrile (157 mg). This was dissolved in methanol (4 ml), aqueous formalin solution (324 μl, 46-38%, 4.23 mmol), sodium cyanoborohydride (80 mg, 1.27 mmol) and acetic acid (87 μl, 1.52 mmol) were successively added, followed by stirring at room temperature for 2.5 hours. The reaction liquid was concentrated under reduced pressure, aqueous 10% sodium carbonate solution was added to the residue, the organic matter was extracted with chloroform. The organic layer was washed with saturated brine, then dried over anhydrous magnesium sulfate, the solvent was concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (chloroform:methanol=40:1) to obtain the entitled compound (84.8 mg, 50%) as a yellow solid.

后处理

  1. temperatureAfter cooling
  2. customthe reaction liquid
  3. concentrationwas concentrated under reduced pressure
  4. customthe residue was purified by silica gel column chromatography (n-hexane:ethyl acetate=10:1→8:1)

来源与证据

ORD记录
ord-11e8b026f97046df91548ee431019828
来源数据集
uspto-grants-2010_06
专利号
US07737166B2

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