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

HRID 17268

反応式

HRID 17268 の反応式
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]

参加物

6

反応物 3

HCID 314042,6-Di-tert-butyl-4-methylphenolHCID 15630117Tert-butyl (3-tri-n-butylstannylcyclopent-2-enyl)carbamateHCID 685849237-Bromo-2-tert-butyl-5-methyl-6-phenyl-1,3-benzoxazole-4-carbonitrile

生成物 1

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

試薬・触媒・溶媒 2

HCID 178418476HCID 178418476、化合物触媒HCID 312751,4-Dioxane溶媒

実験手順

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.

後処理

  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)

出典と根拠

ORDレコード
ord-11e8b026f97046df91548ee431019828
出典データセット
uspto-grants-2010_06
特許番号
US07737166B2

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