Tributylvinyltin → 1-Chloro-3-methyl-2-vinylnaphthalene

HRID 514000ノート

反応式

HRID 514000 の反応式
FC(F)(F)S(O[C:7]1[C:16]([CH3:17])=[CH:15][C:14]2[C:9](=[CH:10][CH:11]=[CH:12][CH:13]=2)[C:8]=1[Cl:18])(=O)=O.[CH2:21]([Sn](CCCC)(CCCC)C=C)[CH2:22]CC.[Cl-].[Li+]>C(OCC)(=O)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>[Cl:18][C:8]1[C:9]2[C:14](=[CH:13][CH:12]=[CH:11][CH:10]=2)[CH:15]=[C:16]([CH3:17])[C:7]=1[CH:21]=[CH2:22]

参加物

6

反応物 3

HCID 81998TributylvinyltinHCID 433294Lithium ChlorideHCID 866915311-Chloro-3-methylnaphthalen-2-yl trifluoromethanesulfonate

生成物 1

HCID 671260761-Chloro-3-methyl-2-vinylnaphthalene

試薬・触媒・溶媒 2

HCID 178418476HCID 178418476、化合物触媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
50 °C

実験手順

To a solution of 1-chloro-3-methylnaphthalen-2-yl trifluoromethanesulfonate (4C) (14.75 g, 45.43 mmol), tributyl(vinyl)tin (14.59 mL, 49.97 mmol) and lithium chloride (5.78 g, 136.29 mmol) was added bis(triphenylphosphine)palladium(II) dichloride under Ar. The reaction mixture was heated at 50° C. for 20 h, then heated at 90° C. for 8 h. The reaction mixture was than cooled to room temperature, diluted with ethyl acetate, washed with 5% lithium chloride solution (3×), brine and dried (MgSO4), filtered and then concentrated and purified by flash column chromatography (silica gel, 0 to 10% ethyl acetate/hexanes) to give 4D contaminated by organotin. The residue was dissolved in dichloromethane and stirred with 10% KF solution overnight. The resulting white mixture was filtered through a pad of Celite and extracted with dichloromethane (2×). The organic layer was concentrated and purified by flash column chromatography (silica gel, 0 to 10% ethyl acetate/hexanes) to give 4D as a pale yellow oil (10.1 g).

後処理

  1. temperatureheated at 90° C. for 8 h
  2. temperaturethan cooled to room temperature
  3. washwashed with 5% lithium chloride solution (3×), brine
  4. dry with materialdried (MgSO4)
  5. filtrationfiltered
  6. concentrationconcentrated
  7. custompurified by flash column chromatography (silica gel, 0 to 10% ethyl acetate/hexanes)

出典と根拠

ORDレコード
ord-3e12b4fff65a480c906bf826f3f23587
出典データセット
uspto-grants-2015_08
特許番号
US09102614B2

反応ノート

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