Trimethylsilylacetylene → 6-Ethynyl-7-methoxy-1,1-dimethyl-3,4-dihydro-1H-naphthalen-2-one

HRID 2275268ノート

反応式

HRID 2275268 の反応式
Br[C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][C:11]=1[O:12][CH3:13])[C:8]([CH3:15])([CH3:14])[C:7](=[O:16])[CH2:6][CH2:5]2.[CH3:17][CH:18](C1C=C(C(C)C)C(C2C=CC=CC=2P(C2CCCCC2)C2CCCCC2)=C(C(C)C)C=1)C.C[Si](C#C)(C)C>C(#N)C.C(OCC)(=O)C>[C:17]([C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][C:11]=1[O:12][CH3:13])[C:8]([CH3:15])([CH3:14])[C:7](=[O:16])[CH2:6][CH2:5]2)#[CH:18]

参加物

6

反応物 3

HCID 66111TrimethylsilylacetyleneHCID 111557942-Dicyclohexylphosphino-2',4',6'-triisoprophylbiphenylHCID 545785436-Bromo-7-methoxy-1,1-dimethyl-3,4-dihydronaphthalen-2(1H)-one

生成物 1

HCID 866638296-Ethynyl-7-methoxy-1,1-dimethyl-3,4-dihydro-1H-naphthalen-2-one収率 430.1%

試薬・触媒・溶媒 2

HCID 6342Acetonitrile溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
85 °C

実験手順

6-Bromo-7-methoxy-1,1-dimethyl-3,4-dihydro-1H-naphthalen-2-one (1 g) was dissolved in acetonitrile (50 ml), added with PdCl2(CH3CN)2 (45 mg), X-phos (168 mg), CsCO3 (1.2 g) and trimethylsilylacetylene (0.9 ml), and the mixture was stirred at 85° C. for 2 hrs. The reaction mixture was diluted with ethyl acetate (100 ml). The organic layer was washed twice with 10% brine and concentrated under reduced pressure. The resulting residues were dissolved in THF (10 ml), added with the THF solution (4 ml) comprising tetrabutylammonium fluoride and stirred at room temperature for 1 hr. The reaction mixture was diluted with ethyl acetate (100 ml). The organic layer was washed twice with 10% brine and concentrated under reduced pressure. The resulting residues were purified by silica gel column (n-hexane/ethyl acetate=9/1) to obtain the title compound (346 mg, two step yield 43%).

後処理

  1. washThe organic layer was washed twice with 10% brine
  2. concentrationconcentrated under reduced pressure
  3. dissolutionThe resulting residues were dissolved in THF (10 ml)
  4. additionadded with the THF solution (4 ml)
  5. stirringstirred at room temperature for 1 hr
  6. additionThe reaction mixture was diluted with ethyl acetate (100 ml)
  7. washThe organic layer was washed twice with 10% brine
  8. concentrationconcentrated under reduced pressure
  9. customThe resulting residues were purified by silica gel column (n-hexane/ethyl acetate=9/1)

出典と根拠

ORDレコード
ord-3efccaaa131846bd910a189d9ebb834d
出典データセット
uspto-grants-2015_09
特許番号
US09126931B2

反応ノート

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