Formaldehyde → 7-bromo-2-methylene-3,4-dihydronaphthalen-1(2H)-one

HRID 1911004ノート

反応式

HRID 1911004 の反応式
[Br:1][C:2]1[CH:11]=[C:10]2[C:5]([CH2:6][CH2:7][CH2:8][C:9]2=[O:12])=[CH:4][CH:3]=1.F[C:14](F)(F)C([O-])=O.C[NH2+]C1C=CC=CC=1.C=O>C1COCC1>[Br:1][C:2]1[CH:11]=[C:10]2[C:5]([CH2:6][CH2:7][C:8](=[CH2:14])[C:9]2=[O:12])=[CH:4][CH:3]=1

参加物

5

反応物 3

HCID 712FormaldehydeHCID 2527317-Bromo-1,2,3,4-tetrahydronaphthalen-1-oneHCID 2724109N-Methylanilinium trifluoroacetate

生成物 1

HCID 111839757-bromo-2-methylene-3,4-dihydronaphthalen-1(2H)-one収率 40.4%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

実験手順

A solution of 7-bromo-3,4-dihydronaphthalen-1(2H)-one (2.00 g, 8.89 mmol) in THF (50 mL) was added to a mixture of N-methylanilinium trifluoroacetate (2.95 g, 13.3 mmol) and paraformaldehyde (1.20 g, 40.0 mmol) at rt. The resulting mixture was heated at reflux for 6 hours. The oil bath was removed and the mixture was allowed to cool to rt. Diethyl ether was added to the reaction mixture, which induced the separation of a red gum. The ethereal solution was decanted from the red gum into a separatory funnel and washed with half-saturated sodium bicarbonate solution. The red gum was triturated with diethyl ether, and the resulting ethereal solution was then used to extract the washing water. The combined organic layers were dried over magnesium sulfate. Filtration and concentration of the organic layer afforded a heavy red oil. The oil was purified using silica gel column chromatography (20:1 hexanes/EtOAc) to afford 7-bromo-2-methylene-3,4-dihydronaphthalen-1(2H)-one (0.850 g, 3.59 mmol, 40% yield) as a thick viscous yellow oil. 1H NMR (400 MHz, chloroform-d) δ 8.23 (d, J=2.0 Hz, 1H), 7.60 (dd, J=8.2, 2.1 Hz, 1H), 7.16 (d, J=8.3 Hz, 1H), 6.26 (q, J=1.3 Hz, 1H), 5.50 (q, J=1.7 Hz, 1H), 3.01-2.91 (m, 2H), 2.91-2.82 (m, 2H).

後処理

  1. temperatureThe resulting mixture was heated
  2. temperatureat reflux for 6 hours
  3. customThe oil bath was removed
  4. additionDiethyl ether was added to the reaction mixture, which
  5. customthe separation of a red gum
  6. customThe ethereal solution was decanted from the red gum into a separatory funnel
  7. washwashed with half-saturated sodium bicarbonate solution
  8. customThe red gum was triturated with diethyl ether
  9. extractionto extract the washing water
  10. dry with materialThe combined organic layers were dried over magnesium sulfate
  11. filtrationFiltration and concentration of the organic layer
  12. customafforded a heavy red oil
  13. customThe oil was purified

出典と根拠

ORDレコード
ord-925a6183470c491c9902a0fa8ea83d42
出典データセット
uspto-grants-2013_12
特許番号
US08604024B2

反応ノート

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