2,7-Dibromo-9-(bis-methylsulfanyl-methylene)fluorene → 2,7-Dibromo-9-(tridecan-7-ylidene)-9H-fluorene

HRID 496319ノート

反応式

HRID 496319 の反応式
[Br:1][C:2]1[CH:14]=[CH:13][C:12]2[C:11]3[C:6](=[CH:7][C:8]([Br:15])=[CH:9][CH:10]=3)[C:5](=[C:16](SC)SC)[C:4]=2[CH:3]=1.[CH2:21]([Mg]Br)[CH2:22][CH2:23][CH2:24][CH2:25][CH3:26]>C1COCC1.C(OCC)C>[Br:1][C:2]1[CH:14]=[CH:13][C:12]2[C:11]3[C:6](=[CH:7][C:8]([Br:15])=[CH:9][CH:10]=3)[C:5](=[C:16]([CH2:13][CH2:14][CH2:2][CH2:3][CH2:4][CH3:12])[CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH3:26])[C:4]=2[CH:3]=1

参加物

5

反応物 2

HCID 121516122,7-Dibromo-9-(bis-methylsulfanyl-methylene)fluoreneHCID 178444609HCID 178444609、化合物

生成物 1

HCID 121516152,7-Dibromo-9-(tridecan-7-ylidene)-9H-fluorene

試薬・触媒・溶媒 2

HCID 3283Diethyl Ether溶媒HCID 8028Tetrahydrofuran溶媒3 回

反応条件

温度
0 °C

実験手順

To a solution of 2,7-dibromo-9-(bis-methylsulfanyl-methylene)fluorene (5.1 g, 12 mmol) in dry THF (80 ml) at 0° C. under nitrogen, was added a solution of lithium tetrachlorocuprate (3 ml of a 0.1M solution in THF, 3 mol %). A solution of hexylmagnesium bromide (13 ml of a 2.0M solution in diethyl ether, 0.026 mol) was added dropwise over 30 min. The reaction was stirred for 2 h, during which time the internal temperature rose to 15° C. The reaction was cooled to 0° C. and further lithium tetrachlorocuprate (1 ml of a 0.1M solution in THF, 1 mol %) was added. The reaction was then stirred for 24 h at 25° C., before quenching and workup as above. Yield (61%). M.p 47-49° C. 1H and 13C NMR spectra as expected. M+=504 (t). Anal. Calcd. For C26H32Br2: C, 61.9; H, 6.4; N, 0.0. Found C, 61.8; H, 6.1; N, <0.3.

後処理

  1. customrose to 15° C
  2. stirringThe reaction was then stirred for 24 h at 25° C.
  3. custombefore quenching
  4. customYield (61%)
  5. customM.p 47-49° C

出典と根拠

ORDレコード
ord-2398ce7e16e1425fafefeb6897fa6b2a
出典データセット
uspto-grants-2005_09
特許番号
US06943275B2

反応ノート

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