Bis(eta-cyclopentadienyl) iron → 1,1'-Bis[2,4,8,10-tetrakis(tert-butyl)-dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl]ferrocene

HRID 399346

反応式

HRID 399346 の反応式
[CH-:1]1[CH:5]=[CH:4][CH:3]=[CH:2]1.[CH-:6]1[CH:10]=[CH:9][CH:8]=[CH:7]1.[Fe+2:11].C([Li])CCC.CN(C)CCN(C)C.[C:25]([C:29]1[CH:52]=[C:51]([C:53]([CH3:56])([CH3:55])[CH3:54])[C:32]2[O:33][P:34](Cl)[O:35][C:36]3[C:41]([C:42]([CH3:45])([CH3:44])[CH3:43])=[CH:40][C:39]([C:46]([CH3:49])([CH3:48])[CH3:47])=[CH:38][C:37]=3[C:31]=2[CH:30]=1)([CH3:28])([CH3:27])[CH3:26]>CCCCCC.O1CCCC1>[C:46]([C:39]1[CH:40]=[C:41]([C:42]([CH3:45])([CH3:44])[CH3:43])[C:36]2[O:35][P:34]([C-:1]3[CH:5]=[CH:4][CH:3]=[CH:2]3)[O:33][C:32]3[C:51]([C:53]([CH3:55])([CH3:54])[CH3:56])=[CH:52][C:29]([C:25]([CH3:28])([CH3:27])[CH3:26])=[CH:30][C:31]=3[C:37]=2[CH:38]=1)([CH3:49])([CH3:48])[CH3:47].[C-:6]1([P:34]2[O:35][C:36]3[C:41]([C:42]([CH3:43])([CH3:44])[CH3:45])=[CH:40][C:39]([C:46]([CH3:48])([CH3:49])[CH3:47])=[CH:38][C:37]=3[C:31]3[CH:30]=[C:29]([C:25]([CH3:28])([CH3:27])[CH3:26])[CH:52]=[C:51]([C:53]([CH3:56])([CH3:55])[CH3:54])[C:32]=3[O:33]2)[CH:10]=[CH:9][CH:8]=[CH:7]1.[Fe+2:11]

参加物

7

反応物 4

HCID 7611Bis(eta-cyclopentadienyl) ironHCID 8037N,N,N',N'-TetramethylethylenediamineHCID 109836102,4,8,10-Tetra-tert-butyl-6-chlorodibenzo[d,f][1,3,2]dioxaphosphepineHCID 178418339Butyllithium

生成物 1

HCID 1317208751,1'-Bis[2,4,8,10-tetrakis(tert-butyl)-dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl]ferrocene収率 47%

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒2 回HCID 8058Hexane溶媒

実験手順

To a solution of 9.5 g (50 mmol) of ferrocene in 250 mL of hexane is added dropwise 67 mL of a 1.6M solution of n-butyl lithium at ambient temperature. The reaction mixture is stirred for 20 minutes and then to the resultant red suspension is added 12.0 g (103 mmol) of N,N,N',N'-tetramethylethylenediamine. A slight exotherm of 10° C. is observed. The reaction mixture is then heated at reflux for two hours during which time an orange suspension forms. The reaction mixture is cooled to room temperature and 100 mL of tetrahydrofuran is then added. The reaction mixture is cooled to -40° C. Then to the cooled reaction mixture is added dropwise a solution of 51.8 g (109 mmol) of 2,4,8,10-tetrakis(tert-butyl)-6-chloro-dibenzo[d,f][1,3,2]dioxaphosphepin in 100 mL of tetrahydrofuran. The reaction mixture is allowed to warm to ambient temperature after the addition is complete. The reaction mixture is then heated at reflux for six hours. After cooling, the mixture is filtered and the filtrate is concentrated under reduced pressure. The residue formed is triturate with 150 mL of hexane. The resultant solid is recrystallized from acetonitrile/tetrahydrofuran mixture to give 25 g (47% yield) of a light brown solid.

後処理

  1. customA slight exotherm of 10° C.
  2. temperatureThe reaction mixture is then heated
  3. temperatureat reflux for two hours during which time an orange suspension forms
  4. temperatureThe reaction mixture is cooled to -40° C
  5. customThen to the cooled reaction mixture
  6. temperatureto warm to ambient temperature
  7. additionafter the addition
  8. temperatureThe reaction mixture is then heated
  9. temperatureat reflux for six hours
  10. temperatureAfter cooling
  11. filtrationthe mixture is filtered
  12. concentrationthe filtrate is concentrated under reduced pressure
  13. customThe residue formed
  14. customis triturate with 150 mL of hexane
  15. customThe resultant solid is recrystallized from acetonitrile/tetrahydrofuran mixture

出典と根拠

ORDレコード
ord-f1bed6f8468948ecad9265df06b35205
出典データセット
uspto-grants-1998_10
特許番号
US05817850

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