Acetic Acid → [2-Amino-5-(trifluoromethyl)benzyl][3,5-bis(trifluoromethyl)benzyl]amine

HRID 217477

反応式

HRID 217477 の反応式
[NH2:1][CH2:2][C:3]1[CH:8]=[C:7]([C:9]([F:12])([F:11])[F:10])[CH:6]=[CH:5][C:4]=1[NH2:13].CN1CCOCC1.[F:21][C:22]([F:36])([F:35])[C:23]1[CH:24]=[C:25]([CH:28]=[C:29]([C:31]([F:34])([F:33])[F:32])[CH:30]=1)[CH2:26]Br.C(O)(=O)C>C(COC)OC.CCOCC.CCCCCC.[Hg]>[NH2:13][C:4]1[CH:5]=[CH:6][C:7]([C:9]([F:11])([F:12])[F:10])=[CH:8][C:3]=1[CH2:2][NH:1][CH2:26][C:25]1[CH:28]=[C:29]([C:31]([F:33])([F:34])[F:32])[CH:30]=[C:23]([C:22]([F:21])([F:35])[F:36])[CH:24]=1

参加物

9

反応物 4

HCID 176Acetic AcidHCID 79724-MethylmorpholineHCID 1225733,5-Bis(trifluoromethyl)benzyl bromideHCID 265967342-(Aminomethyl)-4-(trifluoromethyl)aniline

生成物 1

HCID 59343853[2-Amino-5-(trifluoromethyl)benzyl][3,5-bis(trifluoromethyl)benzyl]amine収率 24%

試薬・触媒・溶媒 4

HCID 23931Mercury触媒HCID 3283Diethyl Ether溶媒HCID 8058Hexane溶媒HCID 80711,2-Dimethoxyethane溶媒

実験手順

In a 500-mL flask equipped with a septum inlet, magnetic stirring bar, and condenser leading to a mercury bubbler was placed 22.8 g (0.12 mol) of [2-(aminomethyl)-4-(trifluoromethyl)phenyl]amine in 218 mL dimethoxyethane. To this reaction flask with stirring was added 26 mL (0.24 mol) N-methylmorpholine and 24 mL (0.13 mol) 3,5-bis(trifluoromethyl)benzyl bromide. The contents were heated to and maintained at reflux under nitrogen for 12 hours. Afterwards, TLC analysis revealed a minor amount of starting material remaining. The contents were cooled to room temperature, diluted with ether and transferred to a separatory funnel and washed with water and brine, dried over magnesium sulfate, filtered and concentrated to afford an oil. The oil was dissolved in hexane, cooled in an ice bath and acetic acid was added slowly while stirring to precipitate solids. The solids were filtered, dissolved in ether, and cooled in an ice bath and stirred while saturated sodium bicarbonate was added slowly until basic. The contents were transferred to a separatory funnel and washed with brine, dried over magnesium sulfate, filtered, and concentrated to give 12 g [2-amino-5-(trifluoromethyl)benzyl][3,5-bis(trifluoromethyl)benzyl]amine as an orange oil. In addition the hexane mother liquor contained significant amounts of product and byproducts. This liquor was concentrated to yield dark yellow oil that was used without further purification in the following step.

後処理

  1. customIn a 500-mL flask equipped with a septum inlet, magnetic stirring bar, and condenser
  2. temperatureThe contents were heated to and
  3. temperaturemaintained
  4. temperatureat reflux under nitrogen for 12 hours
  5. customtransferred to a separatory funnel
  6. washwashed with water and brine
  7. dry with materialdried over magnesium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customto afford an oil
  11. temperaturecooled in an ice bath
  12. stirringwhile stirring
  13. customto precipitate solids
  14. filtrationThe solids were filtered
  15. dissolutiondissolved in ether
  16. temperaturecooled in an ice bath
  17. stirringstirred while saturated sodium bicarbonate
  18. additionwas added slowly until basic
  19. customThe contents were transferred to a separatory funnel
  20. washwashed with brine
  21. dry with materialdried over magnesium sulfate
  22. filtrationfiltered
  23. concentrationconcentrated

出典と根拠

ORDレコード
ord-0d0a92c28e1f462bb7d91e1fc0d72d82
出典データセット
uspto-grants-2012_06
特許番号
US08193365B2

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