4-Bromotoluene → Tolmetin

HRID 1389726ノート

反応式

HRID 1389726 の反応式
[Mg].Br[C:3]1[CH:8]=[CH:7][C:6]([CH3:9])=[CH:5][CH:4]=1.[C:10]([C:12]1[N:16]([CH3:17])[C:15]([CH2:18][C:19]([O-:21])=[O:20])=[CH:14][CH:13]=1)#N.[Ca].C(C1N(C)C(CC(O)=[O:33])=CC=1)#N>O.O1CCCC1>[CH3:17][N:16]1[C:12]([C:10]([C:3]2[CH:8]=[CH:7][C:6]([CH3:9])=[CH:5][CH:4]=2)=[O:33])=[CH:13][CH:14]=[C:15]1[CH2:18][C:19]([OH:21])=[O:20]

参加物

8

反応物 5

HCID 78054-BromotolueneHCID 5460341CalciumHCID 5462224MagnesiumHCID 155715345-cyano-1-methyl-1H-pyrrole-2-acetic acidHCID 202952105-Cyano-1-methylpyrrole-2-acetate

生成物 1

HCID 5509Tolmetin収率 63%

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒

実験手順

To a solution of the Grignard reagent prepared from 0.82 g. (36 mmol) of magnesium and 6.2 g. (36 mmol) of 4-bromotoluene in 15 ml. of anhydrous tetrahydrofuran was added 1.2 g. of solid material which contained about 6.0 mmol of 5-cyano-1-methylpyrrole-2-acetate as the calcium salt and some water which persisted after drying in a vacuum oven. Diphenyl ether (20 g.) was added, and the reaction mixture was heated to remove tetrahydrofuran by distillation until the temperature reached 110° C. The reaction mixture was then heated under reflux for two hours, cooled, and partitioned between ether and dilute aqueous hydrochloric acid. Following a work-up procedure similar to that described for Example 1, there was obtained 130 mg. (13%) of 5-cyano-1-methylpyrrole-2-acetic acid and 970 mg. (yield: 63%, 73% based on unrecovered cyanoacid) of 1-methyl-5-p-toluoylpyrrole-2-acetic acid as brown solids.

後処理

  1. customafter drying in a vacuum oven
  2. additionDiphenyl ether (20 g.) was added
  3. temperaturethe reaction mixture was heated
  4. customto remove tetrahydrofuran
  5. distillationby distillation until the temperature
  6. customreached 110° C
  7. temperatureThe reaction mixture was then heated
  8. temperatureunder reflux for two hours
  9. temperaturecooled
  10. custompartitioned between ether and dilute aqueous hydrochloric acid
  11. customthere was obtained 130 mg

出典と根拠

ORDレコード
ord-c2d22e67c8cd46d9a10ea662fba86948
出典データセット
uspto-grants-1981_01
特許番号
US04246176

反応ノート

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