Hydrochloric Acid → 4-Methylbenzene-1,3-dicarboxylic acid

HRID 397237ノート

反応式

HRID 397237 の反応式
Br[C:2]1[CH:3]=[C:4]([CH:8]=[CH:9][C:10]=1[CH3:11])[C:5]([OH:7])=[O:6].C[Mg+].[Br-].CC[O:17][CH2:18]C.[Li]CCCC.CCCCCC.Cl.C[OH:33]>C1COCC1>[CH3:11][C:10]1[CH:9]=[CH:8][C:4]([C:5]([OH:7])=[O:6])=[CH:3][C:2]=1[C:18]([OH:17])=[O:33]

参加物

9

反応物 7

HCID 313Hydrochloric AcidHCID 887MethanolHCID 3283Diethyl EtherHCID 8058HexaneHCID 821303-Bromo-4-methylbenzoic acidHCID 178418339ButyllithiumHCID 178418689HCID 178418689、化合物

生成物 1

HCID 5957504-Methylbenzene-1,3-dicarboxylic acid

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

反応条件

温度
-78 °C

実験手順

To THF (130 ml) solution of 3-bromo-4-methyl-benzoic acid (5.0 g, 23.25 mmol) under nitrogen and cooled to −78° C. (dryice/methanol) was added MeMgBr in ether (3.0 M, 8.5 ml, 25.57 mmol) at such a rate that the temperature did not exceed −75° C. The temperature was then allowed to rise to −60° C. and after gas evolution had ceased, the solution was cooled again to −78° C. BuLi in hexane (1.6 M, 29.06 ml, 46.50 mmol) was then added dropwise such that the temperature did not rise above −75° C. The mixture was then stirred at this temperature for 15 minutes before crushed dryice (4.4 g, 100 mmol) was added. The precipitate was vigorously stirred as the temperature was allowed to freely rise to ambient temperature. The mixture was made acidic using 6 N HCl and the solid material collected filteration, washed with diethyl ether and dried. Recrystallisation from water afforded off-white pure compound (81%) m.p. 296-298° C. (sublimed). NMR conforms to expected structure.

後処理

  1. customdid not exceed −75° C
  2. customto rise to −60° C.
  3. customdid not rise above −75° C
  4. custombefore crushed dryice (4.4 g, 100 mmol)
  5. additionwas added
  6. stirringThe precipitate was vigorously stirred as the temperature
  7. customto freely rise to ambient temperature
  8. customthe solid material collected filteration
  9. washwashed with diethyl ether
  10. customdried
  11. customRecrystallisation from water afforded off-white pure compound (81%) m.p. 296-298° C. (sublimed)

出典と根拠

ORDレコード
ord-5f555154eb014f07a1c4fbee0b2d32dc
出典データセット
uspto-grants-2003_08
特許番号
US06610269B1

反応ノート

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