反応 #4562

ord-a80267a6bf2b4049a16df416b032a024

反応方程式

O
water
COc1ccc(C[C@H]2C(=O)N[C@H](C)C(=O)N(C)[C@@H]3Cc4ccc(cc4)Oc4cc(ccc4O)C[C@H](C(=O)N[C@@H](C)C(=O)N[C@@H](C)C(=O)N2C)N(C)C3=O)cc1.COc1ccc(C[C@H]2C(=O)N[C@H](C)C(=O)N(C)[C@@H]3Cc4ccc(cc4)Oc4cc(ccc4O)C[C@H](C(=O)N[C@@H](C)C(=O)N[C@@H](C)C(=O)N2C)N(C)C3=O)cc1.COc1ccc(C[C@H]2C(=O)N[C@H](C)C(=O)N(C)[C@@H]3Cc4ccc(cc4)Oc4cc(ccc4O)C[C@H](C(=O)N[C@@H](C)C(=O)N[C@@H](C)C(=O)N2C)N(C)C3=O)cc1.COc1ccc(C[C@H]2C(=O)N[C@H](C)C(=O)N(C)[C@@H]3Cc4ccc(cc4)Oc4cc(ccc4O)C[C@H](C(=O)N[C@@H](C)C(=O)N[C@@H](C)C(=O)N2C)N(C)C3=O)cc1.O.O.O.O.O
TPC-A
→
COc1ccc(C[C@H]2C(=O)N[C@H](C)C(=O)N(C)[C@@H]3Cc4ccc(cc4)Oc4cc(ccc4O)C[C@H](C(=O)N[C@@H](C)C(=O)N[C@@H](C)C(=O)N2C)N(C)C3=O)cc1.COc1ccc(C[C@H]2C(=O)N[C@H](C)C(=O)N(C)[C@@H]3Cc4ccc(cc4)Oc4cc(ccc4O)C[C@H](C(=O)N[C@@H](C)C(=O)N[C@@H](C)C(=O)N2C)N(C)C3=O)cc1.COc1ccc(C[C@H]2C(=O)N[C@H](C)C(=O)N(C)[C@@H]3Cc4ccc(cc4)Oc4cc(ccc4O)C[C@H](C(=O)N[C@@H](C)C(=O)N[C@@H](C)C(=O)N2C)N(C)C3=O)cc1.COc1ccc(C[C@H]2C(=O)N[C@H](C)C(=O)N(C)[C@@H]3Cc4ccc(cc4)Oc4cc(ccc4O)C[C@H](C(=O)N[C@@H](C)C(=O)N[C@@H](C)C(=O)N2C)N(C)C3=O)cc1.O.O.O.O.O
TPC-A
Oc1ccccc1
phenol

反応物

O
water
COc1ccc(C[C@H]2C(=O)N[C@H](C)C(=O)N(C)[C@@H]3Cc4ccc(cc4)Oc4cc(ccc4O)C[C@H](C(=O)N[C@@H](C)C(=O)N[C@@H](C)C(=O)N2C)N(C)C3=O)cc1.COc1ccc(C[C@H]2C(=O)N[C@H](C)C(=O)N(C)[C@@H]3Cc4ccc(cc4)Oc4cc(ccc4O)C[C@H](C(=O)N[C@@H](C)C(=O)N[C@@H](C)C(=O)N2C)N(C)C3=O)cc1.COc1ccc(C[C@H]2C(=O)N[C@H](C)C(=O)N(C)[C@@H]3Cc4ccc(cc4)Oc4cc(ccc4O)C[C@H](C(=O)N[C@@H](C)C(=O)N[C@@H](C)C(=O)N2C)N(C)C3=O)cc1.COc1ccc(C[C@H]2C(=O)N[C@H](C)C(=O)N(C)[C@@H]3Cc4ccc(cc4)Oc4cc(ccc4O)C[C@H](C(=O)N[C@@H](C)C(=O)N[C@@H](C)C(=O)N2C)N(C)C3=O)cc1.O.O.O.O.O
TPC-A

試薬

O=[N+]([O-])[O-].O=[N+]([O-])[O-].[Cu+2]
copper nitrate

溶媒

CC(=O)O
acetic acid
CC(=O)O
acetic acid

反応条件

詳細条件
See reaction.notes.procedure_details.

後処理

  1. 1
    workup.STIRRINGof stirring
  2. 2
    その他the reaction
  3. 3
    抽出the product was extracted with ethyl acetate
  4. 4
    洗浄After washing the
  5. 5
    抽出extract with saturated sodium chloride solution
  6. 6
    その他drying the
  7. 7
    抽出extract over anhydrous magnesium sulfate
  8. 8
    workup.DISTILLATIONthe extract was subjected to distillation
  9. 9
    その他to remove solvent
  10. 10
    その他in vacuo and the product was recrystallized from methanol

実験手順

In 3 ml of acetic acid, 100 mg of TPC-A was dissolved and a solution of copper nitrate (40 mg) in 3 ml of acetic acid was added under stirring. When the color change of the reaction solution from blue to green took place under the continuation of stirring, water was added to cease the reaction and the product was extracted with ethyl acetate. After washing the extract with saturated sodium chloride solution and drying the extract over anhydrous magnesium sulfate, the extract was subjected to distillation to remove solvent, in vacuo and the product was recrystallized from methanol to obtain nitro compound of TPC-A at α-position of phenol thereof (108 mg) as yellow needle crystal having m.p. of 244°-250° C. (decomp) and [α]D22 of -232° (CHCl3).

出典

DOI: 10.6084/m9.figshare.5104873.v1特許: US04725578uspto-grants-1988_02