Hydrochloric Acid → Aminophenazone hydrochloride

HRID 962918

反応式

HRID 962918 の反応式
[ClH:1].[CH3:2][C:3]#[N:4].CC1N(C)N([C:13]2[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=2)C(=O)C=1N(C)C.[CH3:22][N:23]1[C:27](C)=[C:26](NC)C(=O)N1C1C=CC=CC=1.NC1C(=O)N(C2C=CC=CC=2)[N:41]([CH3:51])[C:40]=1C.C(NC1C(=O)N(C2C=CC=CC=2)N(C)C=1C)=[O:54].CN1C(C)=C(NO)C(=O)N1C1C=CC=CC=1.CN(C)C1C(=O)N(C2C=CC=CC=2)N(C)C=1CO.C(NC1C(=O)N(C2C=CC=CC=2)N(C)C=1)=O.C(NC1C(=O)N(C2C=CC=CC=2)N(C)C=1CO)=O>CCOCC.O>[CH3:26][C:27]1[N:23]([CH3:22])[N:4]([C:17]2[CH:18]=[CH:13][CH:14]=[CH:15][CH:16]=2)[C:3](=[O:54])[C:2]=1[N:41]([CH3:51])[CH3:40].[ClH:1]

参加物

13

反応物 10

HCID 313Hydrochloric AcidHCID 21514-AminoantipyrineHCID 6009AminopyrineHCID 6342AcetonitrileHCID 10618MethylaminoantipyrineHCID 726664-(Formylamino)antipyrineHCID 30820313-HydroxymethylaminopyrineHCID 189134594-Formylamino-2-methyl1-phenyl-3-pyrazolin-5-oneHCID 189134602,3-Dimethyl-4-hydroxyamino-1-phenyl-3-pyrazolin-5-oneHCID 189134614-Formylamino-3-hydroxymethyl-2methyl-1-phenyl-3-pyrazolin-5-one

生成物 1

HCID 18913462Aminophenazone hydrochloride

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 3283Diethyl Ether溶媒

実験手順

Aminopyrine hydrochloride was prepared from the free base (Aldrich) by treatment with HCl in ether. lodosobenzene (1650 mg, 7.5 mmol, prepared according to the method of Saltzman et al., Org. Synth., 43:60-61 (1963)) was added with stirring at room temperature in portions every 30 min to a solution of octachloro-octachloro tetrasulfonato Fe(III) porphyrin (6.2 mg 3.9 μmol) in 50 ml of 80:20 H2O:CH3CN containing 678 mg (3.0 mmol) of aminopyrine. Two hr after the last addition of the oxidant, the solution was evaporated under reduced pressure at 50° C. The residue was dissolved in 20 ml of aqueous Na2CO3 solution, and the solution was extracted with CH2Cl2 (3×50 ml). The organic layer was dried over Na2CO3 and evaporated under reduced pressure. The residue was chromatographed on silica gel, eluting with 1:25 methanol:methylene chloride. Seven oxidation products were obtained from the eluate (see Scheme 2): 2,3-dimethyl-4-monomethylamino-1-phenyl-3-pyrazolin5-one (AP-1); 4-amino-2,3-dimethyl-1-phenyl-3-pyrazolin-5-one (AP-2); 4formylamino-2,3-dimethyl-1-phenyl-3-pyrazolin-5-one (AP-3); 2,3-dimethyl-4hydroxyamino-1-phenyl-3-pyrazolin-5-one (AP-4); 4-dimethylamino-3hydroxymethyl-2-methyl-1-phenyl-3-pyrazolin-5-one (AP-5); 4-dimethylamino-2,3-dimethyl-1-phenyl-3-pyrazolin-5-one-4-oxide (AP-6); and 4-dimethyl-2,3dimethyl-1-(4-hydroxyphenyl)-3-pyrazolin-5-one (AP-7), 4-formylamino-2-methyl1-phenyl-3-pyrazolin-5-one (AP-8), and 4-formylamino-3-hydroxymethyl-2methyl-1-phenyl-3-pyrazolin-5-one (AP-9).

後処理

  1. customlodosobenzene (1650 mg, 7.5 mmol, prepared
  2. addition, 43:60-61 (1963)) was added
  3. additionTwo hr after the last addition of the oxidant
  4. customthe solution was evaporated under reduced pressure at 50° C
  5. dissolutionThe residue was dissolved in 20 ml of aqueous Na2CO3 solution
  6. extractionthe solution was extracted with CH2Cl2 (3×50 ml)
  7. dry with materialThe organic layer was dried over Na2CO3
  8. customevaporated under reduced pressure
  9. customThe residue was chromatographed on silica gel
  10. washeluting with 1:25 methanol
  11. customSeven oxidation products were obtained from the eluate (see Scheme 2)

出典と根拠

ORDレコード
ord-71c73e3a87404acf82e5763a8c983f19
出典データセット
uspto-grants-1998_06
特許番号
US05760216

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