Nitrite → 3-Hydroxy-2-methylbenzoic Acid

HRID 583804

反応式

HRID 583804 の反応式
N[C:2]1[C:3]([CH3:11])=[C:4]([CH:8]=[CH:9][CH:10]=1)[C:5]([OH:7])=[O:6].S(=O)(=O)(O)[OH:13].N([O-])=O.[Na+].NC(N)=O.N([O-])=O>O.O.[N+]([O-])([O-])=O.[Cu+2].O.O.O.O.[N+]([O-])([O-])=O.[Cu+2].[N+]([O-])([O-])=O.[N+]([O-])([O-])=O.[Cu-]=O.C1C(NC2N=C(N)N=C(Cl)N=2)=CC(NS(C2C=CC3C(=C4NC5[N-]C(=C6C=5C=C(S([O-])(=O)=O)C=C6)NC5NC(=C6C=5C=CC(S([O-])(=O)=O)=C6)NC5[N-]C(=C6C=5C=C(S([O-])(=O)=O)C=C6)NC=3N4)C=2)(=O)=O)=C(S([O-])(=O)=O)C=1.[Na+].[Na+].[Na+].[Na+].[Cu+2]>[OH:13][C:2]1[C:3]([CH3:11])=[C:4]([CH:8]=[CH:9][CH:10]=1)[C:5]([OH:7])=[O:6]

参加物

10

反応物 5

HCID 946NitriteHCID 1118Sulfuric AcidHCID 1176UreaHCID 27336993-Amino-2-methylbenzoic acidHCID 23668193Sodium Nitrite

生成物 1

HCID 2520233-Hydroxy-2-methylbenzoic Acid

試薬・触媒・溶媒 4

HCID 167780Copper(II) nitrate hemipentahydrate触媒HCID 129651451Reactive Blue 15触媒HCID 178419072HCID 178419072、化合物触媒HCID 962Water溶媒2 回

反応条件

温度
2.5 °C

実験手順

A one-necked 100 mL round-bottomed flask (magnetic stirring) was charged with 1.0 gram (6.6 mM) 3-amino-2-methylbenzoic acid. A warm mixture of 2.3 mL conc. sulfuric acid in 4.3 mL water was added to the flask, the resulting slurry was cooled below 15° C. in an ice bath, and 6.6 grams of ice was added. The reaction mixture was treated via subsurface addition with a solution of 0.6 gram (8.6 mM) sodium nitrite in 6.6 mL ice water with the reaction temperature maintained at 0-5° C. during the addition. After stirring at 0-5° C. for 30 min., a few crystals of urea were added to decompose the excess nitrite. The reaction mixture was then poured into a room temperature solution of 23.8 grams (102.3 mM) copper (II) nitrate hemipentahydrate in 200 mL water. With vigorous stirring, the reaction mixture was treated with 0.9 gram (6.0 mM) copper (I) oxide. The reaction mixture foamed and changed from turquoise blue to dark green in color. Reaction was left stirring for 30 min. The reaction mixture was extracted with diethyl ether (3X), and the organic extracts were combined. The organic extracts were concentrated to approximately one-fourth the original volume, then extracted with 25 mL 1N sodium hydroxide solution. The layers were separated, and the dark-red aqueous layer was acidified to pH=2 using 1N hydrochloric acid solution. The acidified aqueous layer was then extracted with diethyl ether (3X), and the ether extracts were combined, dried (MgSO4), and concentrated to yield a reddish-colored oil. Purification by flash chromatography on silica gel using a gradient of 0-7% methanol/methylene chloride afforded 0.39 grams 36%) of a yellow solid.

後処理

  1. additionwas added to the flask
  2. temperaturethe resulting slurry was cooled below 15° C. in an ice bath
  3. stirringAfter stirring at 0-5° C. for 30 min.
  4. customReaction
  5. waitwas left
  6. stirringstirring for 30 min
  7. extractionThe reaction mixture was extracted with diethyl ether (3X)
  8. concentrationThe organic extracts were concentrated to approximately one-fourth the original volume
  9. extractionextracted with 25 mL 1N sodium hydroxide solution
  10. customThe layers were separated
  11. extractionThe acidified aqueous layer was then extracted with diethyl ether (3X)
  12. dry with materialdried (MgSO4)
  13. concentrationconcentrated
  14. customto yield a reddish-colored oil
  15. customPurification by flash chromatography on silica gel using a gradient of 0-7% methanol/methylene chloride
  16. customafforded 0.39 grams 36%) of a yellow solid

出典と根拠

ORDレコード
ord-5e37293c457f4f1c836612a41608f880
出典データセット
uspto-grants-2005_08
特許番号
US06924286B1

関連ノート

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