Sulfuric Acid → 7-Methyl-5-azaphenanthrene-1,10-dicarboxylic Anhydride

HRID 36624

反応式

HRID 36624 の反応式
[CH:1]1[CH:10]=[C:9]2[C:11]([O:13][C:14](=[O:15])[C:7]3=[C:8]2[C:3](=[C:4]([NH2:16])[CH:5]=[CH:6]3)[CH:2]=1)=[O:12].S(=O)(=O)(O)O.[N+](C1C=CC=CC=1)([O-])=O.[CH3:31][C:32]([CH:34](OC(C)=O)OC(C)=O)=[CH2:33]>C(O)(=O)C.O>[CH3:34][C:32]1[CH:33]=[C:5]2[C:4]([C:3]3[CH:2]=[CH:1][CH:10]=[C:9]4[C:11](=[O:12])[O:13][C:14](=[O:15])[C:7](=[CH:6]2)[C:8]=34)=[N:16][CH:31]=1

参加物

7

反応物 4

HCID 1118Sulfuric AcidHCID 7416NitrobenzeneHCID 25305Methacrolein diacetateHCID 809904-Aminonaphthalene-1,8-dicarboxylic anhydride

生成物 1

HCID 543746177-Methyl-5-azaphenanthrene-1,10-dicarboxylic Anhydride収率 93.7%

試薬・触媒・溶媒 2

HCID 176Acetic Acid溶媒HCID 962Water溶媒

実験手順

A mixture of 4-amino-1,8-naphthalic anhydride (Okazaki, M.; Ishikawa, N. Yuki Gosei Kagaku Kyokai Shi 1956, 14, 398; Chem. Abstr. 1957, 51, 8051c) (28.0 g, 131 mmol), ferrous sulfate heptahydrate (7.20 g, 25.8 mmol), concentrated sulfuric acid (13 mL, 234 mmol), and nitrobenzene (27.0 mL, 262 mmol) in acetic acid (260 mL) was heated to reflux. Methallylidene diacetate (43.5 mL, 262 mmol) was added dropwise over a period of 2.5 h using an addition funnel. After the addition was complete, the reaction mixture was heated for 1.5 h and poured into a beaker of ice/water (500 mL). The aqueous solution was further diluted to 800 mL with water, stirred for 1 h and filtered by suction. The residue was washed with water and dried in vacuo to obtain 32.3 g of a dark brown solid. The crude solid was heated at reflux in acetic acid (80 mL) and filtered hot to obtain 15.63 g (44%) of a light brown solid: mp >290° C.; MS m/e 264 (M+H+); 1H NMR (DMSO-d6, 300 MHz) δ 2.60 (s, 3H), 8.10 (t, 1H), 8.60 (s, 1H), 8.62 (s, 1H), 9.01 (s, 1H), 9.12 (d, 1H), 9.45 (d, 1H).

後処理

  1. temperaturewas heated to reflux
  2. additionAfter the addition
  3. temperaturethe reaction mixture was heated for 1.5 h
  4. filtrationfiltered by suction
  5. washThe residue was washed with water
  6. customdried in vacuo

出典と根拠

ORDレコード
ord-e9d95a6fa62b41938daac5f7d4782911
出典データセット
uspto-grants-1995_05
特許番号
US05416089

関連ノート

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