Acetic Anhydride → 1-Hydroxy-3(carboxymethyl)-3,4-dihydroanthraquinone

HRID 67658Notes

Reaction equation

HRID 67658 reaction equation
[OH:1][C:2]1[C:15]2[C:14](=[O:16])[C:13]3[C:8](=[CH:9][CH:10]=[CH:11][CH:12]=3)[C:7](=[O:17])[C:6]=2[CH2:5][CH2:4][CH:3]=1.[C:18]([O:21]C(=O)C)(=[O:20])[CH3:19].C(C1C2C(=O)C3C(=CC=CC=3)C(=O)C=2CCC=1)(=O)C.BrN1C(=O)CCC1=O>N1C=CC=CC=1.C(Cl)(Cl)(Cl)Cl.O>[OH:1][C:2]1[C:15]2[C:14](=[O:16])[C:13]3[C:8](=[CH:9][CH:10]=[CH:11][CH:12]=3)[C:7](=[O:17])[C:6]=2[CH2:5][CH:4]([CH2:19][C:18]([OH:21])=[O:20])[CH:3]=1

Participants

8

Reactant 4

HCID 7918Acetic AnhydrideHCID 67184N-bromobutanimideHCID 205276501-Acetyl-3,4-dihydroanthraquinone2×HCID 205276551-Hydroxy-3,4-dihydroanthraquinone

Product 1

HCID 205276581-Hydroxy-3(carboxymethyl)-3,4-dihydroanthraquinone

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 1049PyridineSolventHCID 5943Carbon TetrachlorideSolvent

Procedure

1-hydroxy-3,4-dihydroanthraquinone is reacted with 2 moles of acetic anhydride in pyridine for 15 hours. The mixture is poured into water, when 1-acetyl-3,4-dihydro-anthraquinone separates. It is collected, washed and dried at 80° C. and 2 Pa absolute (15 torr). The 1-acetyl-3,4-dihydroanthraquinone is reacted with 2 moles of N-bromosuccinimide while suspended in boiling carbon tetrachloride under reflux for 2 hours. 1-acetyl-3-bromo-3,4-dihydroanthraquinone is collected, dissolved in acetone and treated with ethyl 2-bromoacetate and excess copper powder, under reflux, for 2 hours. The ethyl ester of 1-acetoxy-3(carboxymethyl)-3,4-dihydroanthraquinone is collected and hydrolysed by standing overnight in N sodium hydroxide solution under nitrogen. The free acid, 1-hydroxy-3(carboxymethyl)-3,4-dihydroanthraquinone is then obtained on acidification.

Workup

  1. customIt is collected
  2. washwashed
  3. customdried at 80° C.
  4. temperatureunder reflux for 2 hours
  5. custom1-acetyl-3-bromo-3,4-dihydroanthraquinone is collected
  6. dissolutiondissolved in acetone
  7. additiontreated with ethyl 2-bromoacetate and excess copper powder
  8. temperatureunder reflux, for 2 hours
  9. customThe ethyl ester of 1-acetoxy-3(carboxymethyl)-3,4-dihydroanthraquinone is collected

Sources & evidence

ORD record
ord-1b864dd877af4886ba75a75ea96a0ef8
Source dataset
uspto-grants-1982_08
Patent number
US04346103

Reaction notes

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