Oxalic Acid → HCID 21318712, compound

HRID 2397268Notes

Reaction equation

HRID 2397268 reaction equation
[CH2:1]([Mg]Br)[CH3:2].C#C.[OH:7][C:8]1[C:25]2[CH2:24][CH2:23][C:22](=[O:26])[CH2:21][C:20]=2[C:19]([OH:27])=[C:18]2[C:9]=1[C:10](=[O:29])[C:11]1[CH:12]=[CH:13][CH:14]=[CH:15][C:16]=1[C:17]2=[O:28].C(O)(=O)C(O)=O>O1CCCC1>[C:1]([C:22]1([OH:26])[CH2:21][C:20]2[C:19]([OH:27])=[C:18]3[C:9]([C:10](=[O:29])[C:11]4[CH:12]=[CH:13][CH:14]=[CH:15][C:16]=4[C:17]3=[O:28])=[C:8]([OH:7])[C:25]=2[CH2:24][CH2:23]1)#[CH:2]

Participants

6

Reactant 4

HCID 971Oxalic AcidHCID 6326AcetyleneHCID 130132805,12-Dihydroxy-3,4-dihydrotetracene-2,6,11(1H)-trioneHCID 178418443HCID 178418443, compound2×

Product 1

HCID 21318712HCID 21318712, compoundYield 498.5%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Acetylene, purified by passing it first through a column of alumina, then through concentrated sulfuric acid, was bubbled rapidly through freshly distilled tetrahydrofuran (100 ml) under nitrogen for 30 minutes. Ethylmagnesium bromide (3 ml, 3.15 M in ether, 12.6 mmole) was added in portions. When the frothing subsides, portionwise addition of the ethylmagnesium bromide solution was continued until the total solution had been added. The passage of acetylene was stopped and 7,10-dihydro-6,11-dihydroxy-5,9,12(8H)-naphthacenedione (VII) (250 mg, 0.12 mmole) in dry tetrahydrofuran (240 ml) was added dropwise. An immediate blue color was noted. After addition was completed, the mixture was stirred at room temperature under dry nitrogen overnight. To the dark blue solution was added 5% aqueous oxalic acid solution until the blue color disappeared and the brown reaction mixture extracted with chloroform. The chloroform extracts were washed well with water, dried over anhydrous sodium sulfate and the solvent removed to give a dark residue. The residue was chromatographed on Florisil (100-200 mesh) elution with methylene chloride, then with 2% methanol/methylene chloride yielded 9-ethynyl-7,10-dihydro-6,9,11-trihydroxy-5,12(8H)-naphthacenedione (VIII) (200 mg, 91%) as a red orange solid. m.p. 230° C. with decomposition; IR 6.15, 6.30μ; MS 334 (M+) 317 (M-OH); NMR (CDCl3) 13.40 (s 2H OH's), 8.3 (m 1H aryl), 7.7 (m 1H aryl), 3.1 (m 4H benzylic), 2.5 (s 1H ethynyl), 2.16 (m 2H allylic); UV (CHCl3) 289, 460, 485, 518 nm; PFT (CDCl3) δ13.46 (s 2H OH), 8.34 (m 2H aryl), 7.81 (m 2H aryl), 2.06 (t 2H benzylic), 2.50 (s 1H ethynyl), 2.15 (t 2H allylic).

Workup

  1. customAcetylene, purified
  2. customthrough concentrated sulfuric acid, was bubbled rapidly through freshly distilled tetrahydrofuran (100 ml) under nitrogen for 30 minutes
  3. additionhad been added
  4. additionAfter addition
  5. extractionthe brown reaction mixture extracted with chloroform
  6. washThe chloroform extracts were washed well with water
  7. dry with materialdried over anhydrous sodium sulfate
  8. customthe solvent removed
  9. customto give a dark residue
  10. customThe residue was chromatographed on Florisil (100-200 mesh) elution with methylene chloride

Sources & evidence

ORD record
ord-00e0f52f84d44d09a8ded9d75094e47a
Source dataset
uspto-grants-1977_05
Patent number
US04021457

Reaction notes

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