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3D"AcademicStack3d+.jpg"
Alcohol Oxidation by Metallic Benzoquinone Complexes
Joey Easterling
Randy F. Johnston, Ph.D.
1050 Union University Dr. Jackson, TN, 38305
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3D"AcademicStack3d+.jpg"
Introd= uction
•Linck and Taube discovered that p-benzoquinones and chromium oxidized ethanol.
Linck, R.G.; Taube, H. J. Am. Chem. Soc. 1963, 85, 2187-2189.
.
2+
Foun= d three important things:
1.Hy= pothesized that two chromium moles were required per benzoquinone mole
2.Fo= und that the substitution of the first chromium atom was rapid
3.Fo= und that Cl-1, Br-1, and H2O, among other things, slowed the react= ion
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file:///C:/CED92365/JoeyE_files/slide0003.htm Content-Transfer-Encoding: quoted-printable Content-Type: text/html; charset="us-ascii" Slide 1
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Further Study
•A later, in depth study on the reaction o= f chloranilic acid, chromium, and ethanol provides some very important information:
•Two chromium atoms p= er benzoquinone atom are, in fact, necessary for alcohol oxidation
•The reduced chromium= and chloranilic acid complex is a semiquinone bridged polynuclear complex
•
•
Holwerd= a, R.A. Johnston, R. F. Inorg. Chem. 1985, 24, 153-159.
Reac= tion on next slide. Important because this has a characteristic spectrum and gives us a good way to identify reduced benzoquinone, thus a probable completed reaction.
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2+
Note= one electron is centered in the quinone ring, and the other is centered over a chromium ion.
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Object= ives
Which benzoquinones are more effective = oxidizing agents?
What kind of alcohols are more easily oxidized?= 3;
How will changing the metal effect the reaction?&#= 13;
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Soluti= ons Analyzed
•Seventeen alcohols of differing characteristics were used.
•
•Two p-benzoquinones were used, Chloranilic acid and Bromanilic acid.
•
•Two metals = were used, chromium (III) and aluminum.
Alco= hols
2-br= omoethanol 2-butene-1,4-diol 3,butene-1-ol, 2-butyne-1-ol 2-chloroethanol ethanolami= ne 2-methoxyethanol 1,2-ppropanediol 1,3-propanediol 4-(trifluoromethyl)-benzylalcohol
2-bu= tanol
Drie= d: 1-butanol ethanol 2-propanol 1-propanol methanol

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Soluti= on Preparation
•Enough benzoquinone to identify carbonyl = compounds with GCMS. At least 2.5-1 metal moles per benzoquinone moles.
•Four solutions per alcohol:
<= span style=3D'mso-special-format:"numbullet3\,1";position:absolute;left:-7.19%'= >1.Chromium and chloranilic acid
<= span style=3D'mso-special-format:"numbullet3\,1";position:absolute;left:-7.19%'= >2.Chromium and bromanilic acid
<= span style=3D'mso-special-format:"numbullet3\,1";position:absolute;left:-6.39%'= >3.1-1 Chromium and chloranilic acid in excess of aluminum
<= span style=3D'mso-special-format:"numbullet3\,1";position:absolute;left:-7.19%'= >4.Aluminum and chloranilic acid
–
GCMS= work was done comparing with 1-butanol/butanal standards to determine what the minimum concentration of oxidized alcohol product had to be in alcohol solution t= o be identifiable by GCMS analysis. Assuming a 1-1 reaction, at least that concentration of benzoquinone was used.
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3D"AcademicStack3d+.jpg" 3D"Chloranilic
C= hloranilic Acid and Chromium
3D"Chloranilic
C= hloranilic Acid and Aluminum
3D"Joe's
B= romanilic Acid and Chromium
3D"Picture
C= hloranilic Acid, Chromium, and Aluminum
It w= as previously reported that green in chloranilic acid and chromium (III) characterized reduced quinone.
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