General Guidelines for Synthesis and Purification of Quinone Compounds
OCH3 OCH3
3Methoxy1,2benzoquinone was
OH O prepared by silver oxide oxidation of 3
AgO
methoxycatechol.i Catechol (2.01 g), 13 g
of MgSO4, and 11.00 g of AgO were
OH O
combined in 150 mL diethyl ether, stirred
for 1.5 minutes, and then filtered into a round bottom flask. The volume of the solution
was reduced by using a rotary evaporator (without a water bath) until dark red needles
formed and the product was collected by filtration, washed with cold pentane, and stored
in the freezer. The material was dried overnight, under slight vacuum, over P2O5.
OH O
AgO 4Methyl1,2benzoquinone was
prepared by silver oxide oxidation of
O 4methylcatechol (2.45 g, beige
OH
powder) using 15 g of MgSO4 and 11.00 g of AgO in 150 mL diethyl ether. The mixture
was stirred for 1.5 minutes and then filtered into a round bottom flask. The volume of the
solution was reduced to approximately 75 mL by using a rotary evaporator (no water
bath). Red needles formed as the solvent volume was reduced and the flask cooled.
Pentane, 40 mL, was added to the flask and the solution volume was reduced to
approximately 30 mL by a rotary evaporator (without a water bath). Then the product
was collected by filtration and washed with cold pentane. The material was dried
overnight, under slight vacuum, over P2O5. Note: the orthoquinone was found to
sublime and decompose when dried under high vacuum.
OH O
4tertButyl1,2benzoquinone
AgO
was prepared by silver oxide
oxidation of 4tertbutyl
OH O
1
catechol (3.93 g, beige/brown powder) using 15 g of MgSO4 and 10.00 g of AgO in
150 mL diethyl ether. The mixture was stirred for 2 minutes and then filtered into a round
bottom flask. Pentane, 200 mL, was added to the flask and the flask was transferred to the
freezer (-20C). Fine brown/purple needles were formed after cooling. The volume of the
solution was reduced by a rotary evaporator (without a water bath) to give a large crop of
crystals. The collected crystals were washed with cold pentane and dried under vacuum,
over P2O5, for 8 hours.
O 2Methoxy1,4benzoquinone was
O
prepared by
O
OH PhI(OAc)2 phenyliodine (III) diacetate oxidation
of 2methoxyhydroquinone using a
procedure similar to Takata and
HO O
others.ii Methoxyhydroquinone
(2.10 g) was dissolved in 150 mL chloroform and 10.00 g of phenyliodine (III) diacetate
was added. The solution was stirred for 30 minutes and then the solvent volume was
reduced to 30 mL by using a rotary evaporator with a water bath temperature of 40C.
The solution was cooled (-20C) overnight and yellow crystals formed. The material was
recrystallized from 5 mL acetone, collected by filtration and dried under vacuum, over
P2O5, for 8 hours.
2tertButyl1,4benzoquinone was
prepared by silver oxide oxidation1 of 2
OH AgO O
tertbutylhydroquinone. Hydroquinone
(1.92 g), 15 g of MgSO4 and 13.00 g of
AgO were combined in 150 mL diethyl
OH O
ether. The mixture was stirred for 2
minutes and then filtered into a round bottom flask. The volume of the solution was
reduced to 5 mL by using a rotary evaporator (without a water bath). The fine golden
yellow crystals
2
were collected by filtration, recrystallized from pentane, and dried under vacuum, over
P2O5, for 8 hours.
Poly(4vinylphenol)
was oxidized with
Fremy's reagentiii to
(KO3S)2NO
give a polymer
containing ortho
quinone structures.
O
Approximately 2 g of
O poly(4vinylphenol)
HO
(MW ~22,000) was dissolved, with stirring, in 100 mL dioxane. Water, 50 mL (pH = 11),
and 2.00 g potassium nitrosodisulfonate (Fremy's reagent) were added. A few drops of
1.0 N sodium hydroxide solution were added to the reaction and the resulting solution
was stirred vigorously for 30 minutes under an argon atmosphere. The reaction was
terminated by adding 50 mL 1.0N HCl. Then 300 mL of water was added, with agitation,
to precipitate the polymer. The solution was filtered and the solid was taken up in
methanol. Methanol was removed under vacuum to give a brown/red solid.
Quinone Modification of Isolated Lignins
Sodium periodate was used to introduce orthoquinone structures into a residual lignin
sample (softwood brownstock, conventional kraft, kappa = 28,). The procedure used was
a slight modification of ones previously reported.iv A 517 mg sample of lignin dissolved
in 25 mL 90% (v/v) dioxane/water was added to 670 mg sodium periodate dissolved in
10 mL water and the solution was stirred in the dark, at room temperature. After 30
minutes, 100 mL water was added and dioxane solvent was removed by using a rotary
evaporator with a water bath temperature of 45C. The treated lignin was recovered by:
3
acid precipitation at pH = 2.0, sample freezing, thawing, centrifugation, and then
decanting. The recovered lignin was freezedried and used for analysis.
Fremy's reagent (potassium nitrosodisulfonate) was used to introduce quinone structures
into a residual lignin sample (softwood brownstock, conventional kraft, kappa = 30.5).
Brownstock residual lignin was oxidized using a procedure modified from the literature.4.
Residual lignin (100 mg) was dissolved in 15 mL of 50 % (v/v) 1,4dioxane/water
adjusted to pH = 8.0 with 0.1 N sodium hydroxide. To the solution was added 450 mg of
Fremy's reagent. The resulting mixture was stirred vigorously under an argon atmosphere
for 1.5 hours. Excess Fremy's reagent in the reaction mixture was decomposed by adding
5 mL of 1.0 N HCl. The 1,4dioxane solvent was removed from the reaction mixture by
vacuum evaporation at a temperature of 45C. The modified lignin was recovered by:
sample freezing, thawing, and then centrifugation. The recovered lignin was washed once
with water (pH = 2.0), freezedried and used for analysis.
Phosphorus(31)NMR: Ortho and ParaQuinone Content
Dry residual lignin (30 mg) was derivatized with 250 L trimethylphosphite and 250 L
anhydrous DMF under an argon atmosphere at room temperature for 2 days. Lignin
samples were previously dried under vacuum at 40C for 24 hours. NMR grade
trimethylphosphite was either used from a freshly opened bottle or purified by distillation
from solution containing sodium metal.
Derivatized lignin samples were prepared for analysis by removing excess
trimethylphosphite under vacuum at 40C for 3 hours. The treated lignins were dissolved
in 450 L of solvent consisting of 60% DMSOd6/pyridine (v/v) containing trimeta
tolylphosphate (0.7 mg/mL) and chromiumacetylacetonate (0.9 mg/mL). Derivatized
ligninquinone structures were hydrolyzed to the openchain phosphate ester by the addi-
tion of 5 L water (0.3 mmol per 30 mg lignin). After 12 hours, the 31PNMR spectrum
of the resulting solution was acquired with a Bruker 400 MHz NMR spectrometer.
4
PhosphorusNMR spectra were acquired under quantitative conditions at 305K.
A 90 pulse was utilized with a 5second pulse delay along with inversegated broad
band proton decoupling. For each spectrum ~1500 scans were collected. The internal
standard trimtolylphosphate ( -16.3 ppm) was used both for quantification and as a
shift reference. The 31PNMR chemical shift of trimetatolylphosphate in DMSOd6
was determined with the aid of 85% H3PO4 as an external shift reference. Previously, the
chemical shift of trimetatolylphosphate was reported as -17.3 ppm (CDCl3 solvent).
Quantification of ligninquinone content was achieved by integrating the areas of the in-
ternal standard, -15.3 to -17.1 ppm, and the phosphateester (quinone adduct)
resonance at -0.3 to -6.0 ppm.
PhosphorousNMR spectrum of trimethylphosphite treated residual lignin treated with
ClO2.
O
O OP(OCH3)3 OP(OCH3)2
P(OCH3)3
H3CO OCH3 H3CO OCH3 H3CO OCH3
O O OCH3
VI VII VIII (31P -1.4 ppm)
Reaction of trimethylphosphite with 2,6dimethoxy1,4benzoquinone (31PNMR
chemical shifts were determined in this study).
5
Reaction of trimethylphosphite with 3,5ditertbutyl1,2benzoquinone and the 31P
NMR spectrum after treatment and hydrolysis.
Figure 1. Reaction of trimethylphosphite with 2,6dimethoxy1,4benzoquinone and the
31
PNMR spectrum after treatment and addition of water.
6
31
PNMR spectra of compounds treated with 50% TMP/DMF for 2 days: A) D0 residual
lignin, B) oxidized PVP, and C) PVP.
All chemicals and equipment need to be handled in accordance with MSDS information,
the IPST@GT safety manual, and the GA Tech Chemical Hygiene Plan.
References
i Cason, J., Chapter 6: Synthesis of Benzoquinones by Oxidation, in Organic Reactions,
Volume 4, Adams, R., Editor, John Wiley and Sons, New York, (1948).
ii Takata, T., Tajima, R., and Ando, W., "Oxidation of Dihydroxy Aromatics by
Hypervalent Iodine Oxides: A Facile Quinone Synthesis", Journal of Organic Chemistry,
48, 4764, (1983).
iii Wozniak, J., Dimmel, D., and Malcolm, E., "The Generation of Quinones from Lignin
and Lignin-Related Compounds", Journal of Wood Chemistry and Technology, 9 (4),
491, (1989).
iv Furman, G.S., "Contribution of Charge-Transfer Complexes to the Color of Kraft
Lignin", Ph.D. Thesis, Institute of Paper Chemistry, Appleton, WI, (1986).
