|Article Title: The Novel Synthesis of 3-(Phenylamino)-1,4-Benzoquinone (Anilino-quinone)|
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بسم الله الرحمن الرحيم
Quinones belong to a class of unsaturated α,β-ketones and have been the focus of attention owing to their important role in cellular respiration and photosynthesis1. The 1,4-naphthoquinone derivatives are toxic metabolites, yet paradoxically can either be potentially carcinogenic or effective anticancer agent2.
Quinones are a valuable class of compounds with interesting physicochemical properties3-5 The redox activity of compounds such as ubiquinone3 and menadione4 play an important role in electron transport within living cells4. The redox activity of naturally-occurring and synthetic quinones is important in drug design. For instance, quinones such as adriamycin5, 7-9
A large number of synthetic and natural organic compounds containing a quinone moiety in their structure have been associated with different biological activities9. Many quinones have been used as antituberculosis agents10, antimalarial agents11, antimicrobials12, antitumor agents13, and fungicides14.15. In most cases, the biological activity of quinones has been related to their redox properties and their capacity to accept one or two electrons to form the corresponding radical-anion (Q) andhydroquinone radical dianion (Q2)16
These intermediate species interact with crucial cellular molecules such as oxygen, DNA and proteins; modifying their biological activity16,17. Therefore, the studies on mechanisms of biological action, as well as the design and synthesis of novel compounds with more selective biological activities, require the understanding of the factors that modify the physicochemical properties of quinone systems. The biological importance of this kind of compounds has motivated an extensive research to evaluate the electrochemical behavior of a given quinone and hydroquinone system20-29.
Many researchers studied the redox kinetics and mechanisms in protic and aprotic solvents20-22. Other researchers have centered their studies on the influence of structural parameters on the redox properties of quinones23-29. It has been previously demonstrated that the presence of intramolecular hydrogen bonds (O…...H–N) is an important factor in the acceptance of the first electron in the electrochemical reduction of the quinone system30.
The electrochemical studies were performed in acetonitrile since quinones and their corresponding anions are not strongly solvated and intramolecular hydrogen bonds become more important in this solvent31. Several investigations have suggested that aprotic solvents indeed mimic cellular nonpolar environment where electron transfer takes place33.
Properties of a given quinone can be modified by directly adding a substituted aniline to the quinone system27. In this type of compounds, the electron-attracting and donor properties of the substituents on the aniline modify their redox properties by either facilitating or interfering with the charge transfer from the substituent to the quinone28.
A quinone is a class of organic compounds that are formally "derived from aromatic compounds [such as benzene or naphthalene] by conversion of an even number of –CH= groups into –C(=O)– groups with any necessary rearrangement of double bonds," resulting in "a fully conjugated cyclic dione structure." The class includes some heterocyclic compounds.
The prototypical member of the class are 1,4-benzoquinone or cyclohexadienedione, often called simply quinone (whence the name of the class). Other important examples are 1,2-benzoquinone (ortho-quinone), 1,4-naphthoquinone and 9,10-anthraquinone.
Quinones are oxidised derivatives of aromatic compounds and are often readily made from reactive aromatic compounds with electron-donating substituents such as phenols and catechols, which increase the nucleophilicity of the ring and contributes to the large redox potential needed to break aromaticity. (Quinones are conjugated but not aromatic). Quinones are electrophilic Michael acceptors stabilised by conjugation. Depending on the quinone and the site of reduction, reduction can either rearomatise the compound or break the conjugation. Conjugate addition nearly always breaks the conjugation.
1,2-Benzoquinone 1,4-Benzoquinone 1,4-Naphthoquinone 9-10-Anthraquinone
The term quinone is also used more generally for a large class of compounds formally derived from aromatic quinones through replacement of some hydrogen atoms by other atoms or radicals.32
Material and Method
Chemicals and Equipment:
Quinone, aniline, distill water, sulfuric acid, beaker , mortar , UV-Vis. & IR spectrophotometers.
In a beaker were placed 1,4-Benzoquinone (1gram), the corresponding aniline (1gram) and the reaction mixture was placed in a mortar and it was grinded for 30 min. in open atmosphere system. The temperature was set at 25-35 0C for 48 hours.
After this time the recrystalized product was filtered and dried. The percentage yield and the m.p. were determined, and UV-VIS , IR spectra were recorded.
This procedure was repeated using an excess of aniline.
In both cases no change of the absorption frequency from C=O was observed. Addition of aniline to the C=C bond of the quinone was suggested (single vN-H absorption) .
This reaction was also carried out (1:1 gram) in methanol and in the presence of sulphuric acid. Similar results were obtained. reaction mixture was placed in a mortar and it was grinded for 30 min. in open atmosphere system. The temperature was at room temperature for 48 hours.
This reaction was also carried out one gram from Benzoquinone and 2 gram from aniline. Similar results were obtained. The reaction mixture was placed in a mortar and it was grinded for 30 min. in open atmosphere system. The temperature was at room temperature for 48 hours. the yield 2,5-Bis (phenyl amino) - 1,4-benzoquinone obtained.
The reaction procedure in access aniline
UV-Vis. Results (1:1 gram) (Green Chemistry)
λmax( nm) Absorbance
UV-Vis. Results Using H+ as a Catalyst
λmax( nm) Abs.
IR Results (1:1 gram) (Green Chemistry)
IR Result (1:1 gram) use in acid catalysis
C=C IR shows 1633.59 nm N-H IR shows at 3425.34 C=O IR shows at 1730.25 nm
Calculation of Theorytical
Mwt of Aniline = 93
Mwt of product= 110
93□(→┴( ) )110
1g□(→┴( ) )X
Practical weight = 1.7
Percentages yield = (Practical )/(Theorytical )×100
Percentages yield = 69%
Conclusion and Discussion:
The synthesis of novel anilino-quinones is presented. At normal conditions by reacting the aniline and quinines without using any solvent (green chemistry). This preparation was also carried out using aniline and quinones in presence of methanol as a solvent. All quinones derivatives were characterized by UV- VIS. & IR spectroscopy.
This compound may have potential ant allergic, antibiotic, anticancer, antifungal, antiviral.
The physical characteristics of 3-(phenylamino) – 1,4-benzoquinone are as follows:
Melting point equal 264 – 266 degree centigrade.
Yield Percentage equal 69%.
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