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ARTIKEL PENELITIAN

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Oxidation of Benzoin Catalyzed by Oxovanadium (IV) Schiff Base Complexes

Tahseen A Alsalim1 ,Jabbar S Hadi1, Omar N Ali1, Hanna S Abbo2 and Salam JJ Titinchi2*
Abstrak
Latar Belakang: Theoxidativetransformationofbenzointobenzilhasbeenaccomplishedbytheuseofawide varietyofreagentsorcatalystsanddifferentreactionprocedures.Theconventionaloxidizingagentsyieldedmainly benzaldehydeor/andbenzoicacidandonlyatraceamountofbenzil.Thelimitsofpracticalutilizationofthese reagentsinvolvestheuseofstoichiometricamountsofcorrosiveacidsortoxicmetallicreagents,whichinturn Fulllistofauthorinformationisavailableattheendofthearticle produceundesirablewastematerialsandrequiredhighreactiontemperatures. Inrecentyears,vanadiumcomplexeshaveattractedmuchattentionfortheirpotentialutilityascatalystsforvarious typesofreactions. Results: Activeandselectivecatalyticsystemsofnewunsymmetricaloxovanadium(IV)Schiffbasecomplexesfor theoxidationofbenzoinisreported.TheSchiffbaseligandsarederivedbetween2-aminoethanoland2-hydroxy-11 3 2 naphthaldehyde(H L2)or3-ethoxysalicylaldehyde(H L );and2-aminophenoland3-ethoxysalicylaldehyde(H L )or 2 2 4 2-hydroxy-1-naphthaldehyde(H L ).TheunsymmetricalSchiffbasesbehaveastridentatedibasicONOdonor 2 ligands.ReactionoftheseSchiffbaseligandswithoxovanadylsulphateaffordedthemononuclearoxovanadium(IV) IV x complexes(V OL.H 2 O),whicharecharacterizedbyvariousphysico-chemicaltechniques. ThecatalyticoxidationactivitiesofthesecomplexesforbenzoinwereevaluatedusingH O asanoxidant.Thebest 2 2 reactionconditionsareobtainedbyconsideringtheeffectofsolvent,reactiontimeandtemperature.Underthe 4 optimizedreactionconditions,VOL catalystshowedhighconversion(>99%)withexcellentselectivitytobenzil (~100%)inashorterreactiontimecomparedtotheothercatalystsconsidered. Conclusion: FourtridentateONOtypeSchiffbaseligandsweresynthesized.Complexationoftheseligandswith IV vanadyl(IV)sulphateleadstotheformationofnewoxovanadium(IV)complexesoftypeV OL.H O. 2 Elementalanalysesandspectraldataofthefreeligandsandtheiroxovanadium(IV)complexeswerefoundtobein goodagreementwiththeirstructures,indicatinghighpurityofallthecompounds. OxovanadiumcomplexeswerescreenedfortheoxidationofbenzointobenzilusingH O asoxidant.Theeffectof 2 2 time,solventandtemperaturewereoptimizedtoobtainmaximumyield.Thecatalyticactivityresultsdemonstrate thatthesecatalyticsystemsarebothhighlyactiveandselectivefortheoxidationofbenzoinundermildreaction conditions. Keywords: TridentateONOSchiffbaseligands,Oxovanadium(IV)complexes,Benzoinoxidation,Benzil

importantsyntheticintermediatesinthesynthesisofmany Background -Dicarbonyl compounds have Liquidphasecatalyticoxidationofalcoholsisafascinating heterocyclic compounds. reaction and is one ofthe mostimportant synthetic diverseapplications reacinorganicand pharmaceutical industionsinorganicchemistry.Oxidationof benzointobenzil tries such as photosensitive and synthetic reagents [ 7 , 8 ] has been extensively studied for the production of and fine photoinitiators for radicalpolymerization [ 9 ].Benzil, -dicarbonyl compounds are chemicals [ 1 - 6 ]. In general in particular, is a standard building block in organic synthesisandisutilizedasanintermediateinthesynthesisof * Correspondence: stitinchi@uwc.ac.za chiralligandsandbiologicallyactivecompounds. 2 DepartmentofChemistry,UniversityoftheWesternCapeBellville,Private -hydroxy The oxidative transformation of an ketone BagX17,Bellville,CapeTown7535,SouthAfrica -diketone (benzoin to benzil) has to the corresponding
2013Alsalimetal.;licenseeChemistryCentralLtd.ThisisanOpenAccessarticledistributedunderthetermsoftheCreative CommonsAttributionLicense( http://creativecommons.org/licenses/by/2.0 ),whichpermitsunrestricteduse,distribution,and reproduction inanymedium,providedtheoriginalworkisproperlycited.

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been accomplished by the use of a wide variety of act as tridentate dibasic ligands. These ligands can coreagents or catalysts and different reaction procedures. ordinate through the imino nitrogen and two oxygen Several reagents have been used for this transformation atoms from the deprotonation of the phenolic groups as such as nitric acid, Th(III) and Y(III) nitrate [ 10 ] and well as from the aliphatic hydroxyl group. The ligands bismuth(III) nitrate-copper(II) acetate [ 11 ]. The convenreact with V(IV) to fill three of the four equatorial cotional oxidizing agents ., viz permanganate, dichromate ordination sites with a water molecule coordinating to or chromic acid yielded chiefly benzaldehyde/benzoic theremainingsite. acid and only a trace of benzil. The limits of practical The IR spectra of the ligands and their complexes utilization of these reagents involves the use of stoichiowere compared to determine any changes during commetric amounts of corrosive acids or toxic metallic plexation and to confirm their structures (Additionalfile reagents,whichinturnproduceundesirablewastemate1 : Figure S1-S3). The IR spectra of the ligands showed a -1 rialsandrequiredhighreactiontemperatures. broad absorption band at 3230 31 17cm attributed to In recent years, vanadium complexes have attracted the stretching vibration of intramolecular hydrogen much attention for their potential utility as catalysts bondedOHgroups[ for 28 ].Thisbanddisappearedoncomvarious types of reactions. Oxovanadium complexes plexation indicating the coordination of vanadium metal ., hydroxylation catalyze various oxidation reactions viz throughOHgroups after deprotonation. Anew medium -1 35 of phenols [ 12 , 13 ], oxidation of sulfides to sulfoxides intensity band near 3400 00cm is attributed to the OH [ 14 , 15 ], oxidation of alcohols [ 15 ], epoxidation of olefins stretching vibration of the coordinated water mol[ 15 - 19 ], hydroxylation of benzene to mono- and ecule dihyto the central metal ion [ 29 ]. A strong band at -1 1629 cm droxybenzenes[ 12 , 20 , 21 ]includingreactionssuchasthe 1648 of the spectra of the ligand was coupling of 2-naphthols as well as Mannich-type reacassigned to the azomethine (C=N) stretching vibration. -1 tions [ 22 - 25 ]. Most recently, the application of various This band shifted to lower frequency(by 30cm 10 ) i n oxovanadium complexes as catalysts in different oxidathe complexes, indicating that the nitrogen atom of the tionreactionshasbeenreviewed[ 26 , 27 ]. azomethine group is coordinated to the metal centre -1 (C O) band at 1114 1116cm In this report we describe the synthesis of Schiff [ base 30 , 31 ]. The phenolic ligands derived by reaction between 2-aminophenol in the or free ligand is shifted towards lower frequency by -1 2-aminoethanol and 2-hydroxy-1-naphthaldehyde10 or 315 cm in the complexes, verifying coordination ethoxysalicylaldehydetoformtridentatedibasicligands via the deprotonated phenolic oxygen. The complexes 987975 of the ONO type. Complexation of these ligands with show a new strong band in the region between -1 vanadyl sulphate produced oxovanadium(IV) com- cm assigned to stretching vibration of V=O [ 32 , 33 ] plexes.Tothebestofourknowledge,thisisthefirstre- which indicates its monomeric nature [ 34 ]. The absence port describing the synthesis of these oxovanadium(IV) of significant bands in the frequency range below 900 -1 complexes. cm demonstrates no V=OV bridge vibration [ 35 , 36 ]. Aspartofourcontinuinginterestinoxidationreactions A similar monomeric nature of related complexes has byvanadiumcomplexes[ 13 ]andconsideringthedemand also been well established crystallographically [ 37 , 38 ]. ofmoreefficientcatalyticsystems,weundertookaninvesThe appearance of two to three new moderately intense -1 500cm tigation of these oxovanadium(IV) complexes as catalysts bands in the low-frequency region of 350 in forbenzionoxidationforthefirsttime. the complexes are assigned to stretching frequencies of (V N) and (V O) bonds i.e. coordination of azomethine nitrogen as well as phenolic oxygen to the vanResultsanddiscussion Synthesisandcharacterization adium metal after deprotonation. The C=C stretching Facile condensation of 2-aminophenol or 2-aminoethanol modes of the benzene ring of the ligand around 1600 -1 and 2-hydroxy-1-naphthaldehyde or 3-ethoxy salicylaldecm does not show any significant shift on complexhyde in 1:1 molar ratio afforded four Schiff base ligands ation. Thus, the IR data indicates that the Schiff bases 2 3 4 . H2L1,HL viz and H L2, respectively (Scheme 1 behaveas ). dibasic tridentateligands coordinating 2 ,HL 2 These tridentate ligands reacted readily with vanadyl through sul- phenolic and alcoholic oxygens and the azofateinmethanoltoformtheoxovanadiumcomplexeswith methinenitrogen. 1 1 3 thesamegeneralstructure(Scheme 2 ). The H NMR spectra of ligand2H L and ligand 2 H L Spectral data and elemental analysis of all the synthedisplayed a broad signal corresponding to the OH prosized ligands and their oxovanadium(IV) complexes ton of the ethanol amine moiety at 5.00 and 5.32 ppm, were in good agreement with their structure, indicating respectively. The phenolic OH protons appeared as thehighpurityofallthecompounds. broad signals at 13.88 and 13.70 ppm, respectively. The 1 2 4 The analytical data of the complexes indicates a HNMR 1:1 spectraofligandsH 2 L andH 2 L displayedthe metal: ligand stoichiometry, and hence the Schiff OH bases phenolic groups as singlets at 9.77 and 14.2, and

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OH N N OH OH
O

N OH

OH

OH N

OH

OH

O CH 3 CH 3

L1
Scheme1Structureoftheligands.

L2

L3

L4

Catalyticactivitystudies 10.35 and 15.7 ppm, respectively [ 39 ]. In all the ligands the azomethine HC=N proton appeared as a singlets The at catalytic activity of oxovanadium complexes for the 8.35 9.43 ppm.Alltheotheraromaticandaliphaticpro-oxidation of benzoin to benzil has been studied and the tons were observed in the expected regions (Additional effect of time, solvent and temperature were optimized file 1 :FigureS4-S7). to produce maximum yield. Oxidation did not proceed The elemental analyses of the ligands and the comwhen the reaction was carried out in the presence of eiplexes are in agreement with their formulation. The ther hydrogen peroxide or oxovanadium complexes elemental analysis of the complexes confirms a 1:1 only. (metal:ligand)stiochiometry. Progressofthereaction(asdeterminedbytheconcenThe result of mass spectra further indicates that tration theV of benzil) was monitored spectrophotometrically (IV) complexes have a monomeric form of 1:1 stiochioand identification of the product was confirmed by GCmetry, where the observed molecular ion peak (m/z) MS analyses which showed that benzil was the only values are consistent with the calculated value inproduct the detectable. No oxidative cleavage products were proposed structure (Additional file 1 : Figure S8-S11). observed. The complexes were non-volatile and difficulties were The electronic spectrum of benzil is characterized by experiencedtorecordtheirmassspectrabyE1methods. an absorption at 283 nm, which is readily differentiated from the other absorption bands of benzil at 260 nm and benzoin 247 nm [ 40 ]. Accordingly, the band at 283nm was used to determine the concentration of the producedbenzil(Figure 1 ). In order to screen the catalytic oxidative potential of the prepared complexes, they were tested for oxidation of benzoin using 2H 2O as an oxidant under different re., temperature, reaction time and action conditions viz type of solvent in order to optimise the conditions for thebestperformanceofthecatalyst. Figure 2 showsthattheabsorbanceat283nmincreases with reaction time as an indication oftheincreasingconcentration of benzil by using one of the catalysts, namely 1 VOL . The maximum benzil yield was found to depend upon the type of catalyst used (Figure 3 ). It is clear from 4 1 Figure 3 that VOL and VOL give higher benzil yields 3 2 compared to VOLand VOL with the same reaction Scheme2 4 time. VOL gave 100% yield after 2 h, while VOL gave

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Figure1 Absorptionspectraofbenzoinandbenzilinacetonitrile.

98 .9 % after a longer reaction time (4 h). The orderobservedusingthepolaraproticsolvent,acetonitrile,com4 of catalytic activity was found to be as follows: VOL pared > to the other two solvents. On the other hand, the 1 3 2 VOL >VOL >VOL . protic solvent, methanol, was not tried as it retards the oxidation of benzoin due to hydrogen bonding with the Effectofsolvent methanol[ 41 ]. . benzene, The influence of three different solvents viz In general, in these solvents, the order of the catalytic carbon tetrachloride and acetonitrile on the rate of performance benof these catalysts after 6 h reaction time as 1 4 3 2 zoinoxidationwasnextstudied. thefollowingVOL VOL >VOL >VOL . Figures 4 , 5 , 6 , 7 illustratetheeffectofsolventuponthe 1 4 rateandyieldofbenzoinusingcatalysts(VOL VOL ).It Effectoftemperature isclearfromthefiguresthatthesolventhasnosignificant effect on the yield and selectivity. However, the reaction Theperformanceofthe catalysts wasinvestigatedattwo rateduringthefirstfourhoursincreasesslightlyasthepodifferent temperatures viz. 30C and 50C in benzene larity of the solvent decreases. Lower reaction rates after5hreactiontime(Figure were 8 ).

Time

1 Figure2 ChangeintheabsorptionspectrawithtimeusingVOL .

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100 80

100 80

) (%

60
VOL1 VOL2 VOL3 VOL4

) 60 eld (% i Y
40 20 0 0 2 4 6 8 10
MeCN CCl4 Benzene

eld 40 i Y
20 0 0 1 2

Time (h)
Figure5 Effectofsolventon%yieldofbenzilusingVOL 2 at50C.

Time (h)
Figure3 Catalyticperformanceofthedifferentcatalystswith timefortheformationofbenzilinbenzeneat50C.

as a function of time in benzene at 50C. The reaction In general, the catalytic activity of the four catalysts profiles (Figure 3 ) showed that the yield of benzil increased with increasing temperature. Figure 8 increased shows with increasing reaction time until a steady that there was a significant increase in benzil yield state using was reached after 2-4 h. However, maximum yield 1 2 3 1 4 VOL , VOL and VOL when the reaction temperature of benzil (>99.9%) was obtained using VOL and VOL , 4 2 3 4 wasincreasedfrom30Cto50C;whileVOL gaveahigh and ca. 90% using VOL and VOL . VOL achieved the benzil yield (97%) even atthelowertemperature i.e.30C maximum conversion within a shorter reaction time andaminorincreaseat50C.At30C,moderateyieldsof than the other catalysts. The selectivity of all the catabenzil were observed in all three solvents. However, lystswasfoundtobeunaffectedwithincreasingreaction the increase in reaction temperature to 50C led to almost timei.e.>99.9%benzil. completeconversionofbenzointobenzil.Excellentselectivity was observed with all the catalysts. Thus from the results above it is clear that 50C is the optimum Experimentalsection Materials temperature for this oxidation. All the catalysts possess Oxavanadium sulfate trihydrate, 2-aminophenol and 2excellentselectivitytowardsbenzilformation. hydroxy-1-naphthaldehyde were obtained from Fluka, 2aminoethanol, 3-ethoxysalicylaldehyde and benzoin were Effectoftime obtained from Merck 30%2H 2 O . All other chemical The catalytic oxidation of benzoin using 2 2 H O as oxireagents were used as such. Solvents were used after dant in the presence of the four catalysts was followed beingpurifiedaccordingtothestandardmethods.
100
100

80
80

) 60 (% d l 40 i Y e
20 0 0 2 4

MeCN CCl4 Benzene

) eld 60 (% i Y 40
20 0 0 2 4 6 8 10 MeCN CCl4 Benzene

at50C. Figure4 Effectofsolventon%yieldofbenzilusingVOL 1

Time (h)

10

Time (h)
Figure6 Effectofsolventon%yieldofbenzilusingVOL 3 at50C.

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Anal. Found: C, 71.69; H, 5.73; N, 6.09. 150C. mp 148 C13 H NO 13 2 requires C, 72.54; H, 6.09; N, 6.51%. IR -1 OH), 3056( (KBr, cm ), 3167br( C-H Ar), 2917C-H ( 80 1 C=N); /ppm): 3.65 aliph.), 1641 ( H NMR (DMSO-d 6 , ) (m, 4 H, 2CH 2 ), 5.00 (br, 1H, OH), 6.64-8.00 (m, 6H, eld (% 60 Ar-H),9.02(s,1H,HC=N),13.88(br,1H,phenolicOH); .+ m/z M = 215 (85%), 214 (66%), 184 (base peak), 170 MeCN i 40 Y (42%).Found215.00,C H NO 13 13 2 requires215.25. CCl4 2 20 H L 2-ethoxy-6-{[(2-hydroxyphenyl)imino]methyl}phenol 2 Benzene 3-Ethoxysalicylaldehyde(1.66g), 2-aminophenol (1.09g), 0 (87% yield) as reddish orange needles (from ethanol); mp 0 2 4 6 8 10 Anal. Found: C, 69.17; H, 5.41; N, 5.13. 172 -174C. Time (h) C H NO C, 70.02; H, 5.88; N, 5.44%. IR (KBr, 4 15 15 requires 3 Figure7 Effectofsolventon%yieldofbenzilusingVOL -1 cm ), 32100 ( OH), 3060( C-H Ar), 2986( C-H aliph.), at50C. C=N).1H NMR (DMSO-d 162 9 s( /ppm): 1.3 (t, 3H, 6 , CH3), 4.06(q,2H,2CH 2 ), 6.78-7.38(m,7H,Ar-H),8.94(s, Physicalmethodsandanalysis 1H,HC=N),9.77(s,1H,OH;aminophenolmoiety),14.20 .+ InfraredspectrawererecordedasKBrpelletsonaBUCK(s, 1H, OH; 3-ethoxysalicylaldehyde moiety). m/z = M 1 .+ 50 0 FT-IR spectrometer. H NMR spectra were recorded 257 (86%),242 (41%) [M-CH3] , 212 (24%) [M.+ onaBruker500(500MHz)spectrometerusingDMSO-d OCH2CH3] , 120 (55%), 69 (base peak). Found 257.00, 6 as a solvent and TMS as internal standard. GC-MSC were H NO 15 15 requires257.29. 3 3 recorded on a Hewlett Packard E1 mass spectrometer H2Lat 2-ethoxy-6-{[(2-hydroxyethyl)imino]methyl}phenol 70eV. Elemental analysis was performed on Euro Vectro 3-Ethoxysalicylaldehyde (1.66 g), 2-aminoethanol EA 3000A analyzer. All catalyzed reaction products (0.61 were g), (81% yield) as yellow crystals (from ethanol); + Anal. Found: C, 62.25; H, 6.91; N, 6.41. visPGInstrumentT-80 analyzedusingUV . mp 88-90C. C11 H NO 15 3 requires C, 63.14; H, 7.23; N, 6.69%. IR -1 28 Preparationmethods (KBr, cm ), 3230 (OH), 3050 (C-H Ar), 2953 66 1 GeneralmethodforpreparationofSchiffbaseligands (C-H aliph.), 1652C=N). ( H NMR (DMSO-d 6 , / Methanolic solutions of the aldehyde and amine were ppm): 1.6 (t, 3H, CH ), 3.70 (t, 2H, 3 2 CH of 2 CH N=CH), mixed at room temperature in a 1: 1 molar ratio using 3.90 (t,2H,CH 2 ofCH OH),5.32(s,1H,OH),6.70-7.91 2 glacialaceticacidasacatalyticagent.Theresultingmix(m, 3H, Ar-H), 8.35(s, 1H, HC=N), 13.70 (br, 1H, OH .+ ture was refluxed for 2 h. The crystalline product was phenolic OH); m/z M = 209 (13%) 11 CH 15NO3, 194 .+ .+ obtained from the deep-yellow coloured solution after (20%) [M-CH CH ] , 69 (base 3 ] , 164 (25%) [M-OCH 2 3 + standingforafewhoursat25C.Theprecipitate wasfilpeak) (C C 15 H NO 2 H 5 NO ). Found 209.00, 11 3 requires tered off and washed with ice-cold methanol. The209.23 pure . 4 compound was obtained by recrystallization from aH suitL 1-{[(2-hydroxyphenyl)imino]methyl}-2-naphthol 2 ablesolvent. 2-Hydroxy-1-naphthaldehyde (1.72 g), 2-aminophenol 1 H2L 1-{[(2-hydroxyethyl)imino]methyl}-2-naphthol (1.09 g), (63% yield) as orange needles (from ethanol); Anal. Found: C, 76.64; H, 4.34; N, 4.96. 2-Hydroxy-1-naphthaldehyde (1.72 g), 2-aminoethanol mp 247-249C. (0.61 g), (69% yield) as orange needles (from ethanol); C17 H NO 13 2 requires C, 77.55; H, 4.98; N, 5.32%. IR -1 (KBr, cm ), 3117( OH), 3053 (C-H Ar), 2960 (C-H 1 aliph.), 1622 ( C=N). H NMR (DMSO-d , /ppm): 6 98.9 97.2 100 100 91.1 89.3 6.74-8.3 5 (m, 10H, Ar-H), 9.43 (s, 1H, HC=N), 10.35 80 (s, 1H, OH phenolic), 15.70 (s, 1H, OH naphthoyl); m/z .+ .+ 61.1 M = 263 (75%), 262 (base peak) [M-H] . Found 54.8 ) (% 60 30C 263.00 . C17 H NO 13 requires263.30. 2 38.6
100 eld 40 i Y
20 0 VOL1 VOL2 VOL3 VOL4

50C

Preparationoftheoxavanadium(IV)complexes

Figure8 Catalyticperformanceofthecatalystsforthe oxidationofbenzoinattworeactiontemperaturesinbenzene after5hreactiontime.

All complexes were prepared according to the following mixture was for 3 h and the products obtained procedure: a stirred hot methanolic solution of VOSO .3H O 4 2 (0.217 g, 1 mmol), was added drop wise to a hot methanolic solution of the ligand (1.5 mmol). The resulting

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were filtered, washed with hot water then methanol and agreement with their structures, indicating high in good driedinairat90C. purityofallthecompounds. 1 -1 VOL Dark green ppt., mp>300C, IR (KBr, cm ); Oxovanadium complexes were screened for the oxidaC-H 3050(C-H arom.), 2936 ( aliph.) 1614( C=N), tion of benzoin to benzil usingH 2 2 O as oxidant.The efV=O). fect of time, solvent and temperature were optimized to 1512(C=C), 1322 (C-N), 1198(-O), 975 ( Anal.Calcd.forC13 H 13 NO V: 4 C,52.35;H, 4.36;N,4.69. obtain maximum yield. The catalytic activity results .+ Found:C,52.51;H,4.23;N,4.51.m/zM =298. demonstrate that these catalytic systems are both highly 2 -1 VOL Brown ppt., mp>300C, IR (KBr, cm ); 3053 active and selective for the oxidation of benzoin under C=N), 2890(C-H aliph.), 1601 (C-H arom.), 2969 ( mildreactionconditions. 1582(C=C), 1294( C-N), 1248(C-O), 987 (V=O). Anal.calcd. for 15 CH NO5V: C, 52.95; H, 4.41; N, 4.11. 15 Additionalfile .+ Found:C,52.51;H,4.23;N,4.39.m/zM =340. 3 -1 1 CVOL Green ppt., mp>300C,IR (KBr,cm ); 3080( Additionalfile1:FigureS1. Ft-IRspectrumofH FigureS2:FT-IR . 2 L 2 2 spectrumH L FigureS3:FT-IRspectrumVOL . FigureS4:H-NMR . 2 H arom.), 2951 (C-H aliph.), 1608 (C=N), 1505 1 2 spectrumH . FigureS6:H-NMR . 2 LFigureS5:H-NMRspectrumH 2 L 3 4 (C=C), 1334C-N), ( 1212(C-O), 981 (V=O).Anal. spectrumH . FigureS8:Mass . 2 LFigureS7:H-NMRspectrumH 2 L 1 2 calcd. for C11 H 15 NO V: spectraH . FigureS10:Massspectra . 5 C, 45.21; H, 5.31; N, 4.79. 2 L FigureS9:MassspectraH 2 L 3 4 .+ H2L .FigureS11:MassspectraH 2 L . Found:C,45.54;H,5.23;N,4.57.m/zM =292. 4 -1 VOL Dark green ppt., mp>300C,IR (KBr,cm ); 3067 C-H C=N), (C-H arom.), 2961 ( aliph.), 1592 ( 1575 Competinginterests (C=C), 1338C-N), ( 1177(C-O), 978 (V=O).Anal. Theauthorsdeclarethattheyhavenocompetinginterests. calcd . for C17 H NO 13 V: 4 C, 58.96; H, 3.75; N, 4.04. contributions Authors .+ Found:C,58.51;H,3.49;N,4.19.m/zM =346. OAcarriedouttheexperimentalwork.TAhelpedinexperimentaland
Catalyticactivitystudy

The catalytic oxidation of benzoin to benzil was outina25mlflask.Inatypicalreaction,anaqueoussoAuthordetails lutionof30%H 2O 2 (0.015mmol)(0.5mLofH 2O 2 stock 1 Departmentchemistry,CollegeofEducation,UniversityofBasrah,Basrah, 2 solution; 0.017 g in 5 mL3CH CN) and benzoin (0.01 g, Iraq. DepartmentofChemistry,UniversityoftheWesternCapeBellville, PrivateBagX17,Bellville,CapeTown7535,SouthAfrica. 0.047 mmol) were mixed in 3 mL of the solvent used and the reaction mixture was magnetically stirred and Received:13November2012Accepted:2January2013 heated at 30C or 50C in an oil bath. An appropriate Published:7January2013 amount of catalyst (0.003 g) was added to the reaction References mixture and with this, the reaction was considered to 1. MallatT,BikerA: Oxidationofalcoholswithmolecularoxygenonsolid begin. Each runwasrepeated twice.Duringthereaction, 3058. catalysts. ChemRev 2004, 104: 3037 the products were analysed after specific time intervals 2. EbitaniK,JiH-B,MizugakiT,KanedaK: HighlyactivetrimetallicRu/CeO2/ vis spectroscopy and later confirmed by GCCoO(OH)catalystforoxidationofalcoholsinthepresenceofmolecular using UV 170. oxygen. JMolCatalA:Chem 2004, 212: 161 after considering the response factors of the authentic 3. MakwanaVD,SonY-C,HowellAR,SuibSL: Theroleoflatticeoxygenin samples. Samples of the reaction mixture (0.1 ml) were selectivebenzylalcoholoxidationusingOMS-2catalyst:Akineticand 52. isotope-labelingstudy. JCatal2002, 210: 46 dilutedwith10mlmixtureofH 2 O:CH 3 CN(1:1)andthe 4. KobayashiS,MiyamuraH,AkiyamaR,IshidT: Highlyactive,immobilized absorbance of the solution was measured spectrophotorutheniumcatalystsforoxidationofalcoholstoaldehydesandketones. metrically The effects of various parameters, such as Preparationanduseinbothbatchandflowsystems. JAmChemSoc 9254. 127: 9251 time of reaction and type of solvent as well as the 2005, Discriminationofactive temperature of the reaction were studied in order5. to FerriD,MondelliC,KrumeichF,BaikerA: palladiumsitesincatalyticliquid-phaseoxidationofbenzylalcohol. J examinetheireffectonthereactionproductpattern. 22986. PhysChemB 2006, 110: 22982
6. JensenDR,SigmanMS: Palladiumcatalystsforaerobicoxidativekinetic resolutionofsecondaryalcoholsbasedonmechanisticinsight. OrgLett Conclusion 65. 2003, 5: 63 FourtridentateONO type Schiff baseligandsweresynthe7. VollhardtKPC,SchoreNE: OrganicChemistry . NewYork:2nded,Freeman; 929. 1994:924 sizedbycondensationof2-aminophenolor2-aminoethanol 8. KiriharaM,OchiaiY,TakizawaS,TakahataH,NemotoH: Aerobicoxidation with3-ethoxysalicylaldehyde and2-hydroxy-1-naphthaldeof -hydroxycarbonylscatalysedbytrichlorooxyvanadium:Efficient hyde. Complexation of these ligands with vanadyl(IV) synthesisof -dicarbonylcompounds. 1388. ChemCommun 1999,:1387 9. SiegelH,EggersdorferM: KetonesinUllmann'sEncyclopaediaofIndustrial sulphate leads to the formation of new oxovanadium(IV) IV Chemistry . Wienheim:Wiley-VCH;2002. complexesoftypeV OL.H 2 O. 10. McKillopA,SwannB,FordME,TaylorEC: Thalliuminorganicsynthesis. ElementalanalysesandspectraldataofthefreeligandsXXXVIII.Oxidationofchalcones,deoxybenzoins,andbenzoinswith 3645. JAmChemSoc1973, 95: 3641 and their oxovanadium(IV) complexes were found to thallium(III)nitrate(TTN). be

discussionpart.JHhelpedinexperimentalanddiscussionpart.HAhelpedin thediscussion,characterizationanddraftthemanuscript.SThelpedinthe discussion,characterizationanddraftthemanuscript.Allauthorsreadand carried approvedthefinalmanuscript.

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