Research Article Oxidative Carbonylation of Aromatic ...downloads.hindawi.com/journals/jchem/2015/210806.pdf · Research Article Oxidative Carbonylation of Aromatic Amines ... substituted

Research ArticleOxidative Carbonylation of Aromatic Amines with CO Catalyzedby 13-Dialkylimidazole-2-selenone in Ionic Liquids

Fengshou Tian1 Yahong Chen1 Xiaofang Wang2 Peng Li2 and Shiwei Lu2

1Department of Chemistry Zhoukou Normal University Zhoukou Henan 466001 China2Dalian Institute of Chemical Physics Chinese Academy of Sciences 457 Zhongshan Road Dalian Liaoning 116023 China

Correspondence should be addressed to Fengshou Tian fengshoutian163com

Received 9 February 2015 Revised 24 March 2015 Accepted 27 March 2015

Academic Editor Andrea Penoni

Copyright copy 2015 Fengshou Tian et alThis is an open access article distributed under the Creative Commons Attribution Licensewhich permits unrestricted use distribution and reproduction in any medium provided the original work is properly cited

13-Dialkylimidazole-2-selenone as a novel substituted selenium heterocyclic catalyst was used to catalyze oxidative carbonylationof aromatic amines with carbon monoxide in the presence of air to symmetrical ureas in up to 97 yield in ionic liquids

1 Introduction

In recent years attention has been paid to a very promisingnonphosgene process for the synthesis of various ureasnamely the reductive carbonylation of nitrocompounds orthe oxidative carbonylation of aromatic amines catalyzedby noble metals including rhodium ruthenium and pal-ladium [1ndash7] However oxidative carbonylation of aminesor reductive carbonylation of nitrocompounds by seleniumcatalysts instead of noble metals has been reported to givesymmetrical ureas [8ndash10] Though these reactions possessthese advantages such as the easily available catalyst andphase-transfer catalyst properties [11 12] selenium-catalyzedcarbonylation reactions have a disadvantage that the volatileselenium-containing intermediates (H

2Se) generated in the

reaction produce unbearable and toxic odour The use ofselenium-containing catalyst is a trend in selenium-catalyzedreaction for safety and green chemistry purposes

In the course of our ongoing investigations on theselenium-catalyzed carbonylation reaction we have discov-ered that symmetrical ureas could be obtained from the car-bonylation of nitrobenzene or substituted nitroarene undersolvent-free conditions [13] or under atmospheric pressure[14] or in ionic liquids [15]

Recently we also have reported the synthesis of 13-dia-lkylimidazole-2-selenones using 13-dialkylimidazolium saltswith selenium inwater or in ethanol or acetone [16 17] Keep-ing this result in mind we reported 13-dialkylimidazole-2-selenone catalyzed oxidative carbonylation of aromatic

amines with carbon monoxide in the presence of oxygen inionic liquids (Scheme 1)

2 Experimental

Imidazolin-2-selenones were synthesized according to theliterature [17] The organic solvents were all of reagent gradeandwere usedwithout further purification Ionic liquids weresynthesized according to the literature [18] Selenium (995)and carbon monoxide (99) and organic amines were allused as purchased Melting points were determined on aTaike X-4 apparatus (Beijing China) and are uncorrected1H and 13C NMR spectra were obtained on a Bruker DRX400 spectrometer Chemical shifts were reported in partsper million relative to tetramethylsilane (120575 units) withdimethylsulfoxide (DMSO-d

6) as solvent

21 General Procedure 5mmol of aniline 046mmol ofselenium-containing catalyst and 025 g [BMIM]BF

4were

sealed in a 100mL stainless steel autoclave The reactorwas pressurized with 02Mpa oxygen and 11Mpa carbonmonoxide and then placed in an oil bath preheated to 90∘Cafter 6 h of the reaction time the apparatus was degassed andthe 13-diaryl urea was separated from [BMIM]BF

4by adding

acetone and water to the reaction mixtures Purification bycolumn chromatography on silica gel or recrystallizationgave the urea product Products were identified by NMRmeasurements andor comparison with authentic samples

Hindawi Publishing CorporationJournal of ChemistryVolume 2015 Article ID 210806 5 pageshttpdxdoiorg1011552015210806

2 Journal of Chemistry

Catalyst (a) (b) (c)

Se

N N

O

N N

Se S

H2N NH2

NH2 + CO CatalystIonic liquid

OC NN

HH

Scheme 1

Table 1 The study of the reaction in different conditions

Entrya Catalyst a (mmol) IL (g) Base Temperature (∘C) Yield ()f

1 046 025 mdash 90 942b 046 025 mdash 90 343c 046 025 mdash 90 254d 046 025 mdash 90 55 046 0 mdash 90 196 046 025e mdash 90 197 046 025 Et3N 90 lt38 046 025 K2CO3 90 lt59 046 025 mdash 60 3410 046 050 mdash 60 5711 046 025 HOAc 90 57aReaction conditions aniline (50mmol) IL is [BMIM]BF4 Pair = 02Mpa Pair + Pco = 13Mpa bcatalyst is selenium ccatalyst is b dcatalyst is c eIL is[BMIM]Cl fisolated yields

3 Results and Discussion

Aniline was treated with 1-butyl-3-methyl-imidazole-2-selenone and carbon monoxide and air in the presence of[BMIM]BF

4at 90∘C for 6 h Oxidative carbonylation of

aniline efficiently led to NN-diphenylurea in 94 yield(Table 1 entry 1) We found that the reaction catalyzed bydifferent catalysts exhibited different yields of urea (Table 1entries 1ndash4) and a is the best catalyst in the reaction Thereaction proceeded very slowly in the absence of ionic liquid(Table 1 entry 5) and the efficiency of use of [BMIM]BF

4

is better than that of use of [BMIM]Cl (Table 1 entries 1and 6) It is well known that the base plays an importantrole during selenium-catalyzed reaction [23 24] In thereaction both Et

3N and K

2CO3

increase the reactionefficiency but no reaction occurs (Table 1 entries 7-8) Thereaction occurred without use of a base (Table 1) The yieldof NN-diphenylurea increased when adding amount of the[BMIM]BF

4or raising the reaction temperature (Table 1

entries 1 8-9) When HOAc was used in the reaction theyield of NN-diphenylurea is up to 57 the reason may bedecomposition of containing selenium catalyst under acidiccondition (Table 1 entry 11)

To test the reusability of the catalyst and the ionicliquid the oxidative carbonylation of aniline was performedusing 1-butyl-3-methyl-imidazole-2-selenone as catalyst inthe presence of CO and air (Pair = 02Mpa Pair + Pco =13Mpa) in ionic liquid at 90∘C for 6 h (Table 2) After thereaction was complete the 13-diaryl urea was separated from[BMIM]BF

4by adding acetone and water to the reaction

mixture the resultant liquor containing the catalyst and ionic

Table 2 Reusability of the catalysts in the reaction

Entrya Cycle Yieldb

1 0 942 1 963 2 994 3 92aReaction conditions catalyst a (046mmol) [BMIM]BF4 (025 g) aniline(50mmol) Pair = 02Mpa Pair + Pco = 13Mpa temperature = 90∘Creaction time = 6 h bisolated yields

liquid was reused with a fresh charge of aniline Catalystexhibited better activity than it did in the original runs Theyield of the symmetrical urea increased upon recycling thecatalyst suggesting that unchanged substrates might haveparticipated in the subsequent reaction (Table 2)

In a fashion similar to the synthesis of symmetricalureas the oxidative carbonylation of aniline was investigatedand the results are summarized in Table 3 It is noteworthythat all aromatic amines could undergo the same type ofreactions under the conditions as stated in Table 3 (entries1ndash6) Increasing steric hindrance on the phenyl rings ofthe substrate obviously dropped to the product yield (17)(Table 3 entry 3) 1-Naphthylamine and 2-aminopyridinegave the corresponding ureas in 41and40 (Table 3 entries5-6) When aniline and 4-methylaniline were used as thesubstrate the yields of the intended products were obtainedin 94 and 97 (Table 3 entries 1 and 2) but using 4-acetylaniline as the substrate the product yield decreased in7 rapidly (Table 3 entry 4)

Journal of Chemistry 3

Table 3 The synthesis of symmetrical ureas from organic amines

Entrya Substrates Products [BMIM]BF4(g) 119879 (∘C) Yield

()c

1 [19] NH2 NHCONH 025 90 94

2 [19] H3C NH2NHCONHH3C CH3 025 90 97

3 [19]NH2

CH3

NHCONH

CH3 H3C025 90 17

4 [19] H3COC NH2H3COC NHCONH COCH3 025 90 7

5 [20]NH2

NHCONH025 90 41

6 [21] NNH2 NHCONH

N N 025 90 40

7 [3] CH2NH2 CH2NHCONHCH2 025 60 70

8 [3] CH2NH2CH2NHCONHCH2 mdash 60 73

9b [22] CH3CH2NH2 CH3CH2NHCONHCH2CH3 mdash 60 52

10 NH NCON mdash 60 0

11 [22] (CH3)(CH2)3NH2 (CH3)(CH2)3NHCONH(CH2)3CH3 mdash 60 91

12 [22] (CH3)2CHNH2 (CH3)2CHNHCONHCH(CH3)2 mdash 60 97

13 [19] NH2 NHCONH mdash 60 98

aReaction conditions catalyst a (010 g) [BMIM]BF4 (025 g) amine (50mmol) Pair + Pco = 13Mpa reaction time = 6 h b65ndash75 aqueous solution cisolatedyields

Aliphatic amines exhibited a higher activity than aro-matic amines in a lower temperature (60∘C) Withoutuse of the ionic liquid the reaction occurs satisfactorily(Table 3 entries 8-9) Complete conversions were achievedfor aliphatic amines over a period of 6 h and the symmetricalureas were obtained in moderate to good yields (52ndash98)after workup (Table 3 entries 7ndash12) When dimethylamineaqueous solution (65ndash75) was used as the substrate theproduct yield was 52 (Table 3 entry 9) but the reaction didnot proceed in the presence of piperidine (Table 3 entry 10)Long-chain aliphatic amines and cyclohexanemethylamineafforded the symmetrical ureas in 91ndash98 yields (Table 3entries 11ndash13)

4 Conclusion

In conclusion we have found a synthetic method for thesymmetrical ureas from amines and selenium-containing

catalyst and carbon monoxide through oxidative carbonyla-tion reaction The odour that exists in elemental selenium-catalyzed carbonylation reactions was not present in thiscatalytic system The in situ generated inorganic seleniumcompounds (such as H

2Se) that are mainly responsible

for the unbearable and toxic odour in selenium-catalyzedcarbonylation reactions can be avoided because of selenium-containing catalyst (the chemical loading of selenium)Although the mechanism for formation of symmetrical ureasusing selenium-containing catalyst has not been clarified thereason may be the result of selenium-containing catalystsdirectly involved in the reaction and avoiding the generationof toxic gases Further studies regarding the mechanism areunderway

Data of Some Products

NN1015840-Diphenylurea 1HNMR (DMSO-d6 400MHz)

868 (s 2H) 747 (m 4H) 729 (m 4H) 698 (m 2H)


13C NMR (DMSO-d6 400MHz) 120575 = 1525 1397

1288 1219 1182NN1015840-Bis(4-methylphenyl)urea 1H NMR (DMSO-d6 400MHz) 850 (s 2H) 733 (d 4H) 707 (d 4H)

224 (s 6H) 13C NMR (DMSO-d6 400MHz) 120575 =

1526 1372 1305 1292 1182 204NN1015840-Bis(2-methylphenyl)urea 1H NMR (DMSO-d6 400MHz) 824 (s 2H) 782 (d 2H) 718minus713 (m

4H) 695 (m 2H) 226 (s 6H) 13CNMR (DMSO-d6

400MHz) 120575 = 1529 1375 1302 1277 1261 12271215 180NN1015840-Bis(4-methoxyphenyl)urea 1H NMR (DMSO-d6 400MHz) 926 (s 2H) 817 (d 4H) 789 (d 4H)

277 (s 6H) 13C NMR (DMSO-d6 400MHz) 120575 =

1957 1515 1436 1307 1301 1291 1173 257NN1015840-Dimethylurea 1HNMR(DMSO-d

6 400MHz)

550 (s 2H) 319 (q 4H) 111 (t 6H) 13C NMR(DMSO-d

6 400MHz) 120575 = 1588 345 151

NN1015840-Diisopropylurea 1H NMR (DMSO-d6

400MHz) 536 (d 2H) 368 (m 2H) 102 (d 12H)13C NMR (DMSO-d

6 400MHz) 120575 = 1566 4038

228

Conflict of Interests

The authors would like to declare that they do not have anycommercial or associative interests that represent a conflict ofinterests in connection with the submitted paper

Acknowledgments

The authors are grateful for financial support from theNatural Science Foundation of Henan Province (Project nos142102310365 and 142300410417) and the Natural ScienceFoundation of Education Department of Henan Province(nos 14A150015 and 15A150087)

References

[1] F Ragaini A Ghitti and S Cenini ldquoMechanistic study of theRu3(CO)12Tetraalkylammonium chloride catalyzed carbony-

lation reactions of nitroarenes to carbamates and ureas acompletely revised picturerdquo Organometallics vol 18 no 24 pp4925ndash4933 1999

[2] I Chiarotto and M Feroci ldquoSelective and environmentallyfriendly methodologies based on the use of electrochemistryfor fine chemical preparation an efficient synthesis of NN1015840-disubstituted ureasrdquo Journal of Organic Chemistry vol 68 no18 pp 7137ndash7139 2003

[3] Z Li Z Y Wang W Zhu Y L Xing and Y L ZhaoldquoCeCl

3sdot7H2O-KI-cataylzed environmentally friendly synthesis

of NN1015840 -disubstituted ureas in water under microwave irradi-ationrdquo Synthetic Communications vol 35 no 17 pp 2325ndash23312005

[4] T Kondo ldquoNovel ruthenium-complex-catalyzed synthesis ofureas from formamides and aminesrdquo Organometallics vol 16no 12 pp 2562ndash2570 1997

[5] S M Islam D Mal B K Palit and C R Saha ldquoReductivecarbonylation of nitroaromatics using RhA(CO)

2rdquo Journal of

Molecular Catalysis A Chemical vol 142 no 2 pp 169ndash1811999

[6] P Wehman L Borst P C J Kamer and P W N M vanLeeuwen ldquoInfluence of an aromatic carboxylic acid as cocatalystin the palladium- catalysed reductive carbonylation of aromaticnitro compoundsrdquo Journal of Molecular Catalysis A Chemicalvol 112 no 1 pp 23ndash36 1996

[7] A M Tafesh and J Weiguny ldquoA review of the selectivecatalytic reduction of aromatic nitro compounds into aromaticamines isocyanates carbamates and ureas usingCOrdquoChemicalReviews vol 96 no 6 pp 2035ndash2052 1996

[8] H S Kim Y J Kim H J Lee M J Chung and S DLee ldquoPreparing N N1015840-disubstituted urea using selenium-basedcatalystrdquo Patent US 6127575 1999

[9] X Zhang D Li X Ma Y Wang and G Zhang ldquoSynthesis ofunsymmetrical 2-pyridyl ureas via selenium-catalyzed oxida-tive carbonylation of 2-aminopyridine with aromatic aminesrdquoSynthesis vol 45 no 10 Article ID SS-2013-F0083-OP pp 1357ndash1363 2013

[10] N Sonoda T Yasuhara K Kondo T Ikeda and S Tsumi ldquoAnew synthesis of ureas The reaction of ammonia or aliphaticamines with carbon monoxide in the presence of seleniumrdquoJournal of the AmericanChemical Society vol 93 no 23 p 63441971

[11] Y Yang and S W Lu ldquoSelenium-catalyzed reductive car-bonylation of nitrobenzene with amines as coreagents to giveunsymmetric phenylureasrdquo Tetrahedron Letters vol 40 no 26pp 4845ndash4846 1999

[12] J Mei Y Yang Y Xue and S Lu ldquoSelective formation ofunsymmetric ureas by selenium-catalyzed oxidative-reductivecarbonylation with COrdquo Journal of Molecular Catalysis AChemical vol 191 no 1 pp 135ndash139 2003

[13] X Wang P Li X Yuan and S Lu ldquoSelenium-catalyzedcarbonylation of nitroarenes to symmetrical 13-diarylureasunder solvent-free conditionsrdquo Journal ofMolecular Catalysis AChemical vol 253 no 1-2 pp 261ndash264 2006

[14] X F Wang S W Lu and Z K Yu ldquoHighly efficient route todiselenides from the reactions of imines and selenium in thepresence of carbon monoxide and waterrdquo Advanced Synthesis ampCatalysis vol 346 pp 929ndash932 2004

[15] X F Wang P Li X H Yuan and S W Lu ldquoSynthesis ofsymmetrical 13-diarylureas by sulfur-catalyzed carbonylationin ionic liquidsrdquo Journal of Molecular Catalysis A Chemical vol255 no 1-2 pp 25ndash27 2006

[16] F S Tian Y H Chen L Wu P Li and S W Lu ldquoAnefficient synthesis of 13-dialkylimidazole-2-selenonesrdquo Journalof Chemical Research vol 38 no 6 pp 375ndash377 2014

[17] F Tian Y Chen P Li and S Lu ldquoAnovelmethod for synthesis of1 3-Dialkylimidazole-2-selenones in waterrdquo Phosphorus Sulfurand Silicon and the Related Elements vol 189 no 9 pp 1391ndash1395 2014

[18] J S Wilkes J A Levisky R A Wilson and C L HusseyldquoDialkylimidazolium chloroaluminate melts a new class ofroom-temperature ionic liquids for electrochemistry spec-troscopy and synthesisrdquo Inorganic Chemistry vol 21 no 3 pp1263ndash1264 1982

[19] M A Pasha and M B M Reddy ldquoEfficient method of syn-thesis of NN1015840-disubstituted ureasthioureas by a zinc chloridecatalyzed thermal reactionrdquo Synthetic Communications vol 39no 16 pp 2928ndash2934 2009


[20] T L Kurth and F D Lewis ldquoGround-State ConformationalEquilibrium and Photochemical Behavior of Syn and AntiNN1015840-Dimethyl-NN1015840-di-1-naphthylurea Protophanesrdquo Journalof the American Chemical Society vol 125 no 45 pp 13760ndash13767 2003

[21] C H Chien M K Leung J K Su G H Li Y H Liuand Y Wang ldquoSubstituent effects on pyrid-2-yl ureas towardintramolecular hydrogen bonding and cytosine complexationrdquoJournal of Organic Chemistry vol 69 no 6 pp 1866ndash1871 2004

[22] M S Khajavi M G Dakamin H Hazarkhani M Hajihadiand F Nikpour ldquoAn efficient one-pot procedure for prepara-tion of symmetrical NN1015840-disubstituted ureas from aromaticand aliphatic amines and urea under microwave irradiationrdquoIranian Journal of Chemistry and Chemical Engineering vol 19no 1 pp 24ndash28 2000

[23] X Liu and S Lu ldquoSelective formation of aromatic aminesby selenium-catalyzed reduction of aromatic nitro compoundswith COH

2O under atmospheric pressurerdquo Journal of Molecu-

lar Catalysis A Chemical vol 212 no 1-2 pp 127ndash130 2004[24] X F Wang G Ling Y Xue and S W Lu ldquoSelenium-catalyzed

reductive carbonylation of 2-nitrophenols to 2-benzoxazonesrdquoEuropean Journal of Organic Chemistry vol 36 no 34 pp 1675ndash1679 2005

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy


Carbohydrate Chemistry

International Journal of


Journal of

Chemistry


Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of


The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of


Chromatography Research International


Applied ChemistryJournal of



Theoretical ChemistryJournal of


Journal of

Spectroscopy

Analytical ChemistryInternational Journal of


Journal of


Quantum Chemistry


Organic Chemistry International

ElectrochemistryInternational Journal of



CatalystsJournal of


Catalyst (a) (b) (c)

Se

N N

O

N N

Se S

H2N NH2

NH2 + CO CatalystIonic liquid

OC NN

HH

Scheme 1

Table 1 The study of the reaction in different conditions

Entrya Catalyst a (mmol) IL (g) Base Temperature (∘C) Yield ()f

1 046 025 mdash 90 942b 046 025 mdash 90 343c 046 025 mdash 90 254d 046 025 mdash 90 55 046 0 mdash 90 196 046 025e mdash 90 197 046 025 Et3N 90 lt38 046 025 K2CO3 90 lt59 046 025 mdash 60 3410 046 050 mdash 60 5711 046 025 HOAc 90 57aReaction conditions aniline (50mmol) IL is [BMIM]BF4 Pair = 02Mpa Pair + Pco = 13Mpa bcatalyst is selenium ccatalyst is b dcatalyst is c eIL is[BMIM]Cl fisolated yields

3 Results and Discussion

Aniline was treated with 1-butyl-3-methyl-imidazole-2-selenone and carbon monoxide and air in the presence of[BMIM]BF

4at 90∘C for 6 h Oxidative carbonylation of

aniline efficiently led to NN-diphenylurea in 94 yield(Table 1 entry 1) We found that the reaction catalyzed bydifferent catalysts exhibited different yields of urea (Table 1entries 1ndash4) and a is the best catalyst in the reaction Thereaction proceeded very slowly in the absence of ionic liquid(Table 1 entry 5) and the efficiency of use of [BMIM]BF

4

is better than that of use of [BMIM]Cl (Table 1 entries 1and 6) It is well known that the base plays an importantrole during selenium-catalyzed reaction [23 24] In thereaction both Et

3N and K

2CO3

increase the reactionefficiency but no reaction occurs (Table 1 entries 7-8) Thereaction occurred without use of a base (Table 1) The yieldof NN-diphenylurea increased when adding amount of the[BMIM]BF

4or raising the reaction temperature (Table 1

entries 1 8-9) When HOAc was used in the reaction theyield of NN-diphenylurea is up to 57 the reason may bedecomposition of containing selenium catalyst under acidiccondition (Table 1 entry 11)

To test the reusability of the catalyst and the ionicliquid the oxidative carbonylation of aniline was performedusing 1-butyl-3-methyl-imidazole-2-selenone as catalyst inthe presence of CO and air (Pair = 02Mpa Pair + Pco =13Mpa) in ionic liquid at 90∘C for 6 h (Table 2) After thereaction was complete the 13-diaryl urea was separated from[BMIM]BF

4by adding acetone and water to the reaction

mixture the resultant liquor containing the catalyst and ionic

Table 2 Reusability of the catalysts in the reaction

Entrya Cycle Yieldb

1 0 942 1 963 2 994 3 92aReaction conditions catalyst a (046mmol) [BMIM]BF4 (025 g) aniline(50mmol) Pair = 02Mpa Pair + Pco = 13Mpa temperature = 90∘Creaction time = 6 h bisolated yields

liquid was reused with a fresh charge of aniline Catalystexhibited better activity than it did in the original runs Theyield of the symmetrical urea increased upon recycling thecatalyst suggesting that unchanged substrates might haveparticipated in the subsequent reaction (Table 2)

In a fashion similar to the synthesis of symmetricalureas the oxidative carbonylation of aniline was investigatedand the results are summarized in Table 3 It is noteworthythat all aromatic amines could undergo the same type ofreactions under the conditions as stated in Table 3 (entries1ndash6) Increasing steric hindrance on the phenyl rings ofthe substrate obviously dropped to the product yield (17)(Table 3 entry 3) 1-Naphthylamine and 2-aminopyridinegave the corresponding ureas in 41and40 (Table 3 entries5-6) When aniline and 4-methylaniline were used as thesubstrate the yields of the intended products were obtainedin 94 and 97 (Table 3 entries 1 and 2) but using 4-acetylaniline as the substrate the product yield decreased in7 rapidly (Table 3 entry 4)




()c

1 [19] NH2 NHCONH 025 90 94

2 [19] H3C NH2NHCONHH3C CH3 025 90 97

3 [19]NH2

CH3

NHCONH

CH3 H3C025 90 17


5 [20]NH2

NHCONH025 90 41

6 [21] NNH2 NHCONH

N N 025 90 40










4 Conclusion







868 (s 2H) 747 (m 4H) 729 (m 4H) 698 (m 2H)


13C NMR (DMSO-d6 400MHz) 120575 = 1525 1397


224 (s 6H) 13C NMR (DMSO-d6 400MHz) 120575 =


4H) 695 (m 2H) 226 (s 6H) 13CNMR (DMSO-d6


277 (s 6H) 13C NMR (DMSO-d6 400MHz) 120575 =


6 400MHz)


6 400MHz) 120575 = 1588 345 151



6 400MHz) 120575 = 1566 4038

228



Acknowledgments


References









2rdquo Journal of

































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of




()c

1 [19] NH2 NHCONH 025 90 94

2 [19] H3C NH2NHCONHH3C CH3 025 90 97

3 [19]NH2

CH3

NHCONH

CH3 H3C025 90 17


5 [20]NH2

NHCONH025 90 41

6 [21] NNH2 NHCONH

N N 025 90 40










4 Conclusion







868 (s 2H) 747 (m 4H) 729 (m 4H) 698 (m 2H)


13C NMR (DMSO-d6 400MHz) 120575 = 1525 1397


224 (s 6H) 13C NMR (DMSO-d6 400MHz) 120575 =


4H) 695 (m 2H) 226 (s 6H) 13CNMR (DMSO-d6


277 (s 6H) 13C NMR (DMSO-d6 400MHz) 120575 =


6 400MHz)


6 400MHz) 120575 = 1588 345 151



6 400MHz) 120575 = 1566 4038

228



Acknowledgments


References









2rdquo Journal of

































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


13C NMR (DMSO-d6 400MHz) 120575 = 1525 1397


224 (s 6H) 13C NMR (DMSO-d6 400MHz) 120575 =


4H) 695 (m 2H) 226 (s 6H) 13CNMR (DMSO-d6


277 (s 6H) 13C NMR (DMSO-d6 400MHz) 120575 =


6 400MHz)


6 400MHz) 120575 = 1588 345 151



6 400MHz) 120575 = 1566 4038

228



Acknowledgments


References









2rdquo Journal of

































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of










Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of

Documents

Research Article Oxidative Carbonylation of Aromatic ...downloads.hindawi.com/journals/jchem/2015/210806.pdf · Research Article Oxidative Carbonylation of Aromatic Amines ... substituted