Research Article Triphenylphosphine Mediated Synthesis of...

Hindawi Publishing CorporationJournal of ChemistryVolume 2013 Article ID 289636 5 pageshttpdxdoiorg1011552013289636

Research ArticleTriphenylphosphine Mediated Synthesis of FunctionalizedBenzo-Fused Coumarins from Some OH Acids and DialkylAcetylene Dicarboxylate

Bita Mohtat1 Semiramis Nahavandian1 Maryam Razaghi1

Saeedeh Farsijani1 and Hoorieh Djahaniani2

1 Chemistry Department Karaj Branch Islamic Azad University PO Box 31485-313 Karaj Iran2 Chemistry Department East Tehtan Branch Islamic Azad University PO Box 163-33955 Tehran Iran

Correspondence should be addressed to Bita Mohtat b mohtatyahoocom

Received 6 February 2013 Accepted 22 July 2013

Academic Editor Silvia Mari

Copyright copy 2013 Bita Mohtat et al This 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

Benzo-fused coumarins are prepared from 4-quinolinol by treatment with PPh3and dialkyl acetylenedicarboxylate Angular

coumarins are prepared from 3-isoquinolinol and 7-hydroxyl coumarine with PPh3and dialkyl acetylenedicarboxylate

1 Introduction

Coumarins comprise a very large class of compoundsfound throughout the plant kingdom [1] The bioactivity ofcoumarin andmore complex related derivatives appears to bebased on the coumarin nucleus [2 3] Coumarin compoundscan display anticancer anticoagulant antimicrobial anti-inflammatory and antioxidant activities [4ndash8]

In addition as an important class of organic heterocyclicdyes coumarin derivatives exhibit unique photochemical andphotophysical properties which render them useful in avariety of applications such as optical brighteners laser dyesnonlinear optical chromophores solar energy collectorsfluorescent labels and probes in biology and medicine andtwo-photon absorption (TPA) materials [9ndash12]

Coumarins have been synthesized by several methods[13ndash18] In the interest of synthesizing new coumarin ringsystems for possible evaluation as biologically active com-pounds we have described a synthesis of carboxymethylcoumarins from 3-hydroxyl pyridine [19] carboxylic systems[19ndash22] we wish to report here the synthesis of some benzo-fused coumarinsThe preparations of coumarins are depictedin Schemes 1 2 and 3

2 Experimental

21 General Compounds 1 2 and Ph3P were obtained from

Fluka and were used without further purification M pElectrothermal-9100 apparatus IR Spectra Shimadzu IR-460 spectrometer 1H- and 13CNMR spectra Bruker DRX-300 AVANCE instrument in CDCl

3at 300 and 75MHz

respectively 120575 in ppm EI-MS (70 eV) Finnigan-MAT-8430mass spectrometer inmz Elemental analyses (C H N) wereperformed with a Heraeus CHN-O-Rapid analyser

22 General Procedure for the Preparation of Compound 3To a stirred solution of 052 g of Ph

3P (2mmoL) and 028 g

1 (2mmoL) in toluene (10mL) was added dropwise a mixtureof 2 (2mmoL) in toluene (2mL) at room temperature over5min The reaction mixture was heated under reflux for24 h The solvent was removed under reduced pressure andthe viscous residue was purified by column chromatography(SiO2 hexaneAcOEt) to afford the pure adducts

Methyl 2-Oxo-2H-pyrano[32-c]quinoline-4-carboxylate (4a)Yellow powder 046 g (90) mp 119ndash121∘C IR (KBr)]maxcm

minus1 1744 (C=O) 1625 (C=N) 1HNMR (300MHzCDCl

3) 120575 408 (s 3H Me) 709 (s 1H CH) 770

2 Journal of Chemistry

N

OH OH

N

abc

2

1 2 3

H

N

O

O

abc

4

4

R R907772

CO2R

CO2RCO2R

CO2R

CO2R

+

Ph3P (15mol-)

Toluene reflux Toluene

MeEt

MeEt

Yield ()

t-Bu t-Bu

200∘C

Scheme 1 Typical procedure for compound 4

N

O

O

ab

MeEt

6 R

N

OH

2

Yield ()7671

5 6

+

RO2C

Ph3P (15mol-)

Toluene reflux

Scheme 2 Procedure for synthesis of compound 6

(t 1H 119869 = 65Hz CH) 788 (t 1H 119869 = 70 CH) 815 (d 1H119869 = 84Hz CH) 845 (d 1H 119869 = 79Hz CH) 971 (s 1HCH) 13CNMR (75MHz CDCl

3) 120575 536 (Me) 1079 (CH)

1177 (CH) 1196 (CH) 1276 (CH) 1293 (C) 1324 (CH) 1417(CH) 1477 (C) 1478 (C) 1489 (C) 1574 (C) 1586 (C=O)1635 (C=O) MS (EI)mz 255 (M+ 98) 227 (57) 196 (84)140 (43) Anal calcd for C

14H9NO4 C 6588 H 355 N 549

Found C 6587 H 357 N 547

Ethyl 2-Oxo-2H-pyrano[32-c]quinoline-4-carboxylate (4b)Yellow powder 041 g (77) mp 128ndash130∘C IR (KBr)]maxcm


3) 120575 147 (t 3H 119869 = 71HzMe) 454 (q 2H 119869 = 71Hz

OCH2) 709 (s 1H CH) 781 (t 1H 119869 = 73Hz CH) 796

(t 1H 119869 = 69 CH) 814 (d 1H 119869 = 84Hz CH) 843 (d1H 119869 = 83Hz CH) 964 (s 1H CH) 13CNMR (75MHzCDCl

3) 120575 143 (Me) 635 (OCH

2) 1079 (CH) 1177 (CH)

1201 (CH) 1276 (CH) 1293 (C) 1324 (CH) 1417 (CH)1477 (C) 1478 (C) 1489 (C) 1574 (C) 1586 (C=O) 1635(C=O) MS (EI) mz 255 (M+ 98) 196 (72) 196 (69) 154(100) Anal calcd for C

15H11NO4 C 6691 H 412 N 520

Found C 6694 H 411 N 519

Tert-butyl 2-Oxo-2H-pyrano[32-c]quinoline-4-carboxylate(4c) Yellow powder 043 g (72) mp 130ndash132∘C IR (KBr)]maxcm


3) 120575 170 (s 9H 3Me) 702 (s 1H CH) 780 (t 1H

119869 = 69Hz CH) 795 (t 1H 119869 = 69 CH) 813 (d 1H119869 = 84Hz CH) 842 (d 1H 119869 = 83Hz CH) 960 (s 1H

CH) 13CNMR (75MHz CDCl3) 120575 281 (3Me) 853 (C)

1079 (CH) 1185 (CH) 1195 (CH) 1286 (CH) 1303 (C)1328 (CH) 1417 (CH) 1477 (C) 1488 (C) 1498 (C) 1574(C) 1593 (C=O) 1634 (C=O) MS (EI) mz 255 (M+ 98)269 (86) 196 (48) 57 (100) Anal calcd for C

17H15NO4 C

6868 H 509 N 471 Found 6870 H 508 N 469

Methyl 3-Oxo-3H-pyrano[23-c]isoquinoline-1-carboxylate(6a) Yellow powder 069 g (76) mp 105ndash107∘C IR (KBr)]maxcm


3) 120575 404 (s 3H Me) 688 (s 1H CH) 755 (t 1H

119869 = 77Hz CH) 767 (t 1H 119869 = 82Hz CH) 770 (d 1H119869 = 81Hz CH) 789 (d 1H 119869 = 81Hz CH) 924 (s 1HCH) 13CNMR (75MHz CDCl

3) 120575 538 (Me) 1103 (C)

1224 (CH) 1230 (CH) 1247 (CH) 1263 (CH) 1271 (CH)1285 (C) 1329 (C) 1402 (CH) 1436 (C) 1581 (C) 1640(C=O) 1664 (C=O) MS (EI)mz 255 (M+ 10) 288 (100)204 (43) 189 (72) 61 (100) Anal calcd for C

14H9NO4 C

6588 H 355 N 549 Found C 6584 H 356 N 547

Ethyl 3-Oxo-3H-pyrano[23-c]isoquinoline-1-carboxylate(6b) Yellow powder 038 g (71) mp 110ndash112∘C IR (KBr)]maxcm


3) 120575 143 (t 3H 119869 = 71HzMe) 435 (q 2H 119869 = 71Hz

OCH2) 692 (s 1H CH) 747 (t 1H 119869 = 73Hz CH) 750

(t 1H 119869 = 80Hz CH) 766 (d 1H 119869 = 82Hz CH) 770(d 1H 119869 = 85Hz CH) 13CNMR (75MHz CDCl

3) 120575 140

(Me) 619 (OCH2) 1109 (C) 1226 (CH) 1235 (CH) 1251

(CH) 1261 (CH) 1277 (CH) 1287 (C) 1331 (C) 1401 (CH)

Journal of Chemistry 3

MeEt

Yield ()Yield ()

O O

O

ab

8 R

O OH

2

7 8

O O OO OO

a

9 R

9

9082

87

+ +

RO2C

Ph3P (15mol-)

Toluene reflux

CO2R

t-Bu

Scheme 3 Procedure for synthesis of compounds 8 9

1436 (C) 1579 (C) 1646 (C=O) 1660 (C=O) MS (EI) mz296 (M+ 10) 277 (100) 201 (43) 183 (52) 77 (68) Analcalcd for C

15H11NO4 C 6691 H 412 N 520 Found C

6694 H 410 N 521

Methyl 28-Dioxo-2H8H-pyrano[32-g]chromene-4-carboxy-late Yellow powder 050 g (90) mp 135ndash137∘C IR (KBr)]maxcm

minus1 1739 (C=O) 1HNMR (300MHz CDCl3) 120575 412

(s 3H Me) 643 (d 1H 119869 = 96Hz CH) 650 (s 1H CH)728 (d 1H 119869 = 87Hz CH) 766 (d 1H 119869 = 87Hz CH)772 (d 1H 119869 = 96Hz CH) 13CNMR (CDCl

3) 120575ppm 538

(OMe) 1054 (C) 1138 (CH) 1149 (C) 1152 (CH) 1158(CH) 1313 (CH) 1429 (CH) 1433 (C) 1561 (C) 1579 (C)1583 (C=O) 1654 (C=O) 1676 (C=O) MS (EI) mz 272(M+ 30) 258 (100) 231 (46) 146 (100) Anal calcd forC14H8O6 C 6177 H 296 Found C 5596 H 309 N 488

Ethyl 28-Dioxo-2H8H-pyrano[32-g]chromene-4-carboxy-late Yellow powder 038 g (67) mp 139ndash141∘C IR (KBr)]maxcm


(t 3H 119869 = 71Hz Me) 435 (q 2H 119869 = 71Hz OCH2) 672

(d 1H 119869 = 96Hz CH) 695 (s 1H CH) 733 (s 1H CH)760 (d 1H 119869 = 96Hz CH) 855 (s 1H CH) 13CNMR(75MHz CDCl

3) 120575 140 (Me) 594 (OCH

2) 1050 (C) 1115

(CH) 1118 (C) 1134 (CH) 1150 (CH) 1317 (CH) 1422(CH) 1437 (C) 1558 (C) 1574 (C) 1613 (C=O) 1659(C=O) 1675 (C=O) MS (EI) mz 314 (M+ 41) 258 (53)231 (65) 170 (24) Anal calcd for C

15H10O6 C 6294 H

352 Found C 6297 H 348

Tert-butyl 28-Dioxo-2H8H-pyrano[32-f]chromene-10-car-boxylate Yellow powder 055 g (87) mp 150ndash152∘C IR(KBr) ]maxcm

minus1 1747 (C=O) 1HNMR (300MHz CDCl3)

120575 165 (s 9H 3Me) 647 (d 1H 119869 = 96Hz CH) 696 (s 1HCH) 730 (s 1H CH) 778 (d 1H 119869 = 96Hz CH) 862 (s1H CH) 13CNMR (75MHz CDCl

3) 120575 293 (3Me) 848 (C)

1052 (C) 1137 (CH) 1166 (C) 1191 (CH) 1273 (CH) 1323(CH) 1422 (CH) 1429 (C) 1559 (C) 1561 (C) 1594 (C=O)1625 (C=O) 1676 (C=O) MS (EI) mz 314 (M+ 41) 277(25) 258 (64) 231 (33) 57 (100) Anal calcd for C

17H14O6

C 6497 H 449 Found C 6495 H 448

3 Result and Discussion

Treatment of 4-hydroxyquinoline 1 with dialkyl acety-lene dicarboxylate 2 and PPh

3in toluene under reflux

afforded dimethyl 2-(4-hydroxy-2-methyl-3-quinolinyl)-2-butenedioate (3) [22] When compound 3 was heated at200ndash205∘C it transformed to methyl 2-oxo-2H-pyrano[32-c]quinoline-4-carboxylate 4 in good yield The analyticaland spectral data of the product agree with the structure 4suggested The products were separated by column chro-matography and identified as 4 based on their elementalanalyses and their IR 1H and 13CNMR spectral dataThe mass spectra of these compounds displayed molecularion peaks at appropriate mz values Its 1HNMR spectrumshowed 3H singlet at 120575 = 408 for only one methoxy groupand a singlet (1H) at 120575 = 709 for methine proton The13CNMR spectrum one carbon appeared for the coumarincarbonyl (120575 = 1586 ppm) and one carbon for the carbonylester moiety (120575 = 1635 ppm) The 1H and 13CNMR spectraof 4b and 4c are similar to those of 4a except for thealkoxy moieties which exhibited characteristic resonanceswith appropriate chemical shifts

Treatment of 3-isoquinolinol 5 with dialkyl acetylenedicarboxylate 2 and PPh

3in refluxing toluene for 24 h and

separation of the reaction mixture by column chromatog-raphy gave methyl 3-oxo-3H-pyrano[23-c]isoquinoline-1-carboxylate 6 in 76 yield (Scheme 3) obviously via areaction sequence similar to that depicted in Scheme 1 Thereaction with di-tert-butyl acetylene dicarboxylate was notdetected because of the bulky group (Scheme 2)

Next we studied the reaction of 7-hydroxy coumarine 7with dialkyl acetylene dicarboxylate and PPh

3in refluxing

toluene which resulted in the formation of the methyl28-dioxo-2H8H-pyrano[32-g]chromene-4-carboxylate 8(Scheme 3) The linear product 9 was detected and isolatedfrom the reaction with di-tert-butyl acetylene dicarboxylatebecause of the bulky group

Mechanistically [13 19] it is conceivable that the reactioninvolves the initial formation of a zwitterionic intermediatebetween Ph

3P and the acetylenic compound and subsequent

protonation of reactive 1 1 adduct followed by electrophilicattack of vinyltriphenylphosphonium cation on the aromatic


N

O

N

H

N

OHO

OMe

H10

4

CO2Me

CO2Me

PPh3+

+

minus

CHCO2MePh3P+

MeO2C

MeO2C

minusPPh3

O

Scheme 4

ring at the ortho position relative to the strong activationgroup The product is presumablyproduced by intramolecu-lar lactonization of the unsaturated diester 10 (Scheme 4)

4 Conclusion

From the above results we conclude that treatment of oxygenatom of the pyran ring belongs to the starting phenolwhile the periselectivity in the construction of this new ringdepends on the higher reactivity of the free o-positions ofthe phenol during the aromatic electrophilic substitutionsequenceThese functionalised coumarinsmay be consideredas potentially useful synthetic intermediates because theypossess atoms with different oxidation states The advantagesof presentmethod are the fact that it performed under neutralcondition and substances are utilized in their basic formwith-out anymodificationThe simplicity of the present proceduremakes it an interesting alternative to other approaches

Acknowledgment

The authors thank the Karaj Branch Islamic Azad Universityfor support of this work

References

[1] R D Murray J Mendez and S A Brown The NaturalCoumarins Occurrence Chemistry and Biochemistry JohnWiley amp Sons 1982

[2] F A Jimenez-Orozco J A Molina-Guarneros N Mendoza-Patino et al ldquoCytostatic activity of coumarin metabolitesand derivatives in the B16- F10 murine melanoma cell linerdquoMelanoma Research vol 9 no 3 pp 243ndash247 1999

[3] G J Finn B Creaven and D A Egan ldquoStudy of the invitro cytotoxic potential of natural and synthetic coumarinderivatives using human normal and neoplastic skin cell linesrdquoMelanoma Research vol 11 no 5 pp 461ndash467 2001

[4] D Yim R P Singh C Agarwal S Lee H Chi and R AgarwalldquoA novel anticancer agent decursin induces G1 arrest and

apoptosis in human prostate carcinoma cellsrdquo Cancer Researchvol 65 no 3 pp 1035ndash1044 2005

[5] M E Riveiro R Vazquez A Moglioni et al ldquoBiochemi-cal mechanisms underlying the pro-apoptotic activity of 78-dihydroxy-4-methylcoumarin in human leukemic cellsrdquo Bio-chemical Pharmacology vol 75 no 3 pp 725ndash736 2008

[6] I Kostova S Raleva P Genova and R Argirova ldquoStructure-activity relationships of synthetic coumarins as HIV-1inhibitorsrdquo Bioinorganic Chemistry and Applications vol2006 Article ID 68274 9 pages 2006

[7] B FGage ldquoPharmacogenetics-based coumarin therapyrdquoHema-tology vol 2006 no 1 pp 467ndash473 2006

[8] D A Ostrov J A Hernandez Prada P E Corsino K AFinton N Le and T C Rowe ldquoDiscovery of novel DNA gyraseinhibitors by high-throughput virtual screeningrdquo AntimicrobialAgents and Chemotherapy vol 51 no 10 pp 3688ndash3698 2007

[9] R M Melavanki R A Kusanur M V Kulakarni and J SKadadevarmath ldquoRole of solvent polarity on the fluorescencequenching of newly synthesized 78-benzo-4-azidomethylcoumarin by aniline in benzene-acetonitrile mixturesrdquo Journalof Luminescence vol 128 no 4 pp 573ndash577 2008

[10] T Z Yu P Zhang Y L Zhao H Zhang J Meng andD W Fan ldquoSynthesis and photoluminescent properties oftwo novel tripodal compounds containing coumarin moietiesrdquoSpectrochimica Acta A vol 73 no 1 pp 168ndash173 2009

[11] H Turki S Abid S Fery-Forgues and R El Gharbi ldquoOpticalproperties of newfluorescent iminocoumarins part 1rdquoDyes andPigments vol 73 no 3 pp 311ndash316 2007

[12] X Li Y X Zhao T Wang M Q Shi and F P WuldquoCoumarin derivatives with enhanced two-photon absorptioncross-sectionsrdquo Dyes and Pigments vol 74 no 1 pp 108ndash1122007

[13] I Yavari R Amiri and M Haghdadi ldquoTriphenyphosphine-mediated efficient synthesis of functionalized 2-OXO-2H-Chromenesrdquo Phosphorus Sulfur and Silicon and the RelatedElements vol 179 no 11 pp 2163ndash2168 2004

[14] E Galariniotou V Fragos A Makri K E Litinas and D NNicolaides ldquoSynthesis of novel pyridocoumarins and benzo-fused 6-azacoumarinsrdquo Tetrahedron vol 63 no 34 pp 8298ndash8304 2007


[15] S D Kudale and M N Deodhar ldquoSynthesis and evaluationof some coumarin containing potential antimicrobial agentsrdquoJournal of Chemistry vol 9 no 4 pp 2493ndash2500 2012

[16] M A Hosny M A Radwan and E A El-Sawy ldquoSynthesis andanticancer activity of some new derivatives of coumarin andquinolinyl mercaptotriazolesrdquo Journal of Chemistry vol 9 no4 pp 1737ndash1745 2012

[17] D Kini andMGhate ldquoSynthesis and oral hypoglycemic activityof 3-[51015840-Methyl-21015840- aryl-31015840-(thiazol-21015840-yl amino) thiazolidin-41015840-one]coumarin Derivativesrdquo Journal of Chemistry vol 8 no1 pp 386ndash390 2011

[18] J L Du L I Li and D H Zhang ldquoUltrasound promotedsynthesis of 3-carboxycoumarins in aqueous mediardquo Journal ofChemistry vol 3 p 1 2006

[19] B Mohtat I Yavari R E Ameri and E Salahia ldquoSynthesisof aza coumarines by nucleophilic addition of acetylenic esterscatalysed by Ph

3PrdquoCroaticaChemicaActa vol 84 no 1 pp 123ndash

126 2011[20] B Mohtat S Azimzadeh H Djahaniani and L Pirhadi ldquoPh

3P

catalyzed synthesis of alkyl 2-(4-oxopyridin-1(4H)-Yl) acrylatesby nucleophilic addition to alkyl propiolatesrdquo South AfricanJournal of Chemistry vol 63 pp 204ndash206 2010

[21] B Mohtat Z N Azar S Nahavandian H Djahanianiand A Ahmadi ldquoSynthesis of dialkyl 2-(4-oxopyridin-1(4H)-yl)dicarboxylates through the reaction of 4-hydroxypyridineand dialkyl acetylenedicarboxylate in the presence of triph-enylphosphinerdquo Journal of the Mexican Chemical Society vol55 no 3 pp 194ndash196 2011

[22] B Mohtat S Nahavandian N Z Azar H Djahaniani andZ Hossaini ldquoTriphenylphosphine-promoted c-vinylation of 4-hydroxyquinolinesrdquo Zeitschrift fur Naturforschung vol 66 no7 pp 700ndash704 2011

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

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Carbohydrate Chemistry

International Journal of


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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


N

OH OH

N

abc

2

1 2 3

H

N

O

O

abc

4

4

R R907772

CO2R

CO2RCO2R

CO2R

CO2R

+

Ph3P (15mol-)

Toluene reflux Toluene

MeEt

MeEt

Yield ()

t-Bu t-Bu

200∘C

Scheme 1 Typical procedure for compound 4

N

O

O

ab

MeEt

6 R

N

OH

2

Yield ()7671

5 6

+

RO2C

Ph3P (15mol-)

Toluene reflux

Scheme 2 Procedure for synthesis of compound 6

(t 1H 119869 = 65Hz CH) 788 (t 1H 119869 = 70 CH) 815 (d 1H119869 = 84Hz CH) 845 (d 1H 119869 = 79Hz CH) 971 (s 1HCH) 13CNMR (75MHz CDCl

3) 120575 536 (Me) 1079 (CH)

1177 (CH) 1196 (CH) 1276 (CH) 1293 (C) 1324 (CH) 1417(CH) 1477 (C) 1478 (C) 1489 (C) 1574 (C) 1586 (C=O)1635 (C=O) MS (EI)mz 255 (M+ 98) 227 (57) 196 (84)140 (43) Anal calcd for C

14H9NO4 C 6588 H 355 N 549

Found C 6587 H 357 N 547

Ethyl 2-Oxo-2H-pyrano[32-c]quinoline-4-carboxylate (4b)Yellow powder 041 g (77) mp 128ndash130∘C IR (KBr)]maxcm


3) 120575 147 (t 3H 119869 = 71HzMe) 454 (q 2H 119869 = 71Hz

OCH2) 709 (s 1H CH) 781 (t 1H 119869 = 73Hz CH) 796

(t 1H 119869 = 69 CH) 814 (d 1H 119869 = 84Hz CH) 843 (d1H 119869 = 83Hz CH) 964 (s 1H CH) 13CNMR (75MHzCDCl

3) 120575 143 (Me) 635 (OCH

2) 1079 (CH) 1177 (CH)

1201 (CH) 1276 (CH) 1293 (C) 1324 (CH) 1417 (CH)1477 (C) 1478 (C) 1489 (C) 1574 (C) 1586 (C=O) 1635(C=O) MS (EI) mz 255 (M+ 98) 196 (72) 196 (69) 154(100) Anal calcd for C

15H11NO4 C 6691 H 412 N 520

Found C 6694 H 411 N 519

Tert-butyl 2-Oxo-2H-pyrano[32-c]quinoline-4-carboxylate(4c) Yellow powder 043 g (72) mp 130ndash132∘C IR (KBr)]maxcm


3) 120575 170 (s 9H 3Me) 702 (s 1H CH) 780 (t 1H

119869 = 69Hz CH) 795 (t 1H 119869 = 69 CH) 813 (d 1H119869 = 84Hz CH) 842 (d 1H 119869 = 83Hz CH) 960 (s 1H

CH) 13CNMR (75MHz CDCl3) 120575 281 (3Me) 853 (C)

1079 (CH) 1185 (CH) 1195 (CH) 1286 (CH) 1303 (C)1328 (CH) 1417 (CH) 1477 (C) 1488 (C) 1498 (C) 1574(C) 1593 (C=O) 1634 (C=O) MS (EI) mz 255 (M+ 98)269 (86) 196 (48) 57 (100) Anal calcd for C

17H15NO4 C

6868 H 509 N 471 Found 6870 H 508 N 469

Methyl 3-Oxo-3H-pyrano[23-c]isoquinoline-1-carboxylate(6a) Yellow powder 069 g (76) mp 105ndash107∘C IR (KBr)]maxcm


3) 120575 404 (s 3H Me) 688 (s 1H CH) 755 (t 1H

119869 = 77Hz CH) 767 (t 1H 119869 = 82Hz CH) 770 (d 1H119869 = 81Hz CH) 789 (d 1H 119869 = 81Hz CH) 924 (s 1HCH) 13CNMR (75MHz CDCl

3) 120575 538 (Me) 1103 (C)

1224 (CH) 1230 (CH) 1247 (CH) 1263 (CH) 1271 (CH)1285 (C) 1329 (C) 1402 (CH) 1436 (C) 1581 (C) 1640(C=O) 1664 (C=O) MS (EI)mz 255 (M+ 10) 288 (100)204 (43) 189 (72) 61 (100) Anal calcd for C

14H9NO4 C

6588 H 355 N 549 Found C 6584 H 356 N 547

Ethyl 3-Oxo-3H-pyrano[23-c]isoquinoline-1-carboxylate(6b) Yellow powder 038 g (71) mp 110ndash112∘C IR (KBr)]maxcm


3) 120575 143 (t 3H 119869 = 71HzMe) 435 (q 2H 119869 = 71Hz

OCH2) 692 (s 1H CH) 747 (t 1H 119869 = 73Hz CH) 750

(t 1H 119869 = 80Hz CH) 766 (d 1H 119869 = 82Hz CH) 770(d 1H 119869 = 85Hz CH) 13CNMR (75MHz CDCl

3) 120575 140

(Me) 619 (OCH2) 1109 (C) 1226 (CH) 1235 (CH) 1251

(CH) 1261 (CH) 1277 (CH) 1287 (C) 1331 (C) 1401 (CH)


MeEt

Yield ()Yield ()

O O

O

ab

8 R

O OH

2

7 8

O O OO OO

a

9 R

9

9082

87

+ +

RO2C

Ph3P (15mol-)

Toluene reflux

CO2R

t-Bu



15H11NO4 C 6691 H 412 N 520 Found C

6694 H 410 N 521




3) 120575ppm 538




(t 3H 119869 = 71Hz Me) 435 (q 2H 119869 = 71Hz OCH2) 672


3) 120575 140 (Me) 594 (OCH

2) 1050 (C) 1115


15H10O6 C 6294 H

352 Found C 6297 H 348




3) 120575 293 (3Me) 848 (C)


17H14O6

C 6497 H 449 Found C 6495 H 448









3in refluxing






N

O

N

H

N

OHO

OMe

H10

4

CO2Me

CO2Me

PPh3+

+

minus

CHCO2MePh3P+

MeO2C

MeO2C

minusPPh3

O

Scheme 4


4 Conclusion


Acknowledgment


References
























3P













Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


MeEt

Yield ()Yield ()

O O

O

ab

8 R

O OH

2

7 8

O O OO OO

a

9 R

9

9082

87

+ +

RO2C

Ph3P (15mol-)

Toluene reflux

CO2R

t-Bu



15H11NO4 C 6691 H 412 N 520 Found C

6694 H 410 N 521




3) 120575ppm 538




(t 3H 119869 = 71Hz Me) 435 (q 2H 119869 = 71Hz OCH2) 672


3) 120575 140 (Me) 594 (OCH

2) 1050 (C) 1115


15H10O6 C 6294 H

352 Found C 6297 H 348




3) 120575 293 (3Me) 848 (C)


17H14O6

C 6497 H 449 Found C 6495 H 448









3in refluxing






N

O

N

H

N

OHO

OMe

H10

4

CO2Me

CO2Me

PPh3+

+

minus

CHCO2MePh3P+

MeO2C

MeO2C

minusPPh3

O

Scheme 4


4 Conclusion


Acknowledgment


References
























3P













Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


N

O

N

H

N

OHO

OMe

H10

4

CO2Me

CO2Me

PPh3+

+

minus

CHCO2MePh3P+

MeO2C

MeO2C

minusPPh3

O

Scheme 4


4 Conclusion


Acknowledgment


References
























3P













Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of









3P













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

Research Article Triphenylphosphine Mediated Synthesis of...

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