Microwave-Assisted Synthesis of Organophosphorus Compounds

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  • This article was downloaded by: [University of Chicago Library]On: 03 June 2013, At: 01:46Publisher: Taylor & FrancisInforma Ltd Registered in England and Wales Registered Number: 1072954 Registeredoffice: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK

    Phosphorus, Sulfur, and Silicon and theRelated ElementsPublication details, including instructions for authors andsubscription information:http://www.tandfonline.com/loi/gpss20

    Microwave-Assisted Synthesis ofOrganophosphorus CompoundsErika Blint a b , Eszter Fazekas a , Judit Takcs a , dm Tajti a ,Amadej Juranovi c , Marijan Koevar c & Gyrgy Keglevich aa Department of Organic Chemistry and Technology , BudapestUniversity of Technology and Economics , Budapest , Hungaryb Research Group of the Hungarian Academy of Sciences at theDepartment of Organic Chemistry and Technology, BudapestUniversity of Technology and Economics , Budapest , Hungaryc Faculty of Chemistry and Chemical Technology, University ofLjubljana , Ljubljana , SloveniaAccepted author version posted online: 14 Nov 2012.Publishedonline: 08 May 2013.

    To cite this article: Erika Blint , Eszter Fazekas , Judit Takcs , dm Tajti , Amadej Juranovi, Marijan Koevar & Gyrgy Keglevich (2013): Microwave-Assisted Synthesis of OrganophosphorusCompounds, Phosphorus, Sulfur, and Silicon and the Related Elements, 188:1-3, 48-50

    To link to this article: http://dx.doi.org/10.1080/10426507.2012.743544

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  • Phosphorus, Sulfur, and Silicon, 188:4850, 2013Copyright C Taylor & Francis Group, LLCISSN: 1042-6507 print / 1563-5325 onlineDOI: 10.1080/10426507.2012.743544

    MICROWAVE-ASSISTED SYNTHESIS OFORGANOPHOSPHORUS COMPOUNDS

    Erika Balint,1,2 Eszter Fazekas,1 Judit Takacs,1 Adam Tajti,1Amadej Juranovic,3 Marijan Kocevar,3 and Gyorgy Keglevich11Department of Organic Chemistry and Technology, Budapest University ofTechnology and Economics, Budapest, Hungary2Research Group of the Hungarian Academy of Sciences at the Department ofOrganic Chemistry and Technology, Budapest University of Technology andEconomics, Budapest, Hungary3Faculty of Chemistry and Chemical Technology, University of Ljubljana,Ljubljana, SloveniaGRAPHICAL ABSTRACT

    RNH2 + +(HCHO)nNR

    O

    O

    + NR

    O

    O

    PO>P(O)H

    RNHCH2P(O)< RN(CH2P(O)P(O)H

    (R1O)2P(O)H

    (R2O)2P(O)H

    POR2O

    R1O H

    Abstract Kabachnik-Fields reactions of a variety of amines, phospha-Michael additions tomaleimide derivatives and alcoholysis of dialkyl phosphites were studied under microwaveconditions.

    Keywords Microwave; Kabachnik-Fields reaction; phospha-Michael addition; alcoholysis

    Kabachnik-Fields (phospha-Mannich) reactions, phospha-Michael additions and al-coholysis take place usually in the presence of catalysts and solvents.1 It was found thatthese reactions do not need any solvent and catalyst under microwave (MW) conditions.

    The Kabachnik-Fields reaction of pyran-2-one derivatives (1) was carried out withformaldehyde and >P(O)H species, such as dialkyl phosphites or diphenylphosphine ox-ide at 120C without any solvent and catalyst under MW conditions (Scheme 1). Usingdiphenylphosphine oxide as the P-reagent, it was better to carry out the condensation inacetonitrile.

    The three-component condensations of amines, two equivalents of paraformaldehydeand two equivalents of a >P(O)H species, such as dialkyl phosphites, ethyl phenyl-H-phosphinate or diphenylphosphine oxide were performed at 100C, in most cases, in theabsence of any solvents and catalysts to give the bis(>P(O)) products (3) in yields of5598% (Scheme 2).2

    Received 16 July 2012; accepted 14 October 2012.This project was partially supported by the Hungarian Scientific Research Fund (OTKA K83118) and by

    the Slovenian-Hungarian Scientific Research program (Project No. BI-HU/11-12-005 and 2011-0637).Address correspondence to Gyorgy Keglevich, Department of Organic Chemistry and Technology, Budapest

    University of Technology and Economics, 1521 Budapest, Hungary. E-mail: ebalint@mail.bme.hu

    48

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  • MICROWAVE-ASSISTED SYNTHESES 49

    O O

    NH2+ +

    MW O O

    NH CH2 PO

    R

    Me

    O

    Me

    O

    120 C, 1.52 hP

    Y

    Y

    O

    H no solvent(HCHO)n Y

    Y

    Y = OMe, OEt, OBu, PhR = Me, Ph 7498%

    R

    1 2

    Scheme 1

    100 C, 11.5 hPY1

    Y2

    O

    HNH2R + + 2

    MW

    NRCH2CH2

    P

    P

    O

    O

    Y1Y2

    Y1Y2

    R = cHex, Bn, 4-MeOPh Y1

    Y2OMeOMe

    OEtOEt

    OBnOBn

    OEtPh

    Ph

    Ph

    no solvent2 (HCHO)n

    OBuOBu

    3

    Scheme 2

    After double deoxygenation of the bis(diphenylphosphinoylmethyl)amines (3, Y =Ph), the bisphosphines (4) thus obtained were converted to the platinum complexes (5) inyields of 4560% (Scheme 3).

    80 C, 3 daysPhSiH3, N2

    NCH2

    CH2 PPh2

    PPh2

    Pt(PhCN)2Cl2, N225 C, 1 day

    ..

    ..

    R NCH2

    CH2 P

    PPtCl2

    Ph

    PhPh

    Ph

    R

    45

    R = cHex, Bn, 4-MeOPh, Ph, 4-MePh

    NCH2

    CH2 P

    P

    O

    O

    R

    PhPh

    PhPh

    ArH ArH

    3, Y = Ph4560%

    Scheme 3

    We have also studied the phospha-Michael addition of>P(O)H species to N-methyl-and N-phenylmaleimide under MW conditions at 175C (Scheme 4).3 The maleic deriva-tives (6) were obtained in yields of 7198%, in most cases, without the use of any solvents.

    PY1

    Y2

    O

    HN

    O

    O

    R + N

    O

    O

    RPO

    6

    Y1

    Y2no solvent

    Y1

    Y2OMeOMe

    OEtOEt

    OEtPh

    PhPh

    175 C, 2.53 h

    R = Me, Ph

    or MW

    Scheme 4

    It was found that in the alcoholysis of dialkyl phosphites (7), the dialkyl phosphitewith two different alkyl groups (8) was the main product under lower temperature, but

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  • 50 E. B ALINT ET AL.

    the fully transesterified product (9) was the exclusive product under higher temperature(Scheme 5).

    MW

    +

    100175 C

    R2 PHOOR2O

    R1O HP

    OR1O

    R1O H

    R1 = Me, Et, Bu R2 = Me, Et, iPr, Bu

    POR2O

    R2O H+

    12 h

    (25 or 50 eq.)7 8 9

    Scheme 5

    REFERENCES

    1. Keglevich, G.; Balint, E.; Kiss, N. Zs.; Jablonkai, E.; Grun, A. Curr. Org. Chem. in press.2. Balint, E.; Fazekas, E.; Pinter, G.; Szollosy, A.; Holczbauer, T.; Czugler, M.; Drahos, L.;

    Kortvelyesi, T.; Keglevich, G. Curr. Org. Chem. 2012, 16, 547-554.3. Balint, E.; Takacs, J.; Drahos, L.; Keglevich, G. Heteroatom Chem. 2012, 23, 235-240.

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