Central European Journal of Chemistry

, Volume 2, Issue 4, pp 672–685 | Cite as

Structural factors influencing the reaction rates of 4-aryloxy-7-nitrobenzofurazans with amino acids

  • Marioara Bem
  • Marilena Vasilescu
  • Miron T. Caproiu
  • Constantin Draghici
  • Adrian Beteringhe
  • Titus Constantinescu
  • Mircea D. Banciu
  • Alexandru T. Balaban
Article
  • 137 Downloads

Abstract

An interesting observation was made when studying the SNAr reaction between several 4-aryloxy-7-nitrobenzofurazans (2) and several amino acids leading to the apparition of detectable fluorescence from the substitution products3. Acidic amino acids reacted very slowly=while basic amino acids react fastest with2 having an unsubstituted phenyl or a 4-formyl-phenyl Ar group. Amongst neutral amino acids, proline reacts fastest at room temperature after 100 min. With2 having a methoxy-subtituted Ar group.

Keywords

4-Aryloxy-7-nitrobenzofurazans amino acids SNAr reaction fluorescence 

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References

  1. [1]
    P.B. Ghosh and M.W. Whitehouse: “7-Chloro-4-nitrobenzo-2-oxa-1,3-diazole: a new fluorogenic reagent for amino acids and the other amines”,Biochem. J., Vol. 108, (1968), pp. 155–156.Google Scholar
  2. [2]
    D.J. Birkett, N.C. Price, G.K. Radda and A.G. Salmon: “The reactivity of SH groups with a fluorogenic reagent”,FEBS Letters, Vol. 6, (1970), pp. 346–348.CrossRefGoogle Scholar
  3. [3]
    D. Lancet and I. Pecht: “Spectroscopic and immunochemical studies withnitrobenzoxadiazolealanine, a fluorescent dinitrophenyl analogue”,Biochemistry, Vol. 16, (1977), pp. 5150–5157.CrossRefGoogle Scholar
  4. [4]
    S. Uchiyama, T. Santa, T. Fukushima, H. Homma and K. Imai: “Effects of the substituent groups at the 4- and 7-position on the fluorescence characteristics of benzofurazan compounds”,J. Chem. Soc., Perkin Trans. 2, (1988), pp. 2165–2173.Google Scholar
  5. [5]
    S. Uchiyama, T. Santa and K. Imai: “Semi-empirical PM3 calculation reveals the relationships between the fluorescence characteristics of 4,7-disubstitutited benzofurazan compounds, the LUMO energy and the dipole moment directed from the 4-and 7-position”,J. Chem. Soc., Perkin Trans. 2, (1999) pp. 569–576.Google Scholar
  6. [6]
    S. Uchiyama, T. Santa, N. Okiyama, K. Azuma and K. Imai: “Semi-empirical PM3 calculations predict the fluorescence quantum yields (Φ) of 4-monosubstituted benzofurazan compounds”,J. Chem. Soc., Perkin Trans. 2, (2000), pp. 1199–1207.Google Scholar
  7. [7]
    S. Uchiyama, T. Santa and K. Imai: “Study on the fluorescent ‘on-off’ properties of benzofurazan compounds bearing an aromatic substituent group and design offluorescent ‘on-off’ derivatization reagents”,Analyst, Vol. 125, (2000), pp. 1839–1845.CrossRefGoogle Scholar
  8. [8]
    S. Uchiyama, T. Santa, N. Okiyama, T. Fukushima and K. Imai: “Fluorogenic and fluorescent labeling reagents with a benzofurazan skeleton”,Biomed. Chromatogr., Vol. 15, (2001), pp. 295–318; and references cited herein.CrossRefGoogle Scholar
  9. [9]
    M. Onoda, S. Uchiyama, T. Santa and K. Imai: “The effects of spacer length on the fluorescence quantum yields of the benzofurazan compounds bearing a donor-acceptorsystem”,Luminescence, Vol. 17, (1002), pp. 11–14.CrossRefGoogle Scholar
  10. [10]
    C. Toriumi and K. Imai: “Determination of insulin in a single islet of langerhans by high-performance liquid chromatography with fluorescence detection”,Anal. Chem., Vol. 74, (2002), pp. 2321–2327.CrossRefGoogle Scholar
  11. [11]
    M. Onoda, S. Uchiyama, T. Santa and K. Imai: “A photoinduced electron-transfer reagent for peroxyacetic acid, 4-ethylthioacetylamino-7-phenylsulfonyl-2,1,3-benzoxadiazole, based on the method for prodicting the fluorescence quantum yields”,Anal. Chem., Vol. 74, (2002), pp. 4089–4096.CrossRefGoogle Scholar
  12. [12]
    T. Kajiro, Y. Nakajima, T. Fukushima and K. Imai: “A method to evaluate the reninangiotensin system in rat renal cortex using a microdialysis technique combined with HPLC-fluorecence detection”,Anal. Chem., Vol. 74, (2002), pp. 4519–4525.CrossRefGoogle Scholar
  13. [13]
    N. Okiyama, T. Santa, A. Toriba, K. Nakagomi, K. Imai, H. Hiranuma and H. Tanaka: “An automated fluorescence protein sequencer using 7-methylthio-4-(2,1,3-benzoxadiazolyl) isothiocyanate (MTBD-NCS) as an Edman reagent”,Biomed. Chromatogr., Vol. 16, (2002), pp. 183–186.CrossRefGoogle Scholar
  14. [14]
    T. Santa, D. Matsumura, C. Huang, C. Kitada and K. Imai: “Design and synthesis of a hydro[hilic fluorescent derivatization reagent for carboxylic acids, 4-N-(4-N-aminoethyl) piperazino-7-nitro-2,1,3-benzoxadiazole (NBD-PZ-NH2), and its application to capillary electrophoresis with laser-induced fluorescence detection”,Biomed. Chromatogr., Vol. 16, (2002), pp. 523–528.CrossRefGoogle Scholar
  15. [15]
    C.Z. Huang, T. Santa and K. Imai: “Development of 7-(N,N-dimethylamino-sulphonyl)-4-(N-2-aminoethyl) piperazino-2,1,3-benzoxadiazole as a water-soluble fluorogenic reagent for the sensitive liquid chromatographic determination ofsaturated carboxylic acids”,Analyst, Vol. 127, (2002), pp. 741–747.CrossRefGoogle Scholar
  16. [16]
    K. Okabe, R. Wada, K. Ohno, S. Uchiyama, T. Santa and K. Imai: “Development of hydrophilic fluorogenic derivatization reagents for thiols: 4-(N-acetylaminosulfonyl)-7-fluoro-2,1,3-benzoxadiazole and 4-(N-trichloroacetylamino-sulfonyl)-7-fluoro-2,1,3-benzoxadiazole”,J. Chromatogr. A, Vol. 982, (2002), pp. 111–118.CrossRefGoogle Scholar
  17. [17]
    N. Okiyama, S. Uchiyama, M. Onoda, K. Imai and T. Santa: “Synthesis and fluorescence properties of 4,5-, 4,6- and 5,6-disubstituted benzofurazan (2,1,3- benzoxadiazole)compounds”,Heterocycles, Vol. 58, (2002), pp. 165–173.CrossRefGoogle Scholar
  18. [18]
    S. Uchiyama, K. Takehira, S. Kohtani, T. Santa, R. Nakagaki, S. Tobita and K. Imai: “Photophysical study of 5-substituted benzofurazan compounds as fluorogenic probes”,Phys. Chem. Chem. Phys. Vol. 4, (2002), pp. 4514–4522.CrossRefGoogle Scholar
  19. [19]
    S. Uchiyama, K. Takehira, S. Kohtani, K. Imai, R. Nakagaki, S. Tobita and T. Santa: “Fluorescence on-off switching mechanism of benzofurazans”,Org. Biomol. Chem., Vol. 1, (2003), pp. 1067–1072.CrossRefGoogle Scholar
  20. [20]
    T. Fukushima, N. Usui, T. Santa and K. Imai: “Recent progress in derivatization methods for LC and CE analysis”,J. Pharm. Biomed. Anal., Vol. 30, (2003), pp. 1655–1687.CrossRefGoogle Scholar
  21. [21]
    Y. Watanabe and K. Imai: “Pre-column labelling for high-performance liquid chromatography of amino acids with 7-fluoro-4-nitrobenzo-2-oxa-1,3-diazole and its application to protein hydrolysates”,J. Chromatogr., Vol. 239, (1982), pp. 723–732.CrossRefGoogle Scholar
  22. [22]
    T. Toyo'oka and K. Imai: “New fluorogenic reagent having halogenobenzofurazan structure for thiols: 4-(aminosulfonyl)-7-fluoro-2,1,3-benzoxadiazole”,Anal. Chem., Vol. 56, (1984), pp. 2461–2464.CrossRefGoogle Scholar
  23. [23]
    K. Imai, T. Toyo'oka and H. Miyano: “Fluorogenic reagents for primary andsecondary amines and thiols in high-performance liquid chromatography”,Analyst, Vol. 109, (1984), pp 1365–1373 and references cited herein.CrossRefGoogle Scholar
  24. [24]
    T. Toyo'oka, T. Suzuki, Y. Saito, S. Uzu and K. Imai: “Fluorogenic reagentfor thiols: 4-(N,N-dimethylaminosulphonyl)-7-fluoro-2,1,3-benzoxadiazole”,Analyst, Vol. 114 (1989), pp. 413–419.CrossRefGoogle Scholar
  25. [25]
    T. Toyo'oka, T. Suzuki, Y. Saito, S. Uzu and K. Imai: “Evaluation of benzofurazan derivatives as fluorogenic reagents for thiols and amines using high-performance liquidchromatography”,Analyst, Vol. 114, (1989), pp. 1233–1240.CrossRefGoogle Scholar
  26. [26]
    K. Iwaki, N. Okumura, M. Yamazaki, N. Nimura and T. Kinoshita: “Precolumn derivatization technique for high-performance liquid chromatographic determination of penicillins with fluorescence detection”,J. Chromatogr., Vol. 504 (1990), pp. 359–367.CrossRefGoogle Scholar
  27. [27]
    T. Toyo'oka, Yi-M. Liu, H. Jinno, N. Hanioka, M. Ando and K. Imai: “Chiral separation of amines by high-performance: liquid chromatography after tagging with 4-(n,N-dimethylaminosulphonyl)-7-(2-chloroformylpyrrolidin-1-yl)-2,1,3-benzoxadiazole”,Biomed. Chromatogr., Vol. 8, (1994), pp. 85–89.CrossRefGoogle Scholar
  28. [28]
    T. Toyo'oka, Yi-M. Liu, N. Hanioka, H. Jinno, M. Ando and K. Imai: “Resolution of enantiomers of alcohols and amines by high-performance liquid chromatography after derivatization with a novel fluorescent chiral reagent”,J. Chromatogr. A, Vol. 675, (1994), pp. 79–88.CrossRefGoogle Scholar
  29. [29]
    K. Matsumoto, Y. Ichitani, N. Ogasawara, H. Yuki and K. Imai: “Precolumn fluorescence derivatization of carnitine and acylcarnitines with 4-(2-aminoethylamino)-7-nitro-2,1,3-benzoxadiazole prior to high-performance liquid chromatography”,J. Chromatogr. A, Vol. 678, (1994), pp. 241–247.CrossRefGoogle Scholar
  30. [30]
    H. Matsunaga, T. Santa, K. Hagiwara, H. Homma, K. Imai, S. Uzu, K. Nakashima and S. Akiyama: “Development of an efficient amino acid sequencing method using fluorescent Edman reagent 7-[(N,N-dimethylamino)sulfonyl]-2,1,3-benzoxadiazol-4-yl isothiocyanate”,Anal. Chem., Vol. 67, (1995), pp. 4276–4282.CrossRefGoogle Scholar
  31. [31]
    T. Santa, A. Takeda, S. Uchiyama, T. Fukushima, H. Homma, S. Suzuki, H. Yokosu, C.K. Lim and K. Imai: “N-(4-nitro-2,1,3-benzoxadiazoyl-7-yl)-N-methyl-2-aminoacetohydrazide (NBD-CO-Hz) as a precolumn fluorescent derivatization reagent for carboxylic acids in high-performance liquid chromatography”,J. Pharm. Biomed. Chromatogr., Vol. 17, (1998), pp. 1065–1070.Google Scholar
  32. [32]
    A. Toriba, K. Azuma, T. Santa and K. Imai: “Development of an amino acid sequence and D/L-configuration determination method of peptide with a new fluorescence Edman reagent, 7-methylthio-4-(2,1,3-benzoxadiazolyl) isothiocyanate”,Anal. Chem., Vol. 72, (2000), pp. 732–739.CrossRefGoogle Scholar
  33. [33]
    T. Kajiro, T. Fukushima, T. Santa and K. Imai: “Development of water-soluble fluorogenic reagents having a 2,1,3-benzoxadiazole structure and their application tothe determination of peptides”,Analyst, Vol. 125, (2000), pp. 1115–1121.CrossRefGoogle Scholar
  34. [34]
    X. Guo, T. Fukushima, F. Li and K. Imai: “Determination of fluoxetine enantiomers in rat plasma by pre-column fluorescence derivatization and column-switching high- performance liquid chromatography”,Analyst, Vol. 127, (2002), pp. 480–484.CrossRefGoogle Scholar
  35. [35]
    J.F. Lawrence and R.W. Frei; “Fluorigenic labelling of N-methyl- and N,N-dimethylcarbamates with 4-chloro-7-nitrobenzo-2,1,3-oxadiazole”,Anal. Chem., Vol. 44, (1972), pp. 2046–2049.CrossRefGoogle Scholar
  36. [36]
    R.W. Frei and J.F. Lawrence: “Fluorogenic labelling in high-speed liquid chromatography”,J. Chromatogr., Vol. 83, (1973), pp. 321–330.CrossRefGoogle Scholar
  37. [37]
    J.F. Lawrence and R.W. Frei: Chemical Derivatization In Liquid Chromatography, Elsevier, Amsterdam, 1976, p. 163, 190; K. Blau and G. King: Handbook of Derivatives for Chromatography, Heyden, London, 1977, p. 367.Google Scholar
  38. [38]
    G.J. Krol, J.M. Banovsky, C.A. Mannan, R.E. Pickering, and B.T. Kho: “Trace analysis of the mif analogue pareptide in blood plasma by high-performance liquid chromatography and short-wavelength excitation fluorometry”,J. Chromatogr., Vol. 163, (1979), pp. 383–389.Google Scholar
  39. [39]
    H. Umagat, P. Kucera and L.-F. Wen: “Total amino acid analysis using pre-column fluorescence derivatization”,J. Chromatogr., Vol. 239, (1982), pp. 463–474.CrossRefGoogle Scholar
  40. [40]
    F. Van Hoof and A. Heyndrickx: “Thin layer chromatographic-spectrophotofluorometric analysis of amphetamine analogs and amphetamine analogs after reaction with 4-chloro-7-nitrobenzo-2,1,3-oxadiazole”,Anal. Chem., Vol. 46, (1974), pp. 286–288.CrossRefGoogle Scholar
  41. [41]
    H.-J. Klimisch and L. Stadler: “Mikroquantitative Bestimmung von aliphatischen Aminen mit 7-Chloro-4-nitrobenzo-2-oxa-1,3-diazol”,J. Chromatogr.,Vol. 90, (1974), pp. 141–148.CrossRefGoogle Scholar
  42. [42]
    M. Ahnoff, I. Grundevik, A. Arfwidsson, J. Fonselius and B.-A. Persson: “Derivatization with 4-chloro-7-nitrobenzofurazan for liquid chromatographic determination of hydroxyproline in collagen hydrolysate”,Anal. Chem., Vol. 53, (1981), pp. 485–489.Google Scholar
  43. [43]
    S. Al-Kindy, T. Santa, T. Fukushima, H. Homma and K. Imai: “Enantiomeric determination of amines by high-performance liquid chromatography using chiral fluorescent derivatization reagents”,Biomed. Chromatogr., Vol. 12, (1988), pp. 276–280.CrossRefGoogle Scholar
  44. [44]
    D. Nourescu, E.N. Hristea, M.T. Caproiu, A.C. Radutiu, M. Vasilescu, M. Bem and T. Constantinescu: “Synthesis and properties of the new estrone and estradiol derivatives of C-3 phenoxy ether type involving a 4-nitrobenzofurazan moiety”,Proc. Rom. Acad. (Series B), Vol. 1, (2001), pp. 7–11.Google Scholar
  45. [45]
    M. Bem, M.T. Caproiu, D. Stoicescu, T. Constantinescu and A.T. Balaban: “Synthesis of 4-aryloxy-7-nitrobenzofurazan derivatives from 4-chloro-7-nitro benzofurazan and various phenoxide anions (including pharmaceuticals) in the presence of crown ethers”,CEJC, Vol. 3, (2003), pp. 260–276.Google Scholar
  46. [46]
    M. Bem, D.C. Culita, M.T. Caproiu, T. Constantinescu and M.D. Banciu: “Synthesis of 4-(4′-formylaryloxy)-7-nitrobenzofurazan derivatives from 4-chloro-7-nitrobenzofurazan and some formylphenols in the presence of crown ethers:” Rev. Roum. Chim., Vol. 48, (2003), pp. 387–392.Google Scholar
  47. [47]
    The Merck Index, 13th Ed., Merck & Co., Inc., Whitehouse Station, NJ, 2001, p. 659.Google Scholar
  48. [48]
    L. Johnson, S. Lagerkvist and P. Lindroth: “Derivatization of secondary amino acids with 7-nitro-4-benzofurazanyl ethers”,Anal. Chem., Vol. 54, (1982), pp 939–942.CrossRefGoogle Scholar
  49. [49]
    D.R. Lyde (Ed.): CRC Handbook of Chemistry and Physics, 83rd Ed., CRC Press, Boca Raton, Florida, 2002, p. 1–7.Google Scholar
  50. [50]
    F. Terrier, A.P. Chatrousse and F. Millot: “Concurrent methoxide ion attack at the 5- and 7-carbons of 4-nitrobenzofurazan and 4-nitrobenzofuroxan. A kinetic study in methanol”,J. Org. Chem., Vol. 45, (1980), pp. 2666–2672.CrossRefGoogle Scholar
  51. [51]
    S. Kurbatov, P. Rodriguez-Dafinte, R. Goumont and F. Terrier: “Superelectrophilic heterocycles: facile SNAr−SEAr couplings involving very weak carbon nucleophiles”,Chem. Commun., (2003), pp. 2150–2151.Google Scholar
  52. [52]
    F. Terrier, M. Mokhtari, R. Goumont, J.-C. Hallé and E. Buncel: “High Brønsted βnuc values in SNAr displacement. An indicator of the SET pathway?”,Org. Biol. Chem., Vol. 1, (2003), pp. 1757–1763.CrossRefGoogle Scholar
  53. [53]
    M.R. Crampton, J. Delaney and L.C. Rabbitt: “The reactions of 4-nitrobenzofuroxan with amines in DMSO; kinetic and equilibrium studies”,j. Chem. Soc., Perkin Trans. 2, (1999), pp. 2473–2480.Google Scholar
  54. [54]
    G. Moutires, J. Pinson, F. Terrier and R. Goumont: “Electrochemical oxidation of σ-complex-type intermediates in aromatic nucleophilic substitutions”,Chem.-Eur. J., Vol. 7, (2001), pp. 1712–1719.CrossRefGoogle Scholar
  55. [55]
    J.A. Orvik and J.F. Bunnett: “Kinetics of the separately observable formation and decomposition of the intermediate complex in aromatic nucleophilic substitution. Reactions of 2,4-dinitro-1-naphthyl ethyl ether withn-butyl andt-butylamine in dimethyl sulfoxide solution”,J. Am. Chem. Soc., Vol. 92, (1970), pp. 2417–2427.CrossRefGoogle Scholar
  56. [56]
    J.F. Bunnett, S. Sekiguchi and L.A. Smith: “Kinetics of reactions of cyclic secondary amines with 2,4-dinitro-1-naphthyl ethyl ether in dimethyl sulfoxide solution. Spectacular difference between the behavior of pyrrolidine and piperidine”,J. Am. Chem. Soc., Vol. 103, (1981), pp 4865–4871.CrossRefGoogle Scholar
  57. [57]
    S. Sekiguchi and J. F. Bunnett: “Reactions of secondary amines with their N-(2,4-dinitro-1-naphthyl) derivatives to form Jackson-Meisenheimer adducts. Substantial difference in reaction rates between pyrrolidine and piperidine”,J. Am. Chem. Soc., Vol. 103, (1981), pp. 4871–4874.CrossRefGoogle Scholar
  58. [58]
    T. Fukushima, M. Kato, T. Santa and K. Imai: “Enantiomeric separation and sensitive determination of D,L-amino acids derivatized with fluorogenic benzofurazan reagents on Pirkle types stationary phases”,Biomed. Chromat., Vol. 9, (1995), pp. 10–17.CrossRefGoogle Scholar
  59. [59]
    A.A. Aboderin, R.E.K. Semakula, E. Boedefeld and R.A. Kenner: “Base-promoted cleavage of α-N-NBD [4-nitrobenz-2-oxa-1,3-diazole] peptides”,FEBS Lett., Vol. 34, (1973), pp. 90–94.CrossRefGoogle Scholar
  60. [60]
    M. Ahnoff, I. Grundevik, A. Arfwidsson, J. Fonselius and B.-A. Persson: “Derivatization with 4-chloro-7-nitrobenzofurazan for liquid chromatographic determination of hydroxyproline in collagen hydrolysate”,Anal. Chem., Vol. 53, (1981), pp. 485–489.Google Scholar
  61. [61]
    T. Hohsaka, Y. Ashizuka, H. Sasaki, H. Murakami and M. Sisido: “Incorporation of two different nonnatural amino acids independently into a single protein through extension of the genetic code”,J. Am. Chem. Soc., Vol. 121, (1999), pp. 12194–12195.CrossRefGoogle Scholar
  62. [62]
    T. Hohsaka, Y. Ashizuka, H. Murakami and M. Sisido: “Five-base codons for incorporation of nonnatural amino acids into proteins”,Nucleic Acid Res., Vol. 29, (2001), pp. 3646–3651.CrossRefGoogle Scholar

Copyright information

© Central European Science Journals 2004

Authors and Affiliations

  • Marioara Bem
    • 1
  • Marilena Vasilescu
    • 2
  • Miron T. Caproiu
    • 3
  • Constantin Draghici
    • 3
  • Adrian Beteringhe
    • 1
  • Titus Constantinescu
    • 1
  • Mircea D. Banciu
    • 4
  • Alexandru T. Balaban
    • 5
  1. 1.Laboratory of Supramolecular Chemistry and Interphase ProcessesInstitute “I.G. Murgulescu” of Physical Chemistry of Roumanian AcademyBucharestRoumania
  2. 2.Structure LaboratoryInstitute “I.G. Murgulescu” of Physical Chemistry of Roumanian AcademyBucharestRoumania
  3. 3.Institute “C.D. Nenitzescu” of Organic ChemistryRomanian AcademyBucharestRoumania
  4. 4.Department of Organic Chemistry“Politehnica” University BucharestBucharestRoumania
  5. 5.Department of Marine SciencesTexas A & M University at GalvestonGalvestonUSA

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