Preferences help
enabled [disable] Abstract
Number of results
2004 | 2 | 4 | 672-685
Article title

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

Title variants
Languages of publication
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.
Physical description
1 - 12 - 2004
1 - 12 - 2004
  • [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.
  • [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.[Crossref]
  • [3] D. Lancet and I. Pecht: “Spectroscopic and immunochemical studies withnitrobenzoxadiazolealanine, a fluorescent dinitrophenyl analogue”,Biochemistry, Vol. 16, (1977), pp. 5150–5157.[Crossref]
  • [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.
  • [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.
  • [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.
  • [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.[Crossref]
  • [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.[Crossref]
  • [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.[Crossref]
  • [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.[Crossref]
  • [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.[Crossref]
  • [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.[Crossref]
  • [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.[Crossref]
  • [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.[Crossref]
  • [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.[Crossref]
  • [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.[Crossref]
  • [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.[Crossref]
  • [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.[Crossref]
  • [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.[Crossref]
  • [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.[Crossref]
  • [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.[Crossref]
  • [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.[Crossref]
  • [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.[Crossref]
  • [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.[Crossref]
  • [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.[Crossref]
  • [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.[Crossref]
  • [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.[Crossref]
  • [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.[Crossref]
  • [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.[Crossref]
  • [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.[Crossref]
  • [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. [Crossref]
  • [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.[Crossref]
  • [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.[Crossref]
  • [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.[Crossref]
  • [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.[Crossref]
  • [36] R.W. Frei and J.F. Lawrence: “Fluorogenic labelling in high-speed liquid chromatography”,J. Chromatogr., Vol. 83, (1973), pp. 321–330.[Crossref]
  • [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.
  • [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.
  • [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.[Crossref]
  • [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.[Crossref]
  • [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.[Crossref]
  • [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. [Crossref]
  • [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.<276::AID-BMC747>3.0.CO;2-Y[Crossref]
  • [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.
  • [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.
  • [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.
  • [47] The Merck Index, 13th Ed., Merck & Co., Inc., Whitehouse Station, NJ, 2001, p. 659.
  • [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.[Crossref]
  • [49] D.R. Lyde (Ed.): CRC Handbook of Chemistry and Physics, 83rd Ed., CRC Press, Boca Raton, Florida, 2002, p. 1–7.
  • [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.[Crossref]
  • [51] S. Kurbatov, P. Rodriguez-Dafinte, R. Goumont and F. Terrier: “Superelectrophilic heterocycles: facile SN Ar−SE Ar couplings involving very weak carbon nucleophiles”,Chem. Commun., (2003), pp. 2150–2151. [Crossref]
  • [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.[Crossref]
  • [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. [Crossref]
  • [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.<1712::AID-CHEM17120>3.0.CO;2-G[Crossref]
  • [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.[Crossref]
  • [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.[Crossref]
  • [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.[Crossref]
  • [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.[Crossref]
  • [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.[Crossref]
  • [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. [Crossref]
  • [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.[Crossref]
  • [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.[Crossref]
Document Type
Publication order reference
YADDA identifier
JavaScript is turned off in your web browser. Turn it on to take full advantage of this site, then refresh the page.