Fluorescent Streptocyanine Dyes: Synthesis and Photophysical Properties – Synthesis of a New Hemicarboxonium Salt

Guieu, Valérie; Izquierdo, Albert; Garcia‐Alonso, Sonia; André, Chantal; Madaule, Yves; Payrastre, Corinne

doi:10.1002/ejoc.200600522

Cited by 12 publications

(7 citation statements)

References 25 publications

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“…As a matter of fact, alkylated ketone (or aldehyde) species are quite rare in the literature, and they usually act as reactive intermediates in organic syntheses. [23][24][25] The [Me 2 C=CHC(=OMe)Me] + cation reported in this paper represents the first example of a structurally characterised alkylated ketone: the great ability of haloniobate (halotantalate) anions to stabilise simple, uncommon, organic cations has been already discussed and here finds a confirmation. 11a As concerns the mesityl oxide core, this has been described crystallographically as coordinated in rhenium, 26 nickel 27 or aluminium complexes.…”

Section: Methodssupporting

confidence: 67%

The reactivity of 1,1-dialkoxyalkanes with niobium and tantalum pentahalides. Formation of coordination compounds, C–H and C–C bond activation and the X-ray structure of the stable carboxonium species [Me2CCHC(OMe)Me][NbCl5(OMe)]

2009

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The reactions of the pentahalides NbX5 (X = Cl, Br) with the 1,1-dialkoxyalkanes CHR'(OEt)2 or 1,3-dioxolane yield the coordination adducts NbX5[kappa1-(OEt)CHR'(OEt)] (X = Cl, R' = H, 2a; X = Br, R' = H, 2b; X = Cl, R' = Me, 2c; X = Br, R' = Me, 2d) or NbCl5(kappa1-right angle OCH2OCH2C right angle H2), 3, respectively. Compounds 2a-c and 3 are stable at room temperature, while 2d slowly converts into the alkoxide NbBr4[OCH(Me)OEt], 4. Room-temperature fragmentations are observed upon reacting CH2(OMe)2, CHMe(OMe)2 and CMe2(OMe)2 with MX5 (M = Nb, Ta; X = Cl, Br). The complexes MX5[O(Me)(CH2X)], 5, and [MX3(OMe)2]2, 6, form selectively from MX5/CH2(OMe)2 (M = Nb, Ta; X = Cl, Br), while mixtures of [NbX4(OMe)]2 (X = Cl, 8a; X = Br, 8b) and organic halides are obtained from NbX5/CHMe(OMe)2. Instead, the reaction of NbCl5 with CMe2(OMe)2 affords the stable carboxonium species [Me2C=CHC(=OMe)Me][NbCl5(OMe)], 7, as prevalent product. Furthermore, 1,1-dialkoxyalkanes are generally activated by MF5 (M = Nb, Ta) at room temperature: according to the cases, alcohols, ethers, esters and ketones have been detected in the reaction mixtures after hydrolysis. In agreement with NMR data, the carboxonium ion [Me2C=CHC(=OMe)Me]+ is produced from NbF5/CMe2(OMe)2. The complexes NbF5[OEt(Me)], 9a, and NbF5[O=CH(OEt)], 9b, obtained by addition of CH2(OEt)2 to NbF5, have been characterised by NMR spectroscopy. Trimethyl formate, CH(OMe)3, reacts with NbX5 (X = Cl, Br) with formation of the alkoxides 6 and 8, in admixture with NbX5[O=CH(OMe)] and MeX; otherwise, MF5[O=CH(OMe)] and MF5(OMe2) have been synthesised from MF5/CH(OMe)3 (M = Nb, Ta). Complete screening of the organic fragments produced in the distinct reactions has been carried out by both GC-MS and NMR analyses on the reaction mixtures, after treatment with water. The solid state structures of the mixed halo-alkoxy complexes [TaX3(OMe)(mu-OMe)]2 (X = Cl, 6c; X = Br, 6d) and of the stable alkylated ketone containing species 7 have been ascertained by X-ray diffraction studies.

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Section: Methodssupporting

confidence: 67%

The reactivity of 1,1-dialkoxyalkanes with niobium and tantalum pentahalides. Formation of coordination compounds, C–H and C–C bond activation and the X-ray structure of the stable carboxonium species [Me2CCHC(OMe)Me][NbCl5(OMe)]

2009

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“…1a-c) and one 5C-hemicarboxonium ( Fig. 1d) were synthesized as previously described [19][20][21][22][23].…”

Section: Resultsmentioning

confidence: 99%

Comparison of diffusivities data of streptocyanine dyes by electrochemical and NMR-DOSY methods

André-Barrès

Najjar

Maether

et al. 2012

Journal of Electroanalytical Chemistry

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a b s t r a c tDiffusivity data of streptocyanine dyes in acetonitrile were investigated using both transient voltammetric techniques and NMR-DOSY. Results of voltammetric measurements allow determination of the diffusion coefficient D values in the range of 1.2-1.6 Â 10 À9 m 2 s À1 for the target dyes. Deuterated acetonitrile solvent was used for NMR-DOSY experiments and diffusivities of streptocyanines are given after calibration of acetonitrile on its tracer diffusion value of D Ã ACN of 4.37 Â 10 À9 . The results for the two methods appear to be in good agreement allowing use of the convenient NMR-DOSY method to measure diffusivity of streptocyanine dyes at low concentrations and so giving a direct access to the number of exchanged electrons using limiting current electrochemical techniques. This last method affords a great advantage of obtaining diffusion coefficients by non-electrochemical method.

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“…The proposed post-synthetic labelling of oligonucleotides relies on the versatile methodology developed for streptocyanine dye synthesis (Scheme 1). Reaction of penta-, hepta- or nonacarbon chain carboxonium salts with various nitrogen nucleophiles (amines, imines, hydrazines, and hydrazones) lead to a key hemicarboxonium intermediate [13] that can be further combined with other amines to provide the corresponding fluorescent streptocyanines that have been fully characterized by spectroscopic techniques and X-ray diffraction analysis [14,15,16]. This allows the design of dyes in which the absorption wavelengths can be tuned across the visible and near-infrared spectrum by changing the length of the conjugated chain from three to five methine units and the nature of the terminal substituents with high extinction molar coefficients in the range of 50,000 to 250,000 mol −1 ·L·cm −1 .…”

Section: Resultsmentioning

confidence: 99%

Oligonucleotide Labelling Using a Fluorogenic “Click” Reaction with a Hemicarboxonium Salt

et al. 2013

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Fluorescent Streptocyanine Dyes: Synthesis and Photophysical Properties – Synthesis of a New Hemicarboxonium Salt

Cited by 12 publications

References 25 publications

The reactivity of 1,1-dialkoxyalkanes with niobium and tantalum pentahalides. Formation of coordination compounds, C–H and C–C bond activation and the X-ray structure of the stable carboxonium species [Me2CCHC(OMe)Me][NbCl5(OMe)]

The reactivity of 1,1-dialkoxyalkanes with niobium and tantalum pentahalides. Formation of coordination compounds, C–H and C–C bond activation and the X-ray structure of the stable carboxonium species [Me2CCHC(OMe)Me][NbCl5(OMe)]

Comparison of diffusivities data of streptocyanine dyes by electrochemical and NMR-DOSY methods

Oligonucleotide Labelling Using a Fluorogenic “Click” Reaction with a Hemicarboxonium Salt

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