2,4-Dinitrophenylhydrazones: a modified method for the preparation of these derivatives and an explanation of previous conflicting results

Behforouz, Mohammad; Bolan, Joseph L.; Flynt, Michael S.

doi:10.1021/jo00208a009

Cited by 89 publications

(49 citation statements)

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“…2) 'H-Nuclear magnetic resonance spectra of the reaction products confirm the formation of syn/anti isomeric 2,4-dinitrophenylhydrazones. According to literature [11], washing a freshly precipitated mixture of isomeric 2,4-dinitropheny1hydrazones with hydrogen carbonate solution results in the isolation of one pure isomer. Figure 4 a shows the 'H-NMR spectrum of MIBK-2,4-dinitrophenylhydrazone obtained after the washing procedure, Fig.4b that of the unwashed isomeric mixture.…”

Section: Introductionmentioning

confidence: 99%

Syn/anti isomerization of 2,4-dinitrophenylhydrazones in the determination of airborne unsymmetrical aldehydes and ketones using 2,4-dinitrophenylhydrazine derivation

Binding

Müller

Witting

1996

Fresenius J Anal Chem

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Aldehydes and ketones readily react with 2,4-dinitrophenylhydrazine (2,4-DNPH) to form the corresponding hydrazones. This reaction has been frequently used for the quantification of airborne carbonyl compounds. Since unsymmetrical aldehydes and ketones are known to form isomeric 2,4-dinitrophenylhydrazones (syn/ anti-isomers), the influence of isomerization on the practicability and accuracy of the 2,4-DNPH-method using 2,4-dinitrophenylhydrazine-coated solid sorbent samplers has been studied with three ketones (methyl ethyl ketone (MEK), methyl isopropyl ketone (MIPK), and methyl isobutyl ketone (MIBK)). With all three ketones the reaction with 2,4-DNPH resulted in mixtures of the isomeric hydrazones which were separated by HPLC and GC and identified by mass spectroscopy and (1)H nuclear magnetic resonance spectroscopy. The isomers show similar chromatographic behaviour in HPLC as well as in GC, thus leading to problems in quantification and interpretation of chromatographic results.

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Section: Introductionmentioning

confidence: 99%

Syn/anti isomerization of 2,4-dinitrophenylhydrazones in the determination of airborne unsymmetrical aldehydes and ketones using 2,4-dinitrophenylhydrazine derivation

Binding

Müller

Witting

1996

Fresenius J Anal Chem

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“…To test the reactions with 2, we selected two arylhydrazines (3 and 4) that are commonly used as aldehyde-specific dyes. [12,13] The reactions of aldehydenucleotide 2 with 3 or 4 proceeded at room temperature for approximately 20 hours and gave the corresponding orange (5) or violet (6) hydrazones, which were fully characterized (see the Supporting Information). As the formation of hydrazone in water is inherently a reversible reaction, the yields for the isolated products of 51 and 31 %, respectively, were acceptable and useful.…”

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confidence: 99%

Direct Polymerase Synthesis of Reactive Aldehyde‐Functionalized DNA and Its Conjugation and Staining with Hydrazines

et al. 2010

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Apart from a wide range of novel applications of functionalized DNA in chemical biology, nanotechnology, and material sciences, [1] attachment of reactive functional groups to nucleic acids is needed for further transformations or bioconjugates. The introduction of alkyne, azide, or diene groups either by chemical phosphoramidite synthesis or by enzymatic polymerase synthesis has been achieved and the modified DNA was used for click-chemistry, [2,3] Staudinger ligation, [4] and Diels-Alder reactions.[5] An aldehyde functional group is a very attractive group because of its high and specific reactivity with diverse reagents. However, it was considered too reactive and fragile to be incorporated directly (chemically or enzymatically) [6] and the few successful examples were prepared indirectly by a click reaction with azide derivatives of reducing sugars, [3] or by introduction of 2,3-dihydroxypropyl or 3,4-dihydroxypyrrolidine moieties [7,8] and subsequent oxidative cleavage of the vicinal diols to (di)aldehydes. The syntheses of the nucleoside/nucleotide monomers were laborious multistep procedures and additional post-synthetic steps were required to release the aldehyde function in DNA. [7,8] Metallization [7] or interstrand cross-linking [8] were demonstrated to be very useful applications of aldehyde-modified oligonucleotides (ONs) or DNA. Therefore we decided to develop a simple and efficient direct protocol for construction of aldehyde-modified DNA by application of our two-step (cross-coupling polymerase incorporation) method. [9,10] In addition, we wished to develop a methodology for additional conjugation and staining of aldehyde-modified DNA by hydrazone formation.The methodology of choice involved Suzuki cross-coupling of a halogenated nucleoside triphosphate (dNTP) with an aldehyde-containing boronic acid, and subsequent polymerase incorporation into DNA.[9, 10] Furthermore, we wanted to develop a general methodology for hydrazone formation in aqueous media. To test the first and last steps of our proposed route, we performed the reactions on the model compound 5-iodo-dCMP (1; dCMP = 2'-deoxycytidine-5'-O-monophosphate). Commercially available 5-formylthiophene-2-boronic acid was selected as a suitable carrier for the aldehyde group, and its aqueous-phase cross-coupling with monophosphate 1 proceeded within 40 minutes and gave aldehyde-modified dCMP 2 in 50 % yield (Scheme 1). The next task was the formation of the hydrazone species, which is usually only performed in dry organic solvents (owing to the formation of water in the reaction). To make the reaction amenable to aqueous conditions, we have adapted the protocol developed by Dawson and co-workers [11] for aqueous conjugation of peptides, which uses aqueous ammonium acetate and aniline to facilitate the condensation. To test the reactions with 2, we selected two arylhydrazines (3 and 4) that are commonly used as aldehyde-specific dyes. [12,13] The reactions of aldehydenucleotide 2 with 3 or 4 proceeded at room temperature for approximately 20 ho...

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“…The second (12.6 %) was easily identified as being the (2,4-dinitrophenyl)hydrazone 35 of acetone, while the third one, 36 (1.55%), was shown to derive from 2-butanone. In order to establish the stability of the tertiary alcohol function under the conditions of (2,4-dinitrophenyl)hydrazone formation [26], the starting material 32 was directly subjected to identical treatment: unchanged 32 was recovered. In the same manner, any P-hydroxy ketone formed would have given rise to a stable (2,4-dinitrophenyl)hydrazone [261. N M R Spectra.…”

mentioning

confidence: 99%

Functionalisation of saturated hydrocarbons. Part XI. Oxidation of cedrol, β‐ and γ‐eudesmol, sclareol, manoyl oxide, 1,9‐dideoxyforskolin, methyl trans‐dihydroiasmonate, and tetrahydrolinalool by the ‘Gif system’

Barton

Beloeil

Billion

et al. 1987

Helvetica Chimica Acta

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Dedicated to Professor Tadeus Rrichstrin on the occasion of his 90th birthday (10.V11.87)The oxidation of cedrol (l), p-and y-eudesmol(6 and 7, resp.), sclareol(14), manoyl oxide ( 1 3 , 1,9-didcoxyforskolin (22) (+)-methyl trans-dihydrojasmonate (28), and tetrahydrolinalool(32), nearly all of natural terpenoid origin, by the 'Gifsystem' has afforded a number of novel products (3, 11, and 12, 16/17, 18/19, 26, 29-31, and ketones corresponding to 34-35, resp.). The structures of these compounds were established by spectroscopic techniques including 2D-NMR and, wherc appropriate, by comparison with authentic samples.Introduction. -In the preceding parts of this series [l-61, we reported our findings on the oxidation of saturated hydrocarbons by the 'Gifsystem'. This process, especially in its most elaborate form (catalytic amounts of iron cluster Fe,O(OAc),Pyr, 5, Zn powder, AcOH, pyridine, and air at room temperature) was successfully applied to a variety of simple hydrocarbons [2] [3] and then to more complex molecules such as steroids [4] [5] and terpenoids [l] [6]. As a rule, this oxidising system leads to the formation of ketones as major products, i.e. selective attack on secondary positions. This regioselectivity is rather unusual when compared with other oxidising processes. A noticeable exception was observed in the case of cholestane derivatives where the important side-chain cleavage to give 20-ketones competed with the oxidation of the methylenes of the steroidal nucleus [4]

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2,4-Dinitrophenylhydrazones: a modified method for the preparation of these derivatives and an explanation of previous conflicting results

Cited by 89 publications

References 0 publications

Syn/anti isomerization of 2,4-dinitrophenylhydrazones in the determination of airborne unsymmetrical aldehydes and ketones using 2,4-dinitrophenylhydrazine derivation

Syn/anti isomerization of 2,4-dinitrophenylhydrazones in the determination of airborne unsymmetrical aldehydes and ketones using 2,4-dinitrophenylhydrazine derivation

Direct Polymerase Synthesis of Reactive Aldehyde‐Functionalized DNA and Its Conjugation and Staining with Hydrazines

Functionalisation of saturated hydrocarbons. Part XI. Oxidation of cedrol, β‐ and γ‐eudesmol, sclareol, manoyl oxide, 1,9‐dideoxyforskolin, methyl trans‐dihydroiasmonate, and tetrahydrolinalool by the ‘Gif system’

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