Issue 18, 2012

Reductive amination of glutaraldehyde 2,4-dinitrophenylhydrazone using 2-picoline borane and high-performance liquid chromatographic analysis

Abstract

A typical method for the measurement of glutaraldehyde (GLA) employs 2,4-dinitrophenylhydrazine (DNPH) to form GLA–DNPhydrazone derivatives. However, this method is subject to analytical errors because GLA–DNPhydrazone is a quaternary bis-derivative and forms three geometric isomers (EE, EZ and ZZ) as a result of the two C[double bond, length as m-dash]N double bonds. To overcome this issue, a method for transforming the C[double bond, length as m-dash]N double bond into a C–N single bond, using reductive amination of DNPhydrazone derivatives, has been applied. The amination reaction of GLA–DNPhydrazones with 2-picoline borane is accelerated with catalytic amounts of acid and is completed within 10 minutes in the presence of 100 mmol L−1 phosphoric acid. Reduction of GLA–DNPhydrazone by 2-picoline borane is unique and results in the formation of N-(2,4-dinitrophenyl)-1-piperidinamine (DNPPA). NMR and LC-APCI-MS data confirmed the product identification. DNPPA is very stable and did not change when stored for at least four weeks at room temperature. DNPPA has excellent solubility of 14.6 g L−1 at 20 °C in acetonitrile. The absorption maximum wavelength and the molar absorptivity of DNPPA were 351 nm and 4.2 × 104 L mol−1 cm−1 respectively. Complete separation between the reduced forms of C1–C10 aldehyde DNPhydrazones, including DNPPA, can be achieved by operating the reversed-phase high-performance liquid chromatograph at 351 nm in gradient mode using a C18 amide column. The reductive amination method for GLA overcomes analytical errors caused by EE, EZ and ZZ geometrical isomers.

Graphical abstract: Reductive amination of glutaraldehyde 2,4-dinitrophenylhydrazone using 2-picoline borane and high-performance liquid chromatographic analysis

Article information

Article type
Paper
Submitted
18 Feb 2012
Accepted
08 Jul 2012
First published
09 Jul 2012

Analyst, 2012,137, 4274-4279

Reductive amination of glutaraldehyde 2,4-dinitrophenylhydrazone using 2-picoline borane and high-performance liquid chromatographic analysis

S. Uchiyama, H. Sakamoto, A. Ohno, Y. Inaba, H. Nakagome and N. Kunugita, Analyst, 2012, 137, 4274 DOI: 10.1039/C2AN35230C

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