Characterization data and kinetic studies of novel lipophilic analogues from 2,4-dichlorophenoxyacetic acid and Propanil herbicides

This work describes the data collection of new lipophilic esters and amides herbicides, analogues to 2,4-dichlorophenoxyacetic acid (2,4-D) and Propanil. The data include 1H and 13C NMR spectra and UV–VIS spectroscopic experiments, from the work “Novel lipophilic analogues from 2,4-D and Propanil herbicides: Biological activity and kinetic studies”. The UV–VIS and 1H NMR spectra were employed to kinetic degradation design, and could be used to access new herbicides derivatives with better environmental properties.


Specifications
Organic chemistry Specific subject area Organic synthesis; Physico-Chemistry. Type of data Figures How data were acquired NMR experiments were performed on a Bruker AVANCE 400 NMR spectrometer operating at 9.4T, observing 1 H and 13 C at 400.13 MHz and 100.50 MHz, respectively, equipped with a 5 mm direct detection probe (BBO) with gradient along the z-axis in CDCl 3 or DMSO-d6 solution with TMS as the internal standard. For qNMR 1 H experiments, pulse was calculated by pulsecal. The relaxation delay for use in the acquisition of the quantitative 1 H NMR spectra was determined by T1 measurements with the aid of the pulse sequence inversion recovery, with same parameters as for 1 H spectra changing the τ values from 0.01 to 15 s. 1 H spectra were acquired by using a 30 °pulse sequence (zg) with the following parameters: 30 s of relaxation delay (D1), 16 transients, a spectral width (SW) of 4789.27 Hz ( ∼ 12.0 ppm), 64 K numbers of data (TD), and 6.84 s of acquisition time (AQ). The experiments were performed at 298 K. FIDs were Fourier transformed with line broadening (LB) = 0.3 Hz. The resulting spectra were manually phased and baseline corrected, and referenced to the TMS at δ 0.0 ppm. The kinetic studies were carried by UV-Vis spectroscopy (Agilent Cary). Infrared (IR) spectra were acquired on a Schimadzu IR PRESTIGIE-21. Data format Raw and analyzed data Parameters for data collection The kinetic UV-Vis spectroscopy (Agilent Cary) monitored the region of 190-800 nm under pseudo-first order conditions. An aliquot of 20 μL stock MeCN solution (0.01 mol. L −1 ) was added to a quartz cuvette (10 mm optical path) containing 3 mL of the reaction medium: acid solution (HCl 0.1 mol. L −1 ) or alkaline solution (NaOH 0.1 mol. L −1 ). The reactions were monitored for at least five half-life times, by following the reactant consumption and product formation. The kinetic profiles were fitted with equations, using iterative least-squares software.

Description of data collection
The NMR spectroscopic data were collected from isolated product, from chromatographic column. Kinetic data (UV-VIS and 1 H NMR) were collected from aliquots directly retired from reaction, under alkaline or acid conditions.

Value of the Data
• These data are useful or important because describe the spectroscopic data of the lipophilic amides and esters analogs from classical organochlorides herbicides. In addition, the data showed the kinetic parameters obtained in acid and alkaline hydrolysis after the incorporation of fatty long-chains in herbicides. • This dataset could be useful for other research groups interesting in the characterization of new derivatives of organochlorides herbicides and can benefit kinetic parameter studies relational to organochlorides herbicides degradation in the environmental. • This dataset can be used for application and in the development of experiments in agricultural practices with environmental-friendly agrochemicals. Annually, around 2.5 million tons of agrochemicals are used worldwide and this causes an impact on the environment such as water suppliers and soil.

Data Description
The dataset referring to lipophilic analogues from herbicides 2,4-dichlorophenoxyacetic acid (2,4-D) and Propanil that were obtained from fatty common alkyl chains. The synthesis of new lipophilic esters 6a-c was realized from esterification reaction of herbicide 2,4-D with palmitic (C16:0), stearic (C18:0) and oleic (C18:1) fatty alcohols. The experiments were performed according to previous work using sulfamic acid (H 2 NSO 3 H) catalyst [1] . After synthesis of the fatty esters, the synthesis of lipophilic amides 8a-c from 2,4-D was investigated from different methodologies. The synthesis of new fatty amines 11a-c was derived from 3,4-dichloroaniline, common core present in Propanil, Linuron and Diuron agrochemicals. The lipophilic esters and amides synthesized from 2,4-D and 3,4-dichloroaniline were characterized by 1 H and 13 C NMR, infrared spectroscopy. Afterwards, the lipophilic herbicides 6a-c, 8a-c and 11a-c were submitted to studies of kinetic behavior in aqueous medium, under basic and acid conditions. The degradation's profile was studied by kinetic UV-vis and 1 H NMR experiments.

Kinetic studies by 1 H NMR and UV-vis
The lipophilic herbicides and 2,4-D were submitted to studies of kinetic behavior to determine the degradation's profile in aqueous medium, under basic and acid conditions. The degradation's profile studied by kinetic 1 H NMR and UV-vis are showed in Figs. 31-38 .

NMR characterization experiments
The NMR characterization experiments of lipophilic herbicides 6a-c, 8a-c and 11a-c were performed in NMR 5 mm tube on a Bruker AVANCE 400 NMR spectrometer operating at 9.4T,

Kinetic studies by UV-Vis
The kinetic studies were carried by UV-Vis spectroscopy (Agilent Cary) monitoring in the region of 190-800 nm under pseudo-first order conditions [2] . An aliquot of 20 mL stock solution of the target compounds ( 6c, 8c and 11c ; 0.01 mol.L −1 in acetonitrile) was added to a quartz cuvette (10 mm optical path) containing 3 mL of the reaction medium: acid solution (HCl 0.1 mol.L −1 -acid hydrolysis) or basic solution (NaOH 0.1 mol.L −1 -alkaline hydrolysis). The  reactions were monitored for at least five half-life times, by following the reactant consumption and product formation. The kinetic profiles (absorbance vs time) were fitted with equations, using iterative least-squares software.

Kinetic studies by RMN
The experiments were performed in NMR 5 mm tube using aliquot of 20 mL stock solution of the target compounds ( 6c, 8c and 11c ; 0.01 mol.L −1 in acetonitrile) containing 3 mL of the reaction medium: acid solution (HCl 0.1 mol.L −1 -acid hydrolysis) or basic solution (NaOH 0.1 mol.L −1 -alkaline hydrolysis).
For qNMR 1 H experiments, pulse was calculated by pulsecal . The relaxation delay for use in the acquisition of the quantitative 1 H NMR spectra was determined by T1 measurements with the aid of the pulse sequence inversion recovery, with same parameters as for 1 H spectra changing the τ values from 0.01 to 15 s. 1 H spectra were acquired by using a 30 °pulse sequence ( zg ) with the following parameters: 30 s of relaxation delay (D1), 16 transients, a spectral width (SW) of 4789.27 Hz ( ∼ 12.0 ppm), 64 K numbers of data (TD), and 6.84 s of acquisition time (AQ). The experiments were performed at 298 K. FIDs were Fourier transformed with line broadening (LB) = 0.3 Hz. The resulting spectra were manually phased and baseline corrected, and referenced to the TMS at δ 0.0 ppm.

Declaration of Competing Interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.