Transformation products of the high-volume production chemicals 1-vinyl-2-pyrrolidinone and 2-piperazin-1-ylethanamine formed by UV photolysis
Abstract
This work investigates the reaction of 1-vinyl-2-pyrrolidinone (VP) and 2-piperazin-1-yletanamine (PPE) under UV radiation. Both substances are high-volume production chemicals (production >1000 tons/year) widely used in polymers, coatings and a wide array of applications, which have been classified as mobile chemicals and which can then lead to the formation of persistent and mobile transformation products (TPs). Thus, their reaction with UV light was studied by means of liquid chromatography-quadrupole-time-of-flight-mass spectrometry (LC-QTOF-MS). Both compounds presented a high reactivity, the VP quantum yield was 0.28 mol/E; whereas, PPE had a quantum yield notably higher than 1 (16 mol/E). Five and 7 TPs were identified for VP and PPE, respectively. Some of them had been already reported in literature due to sunlight photodegradation or other oxidation processes, but most of them are reported here for the first time. Finally, the acute and chronical toxicity of precursors and TPs were estimated using two quantitative structure-activity relationship (QSAR) software tools which led to some discrepancies in the estimations, pointing to the need for experimental toxicity assays for these compounds
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Supplementary material to: Transformation products of the high-volume production chemicals 1-vinyl2-pyrrolidinone and 2-piperazin-1-ylethanamine formed by UV photolysis Benigno José Sieira, Rosario Rodil, Rafael Cela, José Benito Quintana, Rosa Montes Department of Analytical Chemistry, Institute of Research on Chemical and Biological Analysis (IAQBUS), Universidade de Santiago de Compostela, 15782, Santiago de Compostela, Spain * Corresponding Authors: R. Rodil ([email protected]) J.B. Quintana ([email protected]) R. Montes ([email protected]) Phone number: +34 881816035 Table S1. VP and PPE properties and structure. Table S2. Photochemical kinetic parameters obtained from non-linear fitting to an exponential decay and calculation of quantum yields (UPW: ultrapure water; SW: surface water). Figure S1. UV photolysis kinetic plots in ultrapure (UPW) and river water (RW) of (A) VP and (B) PPE. Data normalized to time 0 (untreated samples). Figure S2. UV/Vis absorption spectrum of (a) VP and (b) PPE. Figure S3. QTOF product ion spectra of VP and its TPs. (a) VP, (b) VP-86, (c) VP-116 and (d) VP227 Figure S4. TPs formation profiles for VP (a) and PPE (b). Signal of TPs normalized to the signal of their parent chemical at time 0. Figure S5. QTOF product ion spectra of PPE and its TPs. (a) PPE , (b) PPE-87, (c) PPE-115, (d) PPE-126, (e) PPE-146 and (f) PPE-160 Figure S6: Extracted ion chromatograms of VP and identified TP Figure S7: Extracted ion chromatograms of PPE and identified TP Table S3. Summary of EPA T.E.S.T. predicted toxicity endpoints. Note: n.a. means that no prediction was possible Table S4. Summary of ECOSAR predicted toxicity endpoints. Note: in some cases two values were obtained for the same TP, the (*) symbol is used when the estimation is based on the “amide” group class, while the other value was obtained when “aliphatic amine” group class was used.
Table S1. VP and PPE properties and structure. Compound Name 1-vinylpyrrolidin-2-one 2-piperazin-1-ylethanamine Acronym VP PPE CAS Number 88-12-0 140-31-8 Molecular formula C6H9NO C6H15N3 Log D (pH 7.4) (1) 0.38 -4.53 Log P (1) 0.37 -0.86 Boiling point (760 mmHg) (1) 217 ºC 220ºC Consumer uses (2) Washing and cleaning products, cosmetics and personal care products, paints, coatings, and adhesives. Laboratory chemicals. Adhesives, sealants, coatings, paints. pH regulators and water treatment products. Harmonised classification and labelling (CLP00) (2) GHS05 Corrosive, GHS06 Acute toxicity, GHS09 Hazardous to the environment GHS05 Corrosive, GHS07 Health hazard Structure (1) Predicted values, ACDLabs, (2) Data from www.echa.europe.eu
Table S2. Photochemical kinetic parameters obtained from non-linear fitting to an exponential decay and calculation of quantum yields (UPW: ultrapure water; SW: surface water). k (min-1) a t 1/2 (min) a R2 ε (M-1 cm-1) Φ (mol/einstein) a VP (UPW) 0.36 ± 0.03 1.9 ± 0.2 0.9989 4.38∙103 0.28 ± 0.03 VP (SW) 0.33 ± 0.01 1.7 ± 0.1 0.9999 - - PPE (UPW) 0.017 ± 0.001 40 ± 3 0.9728 3.66 16 ± 1 PPE (SW) 0.019 ± 0.002 36 ± 3 0.9908 - - DCF (UPW) 0.50 ± 0.06 1.4 ± 0.2 0.996 5.76∙103 0.292 b a Mean ± 95% confidence interval b Value from (Wols et al., 2012)
Figure S1. UV photolysis kinetic plots in ultrapure (UPW) and river water (RW) of (A) VP and (B) PPE. Data normalized to time 0 (untreated samples).
Figure S2: UV/Vis absorption spectrum of (a) VP and (b) PPE. 200 300 400 500 600 700 800 900 0 0.5 1 1.5 2 2.5 3 Wavelength (nm) Absorbance (AU) 1000 1100 λ max = 237 nm (a) 200 300 400 500 600 700 800 900 0 0.2 0.4 0.6 0.8 1 Wavelength (nm) Absorbance (AU) 1000 1100 (b)
Figure S3. QTOF product ion spectra of VP and its TPs. (a) VP and (b) VP-86
Figure S3 cont. QTOF product ion spectra of VP and its TPs. (c) VP-116 and (d) VP-227
Figure S4. TPs formation profiles for VP (a) and PPE (b). Signal of TPs normalized to the signal of their parent chemical at time 0.
Figure S5: QTOF product ion spectra of PPE and its TPs. (a) PPE , (b) PPE-87 and (c) PPE-115
Table S4. Summary of ECOSAR predicted toxicity endpoints. Note: in some cases two values were obtained for the same TP, the (*) symbol is used when the estimation is based on the “amide” group class, while the other value was obtained when “aliphatic amine” group class was used. Acute toxicity Chronic toxicity Compound Fish 96h LC 50 Daphnid 48 h LC 50 Green Algae 96 h EC50 Fish ChV Daphnid ChV Green Algae ChV VP* 7.23E+02 9.16E+02 4.63E+01 4.38E+00 7.96E+01 1.36E+01 VP-86 1.53E+03 2.11E+03 7.98E+01 7.22E+00 1.49E+02 1.83E+01 VP-116 1.97E+04 3.29E+04 6.50E+02 5.36E+01 1.46E+03 8.57E+01 VP-132 3.40E+04 5.88E+04 1.03E+03 8.37E+01 2.40E+03 1.23E+02 VP-219 8.50E+01 9.60E+00 8.82E+00 5.84E+00 7.48E-01 2.82E+00 VP-227 4.08E+04 6.85E+04 1.33E+03 1.10E+02 3.01E+03 1.73E+02 PPE 5.48E+03 4.31E+02 8.09E+02 1.13E+03 2.37E+01 1.99E+02 PPE-87 1.14E+03 9.83E+01 1.54E+02 1.79E+02 5.89E+00 4.05E+01 PPE-111 2.63E+02 2.58E+01 3.13E+01 2.76E+01 1.76E+00 9.03E+00 PPE-115 4.79E+03 3.77E+02 7.06E+02 9.84E+02 2.07E+01 1.74E+02 PPE-115* 1.91E+04 3.19E+04 6.34E+02 5.24E+01 1.43E+03 8.40E+01 PPE-126 1.05E+03 9.39E+01 1.38E+02 1.49E+02 5.82E+00 3.71E+01 PPE-144 1.54E+04 1.13E+03 2.44E+03 3.94E+03 5.78E+01 5.70E+02 PPE-144* 7.34E+04 1.35E+05 1.94E+03 1.53E+02 4.78E+03 1.95E+02 PPE-146 6.31E+04 4.16E+03 1.11E+04 2.24E+04 1.92E+02 2.40E+03 PPE-160 1.75E+05 1.07E+04 3.31E+04 7.75E+04 4.62E+02 6.79E+03 PPE-160* 1.30E+06 2.99E+06 1.95E+04 1.37E+03 6.04E+04 9.96E+02