ACCESSION: MSBNK-Eawag-EQ418107
RECORD_TITLE: Fipronil-TP RPA 200761; LC-ESI-QFT; MS2; CE: 120%; R=17500; [M+H]+
DATE: 2019.12.03
AUTHORS: K. Kiefer [dtc], J. Hollender [dtc], H. Singer [dtc], M. Stravs [com]
LICENSE: CC BY-SA
COPYRIGHT: Copyright (C) Eawag 2019
PUBLICATION: Kiefer, K.; Mueller, A.; Singer, H.; Hollender, J. New relevant pesticide transformation products in groundwater detected using target and suspect screening for agricultural and urban micropollutants with LC-HRMS. Water Research 2019, 165. DOI: https://doi.org/10.1016/j.watres.2019.114972
COMMENT: CONFIDENCE standard compound
COMMENT: UCHEM_ID 4181
CH$NAME: Fipronil-TP RPA 200761
CH$NAME: 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-(trifluoromethylsulfinyl)pyrazole-3-carboxylic acid
CH$COMPOUND_CLASS: N/A; Environmental Standard
CH$FORMULA: C12H5Cl2F6N3O3S
CH$EXACT_MASS: 454.9333
CH$SMILES: NC1=C(C(=NN1C1=C(Cl)C=C(C=C1Cl)C(F)(F)F)C(O)=O)S(=O)C(F)(F)F
CH$IUPAC: InChI=1S/C12H5Cl2F6N3O3S/c13-4-1-3(11(15,16)17)2-5(14)7(4)23-9(21)8(6(22-23)10(24)25)27(26)12(18,19)20/h1-2H,21H2,(H,24,25)
CH$LINK: PUBCHEM
CID:23079075
CH$LINK: INCHIKEY
OHWPIAZSHNMBAC-UHFFFAOYSA-N
CH$LINK: CHEMSPIDER
16106629
AC$INSTRUMENT: Q Exactive Plus Orbitrap Thermo Scientific
AC$INSTRUMENT_TYPE: LC-ESI-QFT
AC$MASS_SPECTROMETRY: MS_TYPE MS2
AC$MASS_SPECTROMETRY: ION_MODE POSITIVE
AC$MASS_SPECTROMETRY: IONIZATION ESI
AC$MASS_SPECTROMETRY: FRAGMENTATION_MODE HCD
AC$MASS_SPECTROMETRY: COLLISION_ENERGY 120 % (nominal)
AC$MASS_SPECTROMETRY: RESOLUTION 17500
AC$CHROMATOGRAPHY: COLUMN_NAME XBridge C18 3.5um, 2.1x50mm, Waters
AC$CHROMATOGRAPHY: FLOW_GRADIENT 90/10 at 0 min, 50/50 at 4 min, 5/95 at 17 min, 5/95 at 25 min, 90/10 at 25.1 min, 90/10 at 30 min
AC$CHROMATOGRAPHY: FLOW_RATE 200 uL/min
AC$CHROMATOGRAPHY: RETENTION_TIME 8.085 min
AC$CHROMATOGRAPHY: SOLVENT A water with 0.1% formic acid
AC$CHROMATOGRAPHY: SOLVENT B MeOH with 0.1% formic acid
MS$FOCUSED_ION: BASE_PEAK 455.9408
MS$FOCUSED_ION: PRECURSOR_M/Z 455.9406
MS$FOCUSED_ION: PRECURSOR_TYPE [M+H]+
MS$DATA_PROCESSING: RECALIBRATE loess on assigned fragments and MS1
MS$DATA_PROCESSING: REANALYZE Peaks with additional N2/O included
MS$DATA_PROCESSING: WHOLE RMassBank 2.99.1
PK$SPLASH: splash10-066r-1910000000-b0b791a93ddb65fcfde0
PK$ANNOTATION: m/z tentative_formula formula_count mass error(ppm)
59.9902 CH2NS+ 1 59.9902 -0.54
61.9792 CHClN+ 1 61.9792 0.17
62.97 CFS+ 1 62.9699 0.93
62.9871 CH2ClN+ 1 62.987 0.68
63.9851 H2NOS+ 1 63.9852 -0.64
66.9746 CHClF+ 1 66.9745 0.93
68.9794 C3HS+ 1 68.9793 0.86
68.9947 CF3+ 1 68.9947 -0.15
69.9746 C2NS+ 1 69.9746 0.17
75.0041 C3HF2+ 1 75.0041 -0.29
78.9403 CClS+ 1 78.9404 -0.41
81.0135 C5H2F+ 2 81.0135 0.13
82.0088 C4HFN+ 1 82.0088 0.91
84.9652 CClF2+ 1 84.9651 1.1
86.9698 C3FS+ 1 86.9699 -0.96
87.0103 C6HN+ 1 87.0104 -0.83
88.0181 C6H2N+ 1 88.0182 -0.71
90.9745 C3HClF+ 1 90.9745 -0.84
92.9948 C3F3+ 1 92.9947 1.2
96.9839 C5H2Cl+ 2 96.984 -0.06
97.979 C4HClN+ 1 97.9792 -2.17
99.0045 C5HF2+ 1 99.0041 4.11
99.9994 C4F2N+ 2 99.9993 0.33
100.018 C7H2N+ 1 100.0182 -1.34
105.9871 C6H2S+ 4 105.9872 -0.74
106.0089 C6HFN+ 1 106.0088 1.22
108.9652 C3ClF2+ 1 108.9651 0.71
110.9701 C5FS+ 1 110.9699 1.69
113.0133 C7HN2+ 1 113.0134 -1.31
114.9744 ClF2N3+ 2 114.9743 0.32
121.9793 C6HClN+ 1 121.9792 0.45
123.9947 C6H3ClN+ 4 123.9949 -0.9
125.0035 C6H2FO2+ 3 125.0033 0.98
125.0133 F5H2N2+ 2 125.0133 0.2
131.0102 C6H2F3+ 2 131.0103 -0.66
132.0182 C6H3F3+ 2 132.0181 0.3
133.9791 C7HClN+ 1 133.9792 -0.77
134.9806 ClF3HN3+ 2 134.9806 0.04
137.0071 C7HF2N+ 2 137.0072 -0.38
138.0144 C7H2F2N+ 1 138.015 -3.88
139.0225 C7H3F2N+ 1 139.0228 -2.39
141.964 ClF3H2O3+ 4 141.9639 0.39
141.9855 C6H2ClFN+ 2 141.9854 0.76
142.9941 C6HF2O2+ 3 142.9939 1.11
143.0104 C7H2F3+ 2 143.0103 0.92
144.9651 C6ClF2+ 1 144.9651 0.02
145.9727 CClF3N3+ 2 145.9727 -0.46
150.0152 C8H2F2N+ 1 150.015 1.29
150.9509 Cl2F2HN3+ 2 150.951 -0.78
154.9759 C2F3N3S+ 4 154.976 -0.26
156.0059 C7HF3N+ 2 156.0056 1.98
157.0134 C7H2F3N+ 1 157.0134 0.15
157.9933 C8H2N2S+ 6 157.9933 0.17
158.0214 C7H3F3N+ 1 158.0212 1.25
158.9643 C6HClFO2+ 4 158.9644 -0.22
158.9806 C2HClF3N3+ 2 158.9806 0.39
161.9975 C11NO+ 6 161.9974 0.23
164.018 C8H2F2N2+ 1 164.0181 -0.13
165.0254 C8H3F2N2+ 1 165.0259 -3.05
165.9791 C6H2ClF3+ 2 165.9792 -0.11
166.9592 CHClF3NO3+ 5 166.9592 0.28
166.987 C6H3ClF3+ 3 166.987 0.1
168.0054 C8HF3N+ 3 168.0056 -0.81
169.0132 C8H2F3N+ 2 169.0134 -0.87
170.0039 C10HFNO+ 4 170.0037 1.19
170.0212 C8H3F3N+ 1 170.0212 -0.03
171.9757 C4H6ClFO2S+ 3 171.9756 0.96
172.9838 C7H2ClF2N+ 2 172.9838 0.04
173.9919 C2F4N3O2+ 4 173.9921 -1.15
174.9825 CHF6O3+ 8 174.9824 0.09
175.0098 C6H6FNO2S+ 2 175.0098 0.38
175.9902 C7H3F3S+ 9 175.9902 -0.08
176.0186 C9H2F2N2+ 2 176.0181 3.21
176.9717 C7HClF3+ 4 176.9713 2.13
176.9869 ClF4H6N2S+ 6 176.9871 -1.14
177.9622 C6H3Cl2FN+ 5 177.9621 0.75
177.9791 C7H2ClF3+ 2 177.9792 -0.43
178.9699 C6H4Cl2FN+ 7 178.9699 -0.09
178.9868 C2H2ClF4N3+ 3 178.9868 -0.06
181.0133 C9H2F3N+ 2 181.0134 -0.72
183.9759 C8HClF2N+ 3 183.976 -0.41
184.0113 C4H6F2N2O2S+ 3 184.0113 0.26
185.0315 C8H4F3N2+ 1 185.0321 -3.42
185.9744 C3F4N3S+ 8 185.9744 0.03
186.0158 C8H3F3NO+ 3 186.0161 -1.63
187.0238 C8H4F3NO+ 1 187.0239 -0.87
191.982 C7H2ClF3N+ 3 191.9822 -1.27
192.0265 C7H5F3NO2+ 1 192.0267 -0.81
192.9902 C7H3ClF3N+ 5 192.9901 0.97
193.9698 ClF5H4N2S+ 11 193.9698 -0.03
194.9812 C10H2ClF2+ 4 194.9808 2.11
195.0165 C9H2F3N2+ 1 195.0165 0.26
196.0234 C9H3F3N2+ 1 196.0243 -4.31
199.9823 C12H2ClF+ 4 199.9824 -0.35
200.948 C6H2Cl2F3+ 2 200.948 -0.3
200.9856 C10FNO3+ 9 200.9857 -0.13
201.0023 C11HF2NO+ 5 201.0021 1.18
201.9885 C11H3FOS+ 8 201.9883 0.92
203.9823 C8H2ClF3N+ 3 203.9822 0.26
206.9821 C9HF2N2S+ 8 206.9823 -0.92
207.952 C2H3ClF2N2O3S+ 3 207.9515 2.13
208.9477 C3H6Cl2FNO2S+ 4 208.9475 0.99
209.9683 C7H4Cl2F2N+ 6 209.9683 -0.15
209.9897 C5H6ClFN3OS+ 8 209.9899 -0.94
210.9867 C9H2ClF2N2+ 5 210.9869 -0.94
212.9481 C7H2Cl2F3+ 4 212.948 0.43
215.9482 C2ClF5NO3+ 5 215.9481 0.3
215.9821 C9H2ClF3N+ 4 215.9822 -0.81
220.0007 C11HF3NO+ 5 220.0005 0.89
222.0276 C10H3F3N3+ 3 222.0274 1.19
223.0345 C10H4F3N3+ 1 223.0352 -3.1
226.9885 C9H2F3N2S+ 10 226.9885 -0.3
227.9586 C10ClF3O+ 5 227.9584 0.63
230.9931 C9H3ClF3N2+ 6 230.9931 0.01
236.961 C5HClF5NO2+ 7 236.961 -0.2
242.9585 C8H4Cl2F3O+ 11 242.9586 -0.16
245.9695 C7H5Cl2F3NO+ 12 245.9695 0.04
249.0029 C12H4ClF2N2+ 3 249.0026 1.24
258.0039 C10H4ClF3N3+ 4 258.004 -0.5
262.9649 C8H5Cl2F4O+ 13 262.9648 0.17
PK$NUM_PEAK: 122
PK$PEAK: m/z int. rel.int.
59.9902 162080.9 8
61.9792 1266475 62
62.97 366257.1 18
62.9871 456891.3 22
63.9851 519010.7 25
66.9746 119383.9 5
68.9794 240461.5 11
68.9947 3381045.8 167
69.9746 3092624.5 153
75.0041 471443.1 23
78.9403 111045.6 5
81.0135 540512.9 26
82.0088 236614.5 11
84.9652 575442 28
86.9698 292296.8 14
87.0103 182914 9
88.0181 1114855.9 55
90.9745 538922.4 26
92.9948 214896.9 10
96.9839 316116.4 15
97.979 168957.3 8
99.0045 121613.7 6
99.9994 208905 10
100.018 153471 7
105.9871 781468 38
106.0089 856399.9 42
108.9652 241728.3 12
110.9701 203192 10
113.0133 181528.9 9
114.9744 270992 13
121.9793 1719123.5 85
123.9947 1000333.7 49
125.0035 112780.1 5
125.0133 319217.8 15
131.0102 881843.4 43
132.0182 1163916.6 57
133.9791 218494.5 10
134.9806 101847.3 5
137.0071 1089143.6 54
138.0144 263465.5 13
139.0225 222825.5 11
141.964 262145.2 13
141.9855 911470.9 45
142.9452 157822.1 7
142.9941 460967.3 22
143.0104 3192557.8 158
144.9651 231199.6 11
145.9727 245469 12
150.0152 313105.7 15
150.9509 235206.1 11
154.9759 265005.6 13
156.0059 181507.7 9
157.0134 20122130 999
157.9933 345414.2 17
158.0214 811210.4 40
158.9643 900326.2 44
158.9806 1213591.1 60
161.9975 116040.6 5
164.018 242100.6 12
165.0254 233228.4 11
165.9791 14319041 710
166.0215 289766.6 14
166.9592 515439.2 25
166.987 269517 13
168.0054 755262.3 37
169.0132 416699.4 20
170.0039 454225.1 22
170.0212 376265.8 18
171.9757 672875.2 33
172.9838 3544776.8 175
173.9919 467848.4 23
174.9825 2779569.8 137
175.0098 191860.3 9
175.9902 130465.2 6
176.0186 111881.3 5
176.9717 876297.8 43
176.9869 152969.5 7
177.9622 303420.8 15
177.9791 644409 31
178.9699 533822.1 26
178.9868 813607.4 40
181.0133 755612.6 37
183.9759 337367.3 16
184.0113 247261.5 12
185.0315 270643.6 13
185.9744 417658.2 20
186.0158 350407.6 17
187.0238 264805.3 13
191.982 1596999.1 79
192.0265 177279.8 8
192.9902 2413877.5 119
193.9698 408981.6 20
194.9812 229663 11
195.0165 2834496.2 140
196.0234 302377.7 15
199.9823 1161374.4 57
200.948 1533290.6 76
200.9856 383960.9 19
201.0023 642732.4 31
201.9885 132423.7 6
203.9823 3069004.5 152
206.9821 240522.6 11
207.952 399323.3 19
208.9477 358490 17
209.9683 953490.6 47
209.9897 143533.3 7
210.9867 715455.1 35
212.9481 1112503.9 55
215.9482 334297.9 16
215.9821 283594.6 14
220.0007 468916.7 23
222.0276 182126.5 9
223.0345 404795.9 20
226.9885 2017470 100
227.9586 331591.6 16
230.9931 673244.7 33
236.961 218987.4 10
242.9585 599487.6 29
245.9695 241462.6 11
249.0029 411145.8 20
258.0039 129872 6
262.9649 154258.8 7
//
