joint research centre - policija guillou, fabiano reniero, hubert chassaigne, joana lobo vicente,...
TRANSCRIPT
Joint Research CentreThe European Commissions in-house science service
ADMINISTRATIVE ARRANGEMENT JRC-Nr 33619-CLEN2SAND-DG TAXUD-Nr TAXUD/2014/DE/315
Page 1 of 14
Eurodat number 15040014Received on 13 April 2015PACKAGING in 1 glass vialRegistration date 23 April 2015Name of customer Service commun des laboratoires FranceCustomer's identification 2015-25717Customer's information 2015-25717 white powder, SCL Paris, GC-MSAgilent, FT-IRThermo Nicolet iS10, LC-MSBruker Impact LC-Q-TofCustomer's comments hypothetic molecular weight[MH]+ 393.21Hypothetic raw formulaC23H26FN4Ocannabinoid ?
There was/were identified following structure(s) in the sample:
NN
F
F
NH
O
NH2O
Data of identified compound(s)
Claude Guillou, Fabiano Reniero, Hubert Chassaigne, Joana Lobo Vicente, Veronica Holland, Kamil Kolar
European Commission, Joint Research CentreInstitute for Health and Consumer Protection (IHCP)Chemical Assessment and Testing Unitvia E. Fermi, 2749TP 281 I-21027 Ispra (VA) - ItalyPhone: +39 0332 785678Fax: +39 0332 [email protected]://ihcp.jrc.ec.europa.eu
ADMINISTRATIVE ARRANGEMENT JRC-Nr 33619-CLEN2SAND-DG TAXUD-Nr TAXUD/2014/DE/315 BETWEENDG TAXATION AND CUSTOMS UNION (DG TAXUD) AND THE JOINT RESEARCH CENTRE (JRC) for fastrecognition of New Psychoactive Substances (NPS) and identification of unknown chemicalsThis report was generated automatically by Kamil Kolar on 27/05/2015 based on data from the European Customslaboratories and the Joint Research Centre. This report includes sample and molecular information, spectra data andassociated tables and figures. The chemical structure(s) was/were identified by BCIM group chemists on the basis ofanalytical data available. The assignments proposed below were performed by using ACD labs tools in agreementwith the chemical structure identified by analytical experts. Reported data are connected to the sample in thefollowing table:
FW 392.4428IUPAC Name (v.14.01) N-(1-amino-3-methyl-1-oxobutan-2-yl)-1-(5-fluoropentyl)-5-(4-fluorophenyl)-1H-pyrazole-3-carboxamide (named manually)InChI (v.1.04) InChI=1S/C20H26F2N4O2/c1-13(2)18(19(23)27)24-20(28)16-12-17(14-6-8-15(22)9-7-14)26(25-16)11-5-3-4-10-21/h6-9,
12-13,18H,3-5,10-11H2,1-2H3,(H2,23,27)(H,24,28)InChI Key (v.1.04) GSXRDTDYPSATDE-UHFFFAOYSA-NSMILES (v.14.01) NC(=O)C(NC(=O)c2cc(c1ccc(F)cc1)n(CCCCCF)n2)C(C)CFormula C20H26F2N4O2
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Page 2 of 14
NN
F
F
NH
O
NH2O
Data measured by SCL Paris:
Wavenumber (cm-1)3500 3000 2500 2000 1500
%R
efle
ctan
ce
0
8
16
24
32
40
48
56
64
72
80
88
534.19534.19534.19534.19534.19534.19534.19534.19534.19534.19534.19534.19534.19534.19534.19534.19534.19534.19534.19534.19534.19534.19
555.88555.88555.88555.88555.88555.88555.88555.88555.88555.88555.88555.88555.88555.88555.88555.88555.88555.88555.88555.88555.88555.88
597.34597.34597.34597.34597.34597.34597.34597.34597.34597.34597.34597.34597.34597.34597.34597.34597.34597.34597.34597.34597.34597.34
660.98660.98660.98660.98660.98660.98660.98660.98660.98660.98660.98660.98660.98660.98660.98660.98660.98660.98660.98660.98660.98660.98675.45675.45675.45675.45675.45675.45675.45675.45675.45675.45675.45675.45675.45675.45675.45675.45675.45675.45675.45675.45675.45675.45
701.48701.48701.48701.48701.48701.48701.48701.48701.48701.48701.48701.48701.48701.48701.48701.48701.48701.48701.48701.48701.48701.48
747.76747.76747.76747.76747.76747.76747.76747.76747.76747.76747.76747.76747.76747.76747.76747.76747.76747.76747.76747.76747.76747.76
804.17804.17804.17804.17804.17804.17804.17804.17804.17804.17804.17804.17804.17804.17804.17804.17804.17804.17804.17804.17804.17804.17
818.15818.15818.15818.15818.15818.15818.15818.15818.15818.15818.15818.15818.15818.15818.15818.15818.15818.15818.15818.15818.15818.15
839.85839.85839.85839.85839.85839.85839.85839.85839.85839.85839.85839.85839.85839.85839.85839.85839.85839.85839.85839.85839.85839.85
866.36866.36866.36866.36866.36866.36866.36866.36866.36866.36866.36866.36866.36866.36866.36866.36866.36866.36866.36866.36866.36866.36
882.27882.27882.27882.27882.27882.27882.27882.27882.27882.27882.27882.27882.27882.27882.27882.27882.27882.27882.27882.27882.27882.27
958.45958.45958.45958.45958.45958.45958.45958.45958.45958.45958.45958.45958.45958.45958.45958.45958.45958.45958.45958.45958.45958.45
1001.841001.841001.841001.841001.841001.841001.841001.841001.841001.841001.841001.841001.841001.841001.841001.841001.841001.841001.841001.841001.841001.84
1043.781043.781043.781043.781043.781043.781043.781043.781043.781043.781043.781043.781043.781043.781043.781043.781043.781043.781043.781043.781043.781043.78
1135.381135.381135.381135.381135.381135.381135.381135.381135.381135.381135.381135.381135.381135.381135.381135.381135.381135.381135.381135.381135.381135.38
1157.081157.081157.081157.081157.081157.081157.081157.081157.081157.081157.081157.081157.081157.081157.081157.081157.081157.081157.081157.081157.081157.08
1216.861216.861216.861216.861216.861216.861216.861216.861216.861216.861216.861216.861216.861216.861216.861216.861216.861216.861216.861216.861216.861216.86
1273.271273.271273.271273.271273.271273.271273.271273.271273.271273.271273.271273.271273.271273.271273.271273.271273.271273.271273.271273.271273.271273.27
1293.521293.521293.521293.521293.521293.521293.521293.521293.521293.521293.521293.521293.521293.521293.521293.521293.521293.521293.521293.521293.521293.52
1303.161303.161303.161303.161303.161303.161303.161303.161303.161303.161303.161303.161303.161303.161303.161303.161303.161303.161303.161303.161303.161303.16
1390.911390.911390.911390.911390.911390.911390.911390.911390.911390.911390.911390.911390.911390.911390.911390.911390.911390.911390.911390.911390.911390.91
1440.081440.081440.081440.081440.081440.081440.081440.081440.081440.081440.081440.081440.081440.081440.081440.081440.081440.081440.081440.081440.081440.08
1456.961456.961456.961456.961456.961456.961456.961456.961456.961456.961456.961456.961456.961456.961456.961456.961456.961456.961456.961456.961456.961456.96
1505.171505.171505.171505.171505.171505.171505.171505.171505.171505.171505.171505.171505.171505.171505.171505.171505.171505.171505.171505.171505.171505.171528.311528.311528.311528.311528.311528.311528.311528.311528.311528.311528.311528.311528.311528.311528.311528.311528.311528.311528.311528.311528.311528.31
1544.221544.221544.221544.221544.221544.221544.221544.221544.221544.221544.221544.221544.221544.221544.221544.221544.221544.221544.221544.221544.221544.22
1563.51563.51563.51563.51563.51563.51563.51563.51563.51563.51563.51563.51563.51563.51563.51563.51563.51563.51563.51563.51563.51563.5
1640.161640.161640.161640.161640.161640.161640.161640.161640.161640.161640.161640.161640.161640.161640.161640.161640.161640.161640.161640.161640.161640.16
1688.371688.371688.371688.371688.371688.371688.371688.371688.371688.371688.371688.371688.371688.371688.371688.371688.371688.371688.371688.371688.371688.37
1704.761704.761704.761704.761704.761704.761704.761704.761704.761704.761704.761704.761704.761704.761704.761704.761704.761704.761704.761704.761704.761704.76
1714.411714.411714.411714.411714.411714.411714.411714.411714.411714.411714.411714.411714.411714.411714.411714.411714.411714.411714.411714.411714.411714.411748.161748.161748.161748.161748.161748.161748.161748.161748.161748.161748.161748.161748.161748.161748.161748.161748.161748.161748.161748.161748.161748.16
2798.692798.692798.692798.692798.692798.692798.692798.692798.692798.692798.692798.692798.692798.692798.692798.692798.692798.692798.692798.692798.692798.69
2869.082869.082869.082869.082869.082869.082869.082869.082869.082869.082869.082869.082869.082869.082869.082869.082869.082869.082869.082869.082869.082869.08
2956.822956.822956.822956.822956.822956.822956.822956.822956.822956.822956.822956.822956.822956.822956.822956.822956.822956.822956.822956.822956.822956.82
2970.322970.322970.322970.322970.322970.322970.322970.322970.322970.322970.322970.322970.322970.322970.322970.322970.322970.322970.322970.322970.322970.32
3032.513032.513032.513032.513032.513032.513032.513032.513032.513032.513032.513032.513032.513032.513032.513032.513032.513032.513032.513032.513032.513032.513076.393076.393076.393076.393076.393076.393076.393076.393076.393076.393076.393076.393076.393076.393076.393076.393076.393076.393076.393076.393076.393076.39
3192.583192.583192.583192.583192.583192.583192.583192.583192.583192.583192.583192.583192.583192.583192.583192.583192.583192.583192.583192.583192.583192.583276.46
3276.463276.463276.463276.463276.463276.463276.463276.463276.463276.463276.463276.463276.463276.463276.463276.463276.463276.463276.463276.463276.46
3362.283362.283362.283362.283362.283362.283362.283362.283362.283362.283362.283362.283362.283362.283362.283362.283362.283362.283362.283362.283362.283362.28
Title 25717File Name \\s-jrciprna004p-fs-vihcp.jrc.it\ihcp∴I01\BIO_CHEMICAL_INTERACTION_METABONOMICS\CLEN2SAND\!PROPOSED-ST
RUCTURE\CLEN_NAS\15040014\2015-25717\IR.SPADate Stamp 23 Feb 2015 09:01:49 Date 23 Feb 2015 11:02:04Technique Infrared Spectral Region IRX Axis Wavenumber (cm-1) Y Axis %ReflectanceSpectrum Range 525.0251 - 3500.1670 Points Count 6172Data Spacing 0.4821
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Page 3 of 14
m/z50045040035030025020015010050
0
20000
40000
60000
80000
100000
120000
140000
160000
180000
200000
220000
240000
260000
280000
300000
320000
340000
360000
380000
69.100069.100069.100069.100069.100069.100069.100069.100069.100069.100069.100069.100069.100069.100069.100069.100069.100069.100069.100069.100069.100069.1000
132.0000132.0000132.0000132.0000132.0000132.0000132.0000132.0000132.0000132.0000132.0000132.0000132.0000132.0000132.0000132.0000132.0000132.0000132.0000132.0000132.0000132.0000133.0000133.0000133.0000133.0000133.0000133.0000133.0000133.0000133.0000133.0000133.0000133.0000133.0000133.0000133.0000133.0000133.0000133.0000133.0000133.0000133.0000133.0000
134.0000134.0000134.0000134.0000134.0000134.0000134.0000134.0000134.0000134.0000134.0000134.0000134.0000134.0000134.0000134.0000134.0000134.0000134.0000134.0000134.0000134.0000
189.0000189.0000189.0000189.0000189.0000189.0000189.0000189.0000189.0000189.0000189.0000189.0000189.0000189.0000189.0000189.0000189.0000189.0000189.0000189.0000189.0000189.0000 249.1000249.1000249.1000249.1000249.1000249.1000249.1000249.1000249.1000249.1000249.1000249.1000249.1000249.1000249.1000249.1000249.1000249.1000249.1000249.1000249.1000249.1000 277.1000277.1000277.1000277.1000277.1000277.1000277.1000277.1000277.1000277.1000277.1000277.1000277.1000277.1000277.1000277.1000277.1000277.1000277.1000277.1000277.1000277.1000
348.2000348.2000348.2000348.2000348.2000348.2000348.2000348.2000348.2000348.2000348.2000348.2000348.2000348.2000348.2000348.2000348.2000348.2000348.2000348.2000348.2000348.2000
EI+
Comment eb Count 394 Data Type CondensedDate 18 Feb 2015 22:59:16 Date Stamp 18 Feb 15 9:47 pmEstimated Molecular Ion 547.000 File Name 2015-25717_Centroid_EI+Inlet Model GC Ion Mode EI+ Mass Spec Model STUP1Plot Type Stick Retention Time 6.770 Sample Ds CH2Cl2/CH3OH :
2015-25717Scan 1726 Scan Mode Centroid Spectrum Assigned 41.0% [34-549/0-100]TIC 1074.62 Total Signal 4180201
NN
F
F
NH
O
NH2O
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Table of fragments
No. Fragment Structure Formula Label m/z Calc.TIC Calc.(%)
Difference(Da)
m/z Exp. RI Exp.(%)
TIC Exp.(%)
AQI RDBEOriginComment
1 1-5,12-18,21,23(+H)N
+
1
N2
4
5
3
21O23
1213
15
1716
14
F18
C10H6FN2O M - C10H20FN2O 189.046 10.499 -0.046 189.000 100.000 10.499 1.0009.0Manual
2 1-18N1
N2
C+
4
53
6
78
910
F11
1213
1517
16
14
F18
C14H15F2N2 M - C6H11N2O2 249.120 10.905 -0.020 249.100 99.506 10.905 1.0007.5Manual
3 1-5,12-18,20-23,26-28(+H) N1N
2
4
5 3
21O23
12 13
15
1716
14
NH22CH+
2026
27
F18
28
C14H15FN3O M - C6H11FNO 260.119 1.004 -0.019 260.100 9.105 1.004 1.0009.0Manual
4 1-18,21,23 N1N
2
4
5 3
6
7 8
9 10
F11
C+
21
O23
12 13
15
1716
14
F18
C15H15F2N2O M - C5H11N2O 277.115 11.006 -0.015 277.100 99.095 11.006 1.0008.5Manual
5 1-18,20-23,26-28 N1
N2
4
53
6
78
910
F1121O
23
1213
1517
16
14
NH22
CH+
2026 27
F18
28
C19H24F2N3O M - CH2NO 348.188 6.438 0.012 348.200 55.199 6.431 0.9998.5Manual
6 M N+
1N2
4
53
67
89
10
F1121O
23
1213
1517
16
14
NH22
2026
27
F18
19 O25
28
NH224
C20H26F2N4O2 M 392.202 1.365 -0.002 392.200 11.500 1.365 1.0009.0Manual
NN
F
F
NH
O
NH2O
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Data measured by BCIM group at IHCP JRC Ispra
NMR spectraAcquisition Time (sec) 2.7263 Comment 25718 (F) 10mg in 600 uL DMSO-d6Date 14 Apr 2015 17:49:42 Date Stamp 14 Apr 2015 17:49:42File Name \\s-jrciprna004p-fs-vihcp.jrc.it\ihcp∴I01\Bio_Chemical_Interaction_Metabonomics\CLEN2SAND\!KK-proposed-structure-
temp-dir\BCIM_NAS\BCIM_600\15040003\1\PDATA\1\1rFrequency (MHz) 600.13 Nucleus 1HNumber of Transients 16 Origin spectOriginal Points Count 32768 Owner nmrsuPoints Count 65536 Pulse Sequence zg30Receiver Gain 1.91 SW(cyclical) (Hz) 12019.23Solvent DMSO-d6 Spectrum Offset (Hz) 3706.0515Spectrum Type standard Sweep Width (Hz) 12019.05Temperature (degree C) 27.000
Chemical Shift (ppm)8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0
Nor
mal
ized
Inte
nsity
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
M04(s, 5)
M03(s, 24)
M15(m, 28)
M14(s, 27)
M01(d, 22) M09(dd, 20)
M08(td, 6) M11(m, 7)
M02(m, 14,13)
M05(m, 16,15)
M12(m, 9)
M06(s, 24)
M13(br s, 8)
M07(m, 10)
M10(m, 26)
N1
N2
3
4
5
6
7
8
9
10F11
12
13
14
15
16
17
F18
1920
21
NH22
O23
NH224O
2526
CH327
CH328
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Table of assignments and zoomed parts:
No. Atom Exp. Shift(ppm)
Multiplet
1 27 0.93 M142 28 0.95 M153 8 1.32 M134 9 1.64 M125 7 1.80 M116 26 2.11 M107 20 4.27 M098 10 4.40 M079 6 4.50 M0810 24 7.12 M0611 16 7.27 M0512 15 7.27 M0513 5 7.43 M0414 24 7.49 M0315 14 7.83 M0216 13 7.83 M0217 22 8.18 M01
Chemical Shift (ppm)8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3
Nor
mal
ized
Inte
nsity
0
0.1
0.2
0.3
M04(s, 5)
M03(s, 24)M01(d, 22)
M02(m, 14,13)
M05(m, 16,15)
M06(s, 24)
N1
N2
3
4
5
6
7
8
9
10F11
12
13
14
15
16
17
F18
1920
21
NH22
O23
NH224O
2526
CH327
CH328
Chemical Shift (ppm)4.6 4.5 4.4
Nor
mal
ized
Inte
nsity
0
0.05
0.10
0.15M09(dd, 20)
M08(td, 6)
M07(m, 10)
Chemical Shift (ppm)2.0 1.5
Nor
mal
ized
Inte
nsity
0.25
0.50
M15(m, 28)
M14(s, 27)
M11(m, 7)M12(m, 9) M13(br s, 8)M10(m, 26)
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Page 7 of 14
Acquisition Time (sec) 0.9044 Comment 5 mm CPQCI 1H/19F-13C/15N/D Z-GRD Z114073/0012Date 14 Apr 2015 18:02:01 Date Stamp 14 Apr 2015 18:02:01File Name \\s-jrciprna004p-fs-vihcp.jrc.it\ihcp∴I01\Bio_Chemical_Interaction_Metabonomics\CLEN2SAND\!proposed-structure\BCI
M_NAS\BCIM_600\15040014\3\PDATA\1\1rFrequency (MHz) 150.90 Nucleus 13CNumber of Transients 512 Origin spectOriginal Points Count 32768 Owner nmrsuPoints Count 32768 Pulse Sequence jmodReceiver Gain 81.72 SW(cyclical) (Hz) 36231.88Solvent DMSO-d6 Spectrum Offset (Hz) 18108.3359Spectrum Type APT Sweep Width (Hz) 36230.78Temperature (degree C) 27.002
Chemical Shift (ppm)170 160 150 140 130 120 110 100 90 80 70 60 50
Nor
mal
ized
Inte
nsity
-1.00
-0.95
-0.90
-0.85
-0.80
-0.75
-0.70
-0.65
-0.60
-0.55
-0.50
-0.45
-0.40
-0.35
-0.30
-0.25
-0.20
-0.15
-0.10
-0.05
0
0.05
0.10
M12(s) M06(s)
M04(s)
M03(s)
M02(s, 27)
M26(s, 21)M25(s, 3)
M24(s, 4)
M23(s)
M22(s, 12)
M20(s, 14,13)M19(s, 15)
M17(s, 5)
M10(s)
M29(s, 19)
M21(s)M14(s, 20)
M13(s, 6)
M11(s)
M08(s, 26)
M05(s)
M01(s, 28)
M30(m, 8)
M28(m, 9)
M09(dd)
M15(br d, 10)
M27(br d, 17)
N1
N2
3
4
5
6
7
8
9
10F11
12
13
14
15
16
17F18
1920
21
NH22
O23
NH224O
2526
CH327
CH328
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Table of assignments and zoomed parts:
No. Atom Exp. Shift(ppm)
Multiplet
1 28 18.89 M012 27 19.84 M023 8 22.21 M304 9 29.78 M285 7 30.22 M076 26 30.54 M087 6 50.93 M138 20 58.61 M149 10 84.06 M1510 5 105.13 M1711 16 116.05 M1812 15 116.20 M1913 14 127.40 M2014 13 127.40 M2015 12 129.76 M2216 4 137.01 M2417 3 147.91 M2518 21 159.72 M2619 17 162.29 M2720 19 173.05 M29
Chemical Shift (ppm)175 170 165 160 155 150 145 140 135 130 125 120 115
Nor
mal
ized
Inte
nsity
-0.2
-0.1
0
M17(s, 5)
M23(s)
M22(s, 12)
M20(s, 14,13)
M29(s, 19)
M26(s, 21) M25(s, 3)M24(s, 4)
M19(s, 15)
M27(br d, 17)
Chemical Shift (ppm)90 85 80 75 70 65 60 55 50 45 40 35 30
Nor
mal
ized
Inte
nsity
-1.0
-0.5
M12(s)M07(s, 7)
M06(s) M04(s)
M03(s)
M02(s, 27)
M10(s)
M05(s)
M14(s, 20)
M13(s, 6)
M11(s)
M08(s, 26)
M30(m, 8)M28(m, 9)
M09(dd)
M15(br d, 10)
N1
N2
3
4
5
6
7
8
9
10F11
12
13
14
15
16
17F18
1920
21
NH22
O23
NH224O
2526
CH327
CH328
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Acquisition Time (sec) (0.2840, 0.0206) Comment 5 mm CPQCI 1H/19F-13C/15N/D Z-GRD Z114073/0012Date 15 Apr 2015 09:34:54File Name \\s-jrciprna004p-fs-vihcp.jrc.it\ihcp∴I01\Bio_Chemical_Interaction_Metabonomics\CLEN2SAND\!proposed-structure\BCI
M_NAS\BCIM_600\15040014\6\PDATA\1\2rrFrequency (MHz) (600.13, 150.90) Nucleus (1H, 13C)Number of Transients 4 Origin spectOriginal Points Count (2048, 512) Owner nmrsuPoints Count (1024, 1024) Pulse Sequence hsqcedetgpsisp2.3Solvent DMSO-d6 Spectrum Type HSQCSweep Width (Hz) (7204.50, 24851.33) Temperature (degree C) 27.001
7.83, 127.43 (13, 13)(14, 14)
0.93, 18.87 (27, 27)
0.94, 19.83 (28, 28)
7.27, 116.15 (15, 15)(16, 16)
7.43, 105.10 (5, 5)
1.80, 30.21 (7, 7)
4.50, 50.91 (6, 6)
4.27, 58.59 (20, 20)
1.32, 22.20 (8, 8)
2.11, 30.54 (26, 26)
1.64, 29.77 (9, 9)
2.51, 40.21
4.38, 84.60 (10, 10)
8.18, 58.59
15040014.006.001.2rr.man-assign.esp
F2 Chemical Shift (ppm) 8 7 6 5 4 3 2 1 0 -1
F1 C
hem
ical
Shi
ft (p
pm)
24
32
40
48
56
64
72
80
88
96
104
112
120
128
136
144
13, 14 13, 14 13, 14 13, 14 13, 14 13, 14 13, 14 13, 14 13, 14 13, 14 13, 14 13, 14 13, 14 13, 14 13, 14 13, 14 13, 14 13, 14 13, 14 13, 14 13, 14 13, 14
5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 15, 16 15, 16 15, 16 15, 16 15, 16 15, 16 15, 16 15, 16 15, 16 15, 16 15, 16 15, 16 15, 16 15, 16 15, 16 15, 16 15, 16 15, 16 15, 16 15, 16 15, 16 15, 16
6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8
28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27
13, 14 13, 14 13, 14 13, 14 13, 14 13, 14 13, 14 13, 14 13, 14 13, 14 13, 14 13, 14 13, 14 13, 14 13, 14 13, 14 13, 14 13, 14 13, 14 13, 14 13, 14 13, 14
15, 16 15, 16 15, 16 15, 16 15, 16 15, 16 15, 16 15, 16 15, 16 15, 16 15, 16 15, 16 15, 16 15, 16 15, 16 15, 16 15, 16 15, 16 15, 16 15, 16 15, 16 15, 16
5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5
10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10
20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20
6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6
26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9
8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27
N1N
2
3
4
5
67
89
10F11
12
13
14
15
16
17F18
1920
21
NH22
O23
NH224O2526
CH3 27CH328
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Table of assignments:No. F2 Atom F1 Atom F2
(ppm)F1
(ppm)1 5 5 7.43 105.102 6 6 4.50 50.913 7 7 1.80 30.214 8 8 1.32 22.205 9 9 1.64 29.776 9 9 1.32 29.877 10 10 4.38 84.608 13 13 7.83 127.439 14 14 7.83 127.4310 15 15 7.27 116.1511 16 16 7.27 116.1512 20 20 4.27 58.5913 26 26 2.11 30.5414 27 27 0.93 18.8715 28 28 0.94 19.83
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NN
F
F
NH
O
NH2O
MS spectra
Retention Time: 0.823 Ion Mode: ESI+
m/z50045040035030025020015010050
0
1090000
2180000
3270000
4360000
5450000
6540000
7630000
8720000
9810000
10900000
11990000
13080000
14170000
15260000
16350000
17440000
18530000
19620000
20710000
21800000
22890000
M+K
M+Na
M+H84.748484.748484.748484.748484.748484.748484.748484.748484.748484.748484.748484.748484.748484.748484.748484.748484.748484.748484.748484.748484.748484.7484 168.3660168.3660168.3660168.3660168.3660168.3660168.3660168.3660168.3660168.3660168.3660168.3660168.3660168.3660168.3660168.3660168.3660168.3660168.3660168.3660168.3660168.3660180.0505180.0505180.0505180.0505180.0505180.0505180.0505180.0505180.0505180.0505180.0505180.0505180.0505180.0505180.0505180.0505180.0505180.0505180.0505180.0505180.0505180.0505
193.0711193.0711193.0711193.0711193.0711193.0711193.0711193.0711193.0711193.0711193.0711193.0711193.0711193.0711193.0711193.0711193.0711193.0711193.0711193.0711193.0711193.0711
198.0657198.0657198.0657198.0657198.0657198.0657198.0657198.0657198.0657198.0657198.0657198.0657198.0657198.0657198.0657198.0657198.0657198.0657198.0657198.0657198.0657198.0657
212.0849212.0849212.0849212.0849212.0849212.0849212.0849212.0849212.0849212.0849212.0849212.0849212.0849212.0849212.0849212.0849212.0849212.0849212.0849212.0849212.0849212.0849
250.1449250.1449250.1449250.1449250.1449250.1449250.1449250.1449250.1449250.1449250.1449250.1449250.1449250.1449250.1449250.1449250.1449250.1449250.1449250.1449250.1449250.1449
339.0554339.0554339.0554339.0554339.0554339.0554339.0554339.0554339.0554339.0554339.0554339.0554339.0554339.0554339.0554339.0554339.0554339.0554339.0554339.0554339.0554339.0554
393.2115393.2115393.2115393.2115393.2115393.2115393.2115393.2115393.2115393.2115393.2115393.2115393.2115393.2115393.2115393.2115393.2115393.2115393.2115393.2115393.2115393.2115
431.1676431.1676431.1676431.1676431.1676431.1676431.1676431.1676431.1676431.1676431.1676431.1676431.1676431.1676431.1676431.1676431.1676431.1676431.1676431.1676431.1676431.1676ESI+
Combine <84-87> Count 409Data Source Name 15040014_25717_MS mode_50_1000_RES30000_1Data Type p Date 24 Apr 2015Estimated Molecular Ion 996.921File Name \\s-jrciprna004p-fs-vihcp.jrc.it\ihcp∴I01\Bio_Chemical_Interaction_Metabonomics\CLEN2SAND\!proposed-structure\B
CIM_NAS\BCIM_Orbi\15040014_25717\15040014_25717_MS mode_50_1000_RES30000.rawIon Mode ESI+ Mass Spec Model LTQ Orbitrap/LTQ OrbitrapPlot Type Profile Retention Time 0.823Scan 85 Scan Filter FTMS + p ESI Full ms [50.00-1000.00]Scan Mode ms Scan Type FullSpectrum Assigned 27.8% [50-997/0-100] TIC 421.47Total Signal 95607024
No. Fragment Structure Formula Label m/z Calc. TIC Calc.(%)
Difference(Da)
m/z Exp. RI Exp.(%)
TIC Exp.(%)
AQI RDBE Origin Comment
1 M(+H) NH+
1N2
4
53
67
89
10
F1121O
23
1213
1517
16
14
NH22
2026
27
F18
19 O25
28
NH224
C20H27F2N4O2 M + H 393.210 29.502 0.002 393.212 97.507 28.402 0.963 8.5 Manual
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NN
F
F
NH
O
NH2O
Retention Time: 0.978 Ion Mode: ESI+
m/z380360340320300280260240220200180160
0
60000
120000
180000
240000
300000
360000
420000
480000
540000
600000
660000
251.1667251.1667251.1667251.1667251.1667251.1667251.1667251.1667251.1667251.1667251.1667251.1667251.1667251.1667251.1667251.1667251.1667251.1667251.1667251.1667251.1667251.1667260.1667260.1667260.1667260.1667260.1667260.1667260.1667260.1667260.1667260.1667260.1667260.1667260.1667260.1667260.1667260.1667260.1667260.1667260.1667260.1667260.1667260.1667
277.2500277.2500277.2500277.2500277.2500277.2500277.2500277.2500277.2500277.2500277.2500277.2500277.2500277.2500277.2500277.2500277.2500277.2500277.2500277.2500277.2500277.2500 288.1667288.1667288.1667288.1667288.1667288.1667288.1667288.1667288.1667288.1667288.1667288.1667288.1667288.1667288.1667288.1667288.1667288.1667288.1667288.1667288.1667288.1667
305.2500305.2500305.2500305.2500305.2500305.2500305.2500305.2500305.2500305.2500305.2500305.2500305.2500305.2500305.2500305.2500305.2500305.2500305.2500305.2500305.2500305.2500328.3333328.3333328.3333328.3333328.3333328.3333328.3333328.3333328.3333328.3333328.3333328.3333328.3333328.3333328.3333328.3333328.3333328.3333328.3333328.3333328.3333328.3333
348.2500348.2500348.2500348.2500348.2500348.2500348.2500348.2500348.2500348.2500348.2500348.2500348.2500348.2500348.2500348.2500348.2500348.2500348.2500348.2500348.2500348.2500
373.3333373.3333373.3333373.3333373.3333373.3333373.3333373.3333373.3333373.3333373.3333373.3333373.3333373.3333373.3333373.3333373.3333373.3333373.3333373.3333373.3333373.3333
376.1667376.1667376.1667376.1667376.1667376.1667376.1667376.1667376.1667376.1667376.1667376.1667376.1667376.1667376.1667376.1667376.1667376.1667376.1667376.1667376.1667376.1667393.2500393.2500393.2500393.2500393.2500393.2500393.2500393.2500393.2500393.2500393.2500393.2500393.2500393.2500393.2500393.2500393.2500393.2500393.2500393.2500393.2500393.2500
ESI+
Count 1915 Data Type pDate 20 Apr 2015 Estimated Molecular Ion 393.500File Name \\s-jrciprna004p-fs-vihcp.jrc.it\ihcp∴I01\Bio_Chemical_Interaction_Metabonomics\CLEN2SAND\!proposed-structure\BC
IM_NAS\BCIM_Orbi\15040014_25717\15040014_25717_MSMS mode_393_CE 20_105_400.rawIon Mode ESI+ Mass Spec Model LTQ Orbitrap/LTQ OrbitrapPlot Type Profile Retention Time 0.978Scan 120 Scan Filter ITMS + p ESI Full ms2 [email protected] [105.00-400.00]Scan Mode ms2 Scan Type FullSpectrum Assigned 17.5% [149-399/0-100] TIC 654.02Total Signal 4466182.5
No. Fragment Structure Formula Label m/z Calc.TIC Calc.(%)
Difference(Da)
m/z Exp. RI Exp.(%)
TIC Exp.(%)
AQI RDBEOriginComment
1 1-5,12-18,20-23,26-28(+H) N1N
2
4
5 3
21O23
12 13
15
1716
14
NH22CH+
2026
27
F18
28
C14H15FN3O M - C6H11FNO 260.119 0.427 -0.036 260.083 2.356 0.367 0.861 9.0 Manual
2 1-18,21,23 N1N
2
4
5 3
6
7 8
9 10
F11
C+
21
O23
12 13
15
1716
14
F18
C15H15F2N2O M - C5H11N2O 277.115 0.538 -0.031 277.083 2.946 0.472 0.878 8.5 Manual
3 1-18,20-23,26-28 N1
N2
4
53
6
78
910
F1121O
23
1213
1517
16
14
NH22
CH+
2026 27
F18
28
C19H24F2N3O M - CH2NO 348.188 17.513 -0.022 348.167 91.391 14.355 0.820 8.5 Manual
4 1-23,25-28 N1
N2
4
53
6
78
910
F1121O
23
1213
1517
16
14
NH22
20
26 27
F18
C+
19O25
28
C20H24F2N3O2 M - H2N 376.183 1.503 -0.016 376.167 7.737 1.222 0.813 9.5 Manual
5 M(+H) NH+
1N2
4
53 6
7 89
10
F1121O
23
1213
1517
16
14
NH22
2026
27
F18
19 O25
28
NH224
C20H27F2N4O2 M + H 393.210 1.693 0.040 393.250 8.683 1.382 0.816 8.5 Manual
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Fragmentation of the observed molecule and the virtual MS and MSMS spectra predictedby Thermo Scientific Mass Frontier
FNN
F
NH
O
N 2HO
FNN
F
NH
O
N 2HO
H
m/z 393.21
FNN
F
NH
O
N 2HO
FNN
F
NH
O
N 3HO
m/z 393.21
+H
O
NH
ON
N
F
F
m/z 376.18
-NH3
FNN
F
NH
O
N 2HO
FNN
F
NH
OH
N 2HO
m/z 393.21
+H
NH
ON
N
F
F
m/z 348.19
rHC
FNN
F
NH
O
N 2HO
FNN
F
N2H
O
N 2HO
m/z 393.21
+H
ON
N
F
F
m/z 277.11
i
FNN
F
NH
O
N 2HO
FNN
F
NH
OH
N 2HO
m/z 393.21
+H
NH
ON
N
F
F
m/z 348.19
rHCNH
NNH
O
F
m/z 260.12
rHR
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3060
9012
015
018
021
024
027
030
033
036
039
042
045
048
051
054
057
060
063
066
069
072
075
078
081
084
087
090
093
096
099
0
013253850637588100
393.2
118
250.1
4474 250.1
4497
393.2
115
394.2
151
393.2
121
212.0
8436
193.0
7016
251.1
4821
338.3
434
251.1
4799
415.1
937
149.0
2361
100.1
1212
373.2
055
462.0
785
943.0
146
570.4
663
721.9
965
821.4
725
511.9
969
639.5
547
758.1
659
675.6
817
886.0
710
312.0
101
979.7
163
605.3
137
FN
N
F
NHO
N2
HO
H
170
180
190
200
210
220
230
240
250
260
270
280
290
300
310
320
330
340
350
360
370
380
390
013253850637588100
348.1
4
376.0
9739
3.20
277.0
8426
0.093
328.1
628
8.01
305.1
925
1.11
382.8
0920
9.00
231.0
9018
8.998
221.0
1435
6.115
317.1
524
3.110
337.2
7929
4.29
372.6
436
5.28
181.0
7226
9.00
NHO
NN
F
F
O
NHO
NN
F
F
FN
N
F
NHO
N2
HO
H
ON
N
F
FN
HN
NHO
F