Joint Research Centre - Policija...administrative arrangement jrc-nr 33619-clen2sand-dg taxud-nr...

Joint Research CentreThe European Commission's in-house science service

ADMINISTRATIVE ARRANGEMENT JRC-Nr 33619-CLEN2SAND-DG TAXUD-Nr TAXUD/2014/DE/315

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ADMINISTRATIVE ARRANGEMENT JRC-Nr 33619-CLEN2SAND-DG TAXUD-Nr TAXUD/2014/DE/315BETWEEN DG TAXATION AND CUSTOMS UNION (DG TAXUD) AND THE JOINT RESEARCH CENTRE (JRC)for fast recognition of New Psychoactive Substances (NPS) and identification of unknown chemicalsThis report was generated on 02/03/2016 based on data from the European Customs laboratories and the JointResearch Centre. This report includes sample and molecular information, spectral data and associated tables andfigures. The chemical structure(s) was/were identified by Bio-chemical interactions & metabolomics (BCIM) groupchemists on the basis of analytical data available. NMR assignments proposed below were performed by ACD labstools in agreement with the chemical structure identified by analytical experts. Reported data are related to thesample in the following table:

Eurodat number 16020009 Received on 22 February 2016PACKAGING 1* glass vial 50 mg white powderName of customer Belgian Customs LaboratoryCustomer's identification 15BD-00431-01

The following structure(s) was/were identified in the sample:

O

O NH

O

Data of identified compound(s)IUPAC Name (v.14.02) 1-(2H-1,3-benzodioxol-5-yl)-2-(propylamino)propan-1-oneFormula C13H17NO3 FW 235.2790Monoisotopic Mass 235.120843InChI (v.1.04) InChI=1S/C13H17NO3/c1-3-6-14-9(2)13(15)10-4-5-11-12(7-10)17-8-16-11/h4-5,7,9,14H,3,6,8H2,1-2H3InChI Key (v.1.04) YFVKHKCZBSGZPE-UHFFFAOYSA-N SMILES (v.14.02) CC(NCCC)C(=O)c1ccc2OCOc2c1

Claude Guillou, Fabiano Reniero, Hubert Chassaigne, Joana Lobo Vicente, Veronica Holland, Kamil Kolar

European Commission, Joint Research CentreInstitute for Health and Consumer Protection (IHCP)via E. Fermi, 2749TP 281, I-21027 Ispra (VA) - ItalyPhone: +39 0332 785678Fax: +39 0332 [email protected]://ec.europa.eu/jrc/en/institutes/ihcp



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16020009_15BD-00431-01_IR_new.esp

Wavenumber (cm-1)4000 3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200

50

52

54

56

58

60

62

64

66

68

70

72

74

76

78

80

82

84

86

88

90

92

94

96

98

666666666666666666666666666666666666666666666666666666666666666666

710710710710710710710710710710710710710710710710710710710710710710

737737737737737737737737737737737737737737737737737737737737737737

767767767767767767767767767767767767767767767767767767767767767767828

828828828828828828828828828828828828828828828828828828828828828

887887887887887887887887887887887887887887887887887887887887887887

935935935935935935935935935935935935935935935935935935935935935935980980980980980980980980980980980980980980980980980980980980980980

1039103910391039103910391039103910391039103910391039103910391039103910391039103910391039

1089108910891089108910891089108910891089108910891089108910891089108910891089108910891089

1149114911491149114911491149114911491149114911491149114911491149114911491149114911491149

1195119511951195119511951195119511951195119511951195119511951195119511951195119511951195

1228122812281228122812281228122812281228122812281228122812281228122812281228122812281228

1254125412541254125412541254125412541254125412541254125412541254125412541254125412541254

1299129912991299129912991299129912991299129912991299129912991299129912991299129912991299

1351135113511351135113511351135113511351135113511351135113511351135113511351135113511351

1404140414041404140414041404140414041404140414041404140414041404140414041404140414041404

1423142314231423142314231423142314231423142314231423142314231423142314231423142314231423

14351435143514351435143514351435143514351435143514351435143514351435143514351435143514351502150215021502150215021502150215021502150215021502150215021502150215021502150215021502

1591159115911591159115911591159115911591159115911591159115911591159115911591159115911591

1615161516151615161516151615161516151615161516151615161516151615161516151615161516151615

1656165616561656165616561656165616561656165616561656165616561656165616561656165616561656

1693169316931693169316931693169316931693169316931693169316931693169316931693169316931693

176917691769176917691769176917691769176917691769176917691769176917691769176917691769176918441844184418441844184418441844184418441844184418441844184418441844184418441844184418441876187618761876187618761876187618761876187618761876187618761876187618761876187618761876198019801980198019801980198019801980198019801980198019801980198019801980198019801980198020382038203820382038203820382038203820382038203820382038203820382038203820382038203820382050205020502050205020502050205020502050205020502050205020502050205020502050205020502050

21042104210421042104210421042104210421042104210421042104210421042104210421042104210421042163216321632163216321632163216321632163216321632163216321632163216321632163216321632163220822082208220822082208220822082208220822082208220822082208220822082208220822082208220822432243224322432243224322432243224322432243224322432243224322432243224322432243224322432290229022902290229022902290229022902290229022902290229022902290229022902290229022902290

2438243824382438243824382438243824382438243824382438243824382438243824382438243824382438

2528252825282528252825282528252825282528252825282528252825282528252825282528252825282528

2718271827182718271827182718271827182718271827182718271827182718271827182718271827182718

2759275927592759275927592759275927592759275927592759275927592759275927592759275927592759

28132813281328132813281328132813281328132813281328132813281328132813281328132813281328132872287228722872287228722872287228722872287228722872287228722872287228722872287228722872

2929292929292929292929292929292929292929292929292929292929292929292929292929292929292929

2959295929592959295929592959295929592959295929592959295929592959295929592959295929592959

3044304430443044304430443044304430443044304430443044304430443044304430443044304430443044

3194319431943194319431943194319431943194319431943194319431943194319431943194319431943194

33703370337033703370337033703370337033703370337033703370337033703370337033703370337033703423342334233423342334233423342334233423342334233423342334233423342334233423342334233423

3572357235723572357235723572357235723572357235723572357235723572357235723572357235723572362836283628362836283628362836283628362836283628362836283628362836283628362836283628362836663666366636663666366636663666366636663666366636663666366636663666366636663666366636663704370437043704370437043704370437043704370437043704370437043704370437043704370437043704

3902390239023902390239023902390239023902390239023902390239023902390239023902390239023902

Processing and interpretation based on data provided by:Belgian Customs Laboratory

O

O NH

O

Comment POWDER as suchFile Name \\139.191.6.82\ihcp$\I01\BIO_CHEMICAL_INTERACTION_METABONOMICS\CLEN2SAND\!PROPOSED-STRUCTURE\CLEN

_NAS\16020009_15BD-00431-01\15BD-00431-01P.SPDate Stamp wed mar 02 09:30:38 2016 Date wed mar 02 09:30:38 2016Technique Infrared Spectral Region IRX Axis Wavenumber (cm-1) Y Axis %TransmittanceSpectrum Range 650.0000 - 4000.0000 Points Count 3351Data Spacing 1.0000



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File Name \\139.191.6.82\ihcp$\I01\BIO_CHEMICAL_INTERACTION_METABONOMICS\CLEN2SAND\!PROPOSED-STRUCTURE\CLEN_NAS\16020009_15BD-00431-01\15BD-00431-01\15BD-00431 -01 EXTRACTION BASIQUE.SP

Date Stamp fri nov 27 14:10:34 2015 Date fri nov 27 14:10:34 2015Technique Infrared Spectral Region IRX Axis Wavenumber (cm-1) Y Axis %TransmittanceSpectrum Range 650.0000 - 4000.0000 Points Count 3351Data Spacing 1.0000

16020009_15BD-00431-01_IR_EXTRACTION_BASIQUE.esp

Wavenumber (cm-1)4000 3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

2961296129612961296129612961296129612961296129612961296129612961296129612961296129612961

2875287528752875287528752875287528752875287528752875287528752875287528752875287528752875

1672167216721672167216721672167216721672167216721672167216721672167216721672167216721672

1604160416041604160416041604160416041604160416041604160416041604160416041604160416041604

1504150415041504150415041504150415041504150415041504150415041504150415041504150415041504

1489148914891489148914891489148914891489148914891489148914891489148914891489148914891489

1437143714371437143714371437143714371437143714371437143714371437143714371437143714371437

1368136813681368136813681368136813681368136813681368136813681368136813681368136813681368

1352135213521352135213521352135213521352135213521352135213521352135213521352135213521352

1243124312431243124312431243124312431243124312431243124312431243124312431243124312431243

1131113111311131113111311131113111311131113111311131113111311131113111311131113111311131

1105110511051105110511051105110511051105110511051105110511051105110511051105110511051105

1035103510351035103510351035103510351035103510351035103510351035103510351035103510351035

971971971971971971971971971971971971971971971971971971971971971971

932932932932932932932932932932932932932932932932932932932932932932

866866866866866866866866866866866866866866866866866866866866866866

807807807807807807807807807807807807807807807807807807807807807807

749749749749749749749749749749749749749749749749749749749749749749

722722722722722722722722722722722722722722722722722722722722722722 706

706706706706706706706706706706706706706706706706706706706706706

Processing and interpretation based on data provided by:Belgian Customs Laboratory

O

O NH

O

Comment Extracted base



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16020009_15BD-00431-01_EI+.esp

m/z22020018016014012010080604020

M27.20027.20027.20027.20027.20027.20027.20027.20027.20027.20027.20027.20027.20027.20027.20027.20027.20027.20027.20027.20027.20027.200

44.20044.20044.20044.20044.20044.20044.20044.20044.20044.20044.20044.20044.20044.20044.20044.20044.20044.20044.20044.20044.20044.200

65.20065.20065.20065.20065.20065.20065.20065.20065.20065.20065.20065.20065.20065.20065.20065.20065.20065.20065.20065.20065.20065.200

86.20086.20086.20086.20086.20086.20086.20086.20086.20086.20086.20086.20086.20086.20086.20086.20086.20086.20086.20086.20086.20086.200

121.100121.100121.100121.100121.100121.100121.100121.100121.100121.100121.100121.100121.100121.100121.100121.100121.100121.100121.100121.100121.100121.100149.100149.100149.100149.100149.100149.100149.100149.100149.100149.100149.100149.100149.100149.100149.100149.100149.100149.100149.100149.100149.100149.100

178.100178.100178.100178.100178.100178.100178.100178.100178.100178.100178.100178.100178.100178.100178.100178.100178.100178.100178.100178.100178.100178.100 206.200206.200206.200206.200206.200206.200206.200206.200206.200206.200206.200206.200206.200206.200206.200206.200206.200206.200206.200206.200206.200206.200220.200220.200220.200220.200220.200220.200220.200220.200220.200220.200220.200220.200220.200220.200220.200220.200220.200220.200220.200220.200220.200220.200

EI+

Processing and interpretation based on data provided by:Belgian Customs LaboratoryComment MTOH/DCM Count 154Data Type Condensed Date 3:52:48 PMDate Stamp 4 Nov 15 3:22 pm Estimated Molecular Ion 234.2File Name 15BD431_1_Centroid_EI+ Inlet Model GCIon Mode EI+ Mass Spec Model Instrumen Operator VHPlot Type Stick Retention Time 9.336 Sample 15BD-00431-01Scan 1026 Scan Mode Centroid Spectrum Assigned 69.2% [14-237/0-100]Spectrum Type MS TIC 230.85 Total Signal 2978550

O

O NH

O



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No. Fragment Structure Formula Label m/z Calc. TIC Calc.(%)

Difference(Da)

m/z Exp. RI Exp.(%)

TIC Exp.(%)

1 11-12,17(+H) CH +

NH

CH3C2H6N M - C11H11O3 44.049 11.121 0.151 44.200 25.005 11.121

2 11-13,17(-H)CH +

NHCH2

CH3

C3H6N M - C10H11O3 56.049 1.377 0.151 56.200 3.061 1.377

3 11-15(-H) C4H8N M - C9H9O3 70.065 0.686 0.135 70.200 1.509 0.686

4 10-13,16-17(+H)C

O

NH

CH2+

CH3 C4H8NO M - C9H9O2 86.060 45.586 0.140 86.200 100.000 45.585

5 1-6,10,16

C+

O

C7H3O M - C6H14NO2 103.018 0.149 0.082 103.100 0.317 0.149

6 1-6,8,10,16(+H2)

O

C+ O

C7H5O2 M - C6H12NO 121.028 3.493 0.072 121.100 7.424 3.493

7 1-6,8-10,16(+H2)CH2

+ O

O

C8H7O2 M - C5H10NO 135.044 1.887 0.056 135.100 3.966 1.886

8 1-7,10-11,16-17(+H2)O

O

CH+CH3 C9H9O2 M - C4H8NO 149.060 4.607 0.040 149.100 9.574 4.607

9 1-11,17(+H2)O

O

C+ CH3

C10H11O2 M - C3H6NO 163.075 0.172 0.125 163.200 0.354 0.172

10 1-11,16-17(+H) O

O

O

CH+CH3 C10H10O3 M - C3H7N 178.062 0.252 0.038 178.100 0.518 0.250

11 M

O

OO

NH+

CH3

CH3

C13H17NO3 M 235.120 0.038 0.080 235.200 0.075 0.038

Table of fragments



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16020009.001.001.1r.1H.esp

Chemical Shift (ppm)9.5 9.0 8.5 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

2.94

2.91

2.03

1.05

1.06

1.05

1.95

0.95

0.95

1.00

0.94

0.91

M09(d, 3)

DMSO

M08(d, 4)

M07(s, 9)

Water

M02(d, 15)

M10(dd, 2)

M01(t, 17)

M03(sxt, 16)

M04(m, 13)M06(q, 11)

M05(m, 13)

M12(br s, 12)

M11(br s, 12)

Data from BCIM group at JRC, IHCP Ispra NMR spectraAcquisition Time (sec) 2.7263 Comment 15BD-00431-01 Belgium CustomD 0.0002 D1 1 DE 10DS 2 Date 23 Feb 2016 18:09:33Date Stamp 23 Feb 2016 18:09:33File Name \\139.191.6.82\ihcp$\I01\Bio_Chemical_Interaction_Metabonomics\CLEN2SAND\!proposed-structure\BCIM_NAS\BCIM_6

00\16020009_15BD-00431-01\1\PDATA\1\1rFrequency (MHz) 600.1300 GB 0 INSTRUM <spect>LB 0 NS 32 Nucleus 1HNumber of Transients 32 Origin spect Original Points Count 32768Owner nmrsu PC 1PROBHD <5 mm CPQCI 1H/19F-13C/15N/D Z-GRD Z114073/0012 >PULPROG <zg30> Points Count 65536 Pulse Sequence zg30Receiver Gain 1.91 SF 600.13 SFO1 600.133706048414SI 65536 SSB 0 SW(cyclical) (Hz) 12019.23SWH 12019.2307692308 Solvent DMSO-d6Spectrum Offset (Hz) 3706.0515 Spectrum Type standard Sweep Width (Hz) 12019.05TD 65536 TD0 1 TE 300.0009Temperature (degree C) 27.001 UNC1 <1H> WDW 0

1H NMR (600 MHz, DMSO-d6) d ppm 0.93 (t, J=7.43 Hz, 3 H) 1.46 (d, J=7.15 Hz, 3 H) 1.71 (sxt, J=7.63Hz, 2 H) 2.72 - 2.82 (m, 1 H) 2.88 - 2.99 (m, 1 H) 5.13 (q, J=7.03 Hz, 1 H) 6.20 (s, 2 H) 7.14 (d, J=8.07Hz, 1 H) 7.56 (d, J=1.83 Hz, 1 H) 7.73 (dd, J=8.25, 1.83 Hz, 1 H) 8.98 (br s, 1 H) 9.55 (br s, 1 H)

2

3

4

O

O

911

NH2+

1213

O

CH315

16CH3 17



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Table of assignments and zoomed parts:No. Atom Exp. Shift

(ppm)Multiplet

1 17 0.93 M012 15 1.46 M023 16 1.71 M034 13 2.77 M045 13 2.93 M056 11 5.13 M067 9 6.20 M078 4 7.14 M089 3 7.56 M0910 2 7.73 M1011 12 8.98 M1112 12 9.55 M12

2

3

4

O

O

911

NH2+

1213

O

CH315

16CH3 17

Chemical Shift (ppm)9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.01.

05

1.95

0.95

0.95

1.00

0.94

0.91

M09(d, 3) M08(d, 4)

M07(s, 9)

M10(dd, 2)

M06(q, 11)M12(br s, 12) M11(br s, 12)

Chemical Shift (ppm)3.0 2.5 2.0 1.5

2.94

2.91

2.03

1.05

1.06

DMSO

M02(d, 15)

M01(t, 17)

M03(sxt, 16)

M04(m, 13)

M05(m, 13)



of 10

16020009.002.001.1r.13C.esp

Chemical Shift (ppm)180 160 140 120 100 80 60 40

M01(s, 17)

M02(s, 15)

M06(s, 9)

M07(s, 3)

M08(s, 4)

M09(s, 2)

M10(s, 1)M11(s, 5)

M12(s, 6)

M13(s, 10)

M03(s, 16)

M04(s, 13)

M05(s, 11)

DMSO

Acquisition Time (sec) 0.9044 Comment 5 mm CPQCI 1H/19F-13C/15N/D Z-GRD Z114073/0012D 0.0002 D1 2 DE 18DS 4 Date 23 Feb 2016 18:14:44Date Stamp 23 Feb 2016 18:14:44File Name \\139.191.6.82\ihcp$\I01\Bio_Chemical_Interaction_Metabonomics\CLEN2SAND\!proposed-structure\BCIM_NAS\BCIM_6

00\16020009_15BD-00431-01\2\PDATA\1\1rFrequency (MHz) 150.9028 GB 0 INSTRUM <spect>LB 1 NS 256 Nucleus 13CNumber of Transients 256 Origin spect Original Points Count 32768Owner nmrsu PC 1PROBHD <5 mm CPQCI 1H/19F-13C/15N/D Z-GRD Z114073/0012 > PULPROG <jmod>Points Count 32768 Pulse Sequence jmod Receiver Gain 183.05SF 150.902809 SFO1 150.92091733708SI 32768 SSB 0 SW(cyclical) (Hz) 36231.88SWH 36231.884057971 Solvent DMSO-d6Spectrum Offset (Hz) 18108.3359 Spectrum Type APT Sweep Width (Hz) 36230.78TD 65536 TD0 1 TE 300.0019Temperature (degree C) 27.002 UNC1 <13C> WDW 1

13C NMR (151 MHz, DMSO-d6) d ppm 11.44 (s, 1 C) 16.51 (s, 1 C) 19.63 (s, 1 C) 47.32 (s, 1 C) 57.32 (s, 1C) 102.97 (s, 1 C) 108.40 (s, 1 C) 109.04 (s, 1 C) 126.34 (s, 1 C) 127.85 (s, 1 C) 148.72 (s, 1 C) 153.27 (s,1 C) 194.78 (s, 1 C)

1

2

3

4

5

6

O

O

9

1011

NH2+

13

O

CH315

16CH3 17



of 10

Chemical Shift (ppm)192 184 176 168 160 152 144 136 128 120

M12(s, 6)M13(s, 10)

M06(s, 9)

M07(s, 3)

M08(s, 4)

M09(s, 2)

M10(s, 1)

M11(s, 5)

Table of assignments and zoomed parts:No. Atom Exp. Shift

(ppm)Multiplet

1 17 11.44 M012 15 16.51 M023 16 19.63 M034 13 47.32 M045 11 57.32 M056 9 102.97 M067 3 108.40 M07

No. Atom Exp. Shift(ppm)

Multiplet

8 4 109.04 M089 2 126.34 M0910 1 127.85 M1011 5 148.72 M1112 6 153.27 M1213 10 194.78 M13

1

2

3

4

5

6

O

O

9

1011

NH2+

13

O

CH315

16CH3 17

Chemical Shift (ppm)60 55 50 45 40 35 30 25 20

M01(s, 17)M02(s, 15)

M03(s, 16)

M05(s, 11)

M04(s, 13)

DMSO



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Fragmentation of the observed molecule and the virtual MS (EI+) spectrum predicted byThermo Scientific Mass Frontier

1020

3040

5060

7080

9010

011

012

013

014

015

016

017

018

019

020

021

022

023

024

0

013253850637588100

86.2

0

44.2

0

65.2

014

9.10

121.

1013

5.10

56.2

027

.20

70.2

018

.20

77.1

017

8.10

163.

2010

3.10

220.

2019

0.10

206.

2023

3.10

144.

10

OO

NH

O•

O •

O O

O

OH

O

O

O

O

O

NH

N2

H

O

O O

N

NH

Joint Research Centre - Policija...administrative arrangement jrc-nr 33619-clen2sand-dg taxud-nr...

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Transcript of Joint Research Centre - Policija...administrative arrangement jrc-nr 33619-clen2sand-dg taxud-nr...