Electronic Supplementary Information · 1 Electronic Supplementary Information Metal-free...

1

Electronic Supplementary Information

Metal-free regioselective CndashC bond cleavage in 135-triazine derivatives

of β-diketones

Maximilian N Kopylovicha Kamran T Mahmudovab

Matti Haukkac and Armando J L Pombeiroa

a Centro de Quiacutemica Estrutural Complexo I Instituto Superior Teacutecnico Technical University of

Lisbon Av Rovisco Pais 1049ndash001 Lisbon Portugal

b Baku State University Department of Chemistry Z Xalilov Str 23 Az 1148 Baku Azerbaijan

c University of Jyvaumlskylauml Department of Chemistry PO Box 35 FI-40014 University of Jyvaumlskylauml

Finland

Corresponding Authors

kopylovichyahoocom (Maximilian N Kopylovich)

pombeiroistutlpt (Armando J L Pombeiro)

Phone +351 218419237 Fax (+1)-21-846-4455

Electronic Supplementary Material (ESI) for New Journal of ChemistryThis journal is copy The Royal Society of Chemistry and The Centre National de la Recherche Scientifique 2013

2

Table of contents

1 Analytical data for compounds 6minus13 S3

2 X-ray analyses helliphellip S6

3 Copies of 1H

13C NMR spectra of 6helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip S9

4 Copies of 1H


5 Copies of 1H


6 Copies of 1H


7 Copies of 1H

13C NMR spectra of 10helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip S13

8 Copies of 1H


9 Copies of 1H


10 Copies of 1H



3

Analytical data for compounds 6minus13

6 Yield 70 (based on cyanuric chloride) light yellow soluble in methanol ethanol DMSO Anal

Calcd for C8H9N3O4 (M = 21117) C 4550 H 430 N 1990 Found C 4550 H 426 N 1976

MS (ESI) mz 212 [M+H]+ IR (KBr selected bands cm

minus1) 3462 3453 and 3196 ν(NH) 1725 and

1623 ν(C=O) 1H NMR (30013 MHz DMSO-d6) δ 237 (6H 2CH3) 1196 (1H NH) 1322 (2H

NH) 13

C1H NMR (75468 MHz DMSO-d6) 323 (2CH3) 1005 (C=C) 1477 (C=CminusNH) 1558

(2C=O) and 1999 (2C=O)



MS (ESI) mz 226 [MminusH+] IR (KBr selected bands cm

minus1) 3483 3030 and 2831 ν(NH) 1737 and

1634 ν(C=O) 1H NMR (30013 MHz DMSO-d6) δ 237 (3H CH3) 377 (3H OCH3) 1197 (1H

NH) 1359 (2H NH) 13

C1H NMR (75468 MHz DMSO-d6) 321 (CH3) 520 (OCH3) 885 (C=C)

1475 (C=CminusNH) 1562 (2C=O) 1691 and 1988 (2C=O)




4


minus1) 3458 3451 and 3195 ν(NH) 1743 and

1643 ν(C=O) 1H NMR (30013 MHz DMSO-d6) δ 127minus131 (3H CH3) 241 (3H CH3) 425 (2H

CH2) 1196 (1H NH) 1370 (2H NH) 13

C1H NMR (75468 MHz DMSO-d6) 139 (CH3) 323

(CH3) 610 (CH2) 885 (C=C) 1475 (C=CminusNH) 1563 (2C=O) 1688 and 1988 (2C=O)




minus1) 3202 3116 and 2960 ν(NH) 1721 and

1648 ν(C=O) 1H NMR (30013 MHz DMSO-d6) δ 088 and 090 (3H CH3) 128minus131 (3H CH3)

154 and 155 (2H CH2) 274 (2H CH2) 425 and 427 (2H CH2) 1193 (1H NH) 1370 (2H NH)

13C

1H NMR (75468 MHz DMSO-d6) 137 (CH3) 139 (CH3) 185 (CH2) 446 (CH2) 610 (CH2)

885 (C=C) 1475 (C=CminusNH) 1560 (2C=O) 1687 and 2013 (2C=O)

10 Yield 65 (based on 1) light orange crystals soluble in methanol ethanol DMSO Anal Calcd for

C6H7N3O3 (M = 16913) C 4261 H 417 N 2484 Found C 4241 H 420 N 2461 MS (ESI)

mz 170 [M+H]+ IR (KBr selected bands cm

minus1) 3496 3429 and 3080 ν(NH) 1748 1707 1662

ν(C=O) 1H NMR (30013 MHz DMSO-d6) δ 200 (3H CH3) 501 (1H CH) 1124 and 1138 (2H

NH) 1246 (1H NH) 13

C1H NMR (75468 MHz DMSO-d6) 272 (CH3) 823 (C=CH) 1480

(C=CminusNH) 1490 and 1497 (C=O) 1964 (C=O)


5



mz 184 [MminusH+] IR (KBr selected bands cm

minus1) 3410 3176 and 2831 ν(NH) 1743 1644 and 1632

ν(C=O) 1H NMR (30013 MHz DMSO-d6) δ 358 (3H OCH3) 448 (1H CH) 1056 (1H NH)

1116 and 1127 (2H NH) 13

C1H NMR (75468 MHz DMSO-d6) 507 (OCH3) (CH2) 706

(C=CH) 1478 (C=CminusNH) 1488 and 1490 (C=O) 1699 (C=O)




minus1) 3432 3191 and 3066 ν(NH) 1739 1712 and 1682

ν(C=O) 1H NMR (30013 MHz DMSO-d6) δ 115minus119 (3H CH3) 406 (2H CH2) 446 (1H CH)

1059 (1H NH) 1113 and 1125 (2H NH) 13


(CH2) 709 (C=CH) 1477 (C=CminusNH) 1488 and 1489 (C=O) 1695 (C=O)

13 Yield 64 (cyanuric chloride) light orange crystals soluble in methanol ethanol DMSO Anal



6


minus1) 3431 3240 and 3088 ν(NH) 1733 1712

and 1676 ν(C=O) 1H NMR (30013 MHz DMSO-d6) δ 287 (6H 2CH3) 477 (1H CH) 1086 and

1088 (2H NH) 1228 (1H NH) 13

C1H NMR (75468 MHz DMSO-d6) overlapped by solvent

(2CH3) 704 (C=CH) 1465 (C=CminusNH) 1490 and 1499 (C=O) 1690 (C=O)

2 X-ray analyses

Table S1 Crystal data and structure refinement for 6 and 10 Identification code 6 10

Empirical formula C8H9N3O4 C6H7N3O3 Formula weight 21118 16915 Temperature 100(2) K 100(2) K Wavelength 071073 Aring 071073 Aring Crystal system Monoclinic Monoclinic Space group P21c P21c Unit cell dimensions a = 10765(7) Aring a = 90878(6) Aring b = 4612(3) Aring b = 112798(8) Aring c = 17297(11) Aring c = 67696(5) Aring = 90deg = 90deg = 97133(13)deg = 92969(3)deg = 90deg = 90deg

Volume 8521(10) Aring3 69301(8) Aring3 Z 4 4 Density (calculated) 1646 Mgm3 1621 Mgm3 Absorption coefficient 0134 mm-1 0133 mm-1 F(000) 440 352 Crystal size 046 x 011 x 003 mm3 023 x 016 x 008 mm3 Theta range for data collection 191 to 2525deg 224 to 2800deg Index ranges -12lt=hlt=12 -5lt=klt=5 -

20lt=llt=19 -11lt=hlt=11 -14lt=klt=14 -8lt=llt=8

Reflections collected 4187 7656 Independent reflections 1496 [R(int) = 00603] 1667 [R(int) = 00284] Completeness to theta = 2525deg 969 999 Absorption correction Semi-empirical from equiva-

lents Semi-empirical from equiva-lents

Max and min transmission 09954 and 09409 09891 and 09707 Refinement method Full-matrix least-squares on F2 Full-matrix least-squares on F2 Data restraints parameters 1496 0 138 1667 0 122

Goodness-of-fit on F2 0998 1052

Final R indices [Igt2sigma(I)] R1 = 00529 wR2 = 01148 R1 = 00362 wR2 = 00943 R indices (all data) R1 = 01068 wR2 = 01370 R1 = 00470 wR2 = 01009 Largest diff peak and hole 0214 and -0343 eAring-3 0341 and -0226 eAring-3


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Table S2 Bond lengths [Aring] and angles [deg] for 6 and 10

6 10 O(1)-C(1) 1215(4) O(1)-C(1) 12172(15) O(2)-C(2) 1225(4) O(2)-C(2) 12043(15) O(3)-C(5) 1257(4) O(3)-C(5) 12610(15) O(4)-C(7) 1246(4) N(1)-C(3) 13590(15) N(1)-C(3) 1358(4) N(1)-C(1) 13703(15) N(1)-C(1) 1370(4) N(1)-H(1) 091(2) N(1)-H(1) 08754 N(2)-C(1) 13661(15) N(2)-C(2) 1363(4) N(2)-C(2) 13795(16) N(2)-C(1) 1376(4) N(2)-H(2) 0910(19) N(2)-H(2) 08598 N(3)-C(3) 13639(15) N(3)-C(3) 1359(4) N(3)-C(2) 13795(16) N(3)-C(2) 1371(4) N(3)-H(3) 0897(17) N(3)-H(3) 08579 C(3)-C(4) 13698(17)

C(3)-C(4) 1418(4) C(4)-C(5) 14268(17) C(4)-C(5) 1457(4) C(5)-C(6) 14989(17) C(4)-C(7) 1465(4) C(3)-N(1)-C(1) 12503(11) C(5)-C(6) 1503(4) C(1)-N(2)-C(2) 12504(10) C(7)-C(8) 1502(4) C(3)-N(3)-C(2) 12430(11) C(3)-N(1)-C(1) 1245(3) O(1)-C(1)-N(2) 12360(11) C(2)-N(2)-C(1) 1250(3) O(1)-C(1)-N(1) 12153(11) C(3)-N(3)-C(2) 1248(3) N(2)-C(1)-N(1) 11487(10) O(1)-C(1)-N(1) 1226(3) O(2)-C(2)-N(3) 12240(11) O(1)-C(1)-N(2) 1225(3) O(2)-C(2)-N(2) 12287(11) N(1)-C(1)-N(2) 1149(3) N(3)-C(2)-N(2) 11472(11) O(2)-C(2)-N(2) 1227(3) N(1)-C(3)-N(3) 11590(11) O(2)-C(2)-N(3) 1225(3) N(1)-C(3)-C(4) 12112(11) N(2)-C(2)-N(3) 1148(3) N(3)-C(3)-C(4) 12297(10) N(1)-C(3)-N(3) 1159(3) C(3)-C(4)-C(5) 12300(11) N(1)-C(3)-C(4) 1218(3) O(3)-C(5)-C(4) 12204(11) N(3)-C(3)-C(4) 1223(3) O(3)-C(5)-C(6) 11992(11)

C(3)-C(4)-C(5) 1179(3) C(4)-C(5)-C(6) 11804(11) C(3)-C(4)-C(7) 1173(3) C(5)-C(4)-C(7) 1248(3) O(3)-C(5)-C(4) 1213(3) O(3)-C(5)-C(6) 1144(3) C(4)-C(5)-C(6) 1242(3) O(4)-C(7)-C(4) 1214(3) O(4)-C(7)-C(8) 1149(3) C(4)-C(7)-C(8) 1237(3)

Symmetry transformations used to generate equivalent atoms


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Table S3 Hydrogen bonds [Aring and deg] for 6 and 10

Compound DminusHA d(DminusH) d(DA) d(HA) lt(DminusHA)

6i

N(1)-H(1)O(3) 088 2490(3) 176 1398

N(2)-H(2)O(2)1 086 2824(4) 198 1676

N(3)-H(3)O(4) 086 2486(3) 176 1405

10ii

N(1)-H(1)O(3) 091(2) 25996(14) 1873(19) 1349(17)

N(3)-H(3)O(3)1 0897(17) 27412(14) 1852(18) 1705(17)

N(2)-H(2)O(1)2 0910(19) 28167(14) 1907(19) 1776(16)

Symmetry transformations used to generate equivalent atoms i) 1 -xy-12-z+32 ii) 1 -x+1y+12-

z+12 2 -x+2-y-z

6 10

Figure S1 Packing diagrams of 6 and 10 viewed down the crystallographic b and a-axis respectively

The hydrogen bonds are shown as blue lines


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Table of contents

1 Analytical data for compounds 6minus13 S3

2 X-ray analyses helliphellip S6

3 Copies of 1H


4 Copies of 1H


5 Copies of 1H


6 Copies of 1H


7 Copies of 1H


8 Copies of 1H


9 Copies of 1H


10 Copies of 1H



3





minus1) 3462 3453 and 3196 ν(NH) 1725 and


NH) 13


(2C=O) and 1999 (2C=O)




minus1) 3483 3030 and 2831 ν(NH) 1737 and


NH) 1359 (2H NH) 13






4


minus1) 3458 3451 and 3195 ν(NH) 1743 and


CH2) 1196 (1H NH) 1370 (2H NH) 13






minus1) 3202 3116 and 2960 ν(NH) 1721 and



13C






minus1) 3496 3429 and 3080 ν(NH) 1748 1707 1662


NH) 1246 (1H NH) 13




5




minus1) 3410 3176 and 2831 ν(NH) 1743 1644 and 1632


1116 and 1127 (2H NH) 13






minus1) 3432 3191 and 3066 ν(NH) 1739 1712 and 1682


1059 (1H NH) 1113 and 1125 (2H NH) 13






6


minus1) 3431 3240 and 3088 ν(NH) 1733 1712


1088 (2H NH) 1228 (1H NH) 13



2 X-ray analyses











7







8



6i

N(1)-H(1)O(3) 088 2490(3) 176 1398

N(2)-H(2)O(2)1 086 2824(4) 198 1676

N(3)-H(3)O(4) 086 2486(3) 176 1405

10ii

N(1)-H(1)O(3) 091(2) 25996(14) 1873(19) 1349(17)

N(3)-H(3)O(3)1 0897(17) 27412(14) 1852(18) 1705(17)

N(2)-H(2)O(1)2 0910(19) 28167(14) 1907(19) 1776(16)


z+12 2 -x+2-y-z

6 10




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10


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12


13


14


15


16


3





minus1) 3462 3453 and 3196 ν(NH) 1725 and


NH) 13


(2C=O) and 1999 (2C=O)




minus1) 3483 3030 and 2831 ν(NH) 1737 and


NH) 1359 (2H NH) 13






4


minus1) 3458 3451 and 3195 ν(NH) 1743 and


CH2) 1196 (1H NH) 1370 (2H NH) 13






minus1) 3202 3116 and 2960 ν(NH) 1721 and



13C






minus1) 3496 3429 and 3080 ν(NH) 1748 1707 1662


NH) 1246 (1H NH) 13




5




minus1) 3410 3176 and 2831 ν(NH) 1743 1644 and 1632


1116 and 1127 (2H NH) 13






minus1) 3432 3191 and 3066 ν(NH) 1739 1712 and 1682


1059 (1H NH) 1113 and 1125 (2H NH) 13






6


minus1) 3431 3240 and 3088 ν(NH) 1733 1712


1088 (2H NH) 1228 (1H NH) 13



2 X-ray analyses











7







8



6i

N(1)-H(1)O(3) 088 2490(3) 176 1398

N(2)-H(2)O(2)1 086 2824(4) 198 1676

N(3)-H(3)O(4) 086 2486(3) 176 1405

10ii

N(1)-H(1)O(3) 091(2) 25996(14) 1873(19) 1349(17)

N(3)-H(3)O(3)1 0897(17) 27412(14) 1852(18) 1705(17)

N(2)-H(2)O(1)2 0910(19) 28167(14) 1907(19) 1776(16)


z+12 2 -x+2-y-z

6 10




9


10


11


12


13


14


15


16


4


minus1) 3458 3451 and 3195 ν(NH) 1743 and


CH2) 1196 (1H NH) 1370 (2H NH) 13






minus1) 3202 3116 and 2960 ν(NH) 1721 and



13C






minus1) 3496 3429 and 3080 ν(NH) 1748 1707 1662


NH) 1246 (1H NH) 13




5




minus1) 3410 3176 and 2831 ν(NH) 1743 1644 and 1632


1116 and 1127 (2H NH) 13






minus1) 3432 3191 and 3066 ν(NH) 1739 1712 and 1682


1059 (1H NH) 1113 and 1125 (2H NH) 13






6


minus1) 3431 3240 and 3088 ν(NH) 1733 1712


1088 (2H NH) 1228 (1H NH) 13



2 X-ray analyses











7







8



6i

N(1)-H(1)O(3) 088 2490(3) 176 1398

N(2)-H(2)O(2)1 086 2824(4) 198 1676

N(3)-H(3)O(4) 086 2486(3) 176 1405

10ii

N(1)-H(1)O(3) 091(2) 25996(14) 1873(19) 1349(17)

N(3)-H(3)O(3)1 0897(17) 27412(14) 1852(18) 1705(17)

N(2)-H(2)O(1)2 0910(19) 28167(14) 1907(19) 1776(16)


z+12 2 -x+2-y-z

6 10




9


10


11


12


13


14


15


16


5




minus1) 3410 3176 and 2831 ν(NH) 1743 1644 and 1632


1116 and 1127 (2H NH) 13






minus1) 3432 3191 and 3066 ν(NH) 1739 1712 and 1682


1059 (1H NH) 1113 and 1125 (2H NH) 13






6


minus1) 3431 3240 and 3088 ν(NH) 1733 1712


1088 (2H NH) 1228 (1H NH) 13



2 X-ray analyses











7







8



6i

N(1)-H(1)O(3) 088 2490(3) 176 1398

N(2)-H(2)O(2)1 086 2824(4) 198 1676

N(3)-H(3)O(4) 086 2486(3) 176 1405

10ii

N(1)-H(1)O(3) 091(2) 25996(14) 1873(19) 1349(17)

N(3)-H(3)O(3)1 0897(17) 27412(14) 1852(18) 1705(17)

N(2)-H(2)O(1)2 0910(19) 28167(14) 1907(19) 1776(16)


z+12 2 -x+2-y-z

6 10




9


10


11


12


13


14


15


16


6


minus1) 3431 3240 and 3088 ν(NH) 1733 1712


1088 (2H NH) 1228 (1H NH) 13



2 X-ray analyses











7







8



6i

N(1)-H(1)O(3) 088 2490(3) 176 1398

N(2)-H(2)O(2)1 086 2824(4) 198 1676

N(3)-H(3)O(4) 086 2486(3) 176 1405

10ii

N(1)-H(1)O(3) 091(2) 25996(14) 1873(19) 1349(17)

N(3)-H(3)O(3)1 0897(17) 27412(14) 1852(18) 1705(17)

N(2)-H(2)O(1)2 0910(19) 28167(14) 1907(19) 1776(16)


z+12 2 -x+2-y-z

6 10




9


10


11


12


13


14


15


16


7







8



6i

N(1)-H(1)O(3) 088 2490(3) 176 1398

N(2)-H(2)O(2)1 086 2824(4) 198 1676

N(3)-H(3)O(4) 086 2486(3) 176 1405

10ii

N(1)-H(1)O(3) 091(2) 25996(14) 1873(19) 1349(17)

N(3)-H(3)O(3)1 0897(17) 27412(14) 1852(18) 1705(17)

N(2)-H(2)O(1)2 0910(19) 28167(14) 1907(19) 1776(16)


z+12 2 -x+2-y-z

6 10




9


10


11


12


13


14


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6i

N(1)-H(1)O(3) 088 2490(3) 176 1398

N(2)-H(2)O(2)1 086 2824(4) 198 1676

N(3)-H(3)O(4) 086 2486(3) 176 1405

10ii

N(1)-H(1)O(3) 091(2) 25996(14) 1873(19) 1349(17)

N(3)-H(3)O(3)1 0897(17) 27412(14) 1852(18) 1705(17)

N(2)-H(2)O(1)2 0910(19) 28167(14) 1907(19) 1776(16)


z+12 2 -x+2-y-z

6 10




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