SUPPORTING INFORMATION
MICHAEL LARTEY, MARTIJN GILLISEN, BRIAN J. ADZIMA, KENICHI TAKIZAWA, DAVID R. LUEBKE, HUNAID
B. NULWALA
SYNTHESIS AND REACTIVITY RATIOS OF REGIOISOMERIC VINYL-1,2,3-TRIAZOLES WITH STYRENE
General synthesis of monomers
Unless otherwise stated, ACS reagent grade chemicals and solvents were purchased from Sigma Aldrich
and used without further purification. All azides,1 Cp*RuCl(PPh2)3,2 But-3-ynyl methanesulfonate,3 Vinyl
triazoles3,4 (and their respective intermediates) were synthesized according to reported procedures.
SCHEME S1 Synthesis of 1-substituted-4-vinyl triazoles
SCHEME S2 Synthesis of 1-substituted-5-vinyl triazoles
But-3-ynylmethanesulfonate: 1H NMR (200 MHz, CDCl3, ):4.23 (t, J = 6.6 Hz, OCH2CH2, 2H), 3.00 (s,
CH3S, 3H), 2.59 (dt, J = 6.6, 2.6 Hz, OCH2CH2C≡CH, 2H), 2.05 (t, J = 2.6 Hz, CH2C≡CH, 1H). 13C NMR
(CDCl3, ): 78.83 (CH2C≡CH, 1C), 71.03 (CH2C≡CH, 1C), 67.36 (OCH2CH2, 1C), 37.50 (SCH3, 1C), 19.63
(OCH2CH2, 1C). HRMS (ESI MS, m/z):[M]+calcd. for C5H8N3O3S:148.02; found [M+H]+: 149.04.
2-(1-Octyl-1H-1,2,3-triazol-4-yl)ethanol (1a):1H NMR (200 MHz, CDCl3, ): 7.36 (s, triazole H, 1H), 4.32(t,
J= 7.3 Hz, NCH2, 2H), 3.95 (t, J = 5.9 Hz, OCH2CH2, 2H), 2.95 (t, J = 5.8 Hz, OCH2CH2, 2H), 1.89 (m, OH,
NCH2CH2, 3H), 1.28 (m, NCH2CH2[CH2]5CH3, 10H), 0.88 (m, N[CH2]7CH3, 3H).13C NMR (CDCl3, ): 145.65
(NCH=C, 1C), 121.52 (NCH=C, 1C), 61.79 (OCH2CH2, 1C), 50.45 (NCH2, 1C), 31.86 (N[CH2]5CH2, 1C), 30.46
(NCH2CH2, 1C), 29.19 (N[CH2]3CH2, 1C), 29.12 (N[CH2]4CH2, 1C), 28.87 (OCH2CH2, 1C), 26.67 (N[CH2]2CH2,
1
1C), 22.75 (N[CH2]6CH2, 1C), 14.22 (N[CH2]7CH3, 1C). HRMS (ESI MS, m/z): [M]+ calcd. for
C12H23N3O:225.18; found: 225.18.
2-(1-Benzyl-1H-1,2,3-triazol-4-yl)ethanol (2a): 1H NMR (200 MHz, CDCl3, ): 7.39-7.27 (m, ArH, 6H),
5.50(s, PhCH2N, 2H), 3.93 (t, J = 6.0 Hz, OCH2CH2, 2H), 2.92 (t, J = 6.0 Hz, OCH2CH2, 2H), 2.60 (s, OH,1H).
13
C NMR (CDCl3, ):145.88, 134.74, 129.05, 128.66, 128.04, 121.76, 61.32, 54.02, 28.82. FAB (MS,
m/z)[M]+calcd. for C11H13N3O: 203.11; found [M+Na]+: 226.10.
2-(1-Octyl-1H-1,2,3-triazol-4-yl)ethyl methanesulfonate (1b):1H NMR (200 MHz, CDCl3, ): 7.43 (s,
triazole H, 1H), 4.53 (t, J = 6.4 Hz, OCH2CH2, 2H), 4.33 (t, J = 7.3 Hz,NCH2, 2H), 3.19 (t, J = 6.4 Hz,
OCH2CH2, 2H), 2.97 (s, SCH3, 3H), 1.89 (m, NCH2CH2, 2H), 1.26 (m, NCH2CH2[CH2]5CH3, 10H), 0.88 (m,
N[CH2]7CH3, 3H).
2-(1-Benzyl-1H-1,2,3-triazol-4-yl)ethyl methanesulfonate (2b):1H NMR (200 MHz, CDCl3, ): 7.417.23(m, ArH, 6H), 5.51 (s,NCH2, 2H), 4.50 (t, J = 6.4 Hz, OCH2CH2, 2H), 3.15 (t, J = 6.4 Hz, OCH2CH2, 2H),
2.90 (s, SCH3, 3H). 13C NMR (CDCl3, ): 143.27 (NCH=C, 1C), 134.75 (ArC, 1C), 129.30 (NCH=C, 1C), 128.96
(o-Ar, 2C), 128.20 (m-Ar, 2C), 122.26 (p-Ar, 1C), 68.77 (OCH2CH2, 1C), 54.34 (NCH2, 1C), 37.43 (SCH3, 1C),
26.21 (OCH2CH2, 1C). HRMS (ESIMS m/z)[M]+calcd.for C12H15N3O3S: 281.08; found [M+H]+: 282.09.
1-Octyl-4-vinyl-1H-1,2,3-triazole (1):1H NMR (200 MHz, CDCl3, ): 7.49 (s, triazole H, 1H), 6.74 (dd, J =
17.8, 11.2 Hz, CH2=CH, 1H), 5.86 (dd, J = 17.8, 1.2 Hz,trans CH2=CH, 1H), 5.32 (dd, J = 11.2, 1.4 Hz,cis
CH2=CH, 1H), 4.33 (t, J = 7.2 Hz, NCH2CH2, 2H), 1.89 (m, NCH2CH2, 2H), 1.27 (m, NCH2CH2[CH2]5CH3, 10H),
0.87 (t, J = 6.9 Hz, , N[CH2]7CH3, 3H). 13C NMR (CDCl3, ): 146.65 (NCH=C, 1C), 126.09 (CH=CH2, 1C),
120.29 (NCH=C, 1C), 116.13 (CH=CH2, 1C), 50.63 (NCH2, 1C), 32.01 (NCH2CH2, 1C), 30.63 (N[CH2]2CH2, 1C),
29.35 (N[CH2]3CH2, 1C), 29.27 (N[CH2]4CH2, 1C), 26.78 (N[CH2]5CH2, 1C), 22.91 (N[CH2]6CH2, 1C), 14.45
(N[CH2]7CH3, 1C). HRMS (ESI MSm/z) [M]+calcd.for C12H21N3: 207.17; found [M+H]+: 208.18. IR (ATR): ν
(cm-1) 3126, 2896, 2856, 1725, 1644, 1542, 1458, 1437, 1377, 1224, 1141, 1050, 1028.
1-Benzyl-4-vinyl-1H-1,2,3-triazole (2): 1H NMR (200 MHz, CDCl3, ): 7.39-7.24 (s, ArH, triazoleH, 6H),
6.69 (dd, J = 17.8, 11.2 Hz, CH=CH2, 1H), 5.85 (dd, J = 17.8, 1.2 Hz,trans CH=CH2, 1H), 5.51 (s, NCH2, 2H),
5.30 (dd, J = 11.2, 1.0 Hz,cis CH=CH2, 1H). 13C NMR (CDCl3, ): 146.98 (NCH=C, 1C), 134.80 (Ar, NCH2C,
1C), 129.31 (o-Ar, 2C), 128.95 (CH=CH2, 1C), 128.23 (m-Ar, 2C), 125.78 (p-Ar, 1C), 120.28 (CH=CH2, 1C),
116.04 (NCH=CH2, 1C), 54.29 (NCH2, 1C). HRMS(ESI MS m/z) [M]+calcd. for C11H11N3: 185.10; found
[M+H]+: 186.10. IR (ATR): ν (cm-1) 3120, 3104, 3063, 3033, 2950, 1635, 1586, 1540, 1495, 1455, 1400,
1355, 1340. 1328, 1311, 1276, 1205, 1220, 1205, 1158, 1125, 1075, 1061, 1050, 1028, 1007.
2-(1-Octyl-1H-1,2,3-triazol-5-yl)ethyl methanesulfonate (4a):1H NMR (200 MHz, CDCl3, ): 7.57 (s,
triazoleH, 1H), 4.45 (t, J = 6.54 Hz, OCH2CH2, 2H), 4.28 (t, J = 7.33 Hz, NCH2CH2, 2H), 3.14 (t, J = 6.11 Hz,
OCH2CH2, 2H), 1.78 - 1.98 (m, NCH2CH2, 2H), 2.99 (s, SCH3, 3H), 1.22 - 1.38 (m, NCH2CH2[CH2]5CH3, 10H),
0.87 (t, J = 6.32 Hz, N[CH2]7CH3, 3H); HRMS (ESI MS m/z)[M]+calcd.for C12H21N3: 303.42; found [M+H]+:
304.20.
2-(1-Benzyl-1H-1,2,3-triazol-5-yl)ethyl methanesulfonate (5a): 1H NMR (200MHz, CDCl3, ): 7.48 (s,
triazole H, 1H), 7.24 - 7.43 (m, 4H), 7.03 - 7.24 (m, 5H), 4.43 - 4.63 (m, 4H), 4.08 (s, NCH2, 2H), 2.87 (s,
SCH3, 3H).
1-Octyl-5-vinyl-1H-1,2,3-triazole (4):1H NMR (200 MHz, CDCl3, ): 7.73 (s, triazole H, 1H), 6.52 (dd, J =
17.6, 11.2 Hz, CH2=CH, 1H), 5.77 (dd, J = 17.6, 0.9 Hz, trans CH2=CH, 1H), 5.50 (dd, J = 11.2, 0.9 Hz, cis
CH2=CH, 1H), 4.29 (t, J = 7.3 Hz, NCH2CH2, 2H), 1.82 (t, J = 7.0 Hz, NCH2CH2, 2H), 1.04 - 1.43
2
(m,NCH2CH2[CH2]5CH3, 10H), 0.73 - 0.98 (m, N[CH2]7CH3, 3H). 13C NMR (CDCl3, ): 135.7 (CH=CH2, 1C),
131.7 (NCH=C, 1C), 121.1 (NCH=C, 1C), 120.6 (CH2=CH, 48.7 (NCH2, 1C), 32.2 (NCH2CH2, 1C), 30.7
(N[CH2]2CH2, 1C), 29.6 (N[CH2]3CH2, 1C), 29.5 (N[CH2]4CH2, 1C), 27.0 (N[CH2]5CH2, 1C), 23.1 (N[CH2]6CH2,
1C), 14.3 (N[CH2]7CH3, 1C); HRMS (ESI MSm/z) [M]+calcd. for C12H21N3: 207.17; found [M+H]+: 208.18. IR
(ATR): ν (cm-1) 2925, 2856, 1633, 1540, 1465, 1377, 1308, 1222, 1120, 1084, 1043, 974, 919, 824, 771,
723.
1-Benzyl-5-vinyl-1H-1,2,3-triazole (5): 1H NMR (200 MHz, CDCl3, ): 7.80 (s, 1H), 7.09 - 7.41 (m, Ar H, 5H),
6.45 (dd, CH2=CH, 1H), 5.73 (d, J = 17.43 Hz, trans CH2=CH, 1H), 5.57 (s, NCH2, 2H), 5.44 (d, J = 11.87 Hz,
cis CH2=CH, 1H). 13C NMR (CDCl3, ): 135.43 (NCH=C, 1C), 134.70 (Ar, NCH2C, 1C), 131.33 (o-Ar, 2C),
128.80 (CH=CH2, 1C), 128.16 (m-Ar, 2C), 126.82 (p-Ar, 1C), 120.42 (CH=CH2, 1C) 120.19 (NCH=C, 1C),
51.64 (NCH2, 1C). HRMS (ESI MSm/z)[M]+calcd.for C11H11N3: 185.10; found [M+H]+: 186.11. IR (ATR): ν
(cm-1) 3125, 3027, 3033, 3067, 2981, 2953, 1952, 1866, 1710, 1633, 1585, 1539, 1493, 1455, 1439, 1408,
1361, 1329, 1308, 1295, 1278, 1218, 1173, 1125, 1104, 1074, 1048, 1029, 1002, 977, 932.
FIGURE S1 Set up for the synthesis of 1-Methyl-4-vinyl-1,2,3-1H-triazole (3)
Reactivity ratio determination
Reactivity ratios were determined by NLLS with curve fitting of the Mayo-Lewis5 equation (Eq.S1) using
Microcal Origin.
F1 
r1  1 f1 2  f1
r1  r2  2 f1 2  2  2r2  f1  r2
(S1)
where:
F1 = calculated mole fraction of monomer 1 in the polymer
f1= mole fraction of monomer 1 in the feed
r1 = reactivity ratio of monomer 1
r2 = reactivity ratio of monomer 2
3
The joint confidence intervals were calculated using the method previously described by Tidwell and
Mortimer6 and the Maplesoft Maple 11 software package using eq.S2.
ss r1 , r2    F1,det,i  F1,calc,i 
n
i 1
(S2)
where:
ss(r1,r2) = sum of squares value
F1,det,i = determined value of F1 for data point i
F1,calc,i = calculated value of F1 for data point i


ss JCI  ss min  1  np p F  p, n  p 
(3)
where:
ssJCI= ss value at the joint confidence intervals (JCI)
ssmin = the ss value at the minimum
Fα(p,n-p) = the value of the F distribution for p and n-p at confidence level α
p = the number of parameters
n = the number of data points
By taking the contour of ss(r1,r2) at ssJCI, the joint confidence intervals were plotted to give a 95% joint
confidence interval.
TABLE S1 Experimental results of reactivity ratio for 1,4-Vinyl-1,2,3-triazole monomers. Fs and fs
represent the mole fractions of the monomer in polymer and feed respectively. Conversion (Conv.)
refers to mass percent yield of polymer measured by gravimetric analysis.
1-Octyl-4-vinyl-1,2,3-triazole
(1)
1-Benzyl-4-vinyl-1,2,3triazole (2)
1-Methyl-4-vinyl-1,2,3triazole (3)
fs
Fs
Conv.
fs
Fs
Conv.
fs
Fs
Conv.
0.090
0.134
2.39
0.100
0.192
11.48
0.105
0.114
15.23
0.183
0.308
4.79
0.201
0.300
7.12
0.222
0.241
14.12
0.277
0.425
12.26
0.300
0.426
4.59
0.326
0.346
13.50
0.374
0.531
9.64
0.400
0.554
2.62
0.405
0.407
10.23
0.472
0.640
6.45
0.501
0.648
3.43
0.509
0.505
9.13
0.573
0.720
8.38
0.600
0.725
4.21
0.622
0.610
10.87
0.676
0.804
1.96
0.700
0.805
2.45
0.688
0.692
11.12
0.782
0.874
9.43
0.800
0.866
0.43
0.789
0.794
15.97
0.890
0.924
8.19
0.901
0.896
2.25
0.904
0.885
7.91
TABLE S2 Experimental results of reactivity ratio for 1,5-Vinyl-1,2,3-triazole monomers.
4
1-Octyl-5-vinyl-1,2,3-triazole (4)
1-Benzyl-5-vinyl-1,2,3-triazole (5)
fs
Fs
Conv.
fs
Fs
Conv.
0.100
0.069
6.82
0.142
0.238
17.74
0.203
0.220
3.11
0.219
0.354
2.27
0.302
0.312
2.69
0.306
0.356
7.45
0.405
0.362
4.63
0.390
0.369
11.92
0.500
0.433
7.69
0.493
0.388
3.56
0.600
0.445
13.22
0.599
0.515
14.26
0.701
0.532
9.16
0.697
0.554
9.11
0.798
0.536
9.02
0.800
0.637
12.11
0.899
0.661
5.04
0.900
0.917
8.82
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