Kinetics of the Cationization of Cotton
Kinetics of the Cationization of Cotton Timothy S. De Vries*,†, Dan R. Davies†, Michelle C. Miller‡, and William A. Cynecki‡ *Corresponding Author - Tel.: 989-638-8318. E-mail: [email protected] †
Core R&D, The Dow Chemical Company, 1776 Building, Midland, Michigan 48674, United
States. ‡Dow Consumer & Industrial Solutions, The Dow Chemical Company.
1
Supporting Information Table Of Contents
NMR Spectra ............................................................................................................................... 6 Representative HPLC Chromatograms. ....................................................................................... 9 Calibration of HPLC for (2,3-Dihydroxypropyl)trimethylammonium Chloride (5). ................ 10 Calibration of HPLC for (2,3-Epoxypropyl)trimethylammonium Chloride (2). ....................... 12 Hydrolysis of (2,3-Epoxypropyl)trimethylammonium Chloride (2) at 30 °C. .......................... 14 Hydrolysis of (2,3-Epoxypropyl)trimethylammonium Chloride (2) at 40 °C. .......................... 17 Hydrolysis of (2,3-Epoxypropyl)trimethylammonium Chloride (2) at 50 °C. .......................... 20 Hydrolysis of (2,3-Epoxypropyl)trimethylammonium Chloride (2) at 60 °C. .......................... 23 Hydrolysis of (2,3-Epoxypropyl)trimethylammonium Chloride (2) at 70 °C. .......................... 26 Cationization of Cotton with (2,3-Epoxypropyl)trimethylammonium Chloride (2) at 30 °C. .. 29 Cationization of Cotton with (2,3-Epoxypropyl)trimethylammonium Chloride (2) at 50 °C. .. 32 Cationization of Cotton with (2,3-Epoxypropyl)trimethylammonium Chloride (2) at 70 °C. .. 35 Cationization of Cotton with (2,3-Epoxypropyl)trimethylammonium Chloride (2) at 50 °C in 1:1 Tetraglyme-Water. ......................................................................................................... 38 List of Figures Figure S1. 1H NMR Spectrum of (2,3-Dihydroxypropyl)trimethylammonium Chloride (5).... 6 Figure S2. 1H NMR spectrum of 3,3’-oxybis(N,N,N-trimethyl-2-hydroxypropanaminium) dichloride (6).......................................................................................................................... 7 Figure S3. 13C NMR spectrum of 3,3’-oxybis(N,N,N-trimethyl-2-hydroxypropanaminium) dichloride (6).......................................................................................................................... 8 Figure S4. Reaction of 60 g/L EcoFAST™ CR 2000 with 0.1 M excess NaOH at 80 °C, after 80 min: ................................................................................................................................... 9 Figure S5. Calibration Curve for Diol 5 Showing Linear Fit. ................................................. 11 Figure S6. Calibration Curve for Epoxide 2 Showing Linear Fit. ........................................... 13
2
Figure S7. Plots of HPLC Peak Areas vs. Time for Hydrolyses of 2 at Varying [NaOH]xs at 30 °C Showing Fit of Loss of 2 to Exponential Function.................................................... 15 Figure S8. Plots of Observed Rate Constant (k’) vs. [NaOH]xs for Hydrolyses of 2 at 30 °C Showing Fit to Linear Function. .......................................................................................... 16 Figure S9. Plots of HPLC Peak Areas vs. Time for Hydrolyses of 2 at Varying [NaOH]xs at 40 °C Showing Fit of Loss of 2 to Exponential Function (Linear fit to initial rate for slowest reaction with 0.05 M excess NaOH). ...................................................................... 18 Figure S10. Plots of Observed Rate Constant (k’) vs. [NaOH]xs for Hydrolyses of 2 at 40 °C Showing Fit to Linear Function. .......................................................................................... 19 Figure S11. Plots of HPLC Peak Areas vs. Time for Hydrolyses of 2 at Varying [NaOH]xs at 50 °C Showing Fit of Loss of 2 to Exponential Function (Linear fit to initial rate for slowest reaction with 0.02 M excess NaOH). ...................................................................... 21 Figure S12. Plots of Observed Rate Constant (k’) vs. [NaOH]xs for Hydrolyses of 2 at 50 °C Showing Fit to Linear Function. .......................................................................................... 22 Figure S13. Plots of HPLC Peak Areas vs. Time for Hydrolyses of 2 at Varying [NaOH]xs at 60 °C Showing Fit of Loss of 2 to Exponential Function (Linear fit to initial rate for slowest reaction with 0.01 M excess NaOH). ...................................................................... 24 Figure S14. Plots of Observed Rate Constant (k’) vs. [NaOH]xs for Hydrolyses of 2 at 60 °C Showing Fit to Linear Function. .......................................................................................... 25 Figure S15. Plots of HPLC Peak Areas vs. Time for Hydrolyses of 2 at Varying [NaOH]xs at 70 °C Showing Fit of Loss of 2 to Exponential Function (Linear fit to initial rate for slowest reaction with 0.005 M excess NaOH). .................................................................... 27 Figure S16. Plots of Observed Rate Constant (k’) vs. [NaOH]xs for Hydrolyses of 2 at 70 °C Showing Fit to Linear Function. .......................................................................................... 28 Figure S17. Plots of Concentrations vs. Time and Predicted Concentrations vs. Time for Reactions of 2 with Cotton at Varying [NaOH]xs at 30 °C. ................................................. 31 Figure S18. Plots of Concentrations vs. Time and Predicted Concentrations vs. Time for Reactions of 2 with Cotton at Varying [NaOH]xs at 50 °C. ................................................. 34 Figure S19. Plots of Concentrations vs. Time and Predicted Concentrations vs. Time for Reactions of 2 with Cotton at Varying [NaOH]xs at 70 °C. ................................................. 37
3
List of Tables Table S1. Sample preparation for Diol 5 Calibration............................................................... 10 Table S2. HPLC Peak Areas for Diol 5 Calibration. ............................................................... 10 Table S3. Sample preparation for Epoxide 2 Calibration. ....................................................... 12 Table S4. HPLC Peak Areas for Epoxide 2 Calibration. ......................................................... 12 Table S5. HPLC Peak Areas for Aliquots from Hydrolyses of 2 at Varying [NaOH]xs at 30 °C and Observed Rate Constants. ............................................................................................. 14 Table S6. HPLC Peak Areas for Aliquots from Hydrolyses of 2 at Varying [NaOH]xs at 40 °C and Observed Rate Constants. ............................................................................................. 17 Table S7. HPLC Peak Areas for Aliquots from Hydrolyses of 2 at Varying [NaOH]xs at 50 °C and Observed Rate Constants. ............................................................................................. 20 Table S8. HPLC Peak Areas for Aliquots from Hydrolyses of 2 at Varying [NaOH]xs at 60 °C and Observed Rate Constants. ............................................................................................. 23 Table S9. HPLC Peak Areas for Aliquots from Hydrolyses of 2 at Varying [NaOH]xs at 70 °C and Observed Rate Constants. ............................................................................................. 26 Table S10. HPLC Peak Areas for Aliquots from Reaction of 2 with Cotton at Varying [NaOH]xs at 30 °C and Corresponding Analyte Concentrations. ........................................ 29 Table S11. Parameters Fit to Variables in equations 2-5 for Predicted Concentrations in Table S10. ...................................................................................................................................... 30 Table S12. HPLC Peak Areas for Aliquots from Reaction of 2 with Cotton at Varying [NaOH]xs at 50 °C and Corresponding Analyte Concentrations. ........................................ 32 Table S13. Parameters Fit to Variables in equations 2-5 for Predicted Concentrations in Table S12. ...................................................................................................................................... 33 Table S14. HPLC Peak Areas for Aliquots from Reaction of 2 with Cotton at Varying [NaOH]xs at 70 °C and Corresponding Analyte Concentrations. ........................................ 35 Table S15. Parameters Fit to Variables in equations 2-5 for Predicted Concentrations in Table 14.......................................................................................................................................... 36 Table S16. HPLC Peak Areas for Aliquots from Hydrolysis of 2 with 0.2 M NaOH in 1:1 Tetraglyme-Water in the Absence of Cotton at 50 °C and Corresponding Analyte Concentrations. .................................................................................................................... 38 Table S17. Parameters Fit to Variables in equations 2-5 for Predicted Concentrations in Table S16. ...................................................................................................................................... 38 4
Table S18. HPLC Peak Areas for Aliquots from Reaction of 2 with 0.2 M NaOH in 1:1 Tetraglyme-Water in the Presence of Cotton at 50 °C and Corresponding Analyte Concentrations. .................................................................................................................... 38 Table S19. Parameters Fit to Variables in equations 2-5 for Predicted Concentrations in Table 18.......................................................................................................................................... 38
5
NMR Spectra Figure S1. 1H NMR Spectrum of (2,3-Dihydroxypropyl)trimethylammonium Chloride (5).
NMe 3+ Cl–
HO OH 5
9.00
2.16
12.27
1.00
0.95
0.96
H2O
1
H NMR spectrum of aqueous solution of diol 5 in d6-DMSO. The sharp singlet at δ3.45 ppm integrates to 10.27 after 2H is subtracted out for the diol multiplet in that region. This gives a mol ratio of 5.14:1 water to 5, or 64.7 w/w% 5.
6
Figure S2. 1H NMR spectrum of 3,3’-oxybis(N,N,N-trimethyl-2-hydroxypropanaminium) dichloride (6).
Me3 N Cl–
O OH
OH
H2O
NMe3 Cl–
6
1.01
MeCN
3.40
8.41 5.55 18.62
2.08
2.00
d6-DMSO
1
H NMR spectrum (in d6-DMSO) of the hygroscopic white powder recovered from IPA-MeCN in the purification of dimer 6 (relative stereochemistry not determined). Already contaminated with water, although not left on Büchner funnel long enough to remove all acetonitrile.
7
Me3 N Cl–
O OH
OH 6
40.54 40.37 40.20 40.04 39.87 39.70 39.53
53.91
64.58
68.43
73.67
Figure S3. 13C NMR spectrum of 3,3’-oxybis(N,N,N-trimethyl-2-hydroxypropanaminium) dichloride (6).
NMe3 Cl–
d6 -
13
C NMR spectrum (125.6707 MHz, obtained on a Varian 500 MHz NMR Spectrometer, in d6DMSO) of 6 recrystallized from IPA-MeCN.
8
Representative HPLC Chromatograms. Figure S4. Reaction of 60 g/L EcoFAST™ CR 2000 with 0.1 M excess NaOH at 80 °C, after 80 min:
Figure S4a. Chromatogram from Refractive Index Detector signal. Peak at 4.4 minutes corresponds to diol 5, peak at 5.3 minutes to epoxide 2, and peak at 18.9 minutes to dimer 6.
Figure S4b. Chromatogram from Diode Array Detector signal (254 nm). Peak at 11.1 minutes corresponds to the PhS(O)Me internal standard.
™ Trademark of The Dow Chemical Company 9
Calibration of HPLC for (2,3-Dihydroxypropyl)trimethylammonium Chloride (5).
Table S1. Sample preparation for Diol 5 Calibration. Sample 1 2 3 4 5 6 7 8 9 10 11
PhS(O)Me (mL) 10 9.9 9.9 9.8 9.8 9.7 9.6 2.05 2 2 2
5 (mg) 11.2 54.2 124.2 176.1 249.6 355.8 482.2 179 242.4 366.9 496.1
PhS(O)Me (mg) 2.570 2.544 2.544 2.519 2.519 2.493 2.467 0.527 0.514 0.514 0.514
mmol 5/mg PhS(O)Me 0.017 0.081 0.186 0.267 0.378 0.544 0.745 1.296 1.799 2.722 3.681
5 (mmol) 0.043 0.207 0.474 0.672 0.952 1.357 1.839 0.683 0.924 1.399 1.892
Table S2. HPLC Peak Areas for Diol 5 Calibration. Run 1 Sample 1 2 3 4 5 6 7 8 9 10 11
5 21048 115805 239424 289412 436323 690221 820888 1466780 1835931 2891088 4471610
PhS(O)Me 584.1 614.5 575.7 489 511.5 558.9 482.9 484.2 435.8 453.8 516
Run 2 5 21297 101949 230782 288331 401968 634657 752551 1322160 1778160 2680309 4389220
PhS(O)Me 541 577.2 551.2 472.3 474.1 500.2 439.2 447.4 425.9 425.5 507.5
Run 3 5 19874 107908 231264 288500 400034 615316 755382 1340070 1803160 2710350 4392840
PhS(O)Me 542.2 569.9 554.2 483.9 476.1 502.6 450 440.6 433.1 430.2 510.3
Avg. Peak Area Ratio 37 185 417 599 847 1242 1697 3009 4184 6324 8641
10
Figure S5. Calibration Curve for Diol 5 Showing Linear Fit.
mmol 5 / mg PhS(O)Me
4.0 3.5
y = 0.0004285x R² = 0.9999
3.0 2.5 2.0 1.5 1.0 0.5 0.0 0
2000
4000
6000
8000
10000
Peak Area for 5 / Peak Area for PhS(O)Me
11
Calibration of HPLC for (2,3-Epoxypropyl)trimethylammonium Chloride (2).
Table S3. Sample preparation for Epoxide 2 Calibration. 5 NaOH PhS(O)Me PhS(O)Me 1 (mg) Sample (mL) (mL) (mg) (mmol) a 0.1 1 11.1 9.9 2.568 0.000 a 0.5 2 56 9.5 2.560 0.003 a 1.0 3 98.3 8.9 2.525 0.005 a 1.5 4 151.7 8.4 2.515 0.010 a 2.0 5 198.3 7.8 2.479 0.011 a 3.0 6 299.2 6.7 2.434 0.018 a 4.0 7 405.1 5.7 2.415 0.026 b 1.5 8 153.9 2 0.514 0.008 b 2.0 2 0.514 0.009 9 204.7 b 3.0 10 303.8 2 0.514 0.013 b 4.0 11 397.6 2 0.514 0.020 a b NaOH diluted with aq. PhS(O)Me. NaOH diluted with water.
2 (mmol) 0.039 0.192 0.337 0.518 0.679 1.022 1.383 0.527 0.703 1.043 1.362
mmol 2/mg PhS(O)Me 0.015 0.075 0.133 0.206 0.274 0.420 0.573 1.025 1.367 2.029 2.650
Table S4. HPLC Peak Areas for Epoxide 2 Calibration. Run 1 Sample 1 2 3 4 5 6 7 8 9 10 11
5
1786 3253 4770 7242 9074 13783 14588 20959 29414
2 PhS(O)Me 18774 783.1 72443 626.7 186346 825.2 256071 717.2 339086 736.7 473412 671.3 524523 549.6 953363 546.6 1459460 629.1 2047740 599.3 2345860 521.1
Run 2 5 1843 3800 4490 6481 10539 14117 15888 20322 29573 39591
2 5 PhS(O)Me 18050 467 75125 517.9 2197.3 145188 584.1 3623 167281 462.1 6691 251502 525.5 6887 400091 545.3 13291 436746 443.4 12675 797317 455.3 26566 1221380 530 34800 1724270 509.5 48923 2034180 454.8 64171
Avg. Peak Area Ratio (2 / 2 PhS(O)Me PhS(O)Me) 16296 470.7 31 74727 520.5 134 145134 588.7 239 175957 458 366 252527 528.4 471 408388 548.7 726 435202 435.6 978 797367 461.5 1741 1205710 536 2293 1680950 514 3360 1993570 459.8 4439 Run 3
12
Figure S6. Calibration Curve for Epoxide 2 Showing Linear Fit.
mmol 2 / mg PhS(O)Me
3.0
y = 0.0005973x R² = 0.9998
2.5 2.0 1.5 1.0 0.5 0.0 0
1000
2000
3000
4000
5000
Peak Area for 2 / Peak Area for PhS(O)Me
13
Hydrolysis of (2,3-Epoxypropyl)trimethylammonium Chloride (2) at 30 °C. Table S5. HPLC Peak Areas for Aliquots from Hydrolyses of 2 at Varying [NaOH]xs at 30 °C and Observed Rate Constants. A1
B1 HPLC Peak Areas
Time (min) 10 19.9 39.8 59.7 79.5 119.4 159.2 199.1 238.9
5 20135 40652 70028 101978 132902 192910 252280 310924 354706
2 854221 805580 796805 768343 744091 694984 651708 625621 584031
D1
Time (min) 10 19.9 39.8 59.7 79.5 119.4 159.2 199.1 238.9
5 33951 66664 130696 193068 255673 361103 449873 537728 600869
2 836489 811181 767122 712758 674250 589439 520720 458073 403249
E1 HPLC Peak Areas
Time (min) 10 19.9 39.8 59.7 79.5 119.4 159.2 199.1 238.9
C1 HPLC Peak Areas
5 79990 161734 319560 446332 557544 728477 855459 926974 996867
2 791671 719888 601864 495314 412731 280381 201352 139486 99532
HPLC Peak Areas Time (min) 10 19.9 39.8 59.7 79.5 119.4 159.2 199.1 238.9
5 61611 122046 235044 339492 433390 584225 706259 799193 876308
2 808220 758614 666870 590794 515126 397086 310763 243596 188935
Rate Constants HPLC Peak Areas
Time (min) 10 19.9 39.8 59.7 79.5 119.4 159.2 199.1 238.9
5 105568 209444 396995 557291 672912 849742 950336 1007560 1064160
2 759467 666751 509090 391766 302189 182313 108942 63515 39520
Reaction A1 B1 C1 D1 E1
[NaOH]xs (M) 0.1 0.2 0.4 0.6 0.8
–1
k' (min ) 0.0018 0.0032 0.0064 0.0091 0.013
14
Figure S7. Plots of HPLC Peak Areas vs. Time for Hydrolyses of 2 at Varying [NaOH]xs at 30 °C Showing Fit of Loss of 2 to Exponential Function. 900000 800000 700000 600000 500000 400000 300000 200000 100000 0
0.2 M excess NaOH
y = -1109x + 839086 R² = 0.9806 Diol Epoxide Linear (Epoxide)
0
100 200 Time (min)
Peak Area
Peak Area
0.1 M excess NaOH 900000 800000 700000 600000 500000 400000 300000 200000 100000 0
300
y = 865877e-0.003x R² = 0.9998 Diol Epoxide Expon. (Epoxide)
0
100 200 Time (min)
1000000 900000 800000 700000 600000 500000 400000 300000 200000 100000 0
0.6 M excess NaOH 1200000
y = 858436e-0.006x R² = 0.9999
y = 856858e-0.009x R² = 0.9996
Diol Epoxide Expon. (Epoxide)
Peak Area
1000000 800000
Diol
600000
Epoxide
400000
Expon. (Epoxide)
200000 0
0
100
200
300
0
100
Time (min)
200
300
Time (min)
0.8 M excess NaOH 1200000 1000000 Peak Area
Peak Area
0.4 M excess NaOH
300
Diol
800000 600000
Epoxide
y = 855507e-0.013x R² = 0.9999
400000 200000
Expon. (Epoxide)
0 0
200 Time (min)
400
15
Figure S8. Plots of Observed Rate Constant (k’) vs. [NaOH]xs for Hydrolyses of 2 at 30 °C Showing Fit to Linear Function. Rate Dependence on [NaOH] 0.014 0.012
k' = 0.0159·[NaOH]excess R2 = 0.9961
Rate (min-1)
0.01 0.008 0.006 0.004 0.002 0 0
0.2
0.4
0.6
[NaOH]excess (M)
0.8
1
16
Hydrolysis of (2,3-Epoxypropyl)trimethylammonium Chloride (2) at 40 °C. Table S6. HPLC Peak Areas for Aliquots from Hydrolyses of 2 at Varying [NaOH]xs at 40 °C and Observed Rate Constants. A1
B1 HPLC Peak Areas
Time (min) 11.3 21.3 41.2 61.2 81.1 121 160.8 200.7 240.6
5 23681 41426 78348 112037 149644 220412 283174 322067 375004
2 890830 839929 838037 810227 784216 764744 729706 659616 631226
D1
Time (min) 11.3 21.3 41.2 61.2 81.1 121 160.8 200.7 240.5
5 44155 87782 149090 226630 295565 412468 503258 605380 687181
2 865352 833523 770182 731165 682353 598507 517198 461627 414445
E1 HPLC Peak Areas
Time (min) 11.3 21.3 41.2 61.2 81.1 121 160.8 200.7 240.5
C1 HPLC Peak Areas
5 119701 222509 413701 563529 684248 861577 957288 1042480 1113330
2 782610 705662 585039 466954 376856 254082 157219 107405 75256
HPLC Peak Areas Time (min) 11.3 21.3 41.2 61.2 81.1 121 160.8 200.7 240.6
5 84307 155467 286300 409798 515902 682434 810532 916080 990594
Rate Constants HPLC Peak Areas
Time (min) 11.4 21.4 41.3 61.2 81.1 121 160.8 200.7 240.6
2 812424 752958 652694 562686 494603 368801 287808 218204 169838
5 155466 281580 507987 664709 804743 960037 1054830 1122020 1157880
2 757245 643570 496256 364948 284818 154151 82141 49879 33390
Reaction A1 B1 C1 D1 E1
[NaOH]xs (M) 0.05 0.10 0.20 0.30 0.40
–
k' (min 1 ) 0.0014 0.0032 0.0068 0.0104 0.0140
17
Figure S9. Plots of HPLC Peak Areas vs. Time for Hydrolyses of 2 at Varying [NaOH]xs at 40 °C Showing Fit of Loss of 2 to Exponential Function (Linear fit to initial rate for slowest reaction with 0.05 M excess NaOH). B1: 0.1 M excess NaOH
y = -1038.7x + 880455 R² = 0.974 Diol
Peak Area
Peak Area
A1: 0.05 M excess NaOH 1000000 900000 800000 700000 600000 500000 400000 300000 200000 100000 0
Epoxide Linear (Epoxide)
0
100 200 Time (min)
300
1000000 900000 800000 700000 600000 500000 400000 300000 200000 100000 0
y = 888657e-0.003x R² = 0.9983 Diol Epoxide Expon. (Epoxide)
0
300
D1: 0.3 M excess NaOH
C1: 0.2 M excess NaOH 1200000
1200000
1000000
1000000 800000
y = 864101e-0.007x R² = 0.9995
600000
Epoxide
400000
Expon. (Epoxide)
200000
Peak Area
Diol
Diol
800000 -0.01x
y = 880674e R² = 0.9991
600000
Epoxide
400000
Expon. (Epoxide)
200000
0
0
0
100 200 Time (min)
300
0
100 200 Time (min)
300
E1: 0.4 M excess NaOH 1400000 1200000 Diol
1000000 Peak Area
Peak Area
100 200 Time (min)
800000
y = 864933e-0.014x R² = 0.9973
600000
Epoxide Expon. (Epoxide)
400000 200000 0 0
100 200 Time (min)
300
18
Figure S10. Plots of Observed Rate Constant (k’) vs. [NaOH]xs for Hydrolyses of 2 at 40 °C Showing Fit to Linear Function. Rate Dependence on [NaOH] 0.016 0.014
Rate (min-1)
0.012
k' = 0.0346·[NaOH]excess R2 = 0.998
0.01 0.008 0.006 0.004 0.002 0 0
0.1
0.2
0.3
[NaOH]excess (M)
0.4
0.5
19
Hydrolysis of (2,3-Epoxypropyl)trimethylammonium Chloride (2) at 50 °C. Table S7. HPLC Peak Areas for Aliquots from Hydrolyses of 2 at Varying [NaOH]xs at 50 °C and Observed Rate Constants. A1
B1 HPLC Peak Areas
Time (min) 9.9 19.7 58.3 78.1 97.9 137.7 177.8 300.6 344
5 22050 35088 94688 126124 149237 195276 233049 349979 407431
2 908153 874346 834688 843603 818023 759550 696718 618558 649196
D1
Time (min) 9.9 19.7 58.4 78.1 97.9 137.7 177.8 300.9 344
5 41422 74195 230213 295379 359464 485657 582469 813223 885701
2 871185 834574 745178 686644 644438 567331 496576 340735 296667
E1 HPLC Peak Areas
Time (min) 9.9 19.7 58.4 78.1 97.9 137.7 177.8 303.8 344.1
C1 HPLC Peak Areas
5 106804 216363 566571 687957 793671 941780 1039850 1152050 1217920
2 812799 736974 490722 389118 314271 202425 126707 31731 22976
HPLC Peak Areas Time (min) 9.9 19.7 58.3 78.1 97.9 137.7 177.8 303.5 344
5 75647 143092 412871 520227 610639 762639 882005 1027040 1149240
Rate Constants HPLC Peak Areas
Time (min) 9.9 19.7 58.4 78.1 97.9 137.7
2 850082 778958 606900 527783 454065 337751 249566 98047 82024
5 145318 277209 686437 809708 896470 1039600
2 793957 693208 397615 290762 212877 116407
Reaction A1 B1 C1 D1 E1
[NaOH]xs (M) 0.02 0.05 0.10 0.15 0.20
–
k' (min 1 ) 0.00170 0.00320 0.00720 0.01090 0.01510
20
Figure S11. Plots of HPLC Peak Areas vs. Time for Hydrolyses of 2 at Varying [NaOH]xs at 50 °C Showing Fit of Loss of 2 to Exponential Function (Linear fit to initial rate for slowest reaction with 0.02 M excess NaOH). B1: 0.05 M excess NaOH
A1: 0.02 M excess NaOH
Diol
Peak Area
y = -1144.3x + 914013 R² = 0.9572
Peak Area
1000000 900000 800000 700000 600000 500000 400000 300000 200000 100000 0
Epoxide Linear (Epoxide)
0
200
1000000 900000 800000 700000 600000 500000 400000 300000 200000 100000 0
400
y = 888754e-0.003x R² = 0.9994 Diol Epoxide Expon. (Epoxide)
0
200 Time (min)
Time (min)
C1: 0.10 M excess NaOH 1400000
1200000
1000000
Peak Area
Diol
800000 Epoxide
600000 400000
Expon. (Epoxide)
200000
1000000
Diol
800000
y = 906604e-0.011x R² = 0.9994
600000
Epoxide
400000
Expon. (Epoxide)
200000
0
0 0
200
400
0
200
Time (min)
400
Time (min)
E1: 0.20 M excess NaOH 1200000 1000000
Peak Area
Peak Area
D1: 0.15 M excess NaOH 1400000
y = 908554e-0.007x R² = 0.9987
1200000
400
Diol
800000
y = 935237e-0.015x R² = 0.9996
600000 400000
Epoxide Expon. (Epoxide)
200000 0 0
50
100
150
Time (min)
21
Figure S12. Plots of Observed Rate Constant (k’) vs. [NaOH]xs for Hydrolyses of 2 at 50 °C Showing Fit to Linear Function. Rate Dependence on [NaOH] 0.016
k' = 0.0739·[NaOH]xs R2 = 0.9962
0.014 rate (min-1)
0.012 0.01 0.008 0.006 0.004 0.002 0 0
0.05
0.1
0.15
0.2
0.25
[NaOH]excess (M)
22
Hydrolysis of (2,3-Epoxypropyl)trimethylammonium Chloride (2) at 60 °C. Table S8. HPLC Peak Areas for Aliquots from Hydrolyses of 2 at Varying [NaOH]xs at 60 °C and Observed Rate Constants. A1
B1 HPLC Peak Areas
Time (min) 11.3 21.3 41.2 61.2 81.1 121 160.8 200.7 240.6
5 15596 29674 60403 92502 124346 178076 230413 286714 320098
2 872823 861734 870809 835112 841201 819554 781011 768847 724808
D1
Time (min) 11.3 21.3 41.2 61.2 81.1 121 160.8 200.7 240.5
5 49293 90190 178840 262755 339480 488113 615223 720041 826052
2 881670 845613 806536 741850 682357 593311 515715 441504 396875
E1 HPLC Peak Areas
Time (min) 11.3 21.3 41.2 61.2 81.1 121 160.8 200.7 240.5
C1 HPLC Peak Areas
5 90180 188553 366194 534521 663872 848087 993968 1105540 1186730
2 818579 758756 632998 534231 438712 270155 198096 137703 86094
HPLC Peak Areas Time (min) 11.3 21.3 41.2 61.2 81.1 121 160.8 200.7 240.6
5 60061 133566 273617 395456 513150 684652 831675 951341 1046580
Rate Constants HPLC Peak Areas
Time (min) 11.4 21.4 41.3 61.2 81.1 121 160.8 200.7 240.6
2 857337 803435 729007 637123 557497 418570 323675 253757 194026
5 122537 240901 459716 636034 779484 968990 1085670 1169620 1252150
2 812774 722832 574349 446685 344173 204105 120334 73073 46087
Reaction A1 B1 C1 D1 E1
[NaOH]xs (M) 0.01 0.03 0.05 0.07 0.09
–
k' (min 1 ) 0.00079 0.00360 0.00650 0.00980 0.01270
23
Figure S13. Plots of HPLC Peak Areas vs. Time for Hydrolyses of 2 at Varying [NaOH]xs at 60 °C Showing Fit of Loss of 2 to Exponential Function (Linear fit to initial rate for slowest reaction with 0.01 M excess NaOH). A1: 0.01 M excess NaOH 1000000 900000 800000 700000 y = -499.37x + 877918 600000 R² = 0.6835 500000 400000 300000 200000 100000 0 0 200 Time (min)
B1: 0.03 M excess NaOH 1000000 900000 800000 700000 600000 500000 400000 300000 200000 100000 0
Diol
Peak Area
Peak Area
Diol Epoxide Epoxide (init) Linear (Epoxide (init))
Epoxide
y = 918132e-0.004x R² = 0.9984 0
400
1400000
y = 941084e-0.01x R² = 0.998
1200000 Peak Area
Diol
800000
Epoxide
600000 400000
Expon. (Epoxide)
200000
Diol
1000000 800000
Epoxide
600000 400000
Expon. (Epoxide)
200000 0
0 0
100 200 Time (min)
0
300
100
200
300
Time (min)
E1: 0.09 M excess NaOH 1400000 1200000 Diol
1000000
Peak Area
Peak Area
300
D1: 0.07 M excess NaOH
y = 936178e-0.007x R² = 0.9993
1000000
200
Time (min)
C1: 0.05 M excess NaOH 1200000
100
Expon. (Epoxide)
800000
Epoxide
y = 954324e-0.013x R² = 0.9997
600000 400000
Expon. (Epoxide)
200000 0 0
100
200
300
Time (min)
24
Figure S14. Plots of Observed Rate Constant (k’) vs. [NaOH]xs for Hydrolyses of 2 at 60 °C Showing Fit to Linear Function. Rate Dependence on [NaOH] 0.014 0.012
k' = 0.1376·[NaOH]excess R2 = 0.9901
Rate (min-1)
0.01 0.008 0.006 0.004 0.002 0 0
0.02
0.04
0.06
[NaOH]excess (M)
0.08
0.1
25
Hydrolysis of (2,3-Epoxypropyl)trimethylammonium Chloride (2) at 70 °C. Table S9. HPLC Peak Areas for Aliquots from Hydrolyses of 2 at Varying [NaOH]xs at 70 °C and Observed Rate Constants. A1
B1 HPLC Peak Areas
Time (min) 9.9 20 40.2 60.4 80.6 120.8 161.5 200.1 238.6
5 13948 28105 39418 49684 75889 98185.8 128520 172108 201820
2 935791 951759 945104 924432 966503 950238 968696 1016750 981666
C1 HPLC Peak Areas
a
2corr 929615 939069 919775 887208 914570 873712 864400 881116 825516
Time (min) 9.9 20.1 40.2 60.4 80.5 120.9 161.5 200.2 238.6
5 52166 107539 204449 318411 412925 579484 715779 836763 985204
2 892790 873809 799440 752653 691842 587120 499949 427364 401668
HPLC Peak Areas Time (min) 10 20.1 40.2 60.4 80.5 121 161.8 203.8 238.9
5 102458 210812 394393 562021 719242 948752 1110980 1299170 1332840
2 867873 799033 624154 528154 429600 298720 211162 135301 92285
a Corrected for reduction in volume as follows: Peakcorr = Peakobs*(25 mL – 4 mL*time/240)/25 mL
D1
E1 HPLC Peak Areas
Time (min) 10 20.1 40.2 60.4 80.5 121.3 161.9 204.2 0
5 154990 328981 613566 803335 966512 1141900 1275980 1362730 0
2 785368 668431 483662 332673 234135 112756 49683 27275 0
Rate Constants HPLC Peak Areas
Time (min) 10 20.1 40.3 60.4 81.5 121.4 168.1 207.2 0
5 221525 438009 767071 849357 887123 1251800 1302330 1390340 0
2 753787 597342 363573 215027 106791 48814 15861 12017 0
Reaction A1 B1 C1 D1 E1
[NaOH]xs (M) 0.005 0.02 0.04 0.07 0.10
–
k' (min 1 ) 0.00060 0.00370 0.00960 0.01770 0.02220
26
Figure S15. Plots of HPLC Peak Areas vs. Time for Hydrolyses of 2 at Varying [NaOH]xs at 70 °C Showing Fit of Loss of 2 to Exponential Function (Linear fit to initial rate for slowest reaction with 0.005 M excess NaOH). A1: 0.005 M excess NaOH
B1: 0.02 M excess NaOH 1200000
1000000 900000 y = -402.31x + 934441 R² = 0.8177
Diol
Peak Area
700000 Peak Area
y = 929475e-0.004x R² = 0.9943
1000000
800000 600000
Vol. Corr. Epoxide
500000 400000
Linear (Vol. Corr. Epoxide)
300000 200000
Diol
800000
Epoxide
600000 400000
Expon. (Epoxide)
200000
100000
0
0 0
100
200
0
300
100 200 Time (min)
Time (min)
C1: 0.04 M excess NaOH
D1: 0.07 M excess NaOH
1400000
1600000
1200000
1400000
1000000
1200000 Peak Area
Diol
Diol
1000000
800000 Epoxide
600000
-0.01x
y = 949823e R² = 0.9988
400000
Expon. (Epoxide)
200000
800000
y = 957923e-0.018x R² = 0.9987
600000
Epoxide Expon. (Epoxide)
400000 200000
0
0
0
200
400
0
100
Time (min)
200
300
Time (min)
E1: 0.1 M excess NaOH 1600000 1400000 1200000 1000000 800000 600000 400000 200000 0
Diol
Peak Area
Peak Area
300
Epoxide -0.022x
y = 833301e R² = 0.9833
0
100
200
Expon. (Epoxide)
300
Time (min)
27
Figure S16. Plots of Observed Rate Constant (k’) vs. [NaOH]xs for Hydrolyses of 2 at 70 °C Showing Fit to Linear Function. Rate Dependence on [NaOH] 0.025
k' = 0.2316·[NaOH]xs R2 = 0.9867
rate (min-1)
0.02 0.015 0.01 0.005 0 0
0.02
0.04
0.06
0.08
0.1
0.12
[NaOH]excess (M)
28
Cationization of Cotton with (2,3-Epoxypropyl)trimethylammonium Chloride (2) at 30 °C. Table S10. HPLC Peak Areas for Aliquots from Reaction of 2 with Cotton at Varying [NaOH]xs at 30 °C and Corresponding Analyte Concentrations. A1: 0.2 M excess NaOH HPLC Peak Areas
a
Predicted Concentrationsa
Concentrations (M)
Time (min)
5
2
6
5
2
6
11.6
43736
836822
0
0.0024
0.0634
0.0000
21.6
71906
804832
0
0.0040
0.0618
41.5
123681
717601
0
0.0069
61.4
188223
717108
0
0.0102
4
5
2
6
4
0.0038 0.0022
0.0620
0.0000
0.0053
0.0000
0.0038 0.0040
0.0599
0.0000
0.0056
0.0558
0.0000
0.0068 0.0075
0.0560
0.0000
0.0060
0.0539
0.0000
0.0055 0.0106
0.0523
0.0001
0.0065
81.2
236301
610238
3517
0.0127
0.0456
0.0001
0.0111 0.0135
0.0489
0.0001
0.0069
121.1
333750
573329
14593
0.0182
0.0435
0.0003
0.0072 0.0187
0.0428
0.0002
0.0076
160.9
399424
451289
16066
0.0220
0.0347
0.0004
0.0121 0.0231
0.0375
0.0004
0.0082
200.8
488683
445550
33963
0.0268
0.0341
0.0008
0.0070 0.0270
0.0327
0.0005
0.0088
240.6
535221
344164
40911
0.0291
0.0261
0.0010
0.0125 0.0304
0.0286
0.0006
0.0093
Predicted using the model based on Scheme 4 and equations 2-5. Variables adjusted to fit this data are listed in Table S11.
B1: 0.4 M excess NaOH HPLC Peak Areas
a
Predicted Concentrationsa
Concentrations (M)
Time (min)
5
2
6
5
2
11.7
68784
808718
0
0.0038
0.0618
2
6
4
0.0000
21.7
127906
764784
0
0.0069
41.6
229309
657086
8572
0.0128
61.5
321110
537160
14549
0.0176
81.3
417741
518079
16131
0.0227
121.2
540801
353316
29772
161
671559
305290
200.9
731373
240.7
814162
6
0.0040 0.0044
4
5
0.0595
0.0000
0.0056
0.0573
0.0000
0.0054 0.0078
0.0555
0.0000
0.0061
0.0510
0.0002
0.0054 0.0141
0.0482
0.0001
0.0070
0.0411
0.0003
0.0102 0.0194
0.0419
0.0002
0.0077
0.0392
0.0004
0.0070 0.0240
0.0365
0.0004
0.0083
0.0291
0.0265
0.0007
0.0126 0.0314
0.0274
0.0006
0.0094
48043
0.0360
0.0228
0.0011
0.0085 0.0370
0.0206
0.0009
0.0102
191934
56982
0.0391
0.0143
0.0013
0.0134 0.0411
0.0154
0.0011
0.0108
179963
76132
0.0437
0.0135
0.0018
0.0088 0.0442
0.0115
0.0013
0.0112
Predicted using the model based on Scheme 4 and equations 2-5. Variables adjusted to fit this data are listed in Table S11.
C1: 0.6 M excess NaOH HPLC Peak Areas
a
Predicted Concentrationsa
Concentrations (M)
Time (min)
5
2
6
5
2
2
6
4
11.7
107944
751559
0
0.0060
0.0580
0.0000
6
0.0056 0.0063
4
5
0.0573
0.0000
0.0059
21.7
185248
708038
3085
0.0099
0.0528
0.0001
0.0066 0.0112
0.0516
0.0001
0.0066
41.6
330009
541343
8315
0.0181
0.0413
0.0002
0.0097 0.0193
0.0420
0.0002
0.0077
61.5
455839
471299
20427
0.0245
0.0353
0.0005
0.0089 0.0259
0.0342
0.0004
0.0086
81.4
534524
349895
38151
0.0297
0.0271
0.0009
0.0109 0.0312
0.0277
0.0006
0.0094
121.2
722590
263272
47667
0.0386
0.0196
0.0011
0.0091 0.0390
0.0180
0.0010
0.0105
161
809224
140450
68349
0.0430
0.0104
0.0016
0.0129 0.0440
0.0116
0.0013
0.0112
200.9
916183
120272
73796
0.0482
0.0088
0.0017
0.0091 0.0472
0.0076
0.0015
0.0117
240.7
949597
53711
82156
0.0498
0.0039
0.0019
0.0121 0.0493
0.0049
0.0017
0.0120
Predicted using the model based on Scheme 4 and equations 2-5. Variables adjusted to fit this data are listed in Table S11.
29
D1: 0.8 M excess NaOH HPLC Peak Areas
a
Predicted Concentrationsa
Concentrations (M)
Time (min)
5
2
6
5
2
2
6
4
11.8
133402
748745
0
0.0072
0.0564
0.0000
6
0.0059 0.0084
4
5
0.0549
0.0000
0.0062
21.8
233991
612063
6085
0.0127
0.0464
0.0001
0.0102 0.0144
0.0479
0.0001
0.0070
41.6
405342
491207
12688
0.0222
0.0375
0.0003
0.0092 0.0240
0.0365
0.0004
0.0083
61.5
540775
349644
33313
0.0295
0.0265
0.0008
0.0120 0.0312
0.0277
0.0006
0.0094
81.4
671943
292594
42075
0.0360
0.0218
0.0010
0.0097 0.0367
0.0210
0.0009
0.0101
121.3
812841
139967
66939
0.0431
0.0103
0.0015
0.0130 0.0438
0.0119
0.0013
0.0112
161.1
922912
98818
80297
0.0494
0.0074
0.0019
0.0090 0.0477
0.0069
0.0016
0.0118
201
962463
38296
83479
0.0516
0.0029
0.0019
0.0112 0.0500
0.0040
0.0017
0.0121
240.7
1032970
31840
91111
0.0544
0.0023
0.0021
0.0087 0.0511
0.0025
0.0018
0.0123
Predicted using the model based on Scheme 4 and equations 2-5. Variables adjusted to fit this data are listed in Table S11.
E1: 1.0 M excess NaOH HPLC Peak Areas
a
Predicted Concentrationsa
Concentrations (M)
Time (min)
5
2
6
5
2
2
6
4
11.8
163613
716042
2078
0.0087
0.0533
0.0000
6
0.0074 0.0102
4
5
0.0528
0.0001
0.0064
21.7
284481
607736
10190
0.0154
0.0460
0.0002
0.0077 0.0173
0.0444
0.0002
0.0074
41.6
476065
398390
17306
0.0260
0.0303
0.0004
0.0124 0.0282
0.0314
0.0005
0.0089
61.5
643089
305276
38039
0.0345
0.0228
0.0009
0.0105 0.0357
0.0222
0.0008
0.0100
81.4
734463
193443
50596
0.0395
0.0145
0.0012
0.0132 0.0409
0.0156
0.0011
0.0108
121.3
919297
107979
67351
0.0482
0.0079
0.0015
0.0104 0.0471
0.0077
0.0015
0.0117
161.1
980265
36302
78894
0.0515
0.0027
0.0018
0.0118 0.0500
0.0040
0.0017
0.0121
201
1029700
30612
73271
0.0547
0.0023
0.0017
0.0092 0.0514
0.0022
0.0018
0.0123
240.7
1078340
2283
93555
0.0555
0.0002
0.0021
0.0097 0.0520
0.0014
0.0019
0.0124
Predicted using the model based on Scheme 4 and equations 2-5. Variables adjusted to fit this data are listed in Table S11.
Table S11. Parameters Fit to Variables in equations 2-5 for Predicted Concentrations in Table S10. [2]init =
0.0645
[NaOH]aq / [NaOH]cotton =
2.95
k1 =
0.0198
k2 =
0.0271
k 3' =
0.00796
30
Figure S17. Plots of Concentrations vs. Time and Predicted Concentrations vs. Time for Reactions of 2 with Cotton at Varying [NaOH]xs at 30 °C. A1: 0.2 M excess NaOH B1: 0.4 M excess NaOH 0.07
0.06
epoxide
0.05
diol dimer
0.04
on cotton
0.03
Pred Ep
0.02
PredDiol PredDimer
0.01
Concentration (M)
Concentration (M)
0.07
PredCot'
0.06
epoxide
0.05
diol dimer
0.04
on cotton
0.03
Pred Ep
0.02
PredDiol
0.01
PredDimer
0
PredCot'
0 0
100
200
300
0
100
Time (min)
300
Time (min)
C1: 0.6 M excess NaOH
D1: 0.8 M excess NaOH
0.07
0.06 epoxide
0.05
diol dimer
0.04
on cotton
0.03
Pred Ep
0.02
PredDiol
0.01
PredDimer
0
100
200
diol
0.04
dimer
0.03
on cotton Pred Ep
0.02
PredDiol
0.01
PredCot'
0
epoxide
0.05
Concentration (M)
0.06
PredDimer PredCot'
0
300
0
100
Time (min)
200
300
Time (min)
E1: 1.0 M excess NaOH 0.06 0.05
Concentration (M)
Concentration (M)
200
epoxide diol
0.04
dimer
0.03
on cotton Pred Ep
0.02
PredDiol
0.01
PredDimer PredCot'
0 0
100
200
300
Time (min)
31
Cationization of Cotton with (2,3-Epoxypropyl)trimethylammonium Chloride (2) at 50 °C. Table S12. HPLC Peak Areas for Aliquots from Reaction of 2 with Cotton at Varying [NaOH]xs at 50 °C and Corresponding Analyte Concentrations. A1: 0.05 M excess NaOH HPLC Peak Areas
a
Predicted Concentrationsa
Concentrations (M)
Time (min)
5
2
6
5
2
6
9.7
30482
875978
0
0.0017
0.0662
0.0000
19.7
64926
820547
0
0.0036
0.0636
39.6
127144
785927
0
0.0070
59.5
182132
728856
0
0.0103
4
5
2
6
4
0.0016 0.0018
0.0653
0.0000
0.0023
0.0000
0.0022 0.0037
0.0632
0.0000
0.0025
0.0602
0.0000
0.0022 0.0072
0.0593
0.0000
0.0029
0.0575
0.0000
0.0016 0.0105
0.0555
0.0001
0.0033
79.3
237983
699830
8708
0.0129
0.0529
0.0002
0.0032 0.0135
0.0519
0.0001
0.0036
119.2
329030
605602
10482
0.0181
0.0465
0.0002
0.0043 0.0190
0.0455
0.0003
0.0043
159
434421
561449
21448
0.0231
0.0415
0.0005
0.0038 0.0239
0.0397
0.0004
0.0049
241.9
568390
429292
42591
0.0305
0.0321
0.0010
0.0049 0.0322
0.0297
0.0008
0.0059
281.8
637088
397754
48700
0.0327
0.0284
0.0011
0.0061 0.0355
0.0256
0.0010
0.0063
Predicted using the model based on Scheme 4 and equations 2-5. Variables adjusted to fit this data are listed in Table S13.
B1: 0.10 M excess NaOH HPLC Peak Areas
a
Predicted Concentrationsa
Concentrations (M)
Time (min)
5
2
6
5
2
9.8
65081
827625
0
0.0036
0.0642
2
6
4
0.0000
19.8
120811
779296
0
0.0066
39.7
234886
705106
5939
0.0126
59.6
341960
622238
11097
0.0181
6
0.0016 0.0037
4
5
0.0632
0.0000
0.0025
0.0598
0.0000
0.0030 0.0072
0.0593
0.0000
0.0029
0.0528
0.0001
0.0037 0.0135
0.0520
0.0001
0.0036
0.0459
0.0003
0.0048 0.0189
0.0456
0.0003
0.0043
79.4
431754
544008
19697
0.0227
0.0399
0.0004
0.0059 0.0236
0.0401
0.0004
0.0048
119.3
588660
428936
37453
0.0308
0.0312
0.0008
0.0057 0.0314
0.0307
0.0008
0.0058
159.1
711192
336744
62876
0.0369
0.0243
0.0014
0.0053 0.0373
0.0233
0.0011
0.0065
242
866494
200713
81232
0.0442
0.0143
0.0018
0.0073 0.0459
0.0125
0.0017
0.0076
281.9
933019
154803
87759
0.0469
0.0108
0.0019
0.0078 0.0485
0.0091
0.0019
0.0079
Predicted using the model based on Scheme 4 and equations 2-5. Variables adjusted to fit this data are listed in Table S13.
C1: 0.15 M excess NaOH HPLC Peak Areas
a
Predicted Concentrationsa
Concentrations (M)
Time (min)
5
2
6
5
2
2
6
4
9.9
89504
788272
0
0.0049
0.0605
0.0000
6
0.0040 0.0054
4
5
0.0613
0.0000
0.0027
19.9
176020
739300
6614
0.0095
0.0554
0.0002
0.0043 0.0103
0.0557
0.0001
0.0032
39.8
347784
622629
11924
0.0185
0.0463
0.0003
0.0040 0.0188
0.0458
0.0003
0.0042
59.7
483563
511815
22752
0.0251
0.0371
0.0005
0.0061 0.0256
0.0377
0.0005
0.0051
79.5
592949
412277
39508
0.0308
0.0299
0.0009
0.0069 0.0310
0.0311
0.0008
0.0057
119.4
759030
276240
59955
0.0392
0.0199
0.0013
0.0077 0.0390
0.0211
0.0012
0.0067
159.2
880970
189023
76344
0.0449
0.0134
0.0017
0.0077 0.0443
0.0144
0.0016
0.0074
242
1036680
85187
106355
0.0513
0.0059
0.0023
0.0076 0.0507
0.0063
0.0022
0.0082
282
1074720
54449
107836
0.0526
0.0037
0.0023
0.0085 0.0522
0.0043
0.0023
0.0084
Predicted using the model based on Scheme 4 and equations 2-5. Variables adjusted to fit this data are listed in Table S13.
32
D1: 0.20 M excess NaOH HPLC Peak Areas Time (min)
a
5
2
6
5
2
6
4
5
2
6
4
9.9
118559
770158
0
0.0065
0.0591
0.0000
0.0037 0.0071
0.0593
0.0000
0.0029
19.9
233159
691010
7223
0.0124
0.0511
0.0002
0.0056 0.0133
0.0522
0.0001
0.0036
39.8
439116
543390
19030
0.0232
0.0400
0.0004
0.0054 0.0233
0.0404
0.0004
0.0048
59.7
597959
410309
33614
0.0314
0.0300
0.0008
0.0065 0.0309
0.0312
0.0008
0.0057
79.5
709146
311136
57878
0.0373
0.0228
0.0013
0.0067 0.0366
0.0242
0.0011
0.0064
119.4
878491
177471
84183
0.0456
0.0128
0.0019
0.0072 0.0442
0.0146
0.0016
0.0074
202.2
1043030
57058
110197
0.0529
0.0040
0.0024
0.0076 0.0515
0.0051
0.0023
0.0083
242.1
1116810
33252
115157
0.0547
0.0023
0.0024
0.0076 0.0528
0.0034
0.0024
0.0084
282
1116790
18094
108981
0.0554
0.0013
0.0023
0.0080 0.0535
0.0024
0.0025
0.0085
Predicted using the model based on Scheme 4 and equations 2-5. Variables adjusted to fit this data are listed in Table S13.
E1: 0.233 M excess NaOH
b
HPLC Peak Areas
a
Predicted Concentrationsa
Concentrations (M)
Predicted Concentrationsa
Concentrations (M)
Time (min)
5
2
6
5
2
2
6
4
9.9
130948
756454
0
0.0072
0.0579
0.0000
6
0.0043 0.0082
4
5
0.0581
0.0000
0.0030
19.9
257495
666133
10094
0.0136
0.0492
0.0002
0.0061 0.0152
0.0500
0.0002
0.0038
39.8
484462
505174
24314
0.0254
0.0369
0.0006
0.0060 0.0262
0.0370
0.0005
0.0051
59.7
655158
374514
43124
0.0334
0.0266
0.0010
0.0074 0.0343
0.0272
0.0009
0.0061
79.5
763013
269242
58059
0.0396
0.0195
0.0013
0.0077 0.0400
0.0200
0.0013
0.0068
119.4
929786
141948
85065
0.0477
0.0101
0.0019
0.0078 0.0473
0.0107
0.0018
0.0077
202.1
1052180
37715
105263
0.0541
0.0027
0.0023
0.0079 0.0538
0.0023
0.0024
0.0086
242.1
1116210
20011
120452
0.0546
0.0014
0.0025
0.0084 0.0548
0.0010
0.0025
0.0087
282
1142570
10611
122620
0.0562
0.0007
0.0026
0.0072 0.0553
0.0003
0.0025
0.0088
Predicted using the model based on Scheme 4 and equations 2-5. Variables adjusted to fit this data are listed in Table S13.
b Ran out of NaOH stock solution during reactions. Automated liquid handler delivered less than intended amount. [NaOH]total was also varied and fit to the data in this reaction to arrive at the estimate of 0.233 M.
Table S13. Parameters Fit to Variables in equations 2-5 for Predicted Concentrations in Table S12. [2]init =
0.0674
[NaOH]aq / [NaOH]cotton =
3.00
k1 =
0.0761
k2 =
0.122
k 3' =
0.0265
33
Figure S18. Plots of Concentrations vs. Time and Predicted Concentrations vs. Time for Reactions of 2 with Cotton at Varying [NaOH]xs at 50 °C. A1: 0.05 M excess NaOH B1: 0.10 M excess NaOH
0.07 0.07 epoxide
0.05
diol dimer
0.04
on cotton
0.03
Pred Ep
0.02
PredDiol PredDimer
0.01
Concentration (M)
Concentration (M)
0.06
PredCot'
0.06
epoxide
0.05
diol dimer
0.04
on cotton
0.03
Pred Ep
0.02
PredDiol
0.01
PredDimer
0
PredCot'
0 0
100
200
300
0
100
Time (min)
200
300
Time (min)
C1: 0.15 M excess NaOH 0.07 0.06
D1: 0.20 M excess NaOH 0.07
Dimer (6) Cotton+ (4)
0.03
Pred 2 Pred 5
0.02
Pred 6 0.01
Pred 4
Concentration (M)
Diol (5)
0.04
0.06
epoxide
0.05
diol
0.04
dimer on cotton
0.03
Pred Ep
0.02
PredDiol
0.01
PredDimer
0
PredCot'
0 0
100
200
300
0
100
Time (min)
200
300
Time (min)
E1: 0.233 M excess NaOH 0.07 0.06
Concentration (M)
Concentration (M)
Epoxide (2) 0.05
epoxide
0.05
diol
0.04
dimer on cotton
0.03
Pred Ep
0.02
PredDiol
0.01
PredDimer PredCot'
0 0
100
200
300
Time (min)
34
Cationization of Cotton with (2,3-Epoxypropyl)trimethylammonium Chloride (2) at 70 °C. Table S14. HPLC Peak Areas for Aliquots from Reaction of 2 with Cotton at Varying [NaOH]xs at 70 °C and Corresponding Analyte Concentrations. A1: 0.01 M excess NaOH HPLC Peak Areas
a
Predicted Concentrationsa
Concentrations (M)
Time (min)
5
2
6
5
2
6
9.4
26492
913599
0
0.0014
0.0692
0.0000
19.5
43391
890393
0
0.0024
0.0699
39.4
82761
865030
0
0.0047
59.4
122332
867680
0
0.0069
4
5
2
6
4
-0.0004 0.0010
0.0692
0.0000
0.0001
0.0000
-0.0013 0.0020
0.0687
0.0000
0.0003
0.0686
0.0000
-0.0008 0.0041
0.0679
0.0000
0.0006
0.0678
0.0000
-0.0004 0.0062
0.0671
0.0000
0.0008 0.0011
79.3
162190
848743
0
0.0091
0.0667
0.0000
0.0000 0.0083
0.0663
0.0001
119.4
240138
833650
0
0.0137
0.0661
0.0000
-0.0002 0.0127
0.0648
0.0001
0.0017
159.4
311559
799341
1853
0.0178
0.0638
0.0000
0.0018 0.0173
0.0634
0.0002
0.0023
199.4
384940
769924
3545
0.0225
0.0627
0.0001
0.0026 0.0219
0.0623
0.0003
0.0030
239.4
453650
738014
7761
0.0269
0.0611
0.0002
0.0043 0.0269
0.0613
0.0005
0.0037
Predicted using the model based on Scheme 4 and equations 2-5. Variables adjusted to fit this data are listed in Table S15.
B1: 0.02 M excess NaOH HPLC Peak Areas
a
Predicted Concentrationsa
Concentrations (M)
Time (min)
5
2
6
5
2
2
6
4
9.6
54841
897919
0
0.0030
0.0677
0.0000
6
-0.0004 0.0021
4
5
0.0678
0.0000
0.0003
19.6
100209
863740
0
0.0056
0.0675
0.0000
-0.0021 0.0044
0.0660
0.0000
0.0006
39.5
174991
813970
0
0.0097
0.0626
0.0000
0.0003 0.0087
0.0626
0.0001
0.0012
59.5
247950
760826
4221
0.0139
0.0593
0.0001
0.0009 0.0128
0.0593
0.0001
0.0017
79.6
322426
721275
10606
0.0180
0.0560
0.0003
0.0014 0.0169
0.0563
0.0002
0.0023
119.6
457065
639747
12608
0.0262
0.0511
0.0003
0.0016 0.0247
0.0505
0.0004
0.0034
159.6
582924
567477
22149
0.0337
0.0458
0.0006
0.0028 0.0323
0.0453
0.0007
0.0044
199.6
689982
506230
29705
0.0400
0.0409
0.0007
0.0056 0.0396
0.0407
0.0011
0.0055
239.6
803240
464680
39381
0.0477
0.0384
0.0010
0.0047 0.0469
0.0365
0.0014
0.0065
Predicted using the model based on Scheme 4 and equations 2-5. Variables adjusted to fit this data are listed in Table S15.
C1: 0.04 M excess NaOH HPLC Peak Areas
a
Predicted Concentrationsa
Concentrations (M)
Time (min)
5
2
6
5
2
2
6
4
9.7
96420
838077
0
0.0052
0.0627
0.0000
6
0.0024 0.0051
4
5
0.0644
0.0000
0.0007
19.8
182929
769851
2246
0.0101
0.0593
0.0001
0.0016 0.0101
0.0595
0.0001
0.0014
39.6
338250
664892
10670
0.0186
0.0508
0.0003
0.0027 0.0190
0.0506
0.0002
0.0026
59.6
475095
565237
24469
0.0257
0.0426
0.0006
0.0047 0.0267
0.0429
0.0005
0.0037
79.6
593014
475566
33329
0.0321
0.0358
0.0008
0.0064 0.0335
0.0364
0.0007
0.0046
119.7
804917
353544
59745
0.0441
0.0270
0.0014
0.0056 0.0450
0.0257
0.0013
0.0062
139.7
930058
243491
68720
0.0510
0.0186
0.0016
0.0086 0.0496
0.0218
0.0016
0.0069
199.8
1076150
174733
97574
0.0600
0.0136
0.0024
0.0097 0.0612
0.0136
0.0023
0.0085
239.8
1172800
116563
107000
0.0672
0.0093
0.0026
0.0110 0.0681
0.0096
0.0028
0.0095
Predicted using the model based on Scheme 4 and equations 2-5. Variables adjusted to fit this data are listed in Table S15.
35
D1: 0.06 M excess NaOH HPLC Peak Areas
a
Predicted Concentrationsa
Concentrations (M)
Time (min)
5
2
6
5
2
9.8
135863
811191
4701
0.0072
0.0600
6
2
6
4
0.0616
0.0000
0.0010
19.9
258273
709744
7705
0.0139
0.0534
0.0002
0.0034 0.0145
39.8
464906
561776
23754
0.0255
0.0430
0.0006
0.0030 0.0261
0.0544
0.0001
0.0020
0.0420
0.0005
0.0036
59.7
628807
440368
36052
0.0335
0.0327
0.0008
0.0063 0.0355
79.7
756221
336731
52756
0.0407
0.0252
0.0012
0.0075 0.0430
0.0322
0.0008
0.0049
0.0245
0.0012
119.9
936631
204174
85704
0.0517
0.0157
0.0020
0.0059
0.0080 0.0547
0.0134
0.0019
159.9
1076100
123464
104143
0.0601
0.0096
0.0076
0.0025
0.0088 0.0633
0.0064
0.0025
199.9
1176700
74448
116879
0.0665
0.0088
0.0059
0.0029
0.0098 0.0702
0.0020
0.0029
0.0098
239.9
1279500
46229
125312
0.0741
0.0037
0.0031
0.0087 0.0763
-0.0008
0.0033
0.0107
0.0001
4
5
0.0029 0.0076
Predicted using the model based on Scheme 4 and equations 2-5. Variables adjusted to fit this data are listed in Table S15.
E1: 0.08 M excess NaOH HPLC Peak Areas
a
Predicted Concentrationsa
Concentrations (M)
Time (min)
5
2
6
5
2
2
6
4
10
176989
769018
0
0.0097
0.0589
0.0000
6
0.0017 0.0102
4
5
0.0586
0.0001
0.0014
20
341642
632346
11274
0.0188
0.0485
0.0003
0.0032 0.0188
0.0492
0.0002
0.0026
40
611369
438647
30965
0.0331
0.0331
0.0007
0.0049 0.0320
0.0348
0.0007
0.0044
60
797910
301178
56144
0.0434
0.0229
0.0013
0.0053 0.0413
0.0248
0.0012
0.0057
80
925963
199208
84896
0.0510
0.0153
0.0020
0.0056 0.0480
0.0180
0.0016
0.0067
120
1088560
92891
103977
0.0609
0.0072
0.0025
0.0064 0.0573
0.0097
0.0023
0.0080
160
1168840
39787
118265
0.0654
0.0031
0.0029
0.0093 0.0633
0.0060
0.0027
0.0089
200
1258920
21739
122649
0.0708
0.0017
0.0030
0.0095 0.0681
0.0044
0.0030
0.0095
240
1292140
8326
126954
0.0750
0.0007
0.0032
0.0108 0.0726
0.0036
0.0032
0.0102
Predicted using the model based on Scheme 4 and equations 2-5. Variables adjusted to fit this data are listed in Table S15.
Table S15. Parameters Fit to Variables in equations 2-5 for Predicted Concentrations in Table S14. [2]init =
0.0696
[NaOH]aq / [NaOH]cotton =
3.22
k1 =
0.260
k2 =
0.353
k 3' =
0.113
36
Figure S19. Plots of Concentrations vs. Time and Predicted Concentrations vs. Time for Reactions of 2 with Cotton at Varying [NaOH]xs at 70 °C. 0.01 M excess NaOH 0.02 M excess NaOH
0.08 0.08
0.07 diol
0.05
dimer
0.04
on cotton
0.03
Pred Ep
0.02
PredDiol
0.01
PredDimer
-0.01
0
100
200
diol
0.05
dimer
0.04
on cotton
0.03
Pred Ep
0.02
PredDiol
0.01
PredCot'
0
epoxide
0.06
Concentration (M)
Concentration (M)
0.07
epoxide
0.06
PredDimer
0
300
-0.01
PredCot'
0
100
Time (min)
300
Time (min)
D1: 0.06 M excess NaOH
C1: 0.04 M excess NaOH 0.09
0.08 0.07
0.08
diol
0.05
dimer
0.04
on cotton
0.03
Pred Ep
0.02
PredDiol PredDimer
0.01
Concentration (M)
epoxide
0.06
PredCot'
0 0
100
200
0.07
epoxide
0.06
diol
0.05
dimer
0.04
on cotton
0.03
Pred Ep
0.02
PredDiol
0.01
PredDimer PredCot'
0
300
-0.01 0
Time (min)
50
100
150 200 Time (min)
250
300
E1: 0.08 M excess NaOH 0.08 0.07
Concentration (M)
Concentration (M)
200
epoxide
0.06
diol
0.05
dimer
0.04
on cotton
0.03
Pred Ep
0.02
PredDiol PredDimer
0.01
PredCot'
0 0
100
200
300
Time (min)
37
Cationization of Cotton with (2,3-Epoxypropyl)trimethylammonium Chloride (2) at 50 °C in 1:1 Tetraglyme-Water. Table S16. HPLC Peak Areas for Aliquots from Hydrolysis of 2 with 0.2 M NaOH in 1:1 Tetraglyme-Water in the Absence of Cotton at 50 °C and Corresponding Analyte Concentrations. 0.2 M excess NaOH, 1:1 Tetraglyme-Water, No Cotton HPLC Peak Areas
a
Predicted Concentrationsa
Concentrations (M)
Time (min)
5
2
6
5
2
6
4
2
6
4
10
196508
311535
0
0.0200
0.0443
0.0026
0.0000 0.0192
5
0.0462
0.0008
0.0000
19.9
320230
209721
0
0.0325
0.0297
0.0037
0.0000 0.0310
0.0317
0.0021
0.0000
39.6
461222
93904
0
0.0464
0.0132
0.0050
0.0000 0.0438
0.0142
0.0044
0.0000
59.4
508571
40819
0
0.0507
0.0057
0.0066
0.0000 0.0492
0.0063
0.0057
0.0000
129.8
561940
0
0
0.0544
0.0000
0.0076
0.0000 0.0549
-0.0024
0.0072
0.0000
288.7
579598
0
0
0.0527
0.0000
0.0084
0.0000 0.0549
-0.0024
0.0072
0.0000
Predicted using the model based on Scheme 4 and equations 2-5. Variables adjusted to fit this data are listed in Table S17.
Table S17. Parameters Fit to Variables in equations 2-5 for Predicted Concentrations in Table S16. [2]init =
0.066884
k 1= k 2=
0.179472 0.69623
Table S18. HPLC Peak Areas for Aliquots from Reaction of 2 with 0.2 M NaOH in 1:1 Tetraglyme-Water in the Presence of Cotton at 50 °C and Corresponding Analyte Concentrations. 0.2 M excess NaOH, 1:1 Tetraglyme-Water, With Cotton HPLC Peak Areas
a
Predicted Concentrationsa
Concentrations (M)
Time (min)
5
2
6
5
2
6
4
2
6
4
10
144524
305981
0
0.0154
0.0453
0.0000
0.0000 0.0116
5
0.0465
0.0004
0.0108
19.8
212242
241108
0
0.0225
0.0357
0.0000
0.0000 0.0198
0.0350
0.0010
0.0128
39.6
307434
133072
0
0.0315
0.0190
0.0000
0.0000 0.0306
0.0189
0.0023
0.0156
59.3
357710
69606
0
0.0357
0.0097
0.0000
0.0000 0.0361
0.0103
0.0031
0.0170
129.8
417300
0
0
0.0401
0.0000
0.0000
0.0000 0.0425
-0.0002
0.0042
0.0188
288.7
432821
0
0
0.0424
0.0000
0.0000
0.0000 0.0425
-0.0002
0.0042
0.0188
Predicted using the model based on Scheme 4 and equations 2-5. Variables adjusted to fit this data are listed in Table S19.
Table S19. Parameters Fit to Variables in equations 2-5 for Predicted Concentrations in Table S18. [2]init = [NaOH]aq / [NaOH]cotton =
0.061535 1.64176
k1 (from Table S17) = k2 (from Table S17) = k3 =
0.179472 0.69623 0.067914
38
Core R&D, The Dow Chemical Company, 1776 Building, Midland, Michigan 48674, United
States. ‡Dow Consumer & Industrial Solutions, The Dow Chemical Company.
1
Supporting Information Table Of Contents
NMR Spectra ............................................................................................................................... 6 Representative HPLC Chromatograms. ....................................................................................... 9 Calibration of HPLC for (2,3-Dihydroxypropyl)trimethylammonium Chloride (5). ................ 10 Calibration of HPLC for (2,3-Epoxypropyl)trimethylammonium Chloride (2). ....................... 12 Hydrolysis of (2,3-Epoxypropyl)trimethylammonium Chloride (2) at 30 °C. .......................... 14 Hydrolysis of (2,3-Epoxypropyl)trimethylammonium Chloride (2) at 40 °C. .......................... 17 Hydrolysis of (2,3-Epoxypropyl)trimethylammonium Chloride (2) at 50 °C. .......................... 20 Hydrolysis of (2,3-Epoxypropyl)trimethylammonium Chloride (2) at 60 °C. .......................... 23 Hydrolysis of (2,3-Epoxypropyl)trimethylammonium Chloride (2) at 70 °C. .......................... 26 Cationization of Cotton with (2,3-Epoxypropyl)trimethylammonium Chloride (2) at 30 °C. .. 29 Cationization of Cotton with (2,3-Epoxypropyl)trimethylammonium Chloride (2) at 50 °C. .. 32 Cationization of Cotton with (2,3-Epoxypropyl)trimethylammonium Chloride (2) at 70 °C. .. 35 Cationization of Cotton with (2,3-Epoxypropyl)trimethylammonium Chloride (2) at 50 °C in 1:1 Tetraglyme-Water. ......................................................................................................... 38 List of Figures Figure S1. 1H NMR Spectrum of (2,3-Dihydroxypropyl)trimethylammonium Chloride (5).... 6 Figure S2. 1H NMR spectrum of 3,3’-oxybis(N,N,N-trimethyl-2-hydroxypropanaminium) dichloride (6).......................................................................................................................... 7 Figure S3. 13C NMR spectrum of 3,3’-oxybis(N,N,N-trimethyl-2-hydroxypropanaminium) dichloride (6).......................................................................................................................... 8 Figure S4. Reaction of 60 g/L EcoFAST™ CR 2000 with 0.1 M excess NaOH at 80 °C, after 80 min: ................................................................................................................................... 9 Figure S5. Calibration Curve for Diol 5 Showing Linear Fit. ................................................. 11 Figure S6. Calibration Curve for Epoxide 2 Showing Linear Fit. ........................................... 13
2
Figure S7. Plots of HPLC Peak Areas vs. Time for Hydrolyses of 2 at Varying [NaOH]xs at 30 °C Showing Fit of Loss of 2 to Exponential Function.................................................... 15 Figure S8. Plots of Observed Rate Constant (k’) vs. [NaOH]xs for Hydrolyses of 2 at 30 °C Showing Fit to Linear Function. .......................................................................................... 16 Figure S9. Plots of HPLC Peak Areas vs. Time for Hydrolyses of 2 at Varying [NaOH]xs at 40 °C Showing Fit of Loss of 2 to Exponential Function (Linear fit to initial rate for slowest reaction with 0.05 M excess NaOH). ...................................................................... 18 Figure S10. Plots of Observed Rate Constant (k’) vs. [NaOH]xs for Hydrolyses of 2 at 40 °C Showing Fit to Linear Function. .......................................................................................... 19 Figure S11. Plots of HPLC Peak Areas vs. Time for Hydrolyses of 2 at Varying [NaOH]xs at 50 °C Showing Fit of Loss of 2 to Exponential Function (Linear fit to initial rate for slowest reaction with 0.02 M excess NaOH). ...................................................................... 21 Figure S12. Plots of Observed Rate Constant (k’) vs. [NaOH]xs for Hydrolyses of 2 at 50 °C Showing Fit to Linear Function. .......................................................................................... 22 Figure S13. Plots of HPLC Peak Areas vs. Time for Hydrolyses of 2 at Varying [NaOH]xs at 60 °C Showing Fit of Loss of 2 to Exponential Function (Linear fit to initial rate for slowest reaction with 0.01 M excess NaOH). ...................................................................... 24 Figure S14. Plots of Observed Rate Constant (k’) vs. [NaOH]xs for Hydrolyses of 2 at 60 °C Showing Fit to Linear Function. .......................................................................................... 25 Figure S15. Plots of HPLC Peak Areas vs. Time for Hydrolyses of 2 at Varying [NaOH]xs at 70 °C Showing Fit of Loss of 2 to Exponential Function (Linear fit to initial rate for slowest reaction with 0.005 M excess NaOH). .................................................................... 27 Figure S16. Plots of Observed Rate Constant (k’) vs. [NaOH]xs for Hydrolyses of 2 at 70 °C Showing Fit to Linear Function. .......................................................................................... 28 Figure S17. Plots of Concentrations vs. Time and Predicted Concentrations vs. Time for Reactions of 2 with Cotton at Varying [NaOH]xs at 30 °C. ................................................. 31 Figure S18. Plots of Concentrations vs. Time and Predicted Concentrations vs. Time for Reactions of 2 with Cotton at Varying [NaOH]xs at 50 °C. ................................................. 34 Figure S19. Plots of Concentrations vs. Time and Predicted Concentrations vs. Time for Reactions of 2 with Cotton at Varying [NaOH]xs at 70 °C. ................................................. 37
3
List of Tables Table S1. Sample preparation for Diol 5 Calibration............................................................... 10 Table S2. HPLC Peak Areas for Diol 5 Calibration. ............................................................... 10 Table S3. Sample preparation for Epoxide 2 Calibration. ....................................................... 12 Table S4. HPLC Peak Areas for Epoxide 2 Calibration. ......................................................... 12 Table S5. HPLC Peak Areas for Aliquots from Hydrolyses of 2 at Varying [NaOH]xs at 30 °C and Observed Rate Constants. ............................................................................................. 14 Table S6. HPLC Peak Areas for Aliquots from Hydrolyses of 2 at Varying [NaOH]xs at 40 °C and Observed Rate Constants. ............................................................................................. 17 Table S7. HPLC Peak Areas for Aliquots from Hydrolyses of 2 at Varying [NaOH]xs at 50 °C and Observed Rate Constants. ............................................................................................. 20 Table S8. HPLC Peak Areas for Aliquots from Hydrolyses of 2 at Varying [NaOH]xs at 60 °C and Observed Rate Constants. ............................................................................................. 23 Table S9. HPLC Peak Areas for Aliquots from Hydrolyses of 2 at Varying [NaOH]xs at 70 °C and Observed Rate Constants. ............................................................................................. 26 Table S10. HPLC Peak Areas for Aliquots from Reaction of 2 with Cotton at Varying [NaOH]xs at 30 °C and Corresponding Analyte Concentrations. ........................................ 29 Table S11. Parameters Fit to Variables in equations 2-5 for Predicted Concentrations in Table S10. ...................................................................................................................................... 30 Table S12. HPLC Peak Areas for Aliquots from Reaction of 2 with Cotton at Varying [NaOH]xs at 50 °C and Corresponding Analyte Concentrations. ........................................ 32 Table S13. Parameters Fit to Variables in equations 2-5 for Predicted Concentrations in Table S12. ...................................................................................................................................... 33 Table S14. HPLC Peak Areas for Aliquots from Reaction of 2 with Cotton at Varying [NaOH]xs at 70 °C and Corresponding Analyte Concentrations. ........................................ 35 Table S15. Parameters Fit to Variables in equations 2-5 for Predicted Concentrations in Table 14.......................................................................................................................................... 36 Table S16. HPLC Peak Areas for Aliquots from Hydrolysis of 2 with 0.2 M NaOH in 1:1 Tetraglyme-Water in the Absence of Cotton at 50 °C and Corresponding Analyte Concentrations. .................................................................................................................... 38 Table S17. Parameters Fit to Variables in equations 2-5 for Predicted Concentrations in Table S16. ...................................................................................................................................... 38 4
Table S18. HPLC Peak Areas for Aliquots from Reaction of 2 with 0.2 M NaOH in 1:1 Tetraglyme-Water in the Presence of Cotton at 50 °C and Corresponding Analyte Concentrations. .................................................................................................................... 38 Table S19. Parameters Fit to Variables in equations 2-5 for Predicted Concentrations in Table 18.......................................................................................................................................... 38
5
NMR Spectra Figure S1. 1H NMR Spectrum of (2,3-Dihydroxypropyl)trimethylammonium Chloride (5).
NMe 3+ Cl–
HO OH 5
9.00
2.16
12.27
1.00
0.95
0.96
H2O
1
H NMR spectrum of aqueous solution of diol 5 in d6-DMSO. The sharp singlet at δ3.45 ppm integrates to 10.27 after 2H is subtracted out for the diol multiplet in that region. This gives a mol ratio of 5.14:1 water to 5, or 64.7 w/w% 5.
6
Figure S2. 1H NMR spectrum of 3,3’-oxybis(N,N,N-trimethyl-2-hydroxypropanaminium) dichloride (6).
Me3 N Cl–
O OH
OH
H2O
NMe3 Cl–
6
1.01
MeCN
3.40
8.41 5.55 18.62
2.08
2.00
d6-DMSO
1
H NMR spectrum (in d6-DMSO) of the hygroscopic white powder recovered from IPA-MeCN in the purification of dimer 6 (relative stereochemistry not determined). Already contaminated with water, although not left on Büchner funnel long enough to remove all acetonitrile.
7
Me3 N Cl–
O OH
OH 6
40.54 40.37 40.20 40.04 39.87 39.70 39.53
53.91
64.58
68.43
73.67
Figure S3. 13C NMR spectrum of 3,3’-oxybis(N,N,N-trimethyl-2-hydroxypropanaminium) dichloride (6).
NMe3 Cl–
d6 -
13
C NMR spectrum (125.6707 MHz, obtained on a Varian 500 MHz NMR Spectrometer, in d6DMSO) of 6 recrystallized from IPA-MeCN.
8
Representative HPLC Chromatograms. Figure S4. Reaction of 60 g/L EcoFAST™ CR 2000 with 0.1 M excess NaOH at 80 °C, after 80 min:
Figure S4a. Chromatogram from Refractive Index Detector signal. Peak at 4.4 minutes corresponds to diol 5, peak at 5.3 minutes to epoxide 2, and peak at 18.9 minutes to dimer 6.
Figure S4b. Chromatogram from Diode Array Detector signal (254 nm). Peak at 11.1 minutes corresponds to the PhS(O)Me internal standard.
™ Trademark of The Dow Chemical Company 9
Calibration of HPLC for (2,3-Dihydroxypropyl)trimethylammonium Chloride (5).
Table S1. Sample preparation for Diol 5 Calibration. Sample 1 2 3 4 5 6 7 8 9 10 11
PhS(O)Me (mL) 10 9.9 9.9 9.8 9.8 9.7 9.6 2.05 2 2 2
5 (mg) 11.2 54.2 124.2 176.1 249.6 355.8 482.2 179 242.4 366.9 496.1
PhS(O)Me (mg) 2.570 2.544 2.544 2.519 2.519 2.493 2.467 0.527 0.514 0.514 0.514
mmol 5/mg PhS(O)Me 0.017 0.081 0.186 0.267 0.378 0.544 0.745 1.296 1.799 2.722 3.681
5 (mmol) 0.043 0.207 0.474 0.672 0.952 1.357 1.839 0.683 0.924 1.399 1.892
Table S2. HPLC Peak Areas for Diol 5 Calibration. Run 1 Sample 1 2 3 4 5 6 7 8 9 10 11
5 21048 115805 239424 289412 436323 690221 820888 1466780 1835931 2891088 4471610
PhS(O)Me 584.1 614.5 575.7 489 511.5 558.9 482.9 484.2 435.8 453.8 516
Run 2 5 21297 101949 230782 288331 401968 634657 752551 1322160 1778160 2680309 4389220
PhS(O)Me 541 577.2 551.2 472.3 474.1 500.2 439.2 447.4 425.9 425.5 507.5
Run 3 5 19874 107908 231264 288500 400034 615316 755382 1340070 1803160 2710350 4392840
PhS(O)Me 542.2 569.9 554.2 483.9 476.1 502.6 450 440.6 433.1 430.2 510.3
Avg. Peak Area Ratio 37 185 417 599 847 1242 1697 3009 4184 6324 8641
10
Figure S5. Calibration Curve for Diol 5 Showing Linear Fit.
mmol 5 / mg PhS(O)Me
4.0 3.5
y = 0.0004285x R² = 0.9999
3.0 2.5 2.0 1.5 1.0 0.5 0.0 0
2000
4000
6000
8000
10000
Peak Area for 5 / Peak Area for PhS(O)Me
11
Calibration of HPLC for (2,3-Epoxypropyl)trimethylammonium Chloride (2).
Table S3. Sample preparation for Epoxide 2 Calibration. 5 NaOH PhS(O)Me PhS(O)Me 1 (mg) Sample (mL) (mL) (mg) (mmol) a 0.1 1 11.1 9.9 2.568 0.000 a 0.5 2 56 9.5 2.560 0.003 a 1.0 3 98.3 8.9 2.525 0.005 a 1.5 4 151.7 8.4 2.515 0.010 a 2.0 5 198.3 7.8 2.479 0.011 a 3.0 6 299.2 6.7 2.434 0.018 a 4.0 7 405.1 5.7 2.415 0.026 b 1.5 8 153.9 2 0.514 0.008 b 2.0 2 0.514 0.009 9 204.7 b 3.0 10 303.8 2 0.514 0.013 b 4.0 11 397.6 2 0.514 0.020 a b NaOH diluted with aq. PhS(O)Me. NaOH diluted with water.
2 (mmol) 0.039 0.192 0.337 0.518 0.679 1.022 1.383 0.527 0.703 1.043 1.362
mmol 2/mg PhS(O)Me 0.015 0.075 0.133 0.206 0.274 0.420 0.573 1.025 1.367 2.029 2.650
Table S4. HPLC Peak Areas for Epoxide 2 Calibration. Run 1 Sample 1 2 3 4 5 6 7 8 9 10 11
5
1786 3253 4770 7242 9074 13783 14588 20959 29414
2 PhS(O)Me 18774 783.1 72443 626.7 186346 825.2 256071 717.2 339086 736.7 473412 671.3 524523 549.6 953363 546.6 1459460 629.1 2047740 599.3 2345860 521.1
Run 2 5 1843 3800 4490 6481 10539 14117 15888 20322 29573 39591
2 5 PhS(O)Me 18050 467 75125 517.9 2197.3 145188 584.1 3623 167281 462.1 6691 251502 525.5 6887 400091 545.3 13291 436746 443.4 12675 797317 455.3 26566 1221380 530 34800 1724270 509.5 48923 2034180 454.8 64171
Avg. Peak Area Ratio (2 / 2 PhS(O)Me PhS(O)Me) 16296 470.7 31 74727 520.5 134 145134 588.7 239 175957 458 366 252527 528.4 471 408388 548.7 726 435202 435.6 978 797367 461.5 1741 1205710 536 2293 1680950 514 3360 1993570 459.8 4439 Run 3
12
Figure S6. Calibration Curve for Epoxide 2 Showing Linear Fit.
mmol 2 / mg PhS(O)Me
3.0
y = 0.0005973x R² = 0.9998
2.5 2.0 1.5 1.0 0.5 0.0 0
1000
2000
3000
4000
5000
Peak Area for 2 / Peak Area for PhS(O)Me
13
Hydrolysis of (2,3-Epoxypropyl)trimethylammonium Chloride (2) at 30 °C. Table S5. HPLC Peak Areas for Aliquots from Hydrolyses of 2 at Varying [NaOH]xs at 30 °C and Observed Rate Constants. A1
B1 HPLC Peak Areas
Time (min) 10 19.9 39.8 59.7 79.5 119.4 159.2 199.1 238.9
5 20135 40652 70028 101978 132902 192910 252280 310924 354706
2 854221 805580 796805 768343 744091 694984 651708 625621 584031
D1
Time (min) 10 19.9 39.8 59.7 79.5 119.4 159.2 199.1 238.9
5 33951 66664 130696 193068 255673 361103 449873 537728 600869
2 836489 811181 767122 712758 674250 589439 520720 458073 403249
E1 HPLC Peak Areas
Time (min) 10 19.9 39.8 59.7 79.5 119.4 159.2 199.1 238.9
C1 HPLC Peak Areas
5 79990 161734 319560 446332 557544 728477 855459 926974 996867
2 791671 719888 601864 495314 412731 280381 201352 139486 99532
HPLC Peak Areas Time (min) 10 19.9 39.8 59.7 79.5 119.4 159.2 199.1 238.9
5 61611 122046 235044 339492 433390 584225 706259 799193 876308
2 808220 758614 666870 590794 515126 397086 310763 243596 188935
Rate Constants HPLC Peak Areas
Time (min) 10 19.9 39.8 59.7 79.5 119.4 159.2 199.1 238.9
5 105568 209444 396995 557291 672912 849742 950336 1007560 1064160
2 759467 666751 509090 391766 302189 182313 108942 63515 39520
Reaction A1 B1 C1 D1 E1
[NaOH]xs (M) 0.1 0.2 0.4 0.6 0.8
–1
k' (min ) 0.0018 0.0032 0.0064 0.0091 0.013
14
Figure S7. Plots of HPLC Peak Areas vs. Time for Hydrolyses of 2 at Varying [NaOH]xs at 30 °C Showing Fit of Loss of 2 to Exponential Function. 900000 800000 700000 600000 500000 400000 300000 200000 100000 0
0.2 M excess NaOH
y = -1109x + 839086 R² = 0.9806 Diol Epoxide Linear (Epoxide)
0
100 200 Time (min)
Peak Area
Peak Area
0.1 M excess NaOH 900000 800000 700000 600000 500000 400000 300000 200000 100000 0
300
y = 865877e-0.003x R² = 0.9998 Diol Epoxide Expon. (Epoxide)
0
100 200 Time (min)
1000000 900000 800000 700000 600000 500000 400000 300000 200000 100000 0
0.6 M excess NaOH 1200000
y = 858436e-0.006x R² = 0.9999
y = 856858e-0.009x R² = 0.9996
Diol Epoxide Expon. (Epoxide)
Peak Area
1000000 800000
Diol
600000
Epoxide
400000
Expon. (Epoxide)
200000 0
0
100
200
300
0
100
Time (min)
200
300
Time (min)
0.8 M excess NaOH 1200000 1000000 Peak Area
Peak Area
0.4 M excess NaOH
300
Diol
800000 600000
Epoxide
y = 855507e-0.013x R² = 0.9999
400000 200000
Expon. (Epoxide)
0 0
200 Time (min)
400
15
Figure S8. Plots of Observed Rate Constant (k’) vs. [NaOH]xs for Hydrolyses of 2 at 30 °C Showing Fit to Linear Function. Rate Dependence on [NaOH] 0.014 0.012
k' = 0.0159·[NaOH]excess R2 = 0.9961
Rate (min-1)
0.01 0.008 0.006 0.004 0.002 0 0
0.2
0.4
0.6
[NaOH]excess (M)
0.8
1
16
Hydrolysis of (2,3-Epoxypropyl)trimethylammonium Chloride (2) at 40 °C. Table S6. HPLC Peak Areas for Aliquots from Hydrolyses of 2 at Varying [NaOH]xs at 40 °C and Observed Rate Constants. A1
B1 HPLC Peak Areas
Time (min) 11.3 21.3 41.2 61.2 81.1 121 160.8 200.7 240.6
5 23681 41426 78348 112037 149644 220412 283174 322067 375004
2 890830 839929 838037 810227 784216 764744 729706 659616 631226
D1
Time (min) 11.3 21.3 41.2 61.2 81.1 121 160.8 200.7 240.5
5 44155 87782 149090 226630 295565 412468 503258 605380 687181
2 865352 833523 770182 731165 682353 598507 517198 461627 414445
E1 HPLC Peak Areas
Time (min) 11.3 21.3 41.2 61.2 81.1 121 160.8 200.7 240.5
C1 HPLC Peak Areas
5 119701 222509 413701 563529 684248 861577 957288 1042480 1113330
2 782610 705662 585039 466954 376856 254082 157219 107405 75256
HPLC Peak Areas Time (min) 11.3 21.3 41.2 61.2 81.1 121 160.8 200.7 240.6
5 84307 155467 286300 409798 515902 682434 810532 916080 990594
Rate Constants HPLC Peak Areas
Time (min) 11.4 21.4 41.3 61.2 81.1 121 160.8 200.7 240.6
2 812424 752958 652694 562686 494603 368801 287808 218204 169838
5 155466 281580 507987 664709 804743 960037 1054830 1122020 1157880
2 757245 643570 496256 364948 284818 154151 82141 49879 33390
Reaction A1 B1 C1 D1 E1
[NaOH]xs (M) 0.05 0.10 0.20 0.30 0.40
–
k' (min 1 ) 0.0014 0.0032 0.0068 0.0104 0.0140
17
Figure S9. Plots of HPLC Peak Areas vs. Time for Hydrolyses of 2 at Varying [NaOH]xs at 40 °C Showing Fit of Loss of 2 to Exponential Function (Linear fit to initial rate for slowest reaction with 0.05 M excess NaOH). B1: 0.1 M excess NaOH
y = -1038.7x + 880455 R² = 0.974 Diol
Peak Area
Peak Area
A1: 0.05 M excess NaOH 1000000 900000 800000 700000 600000 500000 400000 300000 200000 100000 0
Epoxide Linear (Epoxide)
0
100 200 Time (min)
300
1000000 900000 800000 700000 600000 500000 400000 300000 200000 100000 0
y = 888657e-0.003x R² = 0.9983 Diol Epoxide Expon. (Epoxide)
0
300
D1: 0.3 M excess NaOH
C1: 0.2 M excess NaOH 1200000
1200000
1000000
1000000 800000
y = 864101e-0.007x R² = 0.9995
600000
Epoxide
400000
Expon. (Epoxide)
200000
Peak Area
Diol
Diol
800000 -0.01x
y = 880674e R² = 0.9991
600000
Epoxide
400000
Expon. (Epoxide)
200000
0
0
0
100 200 Time (min)
300
0
100 200 Time (min)
300
E1: 0.4 M excess NaOH 1400000 1200000 Diol
1000000 Peak Area
Peak Area
100 200 Time (min)
800000
y = 864933e-0.014x R² = 0.9973
600000
Epoxide Expon. (Epoxide)
400000 200000 0 0
100 200 Time (min)
300
18
Figure S10. Plots of Observed Rate Constant (k’) vs. [NaOH]xs for Hydrolyses of 2 at 40 °C Showing Fit to Linear Function. Rate Dependence on [NaOH] 0.016 0.014
Rate (min-1)
0.012
k' = 0.0346·[NaOH]excess R2 = 0.998
0.01 0.008 0.006 0.004 0.002 0 0
0.1
0.2
0.3
[NaOH]excess (M)
0.4
0.5
19
Hydrolysis of (2,3-Epoxypropyl)trimethylammonium Chloride (2) at 50 °C. Table S7. HPLC Peak Areas for Aliquots from Hydrolyses of 2 at Varying [NaOH]xs at 50 °C and Observed Rate Constants. A1
B1 HPLC Peak Areas
Time (min) 9.9 19.7 58.3 78.1 97.9 137.7 177.8 300.6 344
5 22050 35088 94688 126124 149237 195276 233049 349979 407431
2 908153 874346 834688 843603 818023 759550 696718 618558 649196
D1
Time (min) 9.9 19.7 58.4 78.1 97.9 137.7 177.8 300.9 344
5 41422 74195 230213 295379 359464 485657 582469 813223 885701
2 871185 834574 745178 686644 644438 567331 496576 340735 296667
E1 HPLC Peak Areas
Time (min) 9.9 19.7 58.4 78.1 97.9 137.7 177.8 303.8 344.1
C1 HPLC Peak Areas
5 106804 216363 566571 687957 793671 941780 1039850 1152050 1217920
2 812799 736974 490722 389118 314271 202425 126707 31731 22976
HPLC Peak Areas Time (min) 9.9 19.7 58.3 78.1 97.9 137.7 177.8 303.5 344
5 75647 143092 412871 520227 610639 762639 882005 1027040 1149240
Rate Constants HPLC Peak Areas
Time (min) 9.9 19.7 58.4 78.1 97.9 137.7
2 850082 778958 606900 527783 454065 337751 249566 98047 82024
5 145318 277209 686437 809708 896470 1039600
2 793957 693208 397615 290762 212877 116407
Reaction A1 B1 C1 D1 E1
[NaOH]xs (M) 0.02 0.05 0.10 0.15 0.20
–
k' (min 1 ) 0.00170 0.00320 0.00720 0.01090 0.01510
20
Figure S11. Plots of HPLC Peak Areas vs. Time for Hydrolyses of 2 at Varying [NaOH]xs at 50 °C Showing Fit of Loss of 2 to Exponential Function (Linear fit to initial rate for slowest reaction with 0.02 M excess NaOH). B1: 0.05 M excess NaOH
A1: 0.02 M excess NaOH
Diol
Peak Area
y = -1144.3x + 914013 R² = 0.9572
Peak Area
1000000 900000 800000 700000 600000 500000 400000 300000 200000 100000 0
Epoxide Linear (Epoxide)
0
200
1000000 900000 800000 700000 600000 500000 400000 300000 200000 100000 0
400
y = 888754e-0.003x R² = 0.9994 Diol Epoxide Expon. (Epoxide)
0
200 Time (min)
Time (min)
C1: 0.10 M excess NaOH 1400000
1200000
1000000
Peak Area
Diol
800000 Epoxide
600000 400000
Expon. (Epoxide)
200000
1000000
Diol
800000
y = 906604e-0.011x R² = 0.9994
600000
Epoxide
400000
Expon. (Epoxide)
200000
0
0 0
200
400
0
200
Time (min)
400
Time (min)
E1: 0.20 M excess NaOH 1200000 1000000
Peak Area
Peak Area
D1: 0.15 M excess NaOH 1400000
y = 908554e-0.007x R² = 0.9987
1200000
400
Diol
800000
y = 935237e-0.015x R² = 0.9996
600000 400000
Epoxide Expon. (Epoxide)
200000 0 0
50
100
150
Time (min)
21
Figure S12. Plots of Observed Rate Constant (k’) vs. [NaOH]xs for Hydrolyses of 2 at 50 °C Showing Fit to Linear Function. Rate Dependence on [NaOH] 0.016
k' = 0.0739·[NaOH]xs R2 = 0.9962
0.014 rate (min-1)
0.012 0.01 0.008 0.006 0.004 0.002 0 0
0.05
0.1
0.15
0.2
0.25
[NaOH]excess (M)
22
Hydrolysis of (2,3-Epoxypropyl)trimethylammonium Chloride (2) at 60 °C. Table S8. HPLC Peak Areas for Aliquots from Hydrolyses of 2 at Varying [NaOH]xs at 60 °C and Observed Rate Constants. A1
B1 HPLC Peak Areas
Time (min) 11.3 21.3 41.2 61.2 81.1 121 160.8 200.7 240.6
5 15596 29674 60403 92502 124346 178076 230413 286714 320098
2 872823 861734 870809 835112 841201 819554 781011 768847 724808
D1
Time (min) 11.3 21.3 41.2 61.2 81.1 121 160.8 200.7 240.5
5 49293 90190 178840 262755 339480 488113 615223 720041 826052
2 881670 845613 806536 741850 682357 593311 515715 441504 396875
E1 HPLC Peak Areas
Time (min) 11.3 21.3 41.2 61.2 81.1 121 160.8 200.7 240.5
C1 HPLC Peak Areas
5 90180 188553 366194 534521 663872 848087 993968 1105540 1186730
2 818579 758756 632998 534231 438712 270155 198096 137703 86094
HPLC Peak Areas Time (min) 11.3 21.3 41.2 61.2 81.1 121 160.8 200.7 240.6
5 60061 133566 273617 395456 513150 684652 831675 951341 1046580
Rate Constants HPLC Peak Areas
Time (min) 11.4 21.4 41.3 61.2 81.1 121 160.8 200.7 240.6
2 857337 803435 729007 637123 557497 418570 323675 253757 194026
5 122537 240901 459716 636034 779484 968990 1085670 1169620 1252150
2 812774 722832 574349 446685 344173 204105 120334 73073 46087
Reaction A1 B1 C1 D1 E1
[NaOH]xs (M) 0.01 0.03 0.05 0.07 0.09
–
k' (min 1 ) 0.00079 0.00360 0.00650 0.00980 0.01270
23
Figure S13. Plots of HPLC Peak Areas vs. Time for Hydrolyses of 2 at Varying [NaOH]xs at 60 °C Showing Fit of Loss of 2 to Exponential Function (Linear fit to initial rate for slowest reaction with 0.01 M excess NaOH). A1: 0.01 M excess NaOH 1000000 900000 800000 700000 y = -499.37x + 877918 600000 R² = 0.6835 500000 400000 300000 200000 100000 0 0 200 Time (min)
B1: 0.03 M excess NaOH 1000000 900000 800000 700000 600000 500000 400000 300000 200000 100000 0
Diol
Peak Area
Peak Area
Diol Epoxide Epoxide (init) Linear (Epoxide (init))
Epoxide
y = 918132e-0.004x R² = 0.9984 0
400
1400000
y = 941084e-0.01x R² = 0.998
1200000 Peak Area
Diol
800000
Epoxide
600000 400000
Expon. (Epoxide)
200000
Diol
1000000 800000
Epoxide
600000 400000
Expon. (Epoxide)
200000 0
0 0
100 200 Time (min)
0
300
100
200
300
Time (min)
E1: 0.09 M excess NaOH 1400000 1200000 Diol
1000000
Peak Area
Peak Area
300
D1: 0.07 M excess NaOH
y = 936178e-0.007x R² = 0.9993
1000000
200
Time (min)
C1: 0.05 M excess NaOH 1200000
100
Expon. (Epoxide)
800000
Epoxide
y = 954324e-0.013x R² = 0.9997
600000 400000
Expon. (Epoxide)
200000 0 0
100
200
300
Time (min)
24
Figure S14. Plots of Observed Rate Constant (k’) vs. [NaOH]xs for Hydrolyses of 2 at 60 °C Showing Fit to Linear Function. Rate Dependence on [NaOH] 0.014 0.012
k' = 0.1376·[NaOH]excess R2 = 0.9901
Rate (min-1)
0.01 0.008 0.006 0.004 0.002 0 0
0.02
0.04
0.06
[NaOH]excess (M)
0.08
0.1
25
Hydrolysis of (2,3-Epoxypropyl)trimethylammonium Chloride (2) at 70 °C. Table S9. HPLC Peak Areas for Aliquots from Hydrolyses of 2 at Varying [NaOH]xs at 70 °C and Observed Rate Constants. A1
B1 HPLC Peak Areas
Time (min) 9.9 20 40.2 60.4 80.6 120.8 161.5 200.1 238.6
5 13948 28105 39418 49684 75889 98185.8 128520 172108 201820
2 935791 951759 945104 924432 966503 950238 968696 1016750 981666
C1 HPLC Peak Areas
a
2corr 929615 939069 919775 887208 914570 873712 864400 881116 825516
Time (min) 9.9 20.1 40.2 60.4 80.5 120.9 161.5 200.2 238.6
5 52166 107539 204449 318411 412925 579484 715779 836763 985204
2 892790 873809 799440 752653 691842 587120 499949 427364 401668
HPLC Peak Areas Time (min) 10 20.1 40.2 60.4 80.5 121 161.8 203.8 238.9
5 102458 210812 394393 562021 719242 948752 1110980 1299170 1332840
2 867873 799033 624154 528154 429600 298720 211162 135301 92285
a Corrected for reduction in volume as follows: Peakcorr = Peakobs*(25 mL – 4 mL*time/240)/25 mL
D1
E1 HPLC Peak Areas
Time (min) 10 20.1 40.2 60.4 80.5 121.3 161.9 204.2 0
5 154990 328981 613566 803335 966512 1141900 1275980 1362730 0
2 785368 668431 483662 332673 234135 112756 49683 27275 0
Rate Constants HPLC Peak Areas
Time (min) 10 20.1 40.3 60.4 81.5 121.4 168.1 207.2 0
5 221525 438009 767071 849357 887123 1251800 1302330 1390340 0
2 753787 597342 363573 215027 106791 48814 15861 12017 0
Reaction A1 B1 C1 D1 E1
[NaOH]xs (M) 0.005 0.02 0.04 0.07 0.10
–
k' (min 1 ) 0.00060 0.00370 0.00960 0.01770 0.02220
26
Figure S15. Plots of HPLC Peak Areas vs. Time for Hydrolyses of 2 at Varying [NaOH]xs at 70 °C Showing Fit of Loss of 2 to Exponential Function (Linear fit to initial rate for slowest reaction with 0.005 M excess NaOH). A1: 0.005 M excess NaOH
B1: 0.02 M excess NaOH 1200000
1000000 900000 y = -402.31x + 934441 R² = 0.8177
Diol
Peak Area
700000 Peak Area
y = 929475e-0.004x R² = 0.9943
1000000
800000 600000
Vol. Corr. Epoxide
500000 400000
Linear (Vol. Corr. Epoxide)
300000 200000
Diol
800000
Epoxide
600000 400000
Expon. (Epoxide)
200000
100000
0
0 0
100
200
0
300
100 200 Time (min)
Time (min)
C1: 0.04 M excess NaOH
D1: 0.07 M excess NaOH
1400000
1600000
1200000
1400000
1000000
1200000 Peak Area
Diol
Diol
1000000
800000 Epoxide
600000
-0.01x
y = 949823e R² = 0.9988
400000
Expon. (Epoxide)
200000
800000
y = 957923e-0.018x R² = 0.9987
600000
Epoxide Expon. (Epoxide)
400000 200000
0
0
0
200
400
0
100
Time (min)
200
300
Time (min)
E1: 0.1 M excess NaOH 1600000 1400000 1200000 1000000 800000 600000 400000 200000 0
Diol
Peak Area
Peak Area
300
Epoxide -0.022x
y = 833301e R² = 0.9833
0
100
200
Expon. (Epoxide)
300
Time (min)
27
Figure S16. Plots of Observed Rate Constant (k’) vs. [NaOH]xs for Hydrolyses of 2 at 70 °C Showing Fit to Linear Function. Rate Dependence on [NaOH] 0.025
k' = 0.2316·[NaOH]xs R2 = 0.9867
rate (min-1)
0.02 0.015 0.01 0.005 0 0
0.02
0.04
0.06
0.08
0.1
0.12
[NaOH]excess (M)
28
Cationization of Cotton with (2,3-Epoxypropyl)trimethylammonium Chloride (2) at 30 °C. Table S10. HPLC Peak Areas for Aliquots from Reaction of 2 with Cotton at Varying [NaOH]xs at 30 °C and Corresponding Analyte Concentrations. A1: 0.2 M excess NaOH HPLC Peak Areas
a
Predicted Concentrationsa
Concentrations (M)
Time (min)
5
2
6
5
2
6
11.6
43736
836822
0
0.0024
0.0634
0.0000
21.6
71906
804832
0
0.0040
0.0618
41.5
123681
717601
0
0.0069
61.4
188223
717108
0
0.0102
4
5
2
6
4
0.0038 0.0022
0.0620
0.0000
0.0053
0.0000
0.0038 0.0040
0.0599
0.0000
0.0056
0.0558
0.0000
0.0068 0.0075
0.0560
0.0000
0.0060
0.0539
0.0000
0.0055 0.0106
0.0523
0.0001
0.0065
81.2
236301
610238
3517
0.0127
0.0456
0.0001
0.0111 0.0135
0.0489
0.0001
0.0069
121.1
333750
573329
14593
0.0182
0.0435
0.0003
0.0072 0.0187
0.0428
0.0002
0.0076
160.9
399424
451289
16066
0.0220
0.0347
0.0004
0.0121 0.0231
0.0375
0.0004
0.0082
200.8
488683
445550
33963
0.0268
0.0341
0.0008
0.0070 0.0270
0.0327
0.0005
0.0088
240.6
535221
344164
40911
0.0291
0.0261
0.0010
0.0125 0.0304
0.0286
0.0006
0.0093
Predicted using the model based on Scheme 4 and equations 2-5. Variables adjusted to fit this data are listed in Table S11.
B1: 0.4 M excess NaOH HPLC Peak Areas
a
Predicted Concentrationsa
Concentrations (M)
Time (min)
5
2
6
5
2
11.7
68784
808718
0
0.0038
0.0618
2
6
4
0.0000
21.7
127906
764784
0
0.0069
41.6
229309
657086
8572
0.0128
61.5
321110
537160
14549
0.0176
81.3
417741
518079
16131
0.0227
121.2
540801
353316
29772
161
671559
305290
200.9
731373
240.7
814162
6
0.0040 0.0044
4
5
0.0595
0.0000
0.0056
0.0573
0.0000
0.0054 0.0078
0.0555
0.0000
0.0061
0.0510
0.0002
0.0054 0.0141
0.0482
0.0001
0.0070
0.0411
0.0003
0.0102 0.0194
0.0419
0.0002
0.0077
0.0392
0.0004
0.0070 0.0240
0.0365
0.0004
0.0083
0.0291
0.0265
0.0007
0.0126 0.0314
0.0274
0.0006
0.0094
48043
0.0360
0.0228
0.0011
0.0085 0.0370
0.0206
0.0009
0.0102
191934
56982
0.0391
0.0143
0.0013
0.0134 0.0411
0.0154
0.0011
0.0108
179963
76132
0.0437
0.0135
0.0018
0.0088 0.0442
0.0115
0.0013
0.0112
Predicted using the model based on Scheme 4 and equations 2-5. Variables adjusted to fit this data are listed in Table S11.
C1: 0.6 M excess NaOH HPLC Peak Areas
a
Predicted Concentrationsa
Concentrations (M)
Time (min)
5
2
6
5
2
2
6
4
11.7
107944
751559
0
0.0060
0.0580
0.0000
6
0.0056 0.0063
4
5
0.0573
0.0000
0.0059
21.7
185248
708038
3085
0.0099
0.0528
0.0001
0.0066 0.0112
0.0516
0.0001
0.0066
41.6
330009
541343
8315
0.0181
0.0413
0.0002
0.0097 0.0193
0.0420
0.0002
0.0077
61.5
455839
471299
20427
0.0245
0.0353
0.0005
0.0089 0.0259
0.0342
0.0004
0.0086
81.4
534524
349895
38151
0.0297
0.0271
0.0009
0.0109 0.0312
0.0277
0.0006
0.0094
121.2
722590
263272
47667
0.0386
0.0196
0.0011
0.0091 0.0390
0.0180
0.0010
0.0105
161
809224
140450
68349
0.0430
0.0104
0.0016
0.0129 0.0440
0.0116
0.0013
0.0112
200.9
916183
120272
73796
0.0482
0.0088
0.0017
0.0091 0.0472
0.0076
0.0015
0.0117
240.7
949597
53711
82156
0.0498
0.0039
0.0019
0.0121 0.0493
0.0049
0.0017
0.0120
Predicted using the model based on Scheme 4 and equations 2-5. Variables adjusted to fit this data are listed in Table S11.
29
D1: 0.8 M excess NaOH HPLC Peak Areas
a
Predicted Concentrationsa
Concentrations (M)
Time (min)
5
2
6
5
2
2
6
4
11.8
133402
748745
0
0.0072
0.0564
0.0000
6
0.0059 0.0084
4
5
0.0549
0.0000
0.0062
21.8
233991
612063
6085
0.0127
0.0464
0.0001
0.0102 0.0144
0.0479
0.0001
0.0070
41.6
405342
491207
12688
0.0222
0.0375
0.0003
0.0092 0.0240
0.0365
0.0004
0.0083
61.5
540775
349644
33313
0.0295
0.0265
0.0008
0.0120 0.0312
0.0277
0.0006
0.0094
81.4
671943
292594
42075
0.0360
0.0218
0.0010
0.0097 0.0367
0.0210
0.0009
0.0101
121.3
812841
139967
66939
0.0431
0.0103
0.0015
0.0130 0.0438
0.0119
0.0013
0.0112
161.1
922912
98818
80297
0.0494
0.0074
0.0019
0.0090 0.0477
0.0069
0.0016
0.0118
201
962463
38296
83479
0.0516
0.0029
0.0019
0.0112 0.0500
0.0040
0.0017
0.0121
240.7
1032970
31840
91111
0.0544
0.0023
0.0021
0.0087 0.0511
0.0025
0.0018
0.0123
Predicted using the model based on Scheme 4 and equations 2-5. Variables adjusted to fit this data are listed in Table S11.
E1: 1.0 M excess NaOH HPLC Peak Areas
a
Predicted Concentrationsa
Concentrations (M)
Time (min)
5
2
6
5
2
2
6
4
11.8
163613
716042
2078
0.0087
0.0533
0.0000
6
0.0074 0.0102
4
5
0.0528
0.0001
0.0064
21.7
284481
607736
10190
0.0154
0.0460
0.0002
0.0077 0.0173
0.0444
0.0002
0.0074
41.6
476065
398390
17306
0.0260
0.0303
0.0004
0.0124 0.0282
0.0314
0.0005
0.0089
61.5
643089
305276
38039
0.0345
0.0228
0.0009
0.0105 0.0357
0.0222
0.0008
0.0100
81.4
734463
193443
50596
0.0395
0.0145
0.0012
0.0132 0.0409
0.0156
0.0011
0.0108
121.3
919297
107979
67351
0.0482
0.0079
0.0015
0.0104 0.0471
0.0077
0.0015
0.0117
161.1
980265
36302
78894
0.0515
0.0027
0.0018
0.0118 0.0500
0.0040
0.0017
0.0121
201
1029700
30612
73271
0.0547
0.0023
0.0017
0.0092 0.0514
0.0022
0.0018
0.0123
240.7
1078340
2283
93555
0.0555
0.0002
0.0021
0.0097 0.0520
0.0014
0.0019
0.0124
Predicted using the model based on Scheme 4 and equations 2-5. Variables adjusted to fit this data are listed in Table S11.
Table S11. Parameters Fit to Variables in equations 2-5 for Predicted Concentrations in Table S10. [2]init =
0.0645
[NaOH]aq / [NaOH]cotton =
2.95
k1 =
0.0198
k2 =
0.0271
k 3' =
0.00796
30
Figure S17. Plots of Concentrations vs. Time and Predicted Concentrations vs. Time for Reactions of 2 with Cotton at Varying [NaOH]xs at 30 °C. A1: 0.2 M excess NaOH B1: 0.4 M excess NaOH 0.07
0.06
epoxide
0.05
diol dimer
0.04
on cotton
0.03
Pred Ep
0.02
PredDiol PredDimer
0.01
Concentration (M)
Concentration (M)
0.07
PredCot'
0.06
epoxide
0.05
diol dimer
0.04
on cotton
0.03
Pred Ep
0.02
PredDiol
0.01
PredDimer
0
PredCot'
0 0
100
200
300
0
100
Time (min)
300
Time (min)
C1: 0.6 M excess NaOH
D1: 0.8 M excess NaOH
0.07
0.06 epoxide
0.05
diol dimer
0.04
on cotton
0.03
Pred Ep
0.02
PredDiol
0.01
PredDimer
0
100
200
diol
0.04
dimer
0.03
on cotton Pred Ep
0.02
PredDiol
0.01
PredCot'
0
epoxide
0.05
Concentration (M)
0.06
PredDimer PredCot'
0
300
0
100
Time (min)
200
300
Time (min)
E1: 1.0 M excess NaOH 0.06 0.05
Concentration (M)
Concentration (M)
200
epoxide diol
0.04
dimer
0.03
on cotton Pred Ep
0.02
PredDiol
0.01
PredDimer PredCot'
0 0
100
200
300
Time (min)
31
Cationization of Cotton with (2,3-Epoxypropyl)trimethylammonium Chloride (2) at 50 °C. Table S12. HPLC Peak Areas for Aliquots from Reaction of 2 with Cotton at Varying [NaOH]xs at 50 °C and Corresponding Analyte Concentrations. A1: 0.05 M excess NaOH HPLC Peak Areas
a
Predicted Concentrationsa
Concentrations (M)
Time (min)
5
2
6
5
2
6
9.7
30482
875978
0
0.0017
0.0662
0.0000
19.7
64926
820547
0
0.0036
0.0636
39.6
127144
785927
0
0.0070
59.5
182132
728856
0
0.0103
4
5
2
6
4
0.0016 0.0018
0.0653
0.0000
0.0023
0.0000
0.0022 0.0037
0.0632
0.0000
0.0025
0.0602
0.0000
0.0022 0.0072
0.0593
0.0000
0.0029
0.0575
0.0000
0.0016 0.0105
0.0555
0.0001
0.0033
79.3
237983
699830
8708
0.0129
0.0529
0.0002
0.0032 0.0135
0.0519
0.0001
0.0036
119.2
329030
605602
10482
0.0181
0.0465
0.0002
0.0043 0.0190
0.0455
0.0003
0.0043
159
434421
561449
21448
0.0231
0.0415
0.0005
0.0038 0.0239
0.0397
0.0004
0.0049
241.9
568390
429292
42591
0.0305
0.0321
0.0010
0.0049 0.0322
0.0297
0.0008
0.0059
281.8
637088
397754
48700
0.0327
0.0284
0.0011
0.0061 0.0355
0.0256
0.0010
0.0063
Predicted using the model based on Scheme 4 and equations 2-5. Variables adjusted to fit this data are listed in Table S13.
B1: 0.10 M excess NaOH HPLC Peak Areas
a
Predicted Concentrationsa
Concentrations (M)
Time (min)
5
2
6
5
2
9.8
65081
827625
0
0.0036
0.0642
2
6
4
0.0000
19.8
120811
779296
0
0.0066
39.7
234886
705106
5939
0.0126
59.6
341960
622238
11097
0.0181
6
0.0016 0.0037
4
5
0.0632
0.0000
0.0025
0.0598
0.0000
0.0030 0.0072
0.0593
0.0000
0.0029
0.0528
0.0001
0.0037 0.0135
0.0520
0.0001
0.0036
0.0459
0.0003
0.0048 0.0189
0.0456
0.0003
0.0043
79.4
431754
544008
19697
0.0227
0.0399
0.0004
0.0059 0.0236
0.0401
0.0004
0.0048
119.3
588660
428936
37453
0.0308
0.0312
0.0008
0.0057 0.0314
0.0307
0.0008
0.0058
159.1
711192
336744
62876
0.0369
0.0243
0.0014
0.0053 0.0373
0.0233
0.0011
0.0065
242
866494
200713
81232
0.0442
0.0143
0.0018
0.0073 0.0459
0.0125
0.0017
0.0076
281.9
933019
154803
87759
0.0469
0.0108
0.0019
0.0078 0.0485
0.0091
0.0019
0.0079
Predicted using the model based on Scheme 4 and equations 2-5. Variables adjusted to fit this data are listed in Table S13.
C1: 0.15 M excess NaOH HPLC Peak Areas
a
Predicted Concentrationsa
Concentrations (M)
Time (min)
5
2
6
5
2
2
6
4
9.9
89504
788272
0
0.0049
0.0605
0.0000
6
0.0040 0.0054
4
5
0.0613
0.0000
0.0027
19.9
176020
739300
6614
0.0095
0.0554
0.0002
0.0043 0.0103
0.0557
0.0001
0.0032
39.8
347784
622629
11924
0.0185
0.0463
0.0003
0.0040 0.0188
0.0458
0.0003
0.0042
59.7
483563
511815
22752
0.0251
0.0371
0.0005
0.0061 0.0256
0.0377
0.0005
0.0051
79.5
592949
412277
39508
0.0308
0.0299
0.0009
0.0069 0.0310
0.0311
0.0008
0.0057
119.4
759030
276240
59955
0.0392
0.0199
0.0013
0.0077 0.0390
0.0211
0.0012
0.0067
159.2
880970
189023
76344
0.0449
0.0134
0.0017
0.0077 0.0443
0.0144
0.0016
0.0074
242
1036680
85187
106355
0.0513
0.0059
0.0023
0.0076 0.0507
0.0063
0.0022
0.0082
282
1074720
54449
107836
0.0526
0.0037
0.0023
0.0085 0.0522
0.0043
0.0023
0.0084
Predicted using the model based on Scheme 4 and equations 2-5. Variables adjusted to fit this data are listed in Table S13.
32
D1: 0.20 M excess NaOH HPLC Peak Areas Time (min)
a
5
2
6
5
2
6
4
5
2
6
4
9.9
118559
770158
0
0.0065
0.0591
0.0000
0.0037 0.0071
0.0593
0.0000
0.0029
19.9
233159
691010
7223
0.0124
0.0511
0.0002
0.0056 0.0133
0.0522
0.0001
0.0036
39.8
439116
543390
19030
0.0232
0.0400
0.0004
0.0054 0.0233
0.0404
0.0004
0.0048
59.7
597959
410309
33614
0.0314
0.0300
0.0008
0.0065 0.0309
0.0312
0.0008
0.0057
79.5
709146
311136
57878
0.0373
0.0228
0.0013
0.0067 0.0366
0.0242
0.0011
0.0064
119.4
878491
177471
84183
0.0456
0.0128
0.0019
0.0072 0.0442
0.0146
0.0016
0.0074
202.2
1043030
57058
110197
0.0529
0.0040
0.0024
0.0076 0.0515
0.0051
0.0023
0.0083
242.1
1116810
33252
115157
0.0547
0.0023
0.0024
0.0076 0.0528
0.0034
0.0024
0.0084
282
1116790
18094
108981
0.0554
0.0013
0.0023
0.0080 0.0535
0.0024
0.0025
0.0085
Predicted using the model based on Scheme 4 and equations 2-5. Variables adjusted to fit this data are listed in Table S13.
E1: 0.233 M excess NaOH
b
HPLC Peak Areas
a
Predicted Concentrationsa
Concentrations (M)
Predicted Concentrationsa
Concentrations (M)
Time (min)
5
2
6
5
2
2
6
4
9.9
130948
756454
0
0.0072
0.0579
0.0000
6
0.0043 0.0082
4
5
0.0581
0.0000
0.0030
19.9
257495
666133
10094
0.0136
0.0492
0.0002
0.0061 0.0152
0.0500
0.0002
0.0038
39.8
484462
505174
24314
0.0254
0.0369
0.0006
0.0060 0.0262
0.0370
0.0005
0.0051
59.7
655158
374514
43124
0.0334
0.0266
0.0010
0.0074 0.0343
0.0272
0.0009
0.0061
79.5
763013
269242
58059
0.0396
0.0195
0.0013
0.0077 0.0400
0.0200
0.0013
0.0068
119.4
929786
141948
85065
0.0477
0.0101
0.0019
0.0078 0.0473
0.0107
0.0018
0.0077
202.1
1052180
37715
105263
0.0541
0.0027
0.0023
0.0079 0.0538
0.0023
0.0024
0.0086
242.1
1116210
20011
120452
0.0546
0.0014
0.0025
0.0084 0.0548
0.0010
0.0025
0.0087
282
1142570
10611
122620
0.0562
0.0007
0.0026
0.0072 0.0553
0.0003
0.0025
0.0088
Predicted using the model based on Scheme 4 and equations 2-5. Variables adjusted to fit this data are listed in Table S13.
b Ran out of NaOH stock solution during reactions. Automated liquid handler delivered less than intended amount. [NaOH]total was also varied and fit to the data in this reaction to arrive at the estimate of 0.233 M.
Table S13. Parameters Fit to Variables in equations 2-5 for Predicted Concentrations in Table S12. [2]init =
0.0674
[NaOH]aq / [NaOH]cotton =
3.00
k1 =
0.0761
k2 =
0.122
k 3' =
0.0265
33
Figure S18. Plots of Concentrations vs. Time and Predicted Concentrations vs. Time for Reactions of 2 with Cotton at Varying [NaOH]xs at 50 °C. A1: 0.05 M excess NaOH B1: 0.10 M excess NaOH
0.07 0.07 epoxide
0.05
diol dimer
0.04
on cotton
0.03
Pred Ep
0.02
PredDiol PredDimer
0.01
Concentration (M)
Concentration (M)
0.06
PredCot'
0.06
epoxide
0.05
diol dimer
0.04
on cotton
0.03
Pred Ep
0.02
PredDiol
0.01
PredDimer
0
PredCot'
0 0
100
200
300
0
100
Time (min)
200
300
Time (min)
C1: 0.15 M excess NaOH 0.07 0.06
D1: 0.20 M excess NaOH 0.07
Dimer (6) Cotton+ (4)
0.03
Pred 2 Pred 5
0.02
Pred 6 0.01
Pred 4
Concentration (M)
Diol (5)
0.04
0.06
epoxide
0.05
diol
0.04
dimer on cotton
0.03
Pred Ep
0.02
PredDiol
0.01
PredDimer
0
PredCot'
0 0
100
200
300
0
100
Time (min)
200
300
Time (min)
E1: 0.233 M excess NaOH 0.07 0.06
Concentration (M)
Concentration (M)
Epoxide (2) 0.05
epoxide
0.05
diol
0.04
dimer on cotton
0.03
Pred Ep
0.02
PredDiol
0.01
PredDimer PredCot'
0 0
100
200
300
Time (min)
34
Cationization of Cotton with (2,3-Epoxypropyl)trimethylammonium Chloride (2) at 70 °C. Table S14. HPLC Peak Areas for Aliquots from Reaction of 2 with Cotton at Varying [NaOH]xs at 70 °C and Corresponding Analyte Concentrations. A1: 0.01 M excess NaOH HPLC Peak Areas
a
Predicted Concentrationsa
Concentrations (M)
Time (min)
5
2
6
5
2
6
9.4
26492
913599
0
0.0014
0.0692
0.0000
19.5
43391
890393
0
0.0024
0.0699
39.4
82761
865030
0
0.0047
59.4
122332
867680
0
0.0069
4
5
2
6
4
-0.0004 0.0010
0.0692
0.0000
0.0001
0.0000
-0.0013 0.0020
0.0687
0.0000
0.0003
0.0686
0.0000
-0.0008 0.0041
0.0679
0.0000
0.0006
0.0678
0.0000
-0.0004 0.0062
0.0671
0.0000
0.0008 0.0011
79.3
162190
848743
0
0.0091
0.0667
0.0000
0.0000 0.0083
0.0663
0.0001
119.4
240138
833650
0
0.0137
0.0661
0.0000
-0.0002 0.0127
0.0648
0.0001
0.0017
159.4
311559
799341
1853
0.0178
0.0638
0.0000
0.0018 0.0173
0.0634
0.0002
0.0023
199.4
384940
769924
3545
0.0225
0.0627
0.0001
0.0026 0.0219
0.0623
0.0003
0.0030
239.4
453650
738014
7761
0.0269
0.0611
0.0002
0.0043 0.0269
0.0613
0.0005
0.0037
Predicted using the model based on Scheme 4 and equations 2-5. Variables adjusted to fit this data are listed in Table S15.
B1: 0.02 M excess NaOH HPLC Peak Areas
a
Predicted Concentrationsa
Concentrations (M)
Time (min)
5
2
6
5
2
2
6
4
9.6
54841
897919
0
0.0030
0.0677
0.0000
6
-0.0004 0.0021
4
5
0.0678
0.0000
0.0003
19.6
100209
863740
0
0.0056
0.0675
0.0000
-0.0021 0.0044
0.0660
0.0000
0.0006
39.5
174991
813970
0
0.0097
0.0626
0.0000
0.0003 0.0087
0.0626
0.0001
0.0012
59.5
247950
760826
4221
0.0139
0.0593
0.0001
0.0009 0.0128
0.0593
0.0001
0.0017
79.6
322426
721275
10606
0.0180
0.0560
0.0003
0.0014 0.0169
0.0563
0.0002
0.0023
119.6
457065
639747
12608
0.0262
0.0511
0.0003
0.0016 0.0247
0.0505
0.0004
0.0034
159.6
582924
567477
22149
0.0337
0.0458
0.0006
0.0028 0.0323
0.0453
0.0007
0.0044
199.6
689982
506230
29705
0.0400
0.0409
0.0007
0.0056 0.0396
0.0407
0.0011
0.0055
239.6
803240
464680
39381
0.0477
0.0384
0.0010
0.0047 0.0469
0.0365
0.0014
0.0065
Predicted using the model based on Scheme 4 and equations 2-5. Variables adjusted to fit this data are listed in Table S15.
C1: 0.04 M excess NaOH HPLC Peak Areas
a
Predicted Concentrationsa
Concentrations (M)
Time (min)
5
2
6
5
2
2
6
4
9.7
96420
838077
0
0.0052
0.0627
0.0000
6
0.0024 0.0051
4
5
0.0644
0.0000
0.0007
19.8
182929
769851
2246
0.0101
0.0593
0.0001
0.0016 0.0101
0.0595
0.0001
0.0014
39.6
338250
664892
10670
0.0186
0.0508
0.0003
0.0027 0.0190
0.0506
0.0002
0.0026
59.6
475095
565237
24469
0.0257
0.0426
0.0006
0.0047 0.0267
0.0429
0.0005
0.0037
79.6
593014
475566
33329
0.0321
0.0358
0.0008
0.0064 0.0335
0.0364
0.0007
0.0046
119.7
804917
353544
59745
0.0441
0.0270
0.0014
0.0056 0.0450
0.0257
0.0013
0.0062
139.7
930058
243491
68720
0.0510
0.0186
0.0016
0.0086 0.0496
0.0218
0.0016
0.0069
199.8
1076150
174733
97574
0.0600
0.0136
0.0024
0.0097 0.0612
0.0136
0.0023
0.0085
239.8
1172800
116563
107000
0.0672
0.0093
0.0026
0.0110 0.0681
0.0096
0.0028
0.0095
Predicted using the model based on Scheme 4 and equations 2-5. Variables adjusted to fit this data are listed in Table S15.
35
D1: 0.06 M excess NaOH HPLC Peak Areas
a
Predicted Concentrationsa
Concentrations (M)
Time (min)
5
2
6
5
2
9.8
135863
811191
4701
0.0072
0.0600
6
2
6
4
0.0616
0.0000
0.0010
19.9
258273
709744
7705
0.0139
0.0534
0.0002
0.0034 0.0145
39.8
464906
561776
23754
0.0255
0.0430
0.0006
0.0030 0.0261
0.0544
0.0001
0.0020
0.0420
0.0005
0.0036
59.7
628807
440368
36052
0.0335
0.0327
0.0008
0.0063 0.0355
79.7
756221
336731
52756
0.0407
0.0252
0.0012
0.0075 0.0430
0.0322
0.0008
0.0049
0.0245
0.0012
119.9
936631
204174
85704
0.0517
0.0157
0.0020
0.0059
0.0080 0.0547
0.0134
0.0019
159.9
1076100
123464
104143
0.0601
0.0096
0.0076
0.0025
0.0088 0.0633
0.0064
0.0025
199.9
1176700
74448
116879
0.0665
0.0088
0.0059
0.0029
0.0098 0.0702
0.0020
0.0029
0.0098
239.9
1279500
46229
125312
0.0741
0.0037
0.0031
0.0087 0.0763
-0.0008
0.0033
0.0107
0.0001
4
5
0.0029 0.0076
Predicted using the model based on Scheme 4 and equations 2-5. Variables adjusted to fit this data are listed in Table S15.
E1: 0.08 M excess NaOH HPLC Peak Areas
a
Predicted Concentrationsa
Concentrations (M)
Time (min)
5
2
6
5
2
2
6
4
10
176989
769018
0
0.0097
0.0589
0.0000
6
0.0017 0.0102
4
5
0.0586
0.0001
0.0014
20
341642
632346
11274
0.0188
0.0485
0.0003
0.0032 0.0188
0.0492
0.0002
0.0026
40
611369
438647
30965
0.0331
0.0331
0.0007
0.0049 0.0320
0.0348
0.0007
0.0044
60
797910
301178
56144
0.0434
0.0229
0.0013
0.0053 0.0413
0.0248
0.0012
0.0057
80
925963
199208
84896
0.0510
0.0153
0.0020
0.0056 0.0480
0.0180
0.0016
0.0067
120
1088560
92891
103977
0.0609
0.0072
0.0025
0.0064 0.0573
0.0097
0.0023
0.0080
160
1168840
39787
118265
0.0654
0.0031
0.0029
0.0093 0.0633
0.0060
0.0027
0.0089
200
1258920
21739
122649
0.0708
0.0017
0.0030
0.0095 0.0681
0.0044
0.0030
0.0095
240
1292140
8326
126954
0.0750
0.0007
0.0032
0.0108 0.0726
0.0036
0.0032
0.0102
Predicted using the model based on Scheme 4 and equations 2-5. Variables adjusted to fit this data are listed in Table S15.
Table S15. Parameters Fit to Variables in equations 2-5 for Predicted Concentrations in Table S14. [2]init =
0.0696
[NaOH]aq / [NaOH]cotton =
3.22
k1 =
0.260
k2 =
0.353
k 3' =
0.113
36
Figure S19. Plots of Concentrations vs. Time and Predicted Concentrations vs. Time for Reactions of 2 with Cotton at Varying [NaOH]xs at 70 °C. 0.01 M excess NaOH 0.02 M excess NaOH
0.08 0.08
0.07 diol
0.05
dimer
0.04
on cotton
0.03
Pred Ep
0.02
PredDiol
0.01
PredDimer
-0.01
0
100
200
diol
0.05
dimer
0.04
on cotton
0.03
Pred Ep
0.02
PredDiol
0.01
PredCot'
0
epoxide
0.06
Concentration (M)
Concentration (M)
0.07
epoxide
0.06
PredDimer
0
300
-0.01
PredCot'
0
100
Time (min)
300
Time (min)
D1: 0.06 M excess NaOH
C1: 0.04 M excess NaOH 0.09
0.08 0.07
0.08
diol
0.05
dimer
0.04
on cotton
0.03
Pred Ep
0.02
PredDiol PredDimer
0.01
Concentration (M)
epoxide
0.06
PredCot'
0 0
100
200
0.07
epoxide
0.06
diol
0.05
dimer
0.04
on cotton
0.03
Pred Ep
0.02
PredDiol
0.01
PredDimer PredCot'
0
300
-0.01 0
Time (min)
50
100
150 200 Time (min)
250
300
E1: 0.08 M excess NaOH 0.08 0.07
Concentration (M)
Concentration (M)
200
epoxide
0.06
diol
0.05
dimer
0.04
on cotton
0.03
Pred Ep
0.02
PredDiol PredDimer
0.01
PredCot'
0 0
100
200
300
Time (min)
37
Cationization of Cotton with (2,3-Epoxypropyl)trimethylammonium Chloride (2) at 50 °C in 1:1 Tetraglyme-Water. Table S16. HPLC Peak Areas for Aliquots from Hydrolysis of 2 with 0.2 M NaOH in 1:1 Tetraglyme-Water in the Absence of Cotton at 50 °C and Corresponding Analyte Concentrations. 0.2 M excess NaOH, 1:1 Tetraglyme-Water, No Cotton HPLC Peak Areas
a
Predicted Concentrationsa
Concentrations (M)
Time (min)
5
2
6
5
2
6
4
2
6
4
10
196508
311535
0
0.0200
0.0443
0.0026
0.0000 0.0192
5
0.0462
0.0008
0.0000
19.9
320230
209721
0
0.0325
0.0297
0.0037
0.0000 0.0310
0.0317
0.0021
0.0000
39.6
461222
93904
0
0.0464
0.0132
0.0050
0.0000 0.0438
0.0142
0.0044
0.0000
59.4
508571
40819
0
0.0507
0.0057
0.0066
0.0000 0.0492
0.0063
0.0057
0.0000
129.8
561940
0
0
0.0544
0.0000
0.0076
0.0000 0.0549
-0.0024
0.0072
0.0000
288.7
579598
0
0
0.0527
0.0000
0.0084
0.0000 0.0549
-0.0024
0.0072
0.0000
Predicted using the model based on Scheme 4 and equations 2-5. Variables adjusted to fit this data are listed in Table S17.
Table S17. Parameters Fit to Variables in equations 2-5 for Predicted Concentrations in Table S16. [2]init =
0.066884
k 1= k 2=
0.179472 0.69623
Table S18. HPLC Peak Areas for Aliquots from Reaction of 2 with 0.2 M NaOH in 1:1 Tetraglyme-Water in the Presence of Cotton at 50 °C and Corresponding Analyte Concentrations. 0.2 M excess NaOH, 1:1 Tetraglyme-Water, With Cotton HPLC Peak Areas
a
Predicted Concentrationsa
Concentrations (M)
Time (min)
5
2
6
5
2
6
4
2
6
4
10
144524
305981
0
0.0154
0.0453
0.0000
0.0000 0.0116
5
0.0465
0.0004
0.0108
19.8
212242
241108
0
0.0225
0.0357
0.0000
0.0000 0.0198
0.0350
0.0010
0.0128
39.6
307434
133072
0
0.0315
0.0190
0.0000
0.0000 0.0306
0.0189
0.0023
0.0156
59.3
357710
69606
0
0.0357
0.0097
0.0000
0.0000 0.0361
0.0103
0.0031
0.0170
129.8
417300
0
0
0.0401
0.0000
0.0000
0.0000 0.0425
-0.0002
0.0042
0.0188
288.7
432821
0
0
0.0424
0.0000
0.0000
0.0000 0.0425
-0.0002
0.0042
0.0188
Predicted using the model based on Scheme 4 and equations 2-5. Variables adjusted to fit this data are listed in Table S19.
Table S19. Parameters Fit to Variables in equations 2-5 for Predicted Concentrations in Table S18. [2]init = [NaOH]aq / [NaOH]cotton =
0.061535 1.64176
k1 (from Table S17) = k2 (from Table S17) = k3 =
0.179472 0.69623 0.067914
38
