Synthesis and Evaluation of a Photochromic Surfactant for rganic Reactions in Aqueous Media icolas Drillaud, Estelle Banaszak-Léonard, Isabelle Pezron and Christophe Len* Université de Technologie de Compiègne, Transformation Intégrée de la Matière Renouvelable, EA 4297 UTC/ESCM, Centre de recherche de Royallieu, BP 20529, F-60205 Compiègne Cedex, France. Fax: (+33)(0)3 44 97 15 91. E-mail: christophe.len@utc.fr Table of contents 1 MR of 1-(4-butylphenyl)-2-(4-iodophenyl)diazene (2)... 3 13 C MR of 1-(4-butylphenyl)-2-(4-iodophenyl)diazene (2)... 4 1 MR of 1-(4-butylphenyl)-2-(4-(2-(trimethylsilyl)ethynyl)- phenyl)diazene (3)... 5 13 C RM of 1-(4-butylphenyl)-2-(4-(2-(trimethylsilyl)ethynyl)- phenyl)diazene (3)... 6 1 MR of 1-(4-butylphenyl)-2-(4-ethynylphenyl)diazene (4)... 7 13 C MR of 1-(4-butylphenyl)-2-(4-ethynylphenyl)diazene (4)... 8 1 MR of 2,3,4,6-Tetra--acetyl-β-D-glucopyranosyl azide (5)... 9 13 C MR of 2,3,4,6-Tetra--acetyl-β-D-glucopyranosyl azide (5)... 10 1 MR of (1-((2,3,4,6-Tetra--acetyl)-1-β-D-glucopyranosyl)-(1,2,3-triazol-4-yl))-4'-butylazobenzene (6)... 11 13 C MR of (1-((2,3,4,6-Tetra--acetyl)-1-β-D-glucopyranosyl)-(1,2,3-triazol-4-yl))-4'-butylazobenzene (6).. 12 DEPT 135 MR of (1-((2,3,4,6-Tetra--acetyl)-1-β-D-glucopyranosyl)-(1,2,3-triazol-4-yl))-4'-butylazobenzene (6)... 13 CSY - MR of (1-((2,3,4,6-Tetra--acetyl)-1-β-D-glucopyranosyl)-(1,2,3-triazol-4-yl))-4'- butylazobenzene (6)... 14 MBC MR of (1-((2,3,4,6-Tetra--acetyl)-1-β-D-glucopyranosyl)-(1,2,3-triazol-4-yl))-4'-butylazobenzene (6)... 15 1 MR of (1-(1-β-D-glucopyranosyl)-(1,2,3-triazol-4-yl))-4'-butylazobenzene (7)... 16 13 C MR of (1-(1-β-D-glucopyranosyl)-(1,2,3-triazol-4-yl))-4'-butylazobenzene (7)... 17 1 MR of 4-butylazobenzyl-4 -triazologlucuronic acid sodium salt (1)... 18 13 C MR of 4-butylazobenzyl-4 -triazologlucuronic acid sodium salt (1)... 19 1 MR of -p-tolylacetamide (9)... 20 13 C MR of -p-tolylacetamide (9)... 21 1 MR of -(2-hydroxyphenyl)acetamide (10)... 22 13 C MR of -(2-hydroxyphenyl)acetamide (10)... 23 1 MR of -(3-hydroxyphenyl)acetamide (11)... 24 13 C MR of -(3-hydroxyphenyl)acetamide (11)... 25 1 MR of -(4-hydroxyphenyl)acetamide (12)... 26 13 C MR of -(4-hydroxyphenyl)acetamide (12)... 27 1 MR of -(4-(hydroxymethyl)phenyl)acetamide (13)... 28 13 C MR of -(4-(hydroxymethyl)phenyl)acetamide (13)... 29 1 MR of -(3-nitrophenyl)acetamide (15)... 30 13 C MR of -(3-nitrophenyl)acetamide (15)... 31 1 MR of -(4-bromophenyl)acetamide (16)... 32 13 C MR of -(4-bromophenyl)acetamide (16)... 33 1 MR of 4-acetamidobenzoic acid (17)... 34 13 C MR of 4-acetamidobenzoic acid (17)... 35 1
1 MR of -(naphthalen-2-yl)acetamide (18)... 36 13 C MR of -(naphthalen-2-yl)acetamide (18)... 37 1 MR of -methyl--phenylacetamide (19)... 38 13 C MR of -methyl--phenylacetamide (19)... 39 1 MR of -(4-(acetylamino)phenyl)acetamide (20)... 40 13 C MR of -(4-(acetylamino)phenyl)acetamide (20)... 41 1 MR of -propylacetamide (21)... 42 13 C MR of -propylacetamide (21)... 43 1 MR of 1-acetylpiperidine (22)... 44 13 C MR of 1-acetylpiperidine (22)... 45 1 MR of -p-tolylbenzamide (23)... 46 13 C MR of -p-tolylbenzamide (23)... 47 1 MR of -p-tolylhexanamide (24)... 48 13 C MR of -p-tolylhexanamide (24)... 49 2
0.0 3 1.556 1.432 1.414 1.395 1.376 1.358 1.340 I 0.967 0.949 0.936 0.930 1.00 2.711 2.691 2.672 1.687 1.672 1.669 1.664 1.654 1.650 1.643 1.634 1.631 1.611 0.67 0.72 0.64 1 MR of 1-(4-butylphenyl)-2-(4-iodophenyl)diazene (2) 7.260 7.647 7.642 7.626 7.331 7.310 7.863 7.858 7.848 7.841 7.831 7.827 0.64 5.0 0.64 1.28
13 C MR of 1-(4-butylphenyl)-2-(4-iodophenyl)diazene (2) 150 100 50 4 0 152.025 150.713 146.993 138.265 129.150 124.345 122.960 97.170 77.317 77.000 76.683 35.612 33.391 22.330 13.936 I
0.0 2.0 1.0 5 1.434 1.416 1.397 1.378 1.360 1.342 0.970 0.951 0.933 0.284 2.713 2.694 2.674 1.689 1.671 1.651 1.632 1.613 8.34 3.00 2.05 2.03 1.98 1 MR of 1-(4-butylphenyl)-2-(4-(2-(trimethylsilyl)ethynyl)- phenyl)diazene (3) 7.260 7.332 7.312 7.613 7.591 7.860 7.855 7.839 7.834 TMS 8.0 7.0 6.0 5.0 4.0 3.0 1.98 1.87 3.94
13 C RM of 1-(4-butylphenyl)-2-(4-(2-(trimethylsilyl)ethynyl)- phenyl)diazene (3) 150 100 50 6 0 151.999 150.886 146.891 132.751 129.126 125.362 122.945 122.626 104.700 96.774 77.318 77.000 76.682 35.606 33.399 22.335 13.938-0.082 TMS
0.0 7 1.695 1.677 1.657 1.638 1.619 1.441 1.422 1.403 1.384 1.366 1.348 0.976 0.958 0.939 2.719 2.700 2.680 3.00 1.92 2.54 1.72 3.226 0.77 1 MR of 1-(4-butylphenyl)-2-(4-ethynylphenyl)diazene (4) 7.260 7.884 7.868 7.862 7.847 7.646 7.624 7.341 7.320 1.71 1.66 5.0 3.38
13 C MR of 1-(4-butylphenyl)-2-(4-ethynylphenyl)diazene (4) 150 100 50 8 0 152.275 150.838 146.980 132.915 129.125 124.266 122.983 122.670 83.336 79.239 77.318 77.000 76.683 35.601 33.389 30.148 26.877 22.328 13.930
1.0 3.0 2.0 9 0.0 3.811 3.805 3.799 3.793 3.786 3.780 3.774 3.768 2.096 1 MR of 2,3,4,6-Tetra--acetyl-β-D-glucopyranosyl azide (5) 4.180 4.174 4.289 4.277 4.258 4.246 4.149 4.143 2.071 2.024 2.002 1.249 1.231 1.214 1.627 3.00 3.07 3.00 2.94 4.653 4.631 4.950 4.926 4.972 5.097 5.074 5.122 5.188 5.235 5.212 7.260 Ac 3 Ac Ac Ac 1.04 1.04 1.06 1.00 7.0 6.0 5.0 4.0 1.00 1.06 1.07
13 C MR of 2,3,4,6-Tetra--acetyl-β-D-glucopyranosyl azide (5) 150 100 10 50 0 170.575 170.086 169.270 169.172 87.874 73.978 72.553 70.583 67.823 61.611 20.680 20.546 20.522 Ac Ac Ac Ac 3
1 MR of (1-((2,3,4,6-Tetra--acetyl)-1-β-D-glucopyranosyl)-(1,2,3-triazol-4-yl))-4'-butylazobenzene (6) 1.398 1.393 1.379 1.360 0.928 0.910 1.657 1.652 1.637 1.631 1.618 1.976 1.804 2.118 2.023 2.706 2.687 2.667 3.972 3.967 3.958 3.953 3.947 3.942 3.933 3.928 4.217 4.212 4.186 4.180 4.308 4.294 4.276 4.262 5.187 5.163 5.212 5.331 5.308 5.284 5.269 5.926 5.903 5.879 5.706 5.683 7.874 7.853 7.774 7.681 7.660 7.340 7.319 8.019 7.997 Ac Ac Ac Ac 3.00 2.55 2.16 2.89 3.13 3.28 2.86 1.94 0.97 1.04 0.98 0.99 1.17 0.95 0.98 1.98 2.05 0.96 1.98 1.98 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0 11
13 C MR of (1-((2,3,4,6-Tetra--acetyl)-1-β-D-glucopyranosyl)-(1,2,3-triazol-4-yl))-4'-butylazobenzene (6) 170.277 170.061 169.051 168.143 153.187 150.668 147.340 138.680 133.669 129.864 129.121 127.749 123.162 123.028 83.781 77.318 77.000 76.682 74.706 73.194 69.330 67.512 61.780 35.514 33.270 22.215 20.637 20.411 20.110 13.825 Ac Ac Ac Ac 150 100 50 12
DEPT 135 MR of (1-((2,3,4,6-Tetra--acetyl)-1-β-D-glucopyranosyl)-(1,2,3-triazol-4-yl))-4'-butylazobenzene (6) 150 100 50 13 0 133.808 130.002 129.261 123.303 123.167 83.911 74.839 73.330 69.461 67.644 61.917 35.652 33.410 22.353 20.778 20.552 20.252 13.966 Ac Ac Ac Ac
CSY - MR of (1-((2,3,4,6-Tetra--acetyl)-1-β-D-glucopyranosyl)-(1,2,3-triazol-4-yl))-4'-butylazobenzene (6) Ac Ac Ac Ac 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 ppm (t1 8.0 ppm (t2) 7.0 6.0 5.0 4.0 3.0 2.0 1.0 14
MBC MR of (1-((2,3,4,6-Tetra--acetyl)-1-β-D-glucopyranosyl)-(1,2,3-triazol-4-yl))-4'-butylazobenzene (6) 135.0 140.0 5.705.605.50 0 50 100 150 200 ppm (t1 8.0 ppm (t2) 7.0 6.0 5.0 4.0 3.0 2.0 1.0 15
16 1 MR of (1-(1-β-D-glucopyranosyl)-(1,2,3-triazol-4-yl))-4'-butylazobenzene (7) 0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 7.978 7.957 7.949 7.895 7.804 7.781 7.759 7.299 7.278 5.402 5.379 4.374 4.352 4.330 3.971 3.966 3.941 3.936 3.734 3.718 3.687 3.532 3.510 3.488 3.478 3.455 2.932 2.804 2.644 2.625 2.605 2.058 1.617 1.599 1.594 1.579 1.573 1.560 1.541 1.370 1.351 1.333 1.314 1.295 1.277 0.914 0.896 0.877 2.51 3.42 1.82 0.74 0.76 0.85 1.89 1.98 2.09 3.00 0.96 2.63
13 C MR of (1-(1-β-D-glucopyranosyl)-(1,2,3-triazol-4-yl))-4'-butylazobenzene (7) 150 100 17 50 0 154.283 151.881 148.454 140.854 133.290 131.128 130.093 128.974 124.190 123.932 87.228 80.998 78.472 72.570 70.947 62.449 49.686 49.476 49.263 49.050 48.837 48.624 48.411 48.198 36.304 34.392 23.151 14.104
1 MR of 4-butylazobenzyl-4 -triazologlucuronic acid sodium salt (1) 1.344 1.326 0.961 0.943 0.925 3.314 3.310 2.693 2.675 2.655 1.665 1.647 1.628 1.609 1.590 1.418 1.400 1.381 1.363 3.00 2.04 1.96 0.0 2.0 1.0 3.349 3.605 3.582 3.561 1.90 3.0 3.754 3.730 4.126 4.102 3.801 3.778 4.157 4.181 4.372 4.351 4.334 4.312 4.955 5.587 5.567 5.546 7.770 7.748 7.726 7.348 7.328 8.000 7.979 7.954 7.943 7.846 7.826 0.93 0.95 0.91 0.86 0.84 1.91 1.81 2.00 1.93 0.97 8.0 7.0 6.0 5.0 4.0 18
13 C MR of 4-butylazobenzyl-4 -triazologlucuronic acid sodium salt (1) 200 150 100 19 50 0 201.760 156.229 154.434 140.531 140.301 134.399 131.610 131.478 130.709 130.429 124.791 124.372 124.186 87.644 87.609 78.103 78.883 72.581 72.446 49.689 49.546 49.476 49.367 49.333 49.263 49.118 49.050 48.837 48.624 48.490 48.411 48.330 48.285 48.251 48.229 41.701 23.449 18.816 14.141
6.0 5.0 4.0 0.075 0.000000 20 3.0 1.0 0.0 1.941 2.295 2.124 3.00 3.24 2.0 1 MR of -p-tolylacetamide (9) 7.257 7.097 7.076 7.381 7.360 7.753 7.751 7.749 7.746 7.744 7.742 7.740 7.738 7.736 2.05 1.98 8.0 7.0 0.82
13 C MR of -p-tolylacetamide (9) 200 150 100 21 50 0 168.556 135.366 133.812 129.336 120.111 77.318 77.000 76.682 24.331 20.787
5.0 22 4.0 3.0 2.0 2.182 3.13 4.902 3.326 1 MR of -(2-hydroxyphenyl)acetamide (10) 6.836 6.833 6.816 6.797 6.795 6.878 6.860 6.857 7.604 7.601 7.584 7.581 7.009 6.992 6.989 2.10 1.01 8.0 7.0 6.0 1.00
13 C MR of -(2-hydroxyphenyl)acetamide (10) 200 150 100 23 50 0 172.247 149.766 127.129 126.837 123.999 120.640 117.299 49.682 49.469 49.256 49.043 48.830 48.617 48.404 23.473
2.107 3.04 2.0 1 MR of -(3-hydroxyphenyl)acetamide (11) 5.0 24 4.0 3.0 6.550 6.546 6.530 6.526 4.900 3.326 6.918 6.916 6.938 6.936 7.079 7.099 7.119 7.185 7.180 7.175 1.00 1.01 8.0 7.0 6.0 1.04 0.92
13 C MR of -(3-hydroxyphenyl)acetamide (11) 200 150 100 25 50 0 171.636 158.897 140.961 130.500 112.327 112.161 108.410 49.695 49.482 49.269 49.056 48.843 48.630 48.417 23.884
5.0 4.0 26 2.0 3.0 1.0 2.090 3.06 4.895 3.326 1 MR of -(4-hydroxyphenyl)acetamide (12) 6.753 6.731 7.303 7.325 2.00 8.0 7.0 6.0 1.99
13 C MR of -(4-hydroxyphenyl)acetamide (12) 200 150 100 27 50 0 171.388 155.397 131.705 123.404 116.217 49.691 49.478 49.265 49.053 48.840 48.627 48.414 23.531
4.0 28 2.0 3.0 1.0 0.0 2.099 3.00 4.545 2.06 1 MR of -(4-(hydroxymethyl)phenyl)acetamide (13) 4.894 7.293 7.272 7.525 7.504 2.13 2.01 8.0 7.0 6.0 5.0 1.94
13 C MR of -(4-(hydroxymethyl)phenyl)acetamide (13) 200 150 100 29 50 0 171.590 138.993 138.432 128.600 121.110 64.853 23.849
6.0 5.0 4.0 30 3.0 1.0 0.0 2.153 3.00 2.0 4.876 3.306 1 MR of -(3-nitrophenyl)acetamide (15) 7.522 7.502 7.482 7.831 7.829 7.811 7.808 7.916 7.913 7.895 7.892 8.579 8.574 8.569 2 1.03 0.95 0.85 9.0 8.0 7.0 0.78
13 C MR of -(3-nitrophenyl)acetamide (15) 150 100 31 50 0 171.799 149.666 141.126 130.612 126.072 119.072 115.013 48.837 23.741 2
5.0 4.0 32 2.0 3.0 1.0 0.0 2.108 3.13 4.882 3.310 1 MR of -(4-bromophenyl)acetamide (16) 7.430 7.408 7.498 7.475 Br 8.0 7.0 6.0 2.00 1.95
13 C MR of -(4-bromophenyl)acetamide (16) 150 100 33 50 0 171.671 139.278 132.770 122.735 117.380 49.050 23.866 Br
5.0 4.0 34 3.0 1.0 0.0 2.147 3.00 2.0 4.896 3.310 1 MR of 4-acetamidobenzoic acid (17) 7.673 7.651 7.972 7.950 C 1.98 8.0 7.0 6.0 2.01
13 C MR of 4-acetamidobenzoic acid (17) 150 100 35 50 0 171.956 169.499 144.415 131.793 126.914 120.050 49.050 24.049 C
1 MR of -(naphthalen-2-yl)acetamide (18) 5.0 36 0.0 2.204 3.00 7.250 7.462 7.458 7.441 7.432 7.407 7.404 7.383 7.755 7.746 7.733 8.170 3.00 3.67 0.88
13 C MR of -(naphthalen-2-yl)acetamide (18) 150 100 37 50 0 168.758 135.379 133.799 130.630 128.717 127.643 127.533 126.476 125.013 119.949 116.743 77.372 77.054 76.736 24.668
0.0 1.875 2.98 3.271 3.00 38 5.0 1 MR of -methyl--phenylacetamide (19) 7.204 7.186 7.285 7.424 7.404 2.10 1.02 2.13
13 C MR of -methyl--phenylacetamide (19) 200 150 100 39 50 0 170.575 144.623 129.742 127.724 127.096 77.414 77.096 76.778 37.175 22.440
1 MR of -(4-(acetylamino)phenyl)acetamide (20) 9.851 7.472 2.500 2.007 6.00 3.78 1.91 10.0 5.0 0.0 40
13 C MR of -(4-(acetylamino)phenyl)acetamide (20) 200 150 100 41 50 0 167.815 134.525 119.263 39.639 39.430 39.221 23.784
1 MR of -propylacetamide (21) 1.0 5.0 2.0 4.0 42 0.0 0.915 0.897 0.878 3.19 1.522 1.504 1.486 1.468 2.14 1.952 3.00 3.201 3.184 3.167 3.150 1.99 3.0 6.0 5.705 7.0 0.74
13 C MR of -propylacetamide (21) 170.006 41.389 29.724 22.885 11.377 200 150 100 50 0 43
44 0.0 1.501 1.487 1.484 1.474 1.460 1.403 1.394 1.390 1.578 1.575 1.561 1.548 1.541 1.534 1.0 2.0 1 MR of 1-acetylpiperidine (22) 3.0 3.397 3.383 3.369 3.362 3.342 3.319 2.500 1.962 1.376 2.03 2.08 2.10 3.00 4.046 0.97 2.39 4.0
13 C MR of 1-acetylpiperidine (22) 150 100 45 50 0 167.688 46.586 41.546 39.431 25.930 25.188 23.931 21.227
1 MR of -p-tolylbenzamide (23) 6.0 5.0 4.0 46 3.0 7.0 8.0 2.0 1.0 0.0 2.319 3.00 4.874 3.310 3.306 7.507 7.488 7.173 7.152 7.562 7.541 7.920 7.901 1.91 1.85 2.96 1.99
13 C MR of -p-tolylbenzamide (23) 150 100 47 50 0 168.846 137.241 136.376 135.434 132.810 130.281 129.624 128.591 122.450 49.263 49.050 48.837 21.005
0.921 0.905 0.888 1.685 1.667 1.648 1.348 1.339 1.330 1.322 1.312 2.254 2.333 2.314 2.295 3.09 4.09 2.01 3.00 2.01 5.0 48 0.0 1.0 2.0 4.0 3.0 4.891 1 MR of -p-tolylhexanamide (24) 7.076 7.056 7.431 7.410 2.01 8.0 7.0 6.0 1.98
13 C MR of -p-tolylhexanamide (24) 150 100 49 50 0 174.459 137.289 134.677 130.181 121.328 49.475 49.263 49.050 48.837 48.624 37.948 32.579 26.690 23.493 20.998 14.398