Electronic Supplementary Information ESITaking the systhesis of 1,3-dibutylurea as an example: Firstly, DBU (3 mmol, 0.4567 g) and PEG150 (3 mmol, 0.45 g) were charged into a glass

S1

Electronic Supplementary Information

CO2 capture and activation by superbase/polyethylene glycol and its subsequent conversion

Zhen-Zhen Yang, Liang-Nian He,* Ya-Nan Zhao, Bin Li and Bing Yu State Key Laboratory and Institute of Elemento-Organic Chemistry, Nankai University, Tianjin, 300071, People's Republic of China. * Corresponding author: Tel: +86-22-23501493; Fax: +86-22-23501493; E-mail: [email protected]

Table of Contents

page

1. General experimental methods S2

2. Characterization of the absorption system, amidinium/guanidinium alkylcarbonate salts, aziridines, ureas and oxazolidinones S2

3. Reference S7

4. The 1H NMR and 13C NMR Charts, IR spectra for the absorption system, amidinium/guanidinium alkylcarbonate salts, aziridines, ureas and oxazolidinones S8

Electronic Supplementary Material (ESI) for Energy & Environmental ScienceThis journal is © The Royal Society of Chemistry 2011

S2

1. General experimental methods:

Caution

Experiments using compressed gases CO2 are potentially hazardous and must only be carried out by using the appropriate equipment and under rigorous safety precautions.

Materials

Superbases and PEG used in this work were purchased from Alfa Aesar-A Johnson Matthey Company and dried under vacuum at 70 oC for one week before use. CO2 with a purity of 99.999% was commercially available. Amines was refluxed for 10 h with CaH2 and distilled prior to use. NH2PEG150NH2

1 and aziridines2 was synthesized according to the reported method.

Experimental methods

1H NMR spectra was recorded at Bruck 400 spectrometer in CDCl3 and CDCl3 (7.26 ppm) was used as internal reference, 13C NMR was recorded at 100.6 MHz in CDCl3 and CDCl3 (77.0 ppm) was used as internal reference. GC analyses were performed on Shimadzu GC-2014, equipped with a capillary column (RTX-17, 30 m × 0.25 μm) using a flame ionization detector. In situ FTIR was collected on a Mettler Toledo React IR ic10, Diamond ATR probe, using ic IR analysis system. The probe is placed in the middle of the absorption mixture, which is constantly stirred by magnetic whisk, and the spectra are collected in situ during CO2 absorption. Infrared (IR) spectra were recorded on a Bruker Tensor27 FT-IR spectrophotometer with KBr pellets.

General procedure for CO2 absorption

In a typical procedure, CO2 capture was carried out in a 10 mL Schlenk flask. The absorbents were charged into the reactor at room temperature. Then, the air in the flask was replaced by CO2 and a needle was used for CO2 bubbling, which was inserted in the bottom of the flask. The absorption reaction was conducted at 40 oC with a CO2 bubbling rate of 0.1 L/min. The amount of CO2 absorbed was determined by an Analytical Balance within an accuracy of ±0.0001 g every five minutes. Absorption/desorption was determined by several cycles of repeated experiments.

General procedure for synthesis of value-added chemicals using captured CO2

Taking the systhesis of 1,3-dibutylurea as an example: Firstly, DBU (3 mmol, 0.4567 g) and PEG150 (3 mmol, 0.45 g) were charged into a glass tube, in which CO2 was bubbled through a needle. Then, 1-butylamine was added after CO2 absorption reached equilibrium. The tube was placed into a 25 mL stainless steel autoclave and then the mixture was stirred at predetermined temperature for 5 min to reach the equilibration. When the reaction finished, the reactor was cooled in ice-water and CO2 was ejected slowly. An aliquot of sample was taken from the resultant mixture and dissolved in dry CH2Cl2 for GC analysis.

2. Characterization of the absorption system, amidinium/guanidinium alkylcarbonate salts, aziridines, ureas and oxazolidinones

DBU (1,8-diazabicyclo[5.4.0]undec-7-ene):

1H NMR (400 MHz, CDCl3) δ 3.23 (t, 3J = 5.6 Hz, 2 H), 3.13-3.18 (m, 4 H), 2.33-2.35 (m, 2 H), 1.72-1.77 (m, 2 H), 1.60 (s, 4 H), 1.52 (s, 2 H); 13C NMR (100.6 MHz, CDCl3) δ 161.6, 52.8, 48.3, 44.0, 37.2, 29.7, 28.4, 25.9, 22.3. IR 3420, 2924, 2851, 1616, 1486, 1441, 1366, 1312, 1260, 1233, 1183, 1115, 1060, 991, 955 cm-1.

PEG150 (triethylene glycol, MW = 150 Da):

1H NMR (400 MHz, CDCl3) δ 3.71 (t, 3J = 4.8 Hz, 4 H), 3.65 (s, 4 H), 3.59 (t, 3J = 4.8 Hz, 4 H), 3.40 (s, 2 H); 13C NMR (100.6 MHz, CDCl3) δ 72.6, 70.3, 61.5. IR 3446, 2865, 2360, 2341, 2136, 1954, 1653, 1457, 1351, 1082, 937, 889, 830, 571, 525 cm-1.

DBU/PEG150 + CO2:

1H NMR (400 MHz, CDCl3) δ 3.56-3.70 (m, 12 H), 3.29-3.34 (m, 6 H), 2.61 (s, 2 H), 1.85-1.90 (m, 2 H), 1.66-1.67 (m, 4 H), 1.59 (s, 2 H); 13C NMR (100.6 MHz, CDCl3) δ 164.1, 158.5, 72.6, 70.3, 64.1, 61.3, 53.5, 48.4, 40.6, 34.1, 29.3, 27.6, 24.8, 20.8.


S3

Fig. S1 The 1H NMR of DBU, PEG150 and DBU/PEG150 + CO2 (CDCl3, 400 MHz).


S4

Table S1 The comparison of 1H and 13C NMR chemical shifts of DBU, PEG150 and DBU/PEG150 + CO2

DBU DBUPEG150CO2 PEG150

1H NMR

/ppm

1.52 (2H) 1.59 (2H)

1.60 (4H) 1.60-1.67 (4H)

1.72-1.77 (2H) 1.85-1.90 (2H)

2.33-2.35 (2H) 2.61 (2H)

3.13-3.18 (4H)

3.23 (2H) 3.29-3.34 (6H)

3.56-3.70 (12H) 3.59-3.71 (12H)

13C NMR

/ppm

22.3 20.8

25.9 24.8

28.4 27.6

29.7 29.3

37.2 34.1

44.0 40.6

48.3 48.4

52.8 53.5

61.3 61.5

64.1

70.3 70.3

72.6 72.6

158.5

161.6 164.1


S5

0.8

0.85

0.9

0.95

1

2400 2600 2800 3000 3200 3400 3600 3800

Tra

nsm

itta

nce

Wave number / cm-1

0 min

4 min 30 s

5 min

5 min 15 s

6 min

6 min 30 s

8 min 15 s3263 cm‐1

(B)

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0:00:00 0:28:48 0:57:36 1:26:24 1:55:12 2:24:00 2:52:48

Abs

orba

nce

Time

1662 cm-1

1284 cm-1

1572 cm-1

1440 cm-1

(C)

Figure S2. Results of in situ FT-IR spectroscopy monitoring CO2 capture by DBU/PEG150 system at various times

starting from CO2 bubbling; The spectrum of DBU and PEG150 was subtracted; ◆: CO2 began to be bubbled at 40 oC; ◇: Temperature was gradually increased form 40 oC to 120 oC.

‐0.10

0.10.20.30.40.50.60.70.80.91

0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750

Lost of weight%

Temperature/oC

Figure S3. The scanning thermogravimetric analysis (TGA) results for DBU/PEG600+CO2 with a 10 oC min-1

temperature ramping rate to 700 oC.

PEG600 (polyethylene glycol, MW = 600 Da):

1H NMR (400 MHz, CDCl3) δ 3.57-3.69 (m, 44H), 2.75 (s, 2H); 13C NMR (100.6 MHz, CDCl3) δ72.4, 70.4, 70.2, 61.6. IR 3375, 2870, 1636, 1457, 1350, 1297, 1249, 1107, 951, 845, 735, 559 cm-1.

DBU/PEG600 + CO2:

1H NMR (400 MHz, CDCl3) δ 3.59-3.70 (m, 53H), 3.29 (t, 3J = 5.6 Hz, 2H), 3.20-3.24 (m, 4H), 2.46 (s, 2H), 1.78-1.84 (m, 2H), 1.65 (s, 4H), 1.57 (s, 2H); 13C NMR (100.6 MHz, CDCl3) δ 164.6, 157.7, 77.2, 72.0, 69.8, 69.6, 63.5, 60.6, 53.3, 47.9, 38.4, 32.1, 28.5, 26.5, 23.8, 19.4. IR 3350, 2867, 2361, 2343, 1647, 1613, 1456, 1351, 1315, 1291, 1250, 1110, 993, 953, 885, 837, 731, 694, 546, 526 cm-1.

TBD (1,5,7-triazabicyclo[4.4.0]dec-5-ene):

1H NMR (400 MHz, CDCl3) δ 3.29 (t, 3J = 5.6 Hz, 4H), 3.24 (t, 3J = 6 Hz, 4H), 1.96 (m, 4H); 13C NMR (100.6 MHz, CDCl3) δ 151.2, 46.6, 38.0, 20.7. IR 3477, 3418, 3234, 3157, 2967, 2943, 2875, 2797, 2749, 2361, 2343, 1662, 1573, 1477, 1445, 1421, 1378, 1321, 1295, 1202, 1069, 884, 711, 671, 590 cm-1.

TBD/PEG600 + CO2:


S6

1H NMR (400 MHz, CDCl3) δ 3.56-3.68 (m, 62H), 3.21-3.27 (m, 8H), 1.91-1.97 (m, 4H); 13C NMR (100.6 MHz, CDCl3) δ 158.8, 150.7, 77.2, 72.0, 69.9, 69.7, 64.0, 60.7, 46.2, 37.0, 20.3. IR 3308, 3160, 2869, 2362, 1943, 1667, 1574, 1456, 1377, 1350, 1323, 1291, 1252, 1203, 1107, 951, 844, 745, 730, 714 cm-1.

DBN (1,5-diazabicyclo[4.3.0]non-5-ene):

1H NMR (400 MHz, CDCl3) δ 3.28 (t, 3J = 4.8 Hz, 2H), 3.21 (t, 3J = 6.8 Hz, 2H), 3.13 (t, 3J = 6 Hz, 2H), 2.38 (t, 3J = 7.6 Hz, 2H), 1.83-1.91 (m, 2H), 1.70-1.76 (m, 2H); 13C NMR (100.6 MHz, CDCl3) δ160.5, 51.2, 43.8, 42.8, 31.3, 20.6, 19.4. IR 3409, 2929, 2845, 1651, 1496, 1422, 1363, 1288, 1232, 1195, 1133, 1051, 961, 903, 737, 677, 574 cm-1.

DBN/PEG600 + CO2:

1H NMR (400 MHz, CDCl3) δ 3.58-3.72 (m, 58H), 3.31 (t, 3J = 5.6 Hz, 2H), 3.26 (t, 3J = 6.4 Hz, 2H), 3.17 (t, 3J = 6 Hz, 2H), 2.45 (t, 3J = 8 Hz, 2H), 1.88-1.95 (m, 2H), 1.74-1.80 (m, 2H); 13C NMR (100.6 MHz, CDCl3) δ162.8, 157.6, 77.2, 72.0, 69.8, 69.5, 63.4, 60.4, 52.0, 41.9, 38.6, 29.4, 18.5, 18.3. IR 3394, 2870, 2361, 2342, 1681, 1651, 1457, 1350, 1291, 1251, 1107, 952, 837, 747, 730, 698 cm-1.

TMG(tetramethylguanidine):

1H NMR (400 MHz, CDCl3) δ 5.01 (s, 1H), 2.70 (s, 12H); 13C NMR (100.6 MHz, CDCl3) δ 167.9, 39.3. IR 3420, 3334, 3000, 2942, 2845, 2789, 2360, 2341, 1599, 1494, 1458, 1425, 1409, 1382, 1255, 1198, 1145, 1058, 1010, 892, 779, 734, 562, 544 cm-1.

TMG/PEG600 + CO2:

1H NMR (400 MHz, CDCl3) δ 3.55-3.69 (m, 60H), 2.71 (s, 12H); 13C NMR (100.6 MHz, CDCl3) δ 163.6, 157.4, 77.2, 72.1, 69.9, 69.7, 63.4, 60.6, 38.9. IR 3393, 2870, 2361, 2343, 1647, 1472, 1457, 1351, 1277, 1251, 1108, 952, 838, 749 cm-1.

DMICH(N-(1,3-dimethylimidazolidin-2-ylidene)cyclohexanamine):

1H NMR (400 MHz, CDCl3) δ3.38–3.43 (m, 1H), 3.11 (s, 4H), 2.76 (s, 6H), 1.15–1.72 (m, 10H); 13C NMR (100.6 MHz, CDCl3) δ 155.4, 54.0, 44.9, 36.5, 31.3, 25.8, 25.2.

DMICH/PEG600 + CO2:

1H NMR (400 MHz, CDCl3) δ 3.56-3.69 (m, 56H), 3.34-3.39 (m, 1H), 3.17 (s, 4H), 2.79 (s, 6H), 1.54-1.73 (m, 5H), 1.13-1.41 (m, 5H); 13C NMR (100.6 MHz, CDCl3) δ 157.5, 157.3, 124.4, 77.2, 72.3, 70.2, 70.0, 63.6, 61.1, 54.1, 59.2, 44.7, 36.1, 35.0, 34.9, 25.1, 18.0. IR 3393, 2922, 2867, 2361, 2342, 1653, 1635, 1472, 1456, 1350, 1279, 1256, 1109, 1035, 952, 890, 847, 763, 729, 698 cm-1.

NH2PEG150NH2:

1H NMR (400 MHz, CDCl3) δ 3.47 (s, 4 H), 3.35 (t, 3J = 5.2 Hz, 4 H), 2.71 (t, 3J = 5.2 Hz, 4 H), 1.17 (s, 1 H); 13C NMR (100.6 MHz, CDCl3) δ 73.2, 70.0, 41.5. IR 3393, 2869, 1576, 1473, 1375, 1352, 1307, 1114, 817 cm-1.

NH2PEG150NH2/PEG150(molar ratio: 1: 2) + CO2:

1H NMR (400 MHz, CDCl3) δ 3.72 (t, 3J = 4 Hz, 12H), 3.66 (s, 8H), 3.59-3.62 (m, 12H), 3.54 (t, 3J = 4.8 Hz, 2H), 3.26 (s, 1H), 2.89 (s, 2H); 13C NMR (100.6 MHz, CDCl3) δ 162.8, 72.3, 69.8, 68.2, 60.7, 40.9, 39.3. IR 3365, 2870, 2361, 2342, 1576, 1558, 1473, 1457, 1350, 1311, 1117, 1078, 936, 888, 821, 748 cm-1.

1,3-Dipropyl urea:

1H NMR (300 MHz, CDCl3) δ 4.90 (bd, N-H), 3.08 (t, 3J = 6.45 Hz, 4H), 1.41-1.54 (m, 4H), 0.89 (t, 3J = 7.5 Hz, 6H); 13C NMR (75.5 MHz, CDCl3) δ 158.8, 42.1, 23.4, 11.3.

1,3-Diisopropyl urea:

1H NMR (300 MHz, CDCl3) δ 3.80-3.87 (m, 2H), 1.14 (d, 3J = 6.4 Hz, 12H); 13C NMR ( 75.5 MHz, CDCl3) δ 157.0, 42.2, 23.5.

1,3-Dibutyl urea:

1H NMR (400 MHz, CDCl3) δ 4.77 (s, 2 H), 3.12-3.13 (m, 4H), 1.42-1.49 (m, 4H), 1.28-1.37 (m, 4H), 0.91 (t, 3J =

7.2 Hz, 6H); 13C NMR (100.6 MHz, CDCl3) δ 158.7, 40.2, 32.3, 20.0, 13.7.

1,1,3,3-Tetrabutyl urea:

1H NMR (300 MHz, CDCl3) δ 2.56 (t, 3J = 7.2 Hz, 8H), 1.36-1.49 (m, 8H), 1.24-1.33 (m, 8H), 0.87 (t, 3J = 7.2 Hz,

12H); 13C NMR (75.5 MHz, CDCl3) δ 164.3, 49.7, 32.2, 20.5, 13.9.


S7

Octahydro-benzoimidazol-2-one:

1H NMR (300 MHz, D2O) δ 3.12-3.32 (m, 2H), 1.53-1.60 (m, 4H), 1.15-1.35 (m, 4H); 13C NMR (75.5 MHz, D2O)

δ 164.1, 53.3, 32.2, 24.2.

1-Ethyl-2-phenylaziridine:

1H NMR (400 MHz, CDCl3) δ7.18-7.31 (m, 5H), 2.44 (q, 3J = 9.6 Hz, 2H), 2.30 (dd, 3J = 4.4 Hz, 3J = 4.8 Hz, 1H),

1.89 (d, 2J = 4.4 Hz, 1H), 1.65 (d, 2J = 8.8 Hz, 1H), 1.17 (t, 3J = 9.6 Hz, 3H); ESI-MS calcd for C10H13N 147.10,

found 148.31 [M + H]+.

1-Propyl-2-phenylaziridine:

1H NMR (400 MHz, CDCl3) δ 0.95 (t, 3J = 10.0 Hz, 3H), 1.60-1.67 (m, 3H), 1.89 (d, 2J = 4.0 Hz, 1H), 2.24-2.33 (m, 2H), 2.43-2.51 (m, 1H), 7.18-7.31 (m, 5H); ESI-MS calcd for C11H15N 161.12, found 162.28 [M + H]+.

2-(4-Chlorophenyl)-1-ethylaziridine:

1H NMR (300 MHz, CDCl3) δ 1.18 (t, 3J = 6.9 Hz, 3H), 1.65 (d, 2J = 6.6 Hz, 1H), 1.83 (d, 2J = 3.3 Hz, 1H), 2.25-2.46 (m, 3H), 7.15-7.23 (m, 4H); ESI-MS calcd for C10H12NCl 181.66, found 182.13 [M + H]+.

2-(4-Methylphenyl)-1-ethylaziridine:

1H NMR (400 MHz, CDCl3) δ 1.19 (t, 3J = 7.2 Hz, 3H), 1.62 (d, 2J = 6.4 Hz, 1H), 1.86 (d, 2J = 3.2 Hz, 1H), 2.26 (dd, 3J = 3.6 Hz, 3J = 3.2 Hz, 1H), 2.31 (s, 3H), 2.37-2.48 (m, 2H), 7.09-7.15 (m, 4H); ESI-MS calcd for C11H15N 161.24, found 162.20 [M + H]+.

3-Ethyl-5-phenyloxazolidin-2-one:

Colorless liquid; 1H NMR (300 MHz, CDCl3) δ 1.17 (t, 3J = 7.2 Hz, 3H), 3.29-3.45 (m, 3H), 3.92 (t, 3J = 8.7 Hz, 1H), 5.48 (t, 3J = 7.8 Hz, 1H), 7.34-7.42 (m, 5H); 13C NMR (75 MHz, CDCl3) δ 12.4, 38.8, 51.5, 74.2, 125.4, 128.6, 128.8, 138.8, 157.5; ESI-MS calcd for C11H13NO2 191.09, found 192.29 (M + H)+, 214.38 (M + Na)+, 405.01 (2 M + Na)+.

3-Ethyl-4-phenyloxazolidin-2-one:

Colorless liquid; 1H NMR (400 MHz, CDCl3) δ 1.05 (t, 3J = 7.2 Hz, 3H), 2.79-2.88 (m, 1H), 3.48-3.57 (m, 1H), 4.10 (t, 3J = 8.0 Hz, 1H), 4.62 (t, 3J = 8.8 Hz, 1H), 4.81 (t, 3J = 7.2 Hz, 1H), 7.30 7.44 (m, 5H); 13C NMR (75 MHz, CDCl3) δ 12.1, 36.8, 59.3, 69.7, 126.9, 129.0, 129.2, 137.8, 158.1; ESI-MS calcd for C11H13NO2 191.09, found 192.29 (M + H)+ , 214.38 (M + Na)+, 405.01 (2M + Na)+.

3-Propyl-5-phenyloxazolidin-2-one:

Colorless liquid; 1H NMR (300 MHz, CDCl3) δ 0.91 (t, 3J=7.2 Hz, 3H), 1.52-1.61 (m, 2H), 3.18-3.31 (m, 2H) 3.40 (t, 3J=8.0 Hz, 1H), 3.90 (t, 3J=8.8 Hz, 1H), 5.46 (t, 3J=8.0 Hz, 1H), 7.31-7.37 (m, 5H); 13C NMR (75 MHz, CDCl3) δ 10.7, 20.3, 45.5, 51.8, 74.0, 125.2, 128.4, 128.5, 138.7, 157.6; ESI-MS calcd for C12H15NO2 205.11, found 206.30 (M + H)+, 228.30 (M + Na)+, 433.04 (2M + Na)+.

3-Ethyl-5-(4-chlorophenyl)oxazolidin-2-one:

White solid; 1H NMR (400 MHz, CDCl3) δ 1.17 (t, 3J=7.3 Hz, 3H), 3.30-3.43 (m, 2H), 3.69-3.76 (m, 1H), 3.92 (t, 3J=8.7 Hz, 1H), 5.44 (t, 3J=8.0 Hz, 1H), 7.27-7.38 (m, 4H); 13C NMR (100 MHz, CDCl3) δ 12.6, 38.9, 51.5, 73.6, 126.9, 129.1, 134.7, 137.4, 157.4; ESI-MS calcd for C11H12ClNO2 225.67, found 451.64 (2M + H)+.

3-Ethyl-5-p-tolyloxazolidin-2-one:

White solid; 1H NMR (400 MHz, CDCl3) δ 1.18 (t, 3J=7.3 Hz, 3H), 1.62 (d, 3J=6.4 Hz, 1H),1.87 (d, 3J=3.2 Hz, 1H), 2.27 (dd, 3J=6.6 Hz, 2J=3.2 Hz, 1H), 2.31 (s, 3H), 2.36-2.48 (m, 2H), 7.09- 7.15 (m, 4H); 13C NMR (100 MHz, CDCl3) δ 12.6, 21.2, 38.9, 51.6, 74.3, 125.6, 129.5, 135.8, 138.7, 157.7; ESI-MS calcd for C12H15NO2 205.25, found 206.45 (M + H)+, 411.15 (2M + H)+.

3. Reference

(1) Gansow, O. A.; Kausar, A. R.; Triplett, K. B. J. Heterocyclic Chem. 1981, 18, 297.

(2) Du, Y.; Wu, Y.; Liu, A.-H. and He, L.-N. J. Org. Chem. 2008, 73, 4709.


S8

4. The 1H NMR and 13C NMR Charts, IR spectra for the absorption system, amidinium/guanidinium alkylcarbonate salts, urea and oxazolidinones

m (t1)1.02.03.04.05.06.07.08.0

7.2

60

3.2

44

3.2

30

3.2

16

3.1

78

3.1

63

3.1

49

3.1

39

3.1

27

2.3

55

2.3

47

2.3

31

1.7

75

1.7

60

1.7

46

1.7

31

1.7

16

1.6

05

1.5

99

1.5

28

1.5

21

1.9

7

2.0

03

.97

2.0

2

2.0

14

.31

1H NMR ︵CDCl3,400 MHz ︶

N

N

DBU

pm (t1)50100150

16

1.5

28

77

.31

87

7.0

00

76

.68

3

52

.76

2

48

.27

4

44

.01

1

37

.19

0

29

.65

3

28

.40

9

25

.87

12

2.3

48

13C NMR (CDCl3, 100.6 MHz)

N

N

DBU


S9

IR spectrum of DBU:

3420

.05

2923

.90

2850

.87

1615

.84

1486

.14

1441

.37

1365

.97

1312

.70

1260

.80

1233

.90

1183

.28

1115

.35

1060

.70

991.

1695

5.25

500100015002000250030003500

Wavenumber cm-1

2030

4050

6070

8090

100

Tra

nsm

ittan

ce [

%]

ppm (t1)3.04.05.06.07.08.0

7.2

60

3.7

24

3.7

14

3.7

02

3.6

53

3.6

00

3.5

88

3.5

78

3.3

99

2.1

3

4.0

04

.03

4.0

7


HOO

OOH

PEG150


S10

m (t1)60.065.070.075.080.0

77

.31

7

77

.00

0

76

.68

3

72

.62

6

70

.25

4

61

.49

9


HOO

OOH

PEG150

IR spectrum of PEG150:

3446

.33

2864

.78

2360

.51

2341

.54

2135

.87

1953

.69

1652

.89

1456

.71

1351

.03

1081

.84

937.

1388

9.34

830.

42

571.

7552

5.64

500100015002000250030003500

Wavenumber cm-1

4050

6070

8090

100

Tra

nsm

ittan

ce [

%]


S11

pm (t1)1.02.03.04.05.06.07.08.0

7.2

60

5.5

95

4.0

72

4.0

59

4.0

46

3.7

00

3.6

89

3.6

77

3.6

68

3.6

55

3.6

37

3.6

15

3.5

85

3.5

73

3.5

62

3.3

45

3.3

29

3.3

17

3.3

06

3.2

92

2.6

12

1.9

04

1.8

89

1.8

75

1.8

60

1.8

46

1.6

66

1.6

60

1.5

89

2.3

84

.12

1.9

8

2.0

0

6.1

0

11

.95

0.6

7

1H NMR (400 MHz, CDCl3)

N

NH

HOO

OO O

O

DBU/PEG150 + CO2

(t1)-5050100150200250

16

4.0

82

15

8.5

00

77

.31

87

7.0

00

76

.68

1

72

.61

7

70

.47

57

0.3

77

70

.26

8

64

.11

4

61

.39

36

1.3

06

53

.49

0

48

.41

4

40

.59

63

4.1

43

29

.29

6

27

.55

6

24

.82

0

20

.78

1

13C NMR (100.6 MHz,CDCl3)

N

NH

HOO

OO O

O

DBU/PEG150 + CO2


S12

pm (t1)2.03.04.05.06.07.08.0

7.2

60

3.6

92

3.6

33

3.6

20

3.5

92

3.5

80

3.5

70

2.7

47

44

.15

2.0

0

1H NMR ︵CDCl3, 400 MHz ︶

HOO

OHn

PEG600

pm (t1)60.065.070.075.080.0

77

.31

8

77

.00

0

76

.68

2

72

.42

0

70

.43

4

70

.21

0

61

.56

1

13C NMR ︵CDCl3, 100.6 MHz ︶

HOO

OHn

PEG600

IR spectrum of PEG600:


S13

3375

.62

2870

.23

1636

.63

1457

.51

1350

.87

1297

.72

1249

.61

1107

.35

951.

56

845.

50

735.

35

559.

32

500100015002000250030003500

Wavenumber cm-1

4050

6070

8090

100

Tra

nsm

ittan

ce [

%]

m (t1)2.03.04.05.06.07.0

7.2

60

3.7

03

3.6

91

3.6

41

3.6

28

3.6

01

3.5

89

3.3

04

3.2

90

3.2

76

3.2

44

3.2

27

3.2

14

3.2

03

2.4

56

1.8

40

1.8

25

1.8

11

1.7

96

1.7

81

1.6

53

1.5

70

2.0

03

.84

1.8

0

1.9

1

3.7

92

.12

53

.40


HO

On

O

ON

N

H

DBU/PEG600 + CO2


S14

ppm (t1)050100150200

16

4.6

43

15

7.7

11

77

.32

07

7.1

98

77

.00

07

6.6

77

72

.01

86

9.8

56

69

.64

66

3.4

66

60

.58

9

53

.26

5

47

.88

5

38

.37

73

2.0

75

28

.54

32

6.5

40

23

.76

61

9.4

10


HO

On

O

ON

N

H

DBU/PEG600 + CO2

IR spectrum of DBU/PEG600 + CO2:

3350

.98

2867

.55

2361

.89

2343

.43

1647

.39

1613

.75

1456

.53

1351

.25

1315

.41

1291

.75

1250

.16

1110

.30

993.

6995

3.08

885.

4283

7.21

731.

4169

4.29

546.

8252

6.87

500100015002000250030003500

Wavenumber cm-1

2030

4050

6070

8090

100

Tra

nsm

ittan

ce [

%]


S15

m (t1)1.02.03.04.05.06.07.08.0

7.2

60

3.3

00

3.2

86

3.2

72

3.2

53

3.2

38

3.2

24

1.9

93

1.9

79

1.9

64

1.9

49

1.9

35

4.0

0

4.0

63

.59


N

N

N

H

TBD

pm (t1)050100150200

15

1.1

67

77

.31

97

7.0

00

76

.68

0

46

.62

6

37

.98

2

20

.65

2


N

N

N

H

TBD

IR spectrum of TBD:


S16

3477

.40

3418

.84

3234

.43

3157

.01

2967

.65

2943

.41

2875

.58

2797

.91

2749

.74

2361

.66

2343

.40

1662

.97

1573

.68

1477

.29

1445

.96

1421

.74

1378

.76

1321

.86

1295

.91

1202

.65

1069

.73

884.

03

711.

1367

1.55

590.

04

500100015002000250030003500

Wavenumber cm-1

2040

6080

100

Tra

nsm

ittan

ce [

%]

m (t1)1.02.03.04.05.06.07.08.0

7.2

60

3.6

82

3.6

71

3.6

59

3.6

52

3.6

38

3.6

16

3.6

02

3.5

76

3.5

64

3.5

53

3.2

66

3.2

52

3.2

42

3.2

28

3.2

13

1.9

66

1.9

51

1.9

37

1.9

22

1.9

07

4.0

0

8.1

4

62

.47


HO

On

O

ON

N

N

H H

TBD/PEG600 + CO2


S17

m (t1)050100150200

15

8.8

21

15

0.6

86

77

.32

17

7.1

98

77

.00

07

6.6

79

72

.02

5

69

.91

86

9.6

94

64

.01

6

60

.71

9

46

.24

2

37

.02

1

20

.28

1


HO

On

O

ON

N

N

H H

TBD/PEG600 + CO2

IR spectrum of TBD/PEG600 + CO2:

3308

.71

3160

.58

2869

.84

2362

.10

1943

.54

1667

.96

1574

.37

1456

.69

1377

.38

1350

.41

1323

.51

1291

.81

1252

.14

1203

.74

1107

.97

951.

43

844.

62

745.

8573

0.32

714.

07

500100015002000250030003500

Wavenumber cm-1

510

1520

2530

3540

45

Tra

nsm

ittan

ce [

%]


S18

m (t1)1.02.03.04.05.06.07.00

7.2

60

3.2

88

3.2

76

3.2

63

3.2

30

3.2

13

3.1

96

3.1

45

3.1

30

3.1

15

2.4

04

2.3

85

2.3

66

1.9

06

1.8

87

1.8

69

1.8

51

1.8

33

1.7

60

1.7

45

1.7

31

1.7

17

1.7

02

2.0

11

.97

2.0

0

1.9

3

1.9

52

.01


N

N

DBN

m (t1)050100150

16

0.4

67

77

.30

57

7.0

00

76

.67

3

51

.19

3

43

.83

9

42

.84

5

31

.25

4

20

.60

2

19

.44

5


N

N

DBN

IR spectrum of DBN:


S19

3409

.68

2929

.46

2845

.86

1651

.46

1496

.59

1422

.84

1363

.45

1288

.07

1232

.80

1195

.73

1133

.66

1051

.86

961.

0090

3.99

737.

7967

7.86

574.

69

500100015002000250030003500

Wavenumber cm-1

2030

4050

6070

8090

100

Tra

nsm

ittan

ce [

%]

pm (t1)0.05.010.015.0

7.2

60

3.7

21

3.7

10

3.6

98

3.6

48

3.6

39

3.6

34

3.6

08

3.5

96

3.5

85

3.3

25

3.3

11

3.2

97

3.2

78

3.2

62

3.2

44

3.1

86

3.1

71

3.1

56

2.4

71

2.4

51

2.4

31

1.9

50

1.9

32

1.9

13

1.8

95

1.8

76

1.8

02

1.7

88

1.7

73

1.7

59

1.7

44

2.0

42

.00

2.0

7

2.1

4

57

.80

2.0

52

.08


HO

O

N

N

H

O

On

DBN/PEG600 + CO2


S20

pm (t1)050100150

16

2.8

20

15

7.5

88

77

.31

97

7.1

97

77

.00

07

6.6

80

71

.96

6

69

.75

56

9.5

43

63

.37

5

60

.41

85

2.0

10

41

.87

0

38

.60

1

29

.42

3

18

.49

31

8.3

16


HO

O

N

N

H

O

On

DBN/PEG600 + CO2

IR spectrum of DBN/PEG600 + CO2:

3394

.32

2870

.22

2361

.10

2342

.58

1681

.89

1651

.89

1457

.25

1350

.82

1291

.63

1251

.76

1107

.79

952.

68

837.

64

747.

0573

0.52

698.

30

500100015002000250030003500

Wavenumber cm-1

2030

4050

6070

8090

100

Tra

nsm

ittan

ce [

%]


S21

pm (t1)2.03.04.05.06.07.08.0

7.2

60

5.0

10

2.6

96

12

.00

0.7

9


N

NN

H

TMG

pm (t1)050100150200

16

7.9

09

77

.31

77

7.0

00

76

.68

3

39

.25

5


N

NN

H

TMG

IR spectrum of TMG:


S22

3420

.29

3334

.61

3000

.97

2942

.87

2845

.72

2789

.97

2360

.19

2341

.05

1599

.28

1494

.55

1458

.20

1425

.85

1409

.06

1382

.14

1255

.71

1198

.96

1145

.82

1058

.56

1010

.02

892.

74

779.

6673

4.25

562.

7354

4.35

500100015002000250030003500

Wavenumber cm-1

2040

6080

100

Tra

nsm

ittan

ce [

%]

m (t1)1.02.03.04.05.06.07.08.09.0

7.2

60

3.6

89

3.6

78

3.6

66

3.6

24

3.6

17

3.6

04

3.5

76

3.5

63

3.5

53

2.7

08

12

.00

59

.48


HO

ON

NN

H H

n

O

O

TMG/PEG600 + CO2


S23

m (t1)050100150200

16

3.5

66

15

7.3

79

77

.32

27

7.2

02

77

.00

07

6.6

78

72

.05

2

69

.88

56

9.6

61

63

.36

76

0.6

32

60

.59

7

38

.87

9


HO

ON

NN

H H

n

O

O

TMG/PEG600 + CO2

IR spectrum of TMG/PEG600 + CO2:

3393

.32

2870

.92

2361

.87

2343

.40

1647

.60

1472

.96

1457

.38

1351

.05

1277

.73

1251

.37

1108

.13

952.

00

838.

10

749.

14

500100015002000250030003500

Wavenumber cm-1

4050

6070

8090

100

Tra

nsm

ittan

ce [

%]


S24

m (t1)1.02.03.04.05.06.07.08.0

7.2

60

3.4

10

3.4

02

3.2

54

3.1

14

2.7

69

2.7

60

1.7

26

1.7

03

1.5

87

1.5

59

1.3

49

1.3

22

1.2

96

1.2

70

1.2

39

1.2

07

1.1

81

1.1

51

4.0

0

3.9

4

6.1

6

1.1

7

1.0

7

5.0

8

1H NMR ︵CDCl3, 400MHz ︶

NN

N

DMICH

pm (t1)50100150

15

5.4

76

77

.31

97

7.0

00

76

.68

4

54

.08

9

44

.94

5

36

.54

5

31

.39

1

25

.84

9

25

.25

8


NN

N

DMICH


S25

pm (t1)1.02.03.04.05.06.07.08.0

7.2

60

3.6

94

3.6

83

3.6

71

3.6

22

3.6

08

3.5

80

3.5

68

3.5

58

3.3

90

3.3

81

3.3

72

3.3

64

3.3

56

3.3

47

3.3

38

3.1

68

2.7

93

1.7

25

1.6

99

1.5

65

1.5

39

1.4

09

1.3

80

1.3

53

1.3

25

1.2

68

1.2

39

1.2

07

1.1

83

1.1

61

1.1

32

5.3

5

3.9

9

55

.55

1.3

3

4.9

8

5.0

2


HO

On

O

O

N N

N

H

DMICH/PEG600 + CO2

(t1)050100150

15

7.4

68

15

7.2

77

12

4.4

50

77

.31

87

7.1

95

77

.00

07

6.6

79

72

.26

37

0.2

05

69

.99

06

3.6

28

61

.09

2

54

.08

0

49

.21

6

44

.72

0

36

.07

7

34

.95

43

4.9

02

25

.06

1

18

.00

9


HO

On

O

O

N N

N

H

DMICH/PEG600 + CO2

IR spectrum of DMICH/PEG600 + CO2:


S26

3393

.24

2922

.88

2867

.13

2361

.34

2342

.74

1653

.01

1635

.89

1472

.76

1456

.57

1350

.73

1279

.72

1256

.53

1109

.94

1035

.42

952.

1589

0.11

847.

0276

3.89

729.

7269

8.47

500100015002000250030003500

Wavenumber cm-1

3040

5060

7080

9010

0

Tra

nsm

ittan

ce [

%]

1)0.05.010.0

7.2

60

3.5

82

3.4

77

3.4

64

3.4

51

2.8

33

2.8

20

2.8

07

1.3

56

-0.0

57

4.0

0

3.7

4

3.8

43

.93

1H NMR ︵400 MHz,CDCl3 ︶H2N OO

NH2


S27

)050100150200

77

.31

87

7.0

00

76

.68

2

73

.37

67

0.1

61

41

.66

8

13C NMR ︵CDCl3,100.6 MHz ︶

H2N OO

NH2

IR spectrum of NH2PEG150NH2:

3393

.10

2869

.12

2534

.31

2363

.85

2344

.57

1576

.47

1473

.92

1375

.70

1352

.99

1307

.48

1114

.84

881.

1181

7.13

731.

0869

6.38

617.

9757

6.80

518.

20

500100015002000250030003500

Wavenumber cm-1

7075

8085

9095

100

Tra

nsm

ittan

ce [

%]


S28

pm (t1)2.03.04.05.06.07.08.0

7.2

60

3.7

34

3.7

24

3.7

12

3.6

61

3.6

17

3.6

09

3.5

97

3.5

87

3.5

48

3.5

36

3.5

23

3.2

59

2.8

95

7.8

71

2.0

0

0.9

0

2.3

9

12

.57

2.6

4


HOO

OHHN

ONH3

2

O

O

molar ratio: 1: 2

2

ppm (t1)50100150

16

2.8

49

77

.32

07

7.0

00

76

.68

0

72

.28

4

69

.78

76

8.2

25

60

.68

4

40

.94

63

9.3

11

1H NMR ︵CDCl3,100.6 MHz ︶

HOO

OHHN

ONH3

2

O

O

molar ratio: 1: 2

2

IR spectrum of NH2PEG150NH2/PEG150 (molar ratio: 1: 2) + CO2:


S29

3365

.22

2870

.51

2361

.31

2342

.85

1576

.56

1558

.97

1473

.45

1457

.44

1350

.82

1311

.59

1117

.69

1078

.09

936.

6688

8.44

821.

8774

8.97

500100015002000250030003500

Wavenumber cm-1

5060

7080

9010

0

Tra

nsm

ittan

ce [

%]

1,3-Dipropyl urea:

1H NMR (CDCl3, 300 MHz)


S30


1,3-Diisopropyl-urea:



S31



S32

(t1)1.02.03.04.05.06.07.0

7.2

60

4.7

71

3.1

35

3.1

25

1.4

89

1.4

72

1.4

54

1.4

36

1.4

18

1.3

74

1.3

56

1.3

38

1.3

19

1.3

01

1.2

84

0.9

20

0.9

02

0.8

84

6.1

9

4.0

0

3.7

5

1.6

9

1H NMR (CDCl3,400 MHz)NH

NH

O

m (t1)50100150

15

8.7

05

77

.31

77

7.0

00

76

.68

3

40

.22

6

32

.32

6

20

.01

6

13

.74

5

13C NMR (100.6 MHz,CDCl3)NH

NH

O

1,1,3,3-Tetrabutyl urea:



S33


Octahydro-benzoimidazol-2-one:

NHHN

O

1H NMR (D2O, 300 MHz)


S34

13C NMR (D2O, 75.5 MHz)


S35

1)0.05.010.015.0

7.3

16

7.2

92

7.2

88

7.2

69

7.2

53

7.2

36

7.2

31

7.2

08

7.1

86

2.4

79

2.4

55

2.4

32

2.4

08

2.3

17

2.3

05

2.2

95

2.2

84

1.8

98

1.8

87

1.6

59

1.6

37

1.2

21

1.1

97

1.1

73

0.0

00

00

3.0

0

1.1

60

.96

1.0

11

.86

5.0

0

1H NMR (400MHz, CDCl3)

N

Ph

1)0.05.010.015.0

7.3

13

7.2

89

7.2

65

7.2

52

7.2

29

7.2

04

7.1

82

2.5

17

2.4

93

2.4

79

2.4

69

2.4

55

2.4

31

2.3

32

2.3

07

2.2

94

2.2

84

2.2

72

2.2

47

1.8

91

1.8

81

1.6

74

1.6

63

1.6

50

1.6

42

1.6

26

1.6

01

0.9

83

0.9

58

0.9

33

0.0

00

00

4.9

9

3.0

2

2.9

61

.00

1.9

90

.91


N


S36

1)0.05.010.015.0

7.2

65

7.2

60

7.2

37

7.1

86

7.1

57

2.4

69

2.4

45

2.4

21

2.3

97

2.2

84

2.2

73

2.2

62

2.2

51

1.8

41

1.8

31

1.6

63

1.6

42

1.2

08

1.1

84

1.1

61

0.0

00

00

3.0

0

0.9

90

.89

0.9

81

.84

4.1

7


N

Cl

1)0.05.010.0

7.2

59

7.1

48

7.1

27

7.1

10

7.0

90

2.5

00

2.4

82

2.4

71

2.4

65

2.4

53

2.4

36

2.4

22

2.4

05

2.3

93

2.3

87

2.3

76

2.3

58

2.3

52

2.3

16

2.2

80

2.2

72

2.2

64

2.2

56

1.8

75

1.8

67

1.7

03

1.6

33

1.6

17

1.2

06

1.1

88

3.0

0

2.8

71

.38

1.0

91

.12

2.4

5

4.4

8


N

H3C


S37

1)0.05.010.015.0

7.4

24

7.3

98

7.3

81

7.3

68

7.3

53

7.3

43

7.2

71

5.5

08

5.4

82

5.4

55

3.9

53

3.9

24

3.8

95

3.4

59

3.4

33

3.4

18

3.4

06

3.3

95

3.3

70

3.3

65

3.3

40

3.3

16

3.2

93

1.2

03

1.1

79

1.1

55

0.0

00

00

5.3

7

3.2

6

3.0

2

1.0

0

0.9

8


Ph

NO

O

Et

050100150200

15

7.5

78

13

8.8

28

12

8.8

09

12

8.6

75

12

5.4

41

77

.42

4

77

.00

0

76

.57

6

74

.24

3

51

.53

6

38

.86

0

12

.46

4

13C NMR (75MHz,CDCl3)

Ph

NO

O

Et


S38

0.05.00.0

7.4

45

7.4

297

.41

07.

405

7.3

87

7.3

257.

30

8

7.2

73

4.8

414

.819

4.8

01

4.6

46

4.6

24

4.6

02

4.1

26

4.1

064

.08

6

3.5

72

3.5

54

3.5

36

3.5

183

.50

03.

482

2.8

83

2.8

662

.84

82

.830

2.8

13

2.7

95

1.0

72

1.0

541

.03

6

0.0

000

0

2.9

1.0

1.0

0.9

0.9

1.0

5.2

1HNMR, 400 MHz, CDCl3, 3a

N O

Ph

O

Et


1)050100150200

15

8.0

85

13

7.8

84

12

9.2

49

12

9.0

34

12

6.9

9

77

.42

37

7.0

00

76

.57

7

69

.79

5

59.

35

6

36.

854

12

.09

2

13CNMR, 75.0MHz, CDCl3, 3aONEt

O

13C NMR(100.6MHz, CDCl3)


S39

1)0.05.010.0

7.3

77

7.3

62

7.3

49

7.3

32

7.3

10

5.4

80

5.4

60

5.4

40

3.9

27

3.9

06

3.8

84

3.4

21

3.4

01

3.3

81

3.3

13

3.2

95

3.2

78

3.2

60

3.2

35

3.2

18

3.2

01

3.1

83

1.5

93

1.5

75

1.5

57

1.5

38

0.9

35

0.9

16

0.8

98

0.0

00

00

0

5.0

2

3.0

3

1.8

1

1.0

0

1.0

5

0.8

0

2.1

1


Ph

NO

O

t1)050100150200

15

7.6

84

13

8.7

51

12

8.5

82

12

8.4

36

12

5.2

39

77

.42

6

77

.00

0

76

.57

5

74

.02

6

51

.82

4

45

.52

3

20

.35

6

10

.79

1

13C NMR (75MHz, CDCl3)

Ph

NO

O


S40

1)0.05.010.015.0

7.3

90

7.3

63

7.3

09

7.2

82

5.4

85

5.4

58

5.4

32

3.9

54

3.9

25

3.8

96

3.4

61

3.4

38

3.4

14

3.3

87

3.3

61

3.3

37

3.3

13

3.2

90

3.2

66

1.2

01

1.1

77

1.1

53

0.0

00

00

3.2

4

4.1

6

0.9

6

1.0

0

3.1

8

1H NMR (300MHz, CDCl3)NO

O

Cl

m (t1)050100150200

15

7.3

20

13

7.3

99

13

4.6

32

12

9.0

66

12

6.8

63

77

.42

4

77

.00

0

76

.57

6

73

.52

9

51

.46

1

38

.90

8

12

.46

4

13C NMR (75MHz, CDCl3)N

O

O

Cl


S41

m (t1)0.05.010.015.0

7.2

72

7.2

56

7.2

29

7.2

05

7.1

78

5.4

60

5.4

33

5.4

06

3.9

17

3.8

88

3.8

59

3.4

37

3.4

09

3.3

84

3.3

60

3.3

55

3.3

31

3.3

07

3.2

84

2.3

53

1.1

96

1.1

71

1.1

47

0.0

000

0

3.0

5

3.1

6

0.9

1

1.0

0

3.0

9

4.3

2

1H NMR (300 MHz, CDCl3)N

O

O

Me

m (t1)050100150200

15

7.7

10

13

8.6

34

13

5.8

86

12

9.5

56

12

9.5

00

12

9.4

47

12

9.4

00

12

5.6

19

12

5.5

63

12

5.5

10

12

5.4

63

77

.52

2

77

.09

8

76

.67

3

74

.33

2

51

.60

9

38

.88

9

21

.12

3

12

.52

7

13C NMR (75MHz, CDCl3)N

O

O

Me


Documents

Electronic Supplementary Information ESITaking the systhesis of 1,3-dibutylurea as an example: Firstly, DBU (3 mmol, 0.4567 g) and PEG150 (3 mmol, 0.45 g) were charged into a glass