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Supplementary Information Electronic Supplementary Material (ESI) for Green Chemistry. This journal is © The Royal Society of Chemistry 2019 Supplementary Information Highly regioselective and sustainable solar click reaction: A new Post-synthetic modified triazole organic polymer as recyclable photocatalyst for regioselective azide-alkyne cycloaddition reaction Dolly Yadav,a Nem Singh,a Tae Wu Kim,b Jae Young Kim,a No-Joong Parka and Jin-Ook Baeg*a aArtificial Photosynthesis Research Group, Korea Research Institute of Chemical Technology (KRICT), 100 Jang-dong, Yuseong, Daejeon 34114, Republic of Korea E-mail:[email protected] bCenter for Nanomaterials and Chemical Reactions, Institute for Basic Science (IBS), Daejeon 34141, Korea. S. N. Contents Page no. 1. Experimental section S2-S3 2. Safety issues for handling azide compounds S3 3. Synthetic procedure S4-S18 4. Tables S1-S3 S19-S21 5. Figures S1-S12 S20-S28 6. Crystallographic data of 3bd- figure S12, table S4-S5 S29-S31 7. 1H, 13C and 19F NMR figure S13- S28 S32-S86 8. References S86 S1 Experimental Section 1.1 Materials All the reagents utilized in synthesis were purchased from commercial suppliers, unless or otherwise stated. Sodium Azide, disodium 4,4’-diaminostilbene disulfonate, sodium nitrite, 1,8- diazabicyclo[5,4,0]undec-7-ene, propargyl alcohol, propargyl bromide (80% in toluene), perylene tetracarboxylic anhydride were purchased from Sigma Aldrich Korea. 2,6-difluorobenzylbromide, 2,4-difluorobenzylbromide, 3,5-Dimethylbenzylbromide, 4-bromobenzylbromide, 4- fluorobenzylbromide propiolic acid and methyl propiolate were also purchased from Sigma Aldrich. The solvents DMF, DCM, acetone, ethyl acetate were purchase from Junsei Chemicals Company. Caution sodium azide is considered to be explosive, hence necessary precautions fume hood, safety glasses etc should be taken while carrying out the reaction. Also the reaction should not be carried out on large scale. Please refer to section 2 of the supplementary information for safe handling of azides. 1.2 Instruments and Measurements: Single-crystal X-ray crystallography: The X-ray crystal structure analysis was carried out using a Bruker Kappa APEX II CCD detector equipped Mo K ( = 0.71073 Å) microsource with Quazar optics or Cu K ( = 1.54178 Å) microsource with MX optics. The single crystals were mounted on MicroMesh (MiTeGen) with paratone oil. The structure was solved by direct methods (SHELXT- 2014/5), using the SAINT PLUS and SHELXT data package. The refinement results are summarized in Table S4 and S5. The crystallographic data has been deposited in the Cambridge Crystallographic Data Centre (CCDC) in CIF format under deposition numbers 1889079. The S2 copies of the CIF data can be obtained via www.ccdc.cam.ac.uk/data_request/cif and/or from The Director, CCDC, 12 Union Street, Cambridge CB2 1EZ, U.K. (fax, +44-1223- 336-033; e-mail, [email protected]) free of charges. 2. The safety issues for handling of azido compounds:1,2 2.1. Sodium azide (NaN3) Sodium azide is a toxic chemical (LD50 oral = 27 mg/kg for rats) and can be easily absorbed through the skin. Appropriate protection is needed for the safe handling of the chemical (gloves, safety glasses). Heating sodium azide above 275 °C leads to explosion. Sodium azide are relatively safe especially in aqueous solution, unless acidified to form HN3, which is volatile and highly toxic. 2.2. Organic azide Organic azides are potentially explosive substances that decomposed with the slight input of energy from external sources (heat, light, pressure, etc). When the designed organic azides used for the project, we keep in mind the following equation. It is noted that this equation takes into account all nitrogen atoms in the organic azide, not just those in the azido group. All organic azides are stable enough to be stored under –20 ˚C at least for 6 months. S3 3. Synthetic Procedure: 3 3.1 Synthesis of tetra(prop-2-yn-1-yl) 3,6a-dihydroperylene-3,4,9,10-tetracarboxylate (L1): 1,8-Diazabicyclo[5,4,0]undec-7-ene (114 mL, 0.76 mmol) and propargyl alcohol (88 µL, 1.52 mmol) were added to a stirred solution of perylene tetracarboxylic anhydride (74.5 mg, 0.19 mmol) in DMF (3.5 mL) at 60 ˚C and the resulting mixture was stirred for 30 min. Then, a solution of propargyl bromide (80% in toluene, 115 µL, 1.52 mmol) in DMF (0.5 mL) was added dropwise and the solution was stirred for 3 h at the same temperature. A change in the color of solution changed to bright orange was observed as the reaction proceeded. After the completion of the reaction, the crude product was precipitated in water (50 mL) and the solid was filtered out using a G4 glass filter. The solid obtained was dissolved in DCM (30 mL) and washed with water (2 x10 mL) and brine. The organic phase was dried over Na2SO4 and concentrated in vacuum. The 1 residue was purified by thin layer chromatography (TLC) with DCM to afford L1 as a red solid. H NMR (CDCl3, 500 MHz): δ = 8.51 (2H, d, PDI-H), 8.41(2H, t, PDI-H), 8.28 (2H, dd, PDI-H), 8.10 (2H, d, PDI-H), 4.90 (8H, s, -CH2-), 2.10 (4H, s, CH). 3.2 Synthesis of 4,4'-diazidostilbene-2,2’-disulfonic acid disodium salt (L2): 3.7 g 4,4'-diaminostilbene-Z,2'-disulfonic acid was suspended in 10 mL of water in a three neck round bottom flask equipped with a stirrer, thermometer and dropping funnel. 0.8 g of sodium hydroxide was added to the solution. With continuous stirring 1.4g of sodium nitrite in 4 ml of water was added to the reaction. The reaction was cooled to 0° C. and 8 ml. of 6 N hydrochloric acid are added dropwise so that the reaction temperature could be kept in between 0°- 5° C. Thereafter a solution of 1.4 g. of sodium azide in 4 ml. of water is added dropwise at a temperature between 5 ° and 15° C. Stirring is continued for 5 hour. The precipitate was filtered, S4 washed with alcohol and dried. FTIR (cm-1): 2117.4, 1705.4, 1590.6, 1486.6, 1446.4, 1327.0, 1 1293.7, 1190.4, 1081.0, 1025.4, 830.4, 703.9, 623.5. H NMR (DMSO-d6, 500 MHz): δ = 8.05 (1H, 13 s, ArH), 7.65 (1H, d, ArH), 7.52 (1H, d, ArH), 7.13 (1H, dd, ArH). C NMR (DMSO-d6, 125 MHz): δ = 147.56, 137.56, 132.39, 127.63, 127.08, 120.12, 117.88. 3.3 Synthesis of 4,4'-diazidostilbene-2,2’-disulfonochloride(L3): 10 mL of thionyl chloride was added to 1.3 g. of L2 and refluxed for 8 hours. After completion of reaction the excess of thionyl chloride is evaporated and the residue was extracted with 100 ml. of trichloroethane. The solution was evaporated and the residue obtained was washed with ether. Yield: 0.25g. FTIR (cm-1): 2117.4, 1705.4, 1590.6, 1486.6, 1446.4, 1327.0, 1293.7, 1190.4, 1 1081.0, 1025.4, 830.4, 703.9, 623.5. H NMR (DMSO-d6, 500 MHz): δ = 8.05 (1H, s, ArH), 7.65 (1H, 13 d, ArH), 7.52 (1H, d, ArH), 7.13 (1H, dd, ArH). C NMR (DMSO-d6, 125 MHz): δ = 147.56, 137.56, 132.39, 127.63, 127.08, 120.12, 117.88. 3.4 Synthesis of propiolamide (1a): Methyl propiolate (5 mL, 40 mmol) was added to aqueous ammonia (35%, 100 ml) at -10° C for 2 hr. The reaction mixture was extracted with ethyl acetate (50 x 3 mL), passed over MgSO4. The solvent was removed via rotatory evaporation to yield white 1 13 crystalline solid. H NMR (CDCl3, 500 MHz): δ = 5.78 (2H, s, NH2), 2.80 (1H, s, CH). C NMR (CDCl3, 125 MHz): δ = 172.96, 74.26, 22.65. 3.5 General synthesis of representative azide substrates: (a) General synthesis of benzyl azides: Representative benzyl bromide (1 mmol) is suspended in 10 mL acetone, followed by addition of NaN3 (1.5 mmol) in 15 ml DIW. The reaction mixture was stirred overnight. The completion of reaction was conferred through TLC, after which the product S5 was extract with ethyl acetate (15 mL x 3). The organic layer was washed with DIW (20 mL x 5). The organic layer was passed through magnesium sulfate and the solvent was removed through rotatory evaporation to obtain corresponding azides. Precautionary steps for handling of azides should was thoroughly followed (see section 2, ESI). (b) General synthesis of aromatic azides: Into a 100 mL round bottom flask the representative aniline derivative (10 mmol) was suspended in DIW (15 mL), followed by addition of concentrated HCl (4 mL). The reaction mixture was stirred vigorously in an ice-water bath to maintain a temperature of 0 °C for 20-30 min. After which, a freshly prepared, ice cold solution of NaNO2 (10 mmol) in DIW (3 mL) was added dropwise to the reaction mixture, maintaining the reaction temperature between 0-5 °C. After the complete addition of NaNO2, the reaction mixture was further stirred for an additional 30 min. Then a solution of sodium azide (12 mmol) in DIW (5 mL) was added drop wise to the reaction mixture via additional funnel, maintaining the reaction temperature below 5 °C. Upon complete addition of the sodium azide solution, the reaction mixture was stirred for an additional 1h at 0 °C, followed by stirring at rt for another 3 h. The reaction mixture was then extracted with CH2Cl2 (2×50 mL), and combined organic layers was dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure.
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