Supporting information Acyl Radical Reactions in Fullerene Chemistry: Direct Acylation of [60]Fullerene through an Efficient Decatungstate-Photomediated Approach. Manolis D. Tzirakis and Michael rfanopoulos * Department of Chemistry, University of Crete, 71003 Voutes, eraklion, Crete, Greece E-mail: orfanop@chemistry.uoc.gr Table of Contents 1. General Considerations...S2 2. General Procedure for the TBADT-Catalyzed Photochemical Reactions of Aldehydes 1 14 with C 60...S3 3. Synthetic Procedure of trans-2-phenylcyclopropanecarboxaldehyde (14)...S4 4. Synthetic Procedure and Spectral Data of 4-Methoxybenzaldehyde-d 4 (3-d 4 )...S4 5. Synthetic Procedure and Spectral Data of Benzene-1,4-dicarboxaldehyde-d 1 (4-d 1 )...S5 6. Spectral Data of Functionalized Fullerenes 1a 11a, 13a 14a, 9b 12b...S7 7. 1, 13 C NMR, FT-IR, UV-vis Spectra of Functionalized Fullerenes 1a 11a, 13a 14a, 9b 12b...S22 8. 1 and 13 C NMR Spectra of Methyl 4-methoxybenzoate-d 3...S57 9. 1 and 13 C NMR Spectra of 4-Methoxybenzyl alcohol-d 5...S58 10. 1 and 13 C NMR Spectra of 4-Methoxybenzaldehyde-d 4 (3-d 4 )...S59 11. 1 and 13 C NMR Spectra of 1,4-Benzenedimethanol-d 2...S60 12. 1 and 13 C NMR Spectra of Benzene-1,4-dicarboxaldehyde-d 1 (4-d 1 )...S61 13. 1 NMR Spectrum and GC Chromatogram of Equimolar Mixture of 3-d 0 / 3-d 4...S62 14. Procedure and 1 NMR Spectrum of the Reaction of C 60 with Valeraldehyde 6 in the Presence of D 2...S63 15. 1 NMR Spectrum of the Reaction of C 60 with 3-d 0 / 3-d 4...S64 16. 1 NMR Spectrum of the Reaction of C 60 with 4-d 1...S65 S1
1. General Considerations Unless otherwise noted, all materials including dry solvents were obtained from commercial suppliers and used without further purification. Tetrabutylammonium Decatungstate (TBADT) was prepared according to procedure reported in the literature. 1 1 NMR and 13 C NMR spectra were recorded on Bruker AMX-500 Mz (125 Mz for 13 C) and DPX-300 Mz (75 Mz for 13 C) spectrometers, in CDCl 3, CDCl 3 /CS 2 or DCB-d 4 solutions. Chemical shifts are reported in ppm downfield from Me 4 Si, by using the residual solvent peak as internal standard. FT-IR spectra were recorded on a PerkinElmer Fourier transform infrared spectrometer, using KBr pellets. UV-vis spectra were performed on a Shimadzu MultiSpec-1501 UV/Visible spectrometer. PLC analysis was conducted on a Marathon III instrument equipped with a 5C18-MS (4.6 250 mm, Nacalai Tesque) reversed phase column with detection at 310 nm. A mixture of toluene/acetonitrile (1:1 v/v) was used as eluent at 1 ml/min flow rate. Semi-preparative PLC was performed with a Marathon III instrument equipped with a Cosmosil 5PBB column (10 250 mm, Nacalai Tesque) with detection at 310 nm. A mixture of toluene/acetonitrile (4:1 v/v) was used as eluent (unless otherwise noted) at 5 ml/min flow rate. Flash column chromatography was carried out on Si 2 (silica gel 60, SDS, 230-400 mesh ASTM). Evaporation of the solvents was accomplished with a rotary evaporator or by high vacuum distillation. Negative-ion MALDI spectra were recorded for all the new compounds using DCTB as the matrix. GC-MS analysis was performed on a Shimadzu GC MS-QP5050A apparatus equipped with a Supelco capillary column (MDN-5, 30m 0.25mm, 0.25μm film thickness) and a 5971A MS detector. Photochemical reactions were carried out by using a 300-W xenon lamp as the light source. 1 See reference 7b. S2
2. General Procedure for the TBADT-Catalyzed Photochemical Reactions of Aldehydes 1 14 with C 60 Unless otherwise noted in the individual procedures below, a solution of C 60 (20 mg, 0.028 mmol) in a mixture of chlorobenzene/acetonitrile 85:15 (80 ml) was added in a 150-mL glass flask containing a magnetic stirring bar. This solution was degassed by performing three freeze-pump-thaw cycles under argon, and then TBADT (18.5 mg, 0.0056 mmol) and the aldehyde substrate (2.7 mmol) were added. The resulting solution was serum capped and purged for 20 min with argon. This solution was subsequently irradiated at 5 10 C using an ice water bath, while a constant, slow argon stream was maintained over the solution (the progress of all reactions was monitored by PLC). Then, the solvent and the aldehyde 1 14 were distilled from the reaction mixture under reduced pressure, and the remaining crude product was centrifuged three times with acetonitrile PLC grade. The isolated product was further purified by flash column chromatography (eluent: hexane/toluene 4:1 v/v) and/or semi-preparative PLC (eluent: toluene/acetonitrile 4:1 v/v, 5 ml/min flow rate, detection at 310 nm) to afford the fullerene adducts 1a 11a, 13a 14a and 9b 12b, along with a small amount of a complex mixture of several unidentified byproducts. During the purification procedure, we noticed that adducts 1 5 were almost quantitively converted into the hydrogenated fullerene adduct C 60 2 when treated with silica or alumina gel. 2 Thus, adducts 1a 5a were purified with semi-preparative PLC (eluent: toluene/acetonitrile 4:1 v/v, 5 ml/min flow rate, detection at 310 nm). Blank experiments in the absence of TBADT showed that a small but considerable amount of the corresponding fullerene adducts could be formed, in the reaction of aromatic aldehydes 1 4 with C 60. This result should be rationalized on the -atom abstraction ability of the excited triplet state (n-π * ) of the carbonyl group in benzaldehydes. 2 C 60 2 : IR (KBr): ν (cm -1 ) = 2954, 1427, 1263, 1183, 1041, 577, 566, 550, 527; UV-vis (CCl 3 ): λ max (nm) = 257, 328, 405, 433; MS (MALDI, negative, DCTB): m/z 722; 1 NMR (500 Mz, CDCl 3 /CS 2 ): δ 7.00 (s, 1); See also reference 15. S3
3. Synthetic Procedure of trans-2-phenylcyclopropanecarboxaldehyde (14) LiAl 4 PCC Ph TF Ph C 2 Cl 2 Ph 14 trans-2-phenylcyclopropanecarboxaldehyde (14) was prepared following the reported procedure. 3 trans-2-phenylcyclopropanecarboxylic acid was reduced with lithium aluminum hydride in TF to give the corresponding alcohol which was subsequently oxidized using PCC to afford trans-2-phenylcyclopropanecarboxaldehyde. 4. Synthetic Procedure and Spectral Data of 4-Methoxybenzaldehyde-d 4 (3-d 4 ) Na / CD 3 I C 3 DMF CD 3 LiAlD 4 C 3 TF CD 3 D D PCC C 2 Cl 2 CD 3 D 3-d 4 Methyl 4-methoxybenzoate-d 3. Methyl 4-hydroxybenzoate (1.00 g, 6.57 mmol) was dissolved in 12 ml of dry DMF, under an Ar atmosphere. The solution was cooled to 0 C and 315 mg (7.88 mmol) of Na (60% in mineral oil) was added. The mixture was stirred at room temperature for 30 min and 0.9 ml of CD 3 I was added at 0 C. Stirring was continued at room temperature for 30 min and then Et 2 (30 ml) was added to the reaction mixture. The mixture was washed three times with brine, dried over MgS 4 and concentrated in vacuo to afford the desired methyl 4-methoxybenzoate-d 3 (1.00 gr, 90%). 1 NMR (500 Mz, CDCl 3 ): δ 7.99 (d, J = 8.5 z, 2), 6.91 (d, J = 8.5 z, 2), 3,88 (s, 3); 13 C NMR (125 Mz, CDCl3): δ 166.60, 163.23, 131.43, 122.44, 113.44, 54.36 (eptaplet, J C-D = 22 z), 51.59; MS: m/z = 169 (M 31, 138). 4-Methoxybenzyl alcohol-d 5. To a solution of methyl 4-methoxybenzoate-d 3 (1.00 g, 5.91 mmol) in anhydrous TF (60 ml) under an Ar atmosphere at 0 C, was added lithium aluminum deuteride LiAlD 4 (126 mg, 3 mmol). The reaction was then warmed to room temperature and stirred for 90 min. The mixture 3 Baldwin, J. E.; Patapoff, T. W.; Barden, T. C. J. Am. Chem. Soc. 1984, 106, 1421 1426. S4
was treated with 2 and 10% Na, and extracted twice with Et 2. The layers were separated and the organic phase dried (MgS 4 ) and concentrated in vacuo to afford the desired 4-methoxybenzyl alcohol-d 5 (762 mg, 90%). 1 NMR (500 Mz, CDCl 3 ): δ 7.27 (d, J = 8.5 z, 2), 6.91 (d, J = 8.5 z, 2); 13 C NMR (125 Mz, CDCl 3 ): δ 158.64, 132.94, 128.33, 113.49, 63.27 (pentaplet, J C-D = 21.5 z), 54.04 (heptaplet, J C-D = 21.75 z); MS: m/z = 143 (M 30, 113). 4-Methoxybenzaldehyde-d 4 (3-d 4 ). 4-Methoxybenzyl alcohol-d 5 (600 mg, 4.2 mmol) was oxidized to 4-methoxybenzaldehyde-d 4 (3-d 4 ) with PCC (1.08 g, 5.0 mmol) in dry C 2 Cl 2 (30 ml) at room temperature (3-4 hours), under an Ar atmosphere. The reaction mixture was filtered through a plug of Celite - Silica gel to afford 4-methoxybenzaldehyde-d 4 (3-d 4 ) (530 mg, 90%). 1 NMR (500 Mz, CDCl 3 ): δ 7.83 (d, J = 8.5 z, 2), 7.10 (d, J = 8.5 z, 2); 13 C NMR (125 Mz, CDCl 3 ): δ 189.92 (t, J C-D = 26.25 z), 164.20, 131.45, 129.47 (t, J C-D = 3.37 z), 113.90, 54.30 (eptaplet, J C-D = 22 z); MS: m/z = 138 (M 60, 78). 5. Synthetic Procedure and Spectral Data of Benzene-1,4-dicarboxaldehyde-d 1 (4-d 1 ) C 3 LiAlD 4 Et 2 D D PCC TF 4-d 1 D 1,4-Benzenedimethanol-d 2. To a solution of methyl 4-(hydroxymethyl)benzoate (1.0 g, 5.9 mmol) in anhydrous Et 2 (40 ml) under an Ar atmosphere at 0 C, was added lithium aluminum deuteride LiAlD 4 (252 mg, 6 mmol). The reaction mixture was refluxed for 24 h. The mixture was then treated with 2 and 10% Na, and extracted twice with Et 2. The layers were separated and the organic phase dried (MgS 4 ) and concentrated in vacuo to afford the desired 1,4-benzenedimethanol-d 2 (703 mg, 85%). 1 NMR (500 Mz, Acetone-d 6 ): δ 7.30 (s, 4), 4.60 (d, J = 5.5 z, 2), 4.17 (t, J = 5.5 z, 1), 4.13 (s, 1); 13 C NMR (125 Mz, Acetone-d 6 ): δ 141.45, 141.33, 126.88, 126.82, 64.10, 63.41 (pentaplet, J C-D = 21.37 z); MS: m/z = 140 (M 61, 79). S5
Benzene-1,4-dicarboxaldehyde-d 1 (4-d 1 ). 1,4-Benzenedimethanol-d 2 (600 mg, 4.28 mmol) was oxidized to benzene-1,4-dicarboxaldehyde-d 1 (4-d 1 ) with PCC (1.85 g, 8.6 mmol) in dry TF (50 ml) at room temperature (4 hours), under an Ar atmosphere. The reaction mixture was filtered through a plug of Celite - Silica gel to afford benzene-1,4-dicarboxaldehyde-d 1 (4-d 1 ) (520 mg, 90%). 1 NMR (500 Mz, CDCl 3 ): δ 10.14 (s,1), 8.06 (s, 4); 13 C NMR (125 Mz, CDCl 3 ): δ 191.54, 191.23 (t, J C-D = 27 z), 140.05, 139.97 (t, J C-D = 3.62 z), 130.14; MS: m/z = 135 (M 84, 51). S6
6. Spectral Data of Functionalized Fullerenes 1a 11a, 13a 14a, 9b 12b Functionalized Fullerene 1a Compound 1a has been prepared following the general procedure described in Section 2, by using 20 mg (0.0278 mmol) of C 60, 18.5 mg (0.0056 mmol) of TBADT and 295 mg (2.78 mmol) of benzaldehyde, in a mixture of chlorobenzene/acetonitrile 85:15 (80 ml). The progress of the reaction was monitored by analytical PLC (5C18-MS, 4.6 x 250 mm, 1 ml/min, toluene/acetonitrile 1:1, 310 nm). The reaction mixture was irradiated at 5 10 C for 30 min, after which time the solvent was evaporated under reduced pressure. Acetonitrile was then added and the resulting suspension was centrifuged at 4100 rpm for 10min (3 times). Further purification of the resulting precipitate by semi-preparative PLC (5PBB, 10 250 mm, 5 ml/min, toluene/acetonitrile 8:2, 310 nm) afforded ca. 8.0 mg of 1a (0.01 mmol, 35%). IR (KBr): ν (cm -1 ) = 2915, 1672, 1426, 1224, 1180, 1008, 869, 691, 578, 526; UV-vis (CCl 3 ): λ max (nm) = 255, 323, 433; MS (MALDI, negative, DCTB): m/z 826.157; 1 NMR (300 Mz, CS 2 /CDCl 3 ): δ 7.36 (s, 1), 7.68-7.80 (m, 3), 8.70-8.73 (m, 2); 13 C NMR (75 Mz, DCB-d 4 ): δ 196.92, 151.23, 150.31, 146.70, 146.53, 146.25, 145.69, 145.67, 145.51, 145.50, 145.01, 144.96, 144.76, 144.71, 144.68, 143.97, 143.65, 142.52, 142.26, 142.00, 141.89, 141.41, 141.39, 141.36, 141.03, 140.93, 140.88, 139.87, 139.37, 135.84, 135.35, 135.22, 132.89, 128.50, 76.76, 57.21. S7
Functionalized Fullerene 2a Me Compound 2a has been prepared following the general procedure described in Section 2, by using 20 mg (0.0278 mmol) of C 60, 18.5 mg (0.0056 mmol) of TBADT and 334 mg (2.78 mmol) of p-tolualdehyde, in a mixture of chlorobenzene/acetonitrile 85:15 (80 ml). The progress of the reaction was monitored by analytical PLC (5C18-MS, 4.6 x 250 mm, 1 ml/min, toluene/acetonitrile 1:1, 310 nm). The reaction mixture was irradiated at 5 10 C for 50 min, after which time the solvent was evaporated under reduced pressure. Acetonitrile was then added and the resulting suspension was centrifuged at 4100 rpm for 10min (3 times). Further purification of the resulting precipitate by semi-preparative PLC (5PBB, 10 250 mm, 5 ml/min, toluene/acetonitrile 8:2, 310 nm) afforded ca. 8.2 mg of 2a (0.01 mmol, 35%). IR (KBr): ν (cm -1 ) = 2915, 1671, 1604, 1511, 1426, 1233, 1180, 1008, 872, 801, 578, 526; UV-vis (CCl 3 ): λ max (nm) = 257, 325, 433, 485; MS (MALDI, negative, DCTB): m/z 840.015; 1 NMR (300 Mz, DCBd 4 ): δ 8.74 (d, J = 8.1 z, 2), 7.36 (d, J = 8.1 z, 2), 7.13 (s, 1), 2.39 (s, 3); 13 C NMR (75 Mz, DCB-d 4 ): 195.51, 150.44, 149.94, 145.93, 145.78, 145.51, 145.47, 144.90, 144.89, 144.72, 144.23, 144.18, 143.96, 143.91, 143.31, 143.19, 142.93, 141.76, 141.22, 141.12, 140.65, 140.59, 140.55, 140.25, 140.21, 140.11, 139.10, 138.62, 134.58, 134.51, 132.13, 128.62, 128.52, 75.88, 56.74, 20.40. S8
Functionalized Fullerene 3a Me Compound 3a has been prepared following the general procedure described in Section 2, by using 20 mg (0.0278 mmol) of C 60, 18.5 mg (0.0056 mmol) of TBADT and 378 mg (2.78 mmol) of 4-methoxybenzaldehyde, in a mixture of chlorobenzene/acetonitrile 85:15 (80 ml). The progress of the reaction was monitored by analytical PLC (5C18-MS, 4.6 x 250 mm, 1 ml/min, toluene/acetonitrile 1:1, 310 nm). The reaction mixture was irradiated at 5 10 C for 80 min, after which time the solvent was evaporated under reduced pressure. Acetonitrile was then added and the resulting suspension was centrifuged at 4100 rpm for 10min (3 times). Further purification of the resulting precipitate by semipreparative PLC (5PBB, 10 250 mm, 5 ml/min, toluene/acetonitrile 8:2, 310 nm) afforded ca. 8.4 mg of 3a (0.01 mmol, 35%). IR (KBr): ν (cm -1 ) = 2916, 1664, 1597, 1571, 1508, 1460, 1420, 1261, 1238, 1170, 1015, 872, 845, 729, 526; UV-vis (CCl 3 ): λ max (nm) = 257, 325, 432; MS (MALDI, negative, DCTB): m/z 856.033; 1 NMR (500 Mz, CS 2 /CDCl 3 ): δ 8.86 (d, J = 9.0 z, 2), 7.23 (s, 1), 7.19 (d, J = 9.0 z, 2), 4.02 (s, 3); 13 C NMR (75 Mz, CS 2 /CDCl 3 ): δ 195.96, 164.13, 151.77, 151.36, 147.01, 146.83, 146.48, 146.42, 146.30, 146.29, 145.76, 145.74, 145.54, 145.50, 144.71, 144.55, 143.34, 142.79, 142.73, 142.71, 142.25, 142.13, 142.03, 141.81, 141.75, 141.71, 140.67, 140.20, 136.21, 135.81, 132.45, 128.40, 114.50, 77.36, 58.37, 55.66. S9
Functionalized Fullerene 4a C= Compound 4a has been prepared following the general procedure described in Section 2, by using 20 mg (0.0278 mmol) of C 60, 18.5 mg (0.0056 mmol) of TBADT and 373 mg (2.78 mmol) of terephthalaldehyde, in a mixture of chlorobenzene/acetonitrile 85:15 (80 ml). The progress of the reaction was monitored by analytical PLC (5C18-MS, 4.6 x 250 mm, 1 ml/min, toluene/acetonitrile 1:1, 310 nm). The reaction mixture was irradiated at 5 10 C for 25 min, after which time the solvent was evaporated under reduced pressure. Acetonitrile was then added and the resulting suspension was centrifuged at 4100 rpm for 10min (3 times). Further purification of the resulting precipitate by semi-preparative PLC (5PBB, 10 250 mm, 5 ml/min, toluene/acetonitrile 8:2, 310 nm) afforded ca. 9.5 mg of 4a (0.011 mmol, 40%). IR (KBr): ν (cm -1 ) = 2964, 1698, 1503, 1422, 1262, 1094, 1020, 802, 699, 572, 522; UV-vis (CCl 3 ): λ max (nm) = 258, 329, 433; MS (MALDI, negative, DCTB): m/z 854.041; 1 NMR (500 Mz, CS 2 /CDCl 3 ): δ 10.20 (s, 1), 8.66 (d, J = 8.0 z, 2), 8.16 (d, J = 8.0 z, 2), 7.49 (s, 1); 13 C NMR (125 Mz, DCBd 4 /CS 2 ): δ 197.16, 189.60, 152.00, 149.87, 147.44, 147.24, 146.94, 146.54, 146.43, 146.29, 145.82, 145.76, 145.60, 145.51, 145.44, 144.76, 144.33, 143.34, 143.07, 142.83, 142.70, 142.20, 141.99, 141.84, 141.67, 141.56, 141.27, 140.76, 140.47, 140.16, 139.15, 136.31, 135.67, 129.67, 77.58, 57.17. S10
Functionalized Fullerene 5a Compound 5a has been prepared following the general procedure described in Section 2, by using 20 mg (0.0278 mmol) of C 60, 18.5 mg (0.0056 mmol) of TBADT and 195 mg (2.78 mmol) of crotonaldehyde, in a mixture of chlorobenzene/acetonitrile 85:15 (80 ml). The progress of the reaction was monitored by analytical PLC (5C18-MS, 4.6 x 250 mm, 1 ml/min, toluene/acetonitrile 1:1, 310 nm). The reaction mixture was irradiated at 5 10 C for 80 min, after which time the solvent was evaporated under reduced pressure. Acetonitrile was then added and the resulting suspension was centrifuged at 4100 rpm for 10min (3 times). Further purification of the resulting precipitate by semi-preparative PLC (5PBB, 10 250 mm, 5 ml/min, toluene/acetonitrile 8:2, 310 nm) afforded ca. 8.7 mg of 5a (0.011 mmol, 40%). IR (KBr): ν (cm -1 ) = 2849, 1687, 1620, 1431, 1288, 1259, 1094, 1054, 957, 898, 806, 768, 574, 553, 526; UV-vis (CCl 3 ): λ max (nm) = 256, 329, 433; MS (MALDI, negative, DCTB): m/z 790.025; 1 NMR (500 Mz, CS 2 /CDCl 3 ): δ 7.80 (s, 1), 7.77 7.80 (m, 1) 7.67-7.74 (m, 1), 2.21 (dd, J 1 = 7.0 z, J 2 = 1.5 z, 3); 13 C NMR (125 Mz, CS 2 /CDCl 3 ): δ 190.83, 153.46, 150.16, 148.59, 148.58, 147.68, 147.24, 147.15, 146.96, 146.49, 146.23, 146.14, 145.83, 145.57, 145.54, 145.29, 145.23, 144.73, 144.16, 143.28, 142.70, 142.59, 142.40, 142.16, 142.03, 141.70, 141.55, 141.54, 140.63, 140.07, 136.61, 135.17, 126.10, 77.53, 55.45, 19.08. S11
Functionalized Fullerene 6a Compound 6a has been prepared following the general procedure described in Section 2, by using 20 mg (0.0278 mmol) of C 60, 18.5 mg (0.0056 mmol) of TBADT and 239 mg (2.78 mmol) of valeraldehyde, in a mixture of chlorobenzene/acetonitrile 85:15 (80 ml). The progress of the reaction was monitored by analytical PLC (5C18-MS, 4.6 x 250 mm, 1 ml/min, toluene/acetonitrile 1:1, 310 nm). The reaction mixture was irradiated at 5 10 C for 90 min, after which time the solvent was evaporated under reduced pressure. Acetonitrile was then added and the resulting suspension was centrifuged at 4100 rpm for 10min (3 times). Further purification of the resulting precipitate via flash column chromatography on silica (hexane/toluene 8:2) afforded ca. 11.2 mg of 6a (0.014 mmol, 50%). IR (KBr): ν (cm -1 ) = 2919, 2852, 1720, 1460, 1429, 1185, 1121, 1052, 766, 574, 554, 528; UV-vis (CCl 3 ): λ max (nm) = 257, 325, 405, 433; MS (MALDI, negative, DCTB): m/z 806.230; 1 NMR (500 Mz, CS 2 /CDCl 3 ): δ 7.72 (s, 1), 3.73 (t, J = 7 z, 2), 2.07 (m, 2), 1.61 (m, 2), 1.09 (t, J = 7.5 z, 3); 13 C NMR (75 Mz, CS 2 /CDCl 3 ): δ 203.49, 153.48, 150.23, 147.56, 147.27, 147.15, 147.00, 146.53, 146.25, 146.19, 146.18, 145.86, 145.58, 145.56, 145.34, 145.26, 144.76, 144.17, 143.32, 142.76, 142.65, 142.41, 142.22, 142.07, 141.77, 141.61, 141.52, 140.68, 140.18, 136.42, 135.13, 78.70, 55.80, 39.92, 26.98, 22.76, 14.30. S12
Functionalized Fullerene 7a Compound 7a has been prepared following the general procedure described in Section 2, by using 20 mg (0.0278 mmol) of C 60, 18.5 mg (0.0056 mmol) of TBADT and 411 mg (2.78 mmol) of 3-phenylbutyraldehyde, in a mixture of chlorobenzene/acetonitrile 85:15 (80 ml). The progress of the reaction was monitored by analytical PLC (5C18-MS, 4.6 x 250 mm, 1 ml/min, toluene/acetonitrile 1:1, 310 nm). The reaction mixture was irradiated at 5 10 C for 60 min, after which time the solvent was evaporated under reduced pressure. Acetonitrile was then added and the resulting suspension was centrifuged at 4100 rpm for 10min (3 times). Further purification of the resulting precipitate via flash column chromatography on silica (hexane/toluene 8:2) afforded ca. 10.8 mg of 7a (0.012 mmol, 45%). IR (KBr): ν (cm -1 ) = 2915, 1712, 1510, 1427, 1182, 754, 696, 575, 526; UV-vis (CCl 3 ): λ max (nm) = 258, 328, 433; MS (MALDI, negative, DCTB): m/z 868.103; 1 NMR (500 Mz, CS 2 /CDCl 3 ): δ 7.59 (s, 1), 7.30 7.36 (m, 4), 7.20 7.23 (m, 1), 4.06 4.14 (m, 1), 3.81 3.90 (m, 2), 1.58(d, J = 6.5 z, 3); 13 C NMR (125 Mz, CS 2 /CDCl 3 ): δ 202.46, 153.44, 153.30, 149.75, 149.55, 147.56, 147.52, 147.33, 147.12, 147.06, 146.58, 146.55, 146.30, 146.24, 146.22, 146.21, 145.88, 145.86, 145.84, 145.64, 145.63, 145.54, 145.39, 145.34, 145.28, 145.24, 144.79, 144.21, 144.19, 143.34, 143.32, 143.12, 142.78, 142.68, 142.66, 142.42, 142.38, 142.24, 142.11, 141.80, 141.78, 141.66, 141.59, 141.53, 140.69, 140.66, 140.19, 140.08, 136.68, 136.50, 135.18, 135.11, 128.83, 127.11, 126.87, 78.95, 55.49, 48.25, 36.63, 22.02. S13
Functionalized Fullerene 8a Compound 8a has been prepared following the general procedure described in Section 2, by using 20 mg (0.0278 mmol) of C 60, 18.5 mg (0.0056 mmol) of TBADT and 311 mg (2.78 mmol) of cyclohexanecarboxaldehyde, in a mixture of chlorobenzene/acetonitrile 85:15 (80 ml). The progress of the reaction was monitored by analytical PLC (5C18-MS, 4.6 x 250 mm, 1 ml/min, toluene/acetonitrile 1:1, 310 nm). The reaction mixture was irradiated at 5 10 C for 60 min, after which time the solvent was evaporated under reduced pressure. Acetonitrile was then added and the resulting suspension was centrifuged at 4100 rpm for 10min (3 times). Further purification of the resulting precipitate via flash column chromatography on silica (hexane/toluene 8:2) afforded ca. 10.4 mg of 8a (0.012 mmol, 45%). IR (KBr): ν (cm -1 ) = 2917, 1711, 1447, 1428, 1141, 1094, 998, 766, 730, 574, 554, 527; UV-vis (CCl 3 ): λ max (nm) = 260, 325, 434; MS (MALDI, negative, DCTB): m/z 832.069; 1 NMR (500 Mz, CS 2 /CDCl 3 ): δ 7.77 (s, 1), 4.19 4.25 (m, 1), 2.23 2.25 (m, 2), 1.94 2.00 (m, 4), 1.84 1.87 (m, 1), 1.42 1.54 (m, 3); 13 C NMR (125 Mz, CS 2 /CDCl 3 ): δ 206.16, 153.73, 149.77, 147.69, 147.29, 147.17, 147.04, 146.59, 146.31, 146.24, 146.22, 145.93, 145.64, 145.60, 145.39, 145.28, 144.83, 144.21, 143.38, 142.80, 142.69, 142.45, 142.28, 142.10, 141.81, 141.61, 140.68, 140.16, 136.58, 135.10, 78.79, 55.72, 47.05, 30.88, 25.87. S14
Functionalized Fullerenes 9a and 9b 9a 9b Compounds 9a and 9b have been prepared following the general procedure described in Section 2, by using 20 mg (0.0278 mmol) of C 60, 37 mg (0.011 mmol) of TBADT and 356 mg (2.78 mmol) of 2-ethylhexanal, in a mixture of chlorobenzene/acetonitrile 85:15 (80 ml). The progress of the reaction was monitored by analytical PLC (5C18-MS, 4.6 x 250 mm, 1 ml/min, toluene/acetonitrile 1:1, 310 nm). The reaction mixture was irradiated at 5 10 C for 80 min, after which time the solvent was evaporated under reduced pressure. Acetonitrile was then added and the resulting suspension was centrifuged at 4100 rpm for 10min (3 times). Further purification of the resulting precipitate via flash column chromatography on silica (hexane/toluene 8:2) afforded ca. 9.4 mg of 9a (0.011 mmol, 40%) and ca. 0.5 mg of 9b (0.6 μmol, 2%). When the same reaction was carried out at T = -40 C for 80 min, only the adduct 9a was isolated in 35% yield (8.2 mg, 0.01 mmol). 9a: IR (KBr): ν (cm -1 ) = 2917, 1712, 1460, 1427, 1028, 754, 574, 527; UV-vis (CCl 3 ): λ max (nm) = 257, 328, 433; MS (MALDI, negative, DCTB): m/z 848.131; 1 NMR (500 Mz, CDCl 3 /CS 2 ): δ 7.79 (s, 1), 4.24 (m, 1), 2.15 (m, 2), 1.90 (m, 1), 1.80 (m, 1), 1.50 (m, 2), 1.40 (m, 2), 1.14 (t, J = 7.0 z, 3), 0.96 (t, J = 7.0 z, 3); 13 C NMR (125 Mz, CDCl 3 /CS 2 ): δ 207.11, 153.94, 153.93, 149.96, 149.93, 147.76, 147.69, 147.39, 147.27, 147.13, 146.67, 146.40, 146.32, 146.31, 146.01, 146.00, 145.72, 145.66, 145.64, 145.48, 145.36, 144.91, 144.29, 143.47, 143.19, 142.87, 142.76, 142.56, 142.36, 142.19, 141.88, 141.70, 141.69, 141.67, 140.74, 140.15, 140.09, 136.54, 135.18, 79.53, 56.03, 49.46, 32.59, 30.12 26.38, 23.07, 14.10, 12.55. S15
9b: UV-vis (CCl 3 ): λ max (nm) = 256, 324, 433; MS (MALDI, negative, DCTB): m/z 820.135; 1 NMR (500 Mz, CDCl 3 /CS 2 ): δ 6.48 (s, 1), 3.05 (m, 1), 2.94 (m, 2), 2.40 (m, 2), 1.95 (m, 1), 1.86 (m, 1), 1.67 (m, 2), 1.53 (t, J = 7.5 z, 3), 1.13 (t, J = 7.5 z, 3). Functionalized Fullerenes 10a and 10b 10a 10b Compounds 10a and 10b have been prepared following the general procedure described in Section 2, by using 20 mg (0.0278 mmol) of C 60, 18.5 mg (0.0056 mmol) of TBADT and 239 mg (2.78 mmol) of pivalaldehyde, in a mixture of chlorobenzene/acetonitrile 85:15 (80 ml). The progress of the reaction was monitored by analytical PLC (5C18-MS, 4.6 x 250 mm, 1 ml/min, toluene/acetonitrile 1:1, 310 nm). The reaction mixture was irradiated at 5 10 C for 50 min, after which time the solvent was evaporated under reduced pressure. Acetonitrile was then added and the resulting suspension was centrifuged at 4100 rpm for 10min (3 times). Further purification of the resulting precipitate via flash column chromatography on silica (hexane/toluene 8:2) afforded ca. 2.2 mg of 10a (0.003 mmol, 10%) and ca. 3.9 mg of 10b (0.005 mmol, 18%). The same reaction was also carried out by using 5 mg (7 μmol) of C 60, 11.6 mg (3.5 μmol) of TBADT and 120 mg (1.4 mmol) of pivalaldehyde, at T = -40 C. After 25 min, the reaction was concentrated and purified by flash column chromatography on silica (hexane/toluene 8:2) to afford ca. 1.9 mg of 10a (2.4 μmol, 35%) and ca. 0.2 mg of 10b (0.2 μmol, 3%). 10a: IR (KBr): ν (cm -1 ) = 2946, 1697, 1474, 1460, 1426, 1360, 1183, 1056, 1006, 880, 578, 526; UV-vis (CCl 3 ): λ max (nm) = 255, 325, 433, 485; MS (MALDI, negative, DCTB): m/z 806.180; 1 NMR (500 Mz, DCB-d 4 ): δ 6.56 (s, 1), 1.89 (s, 9); 13 C NMR (125 Mz, DCB-d 4 ): δ 210,28, 152,19, 150,94, S16
147,31, 147,17, 147,10, 146,34, 146,27, 146,18, 145,92, 145,71, 145,44, 145,40, 145,35, 144,66, 144,36, 143,23, 142,65, 142,59, 142,05, 142,00, 141,96, 141,74, 141,68, 141,56, 140,51, 139,76, 136,56, 136,37, 75,84, 60,53, 49,00, 27,87. 10b: (Mixture of 1,2 and 1,4-isomers, 5:1 molar ratio) IR (KBr): ν (cm -1 ) = 2959, 2866, 1512, 1462, 1427, 1397, 1370, 1200, 1189, 1094, 904, 764, 730, 583, 573, 554, 527; UV-vis (CCl 3 ): λ max (nm) = 256, 328, 433; MS (MALDI, negative, DCTB): m/z 778.075; 1 NMR (500 Mz, CS 2 /CDCl 3 ): δ 6.69 (s, 1, 1,2- isomer), 6.33 (s, 1, 1,4-isomer), 2.10 (s, 9, 1,2-isomer), 1.90 (s, 9, 1,4-isomer); 13 C NMR (125 Mz, CS 2 /CDCl 3 ): δ 154.52, 153.92, 147.59, 147.31, 147.08, 146.96, 146.83, 146.30, 146.29, 146.14, 146.05, 145.76, 145.28, 145.26, 144.62, 144.42, 143.17, 142.58, 142.56, 142.13, 142.11, 142.00, 141.62, 141.53, 141.38, 140.31, 139.02, 136.43, 136.37, 73.44, 56.96, 48.81, 41.32, 41.13, 27.53, 26.79. Functionalized Fullerene 11a and 11b 11a 11b Compounds 11a and 11b have been prepared following the general procedure described in Section 2, by using 20 mg (0.0278 mmol) of C 60, 18.5 mg (0.0056 mmol) of TBADT and 334 mg (2.78 mmol) of phenylacetaldehyde, in a mixture of chlorobenzene/acetonitrile 85:15 (80 ml). The progress of the reaction was monitored by analytical PLC (5C18-MS, 4.6 x 250 mm, 1 ml/min, toluene/acetonitrile 1:1, 310 nm). The reaction mixture was irradiated at 5 10 C for 60 min, after which time the solvent was evaporated under reduced pressure. Acetonitrile was then added and the resulting suspension was centrifuged at 4100 rpm for 10min (3 times). Further purification of the resulting precipitate via flash column chromatography on silica (hexane/toluene 8:2) afforded ca. 2.3 mg of 11a (0.003 mmol, 10%) and ca. 4.5 mg of 11b (0.0055 mmol, 20%). S17
The same reaction was also carried out by using 20 mg (0.0278 mmol) of C 60, 46 mg (0.014 mmol) of TBADT and 667 mg (5.56 mmol) of phenylacetaldehyde, at T = -50 C. After 70 min, the reaction was concentrated and purified by flash column chromatography on silica (hexane/toluene 8:2) to afford ca. 8.1 mg of 11a (0.01 mmol, 35%). 11a: IR (KBr): ν (cm -1 ) = 2916, 1720, 1493, 1426, 1088, 1037, 752, 703, 575, 527; UV-vis (CCl 3 ): λ max (nm) = 259, 329, 433; MS (MALDI, negative, DCTB): m/z 840.067; 1 NMR (500 Mz, DCB-d 4 /CS 2 ): δ 7.60 (s, 1), 7.20 7.34 (m, 5), 4.88 (s, 2); 13 C NMR (125 Mz, DCB-d 4 /CS 2 ): δ 200.90, 153.56, 150.07, 147.78, 147.55, 147.35, 147.28, 146.82, 146.54, 146.47, 146.45, 146.11, 145.94, 145.87, 145.61, 145.52, 145.04, 144.44, 143.57, 143.31, 143.03, 142.92, 142.66, 142.50, 142.36, 142.04, 141.95, 141.77, 140.92, 140.53, 137.02, 135.40, 133.87, 132.72, 129.26, 79.14, 56.24, 46.37. 11b: IR (KBr): ν (cm -1 ) = 1493, 1460, 1452, 1427, 1259, 1215, 1181, 1064, 1024, 807, 760, 744, 722, 697, 662, 575, 546, 525, 512, 475; UV-vis (CCl 3 ): λ max (nm) = 257, 326, 433, 485; MS (MALDI, negative, DCTB): m/z 812.015; 1 NMR (500 Mz, DCB-d 4 ): δ 7.77 (d, J = 7.5 z, 2), 7.45 (dd, J 1 = J 2 = 7.5 z, 2), 7.35 (t, J = 7.5 z, 1), 6.52 (s, 1), 4,65 (s, 2); 13 C NMR (75 Mz, CS 2 /CDCl 3 ): δ 155.22, 153.75, 147.45, 147.29, 146.92, 146.41, 146.37, 146.27, 146.24, 146.17, 145.77, 145.49, 145.43, 145.38, 144.70, 144.56, 143.22, 142.56, 142.19, 142.03, 141.97, 141.90, 141.65, 141.58, 140.21, 139.96, 136.33, 136.06, 135.74, 131.39, 128.81, 127.82, 65.85, 59.13, 53.20. S18
Functionalized Fullerene 12b Compound 12b has been prepared following the general procedure described in Section 2, by using 20 mg (0.0278 mmol) of C 60, 18.5 mg (0.0056 mmol) of TBADT and 373 mg (2.78 mmol) of 2-phenylpropionaldehyde, in a mixture of chlorobenzene/acetonitrile 85:15 (80 ml). The progress of the reaction was monitored by analytical PLC (5C18-MS, 4.6 x 250 mm, 1 ml/min, toluene/acetonitrile 1:1, 310 nm). The reaction mixture was irradiated at 5 10 C for 2 h, after which time the solvent was evaporated under reduced pressure. Acetonitrile was then added and the resulting suspension was centrifuged at 4100 rpm for 10min (3 times). Further purification of the resulting precipitate via flash column chromatography on silica (hexane/toluene 8:2) afforded ca. 6.9 mg of 12b (0.008 mmol, 30%). IR (KBr): ν (cm -1 ) = 2978, 2921, 1600, 1451, 1427, 1359, 1183, 1024, 762, 700, 580, 552, 527; UV-vis (CCl 3 ): λ max (nm) = 258, 327, 434; MS (MALDI, negative, DCTB): m/z 826.059; 1 NMR (500 Mz, BCB-d 4 /CDCl 3 ): δ 7.75 (d, J = 7.0 z, 2), 7.43 (m, 2), 7.32 (m, 1), 6.58 (s, 1), 4.63 (q, J = 7.0 z, 1), 2.37 (d, J = 7.0 z, 3); 13 C NMR (125 Mz, DCB-d 4 /CS 2 ): δ 154.95, 154.70, 154.43, 154.12, 147.48, 147.29, 147.11, 147.01, 146.94, 146.83, 146.46, 146.45, 146.41, 146.26, 146.20, 145.86, 145.83, 145.51, 145.50, 145.42, 145.40, 144.79, 144.75, 144.60, 144.57, 143.27, 143.24, 143.06, 142.61, 142.59, 142.30, 142.10, 141.86, 141.83, 141.67, 141.57, 141.33, 140.24, 140.22, 139.74, 139.60, 136.65, 136.63, 136.53, 136.48, 128.85, 128.01, 70.33, 58.10, 53.83, 18.46. S19
Functionalized Fullerene 13a Compound 13a has been prepared following the general procedure described in Section 2, by using 20 mg (0.0278 mmol) of C 60, 46 mg (0.014 mmol) of TBADT and 175 mg (2.5 mmol) of cyclopropanecarboxaldehyde, in a mixture of chlorobenzene/acetonitrile 85:15 (80 ml). The progress of the reaction was monitored by analytical PLC (5C18-MS, 4.6 x 250 mm, 1 ml/min, toluene/acetonitrile 1:1, 310 nm). The reaction mixture was irradiated at 5 10 C for 35 min, after which time the solvent was evaporated under reduced pressure. Acetonitrile was then added and the resulting suspension was centrifuged at 4100 rpm for 10min (3 times). Further purification of the resulting precipitate via flash column chromatography on silica (hexane/toluene 8:2) afforded ca. 8.8 mg of 13a (0.011 mmol, 40%). IR (KBr): ν (cm -1 ) = 1702, 1429, 1374, 1183, 1054, 753, 577, 527; UV-vis (CCl 3 ): λ max (nm) = 259, 329, 433; MS (MALDI, negative, DCTB): m/z 790.049; 1 NMR (500 Mz, CDCl 3 /CS 2 ): δ 7.80 (s, 1), 3.56 (m, 1), 1.72 (m, 2), 1.42 (m, 2); 13 C NMR (125 Mz, CDCl 3 /CS 2 ): δ 192.51, 153.41, 150.35, 147.82, 147.32, 147.17, 147.04, 146.56, 146.29, 146.21, 146.20, 145.91, 145.62, 145.59, 145.36, 145.29, 144.79, 144.23, 143.34, 143.09, 142.77, 142.66, 142.44, 142.23, 142.10, 141.78, 141.60, 140.69, 140.17, 136.52, 135.20, 78.72, 55.49, 19.27, 14.61. S20
Functionalized Fullerene 14a Ph Compound 14a has been prepared following the general procedure described in Section 2, by using 20 mg (0.0278 mmol) of C 60, 46 mg (0.014 mmol) of TBADT and 365 mg (2.5 mmol) of 2-phenylcyclopropanecarboxaldehyde, in a mixture of chlorobenzene/acetonitrile 85:15 (80 ml). The progress of the reaction was monitored by analytical PLC (5C18-MS, 4.6 x 250 mm, 1 ml/min, toluene/acetonitrile 1:1, 310 nm). The reaction mixture was irradiated at 5 10 C for 40 min, after which time the solvent was evaporated under reduced pressure. Acetonitrile was then added and the resulting suspension was centrifuged at 4100 rpm for 10min (3 times). Further purification of the resulting precipitate via flash column chromatography on silica (hexane/toluene 8:2) afforded ca. 9.2 mg of 14a (0.011 mmol, 40%). IR (KBr): ν (cm -1 ) = 2848, 1698, 1427, 1391, 1181, 1101, 1058, 904, 731, 694, 580, 526; UV-vis (CCl 3 ): λ max (nm) = 258, 326, 433; MS (MALDI, negative, DCTB): m/z 866.057; 1 NMR (500 Mz, CDCl 3 /CS 2 ): δ 7.80 (s, 1), 7.29 (m, 2), 7.22 (m, 3), 3.74 (m, 1), 3.17 (m, 1), 2.32 (m, 1), 1.89 (m, 1); 13 C NMR (125 Mz, CDCl 3 /CS 2 ): δ 201.90, 153.39, 153.34, 150.17, 150.07, 147.76, 147.67, 147.44, 147.25, 147.24, 147.18, 146.65, 146.64, 146.40, 146.31, 145.99, 145.72, 145.47, 145.39, 144.88, 144.33, 144.32, 143.41, 143.18, 142.86, 142.73, 142.53, 142.52, 142.32, 142.18, 141.86, 141.70, 141.67, 141.66, 140.77, 140.31, 140.29, 139.27, 136.70, 136.56, 135.33, 128.84, 127.20, 126.74, 78.65, 55.59, 32.61, 30.45, 21.67. S21
7. 1, 13 C NMR, FT-IR, UV-vis Spectra of Functionalized Fullerenes 1a 11a, 13a 14a, 9b 12b Compound 1a a) 1 NMR (300 Mz, CDCl 3 /CS 2 ) 8,732 8,728 8,722 8,712 8,705 8,700 7,798 7,793 7,786 7,773 7,765 7,756 7,751 7,745 7,739 7,736 7,732 7,720 7,717 7,712 7,710 7,696 7,690 7,689 7,683 7,358 7,260 1.00 2.94 1.96 9.00 ppm (t1) 8.50 8.00 7.50 7.00 6.50 6.00 5.50 5.00 4.50 4.00 3.50 3.00 b) 13 C NMR (75 Mz, DCB-d 4 ) 196,920 151,240 150,318 146,704 146,539 146,251 145,691 145,674 145,511 145,501 145,018 144,967 144,764 144,716 144,683 143,973 143,659 142,523 142,269 142,003 141,900 141,414 141,390 141,364 141,032 140,931 140,881 139,874 139,380 135,842 135,351 135,223 132,895 128,502 76,768 57,217 CS2 175 150 125 100 75 S22
c) FT-IR (KBr) 2,60 2,4 2,2 2,0 1,8 1,6 %T 1,4 1,2 1,0 0,8 2915,23 1672,12 1425,96 1224,21 1180,12 1008,48 869,40 691,32 578,02 0,6 0,4 0,2 526,03 0,0-0,20 3100,0 2800 2400 2000 1800 1600 1400 1200 1000 800 600 400,0 cm-1 d) UV-vis (CCl 3 ) 1.75 ABS 1.5 1.25 1.0 0.75 0.5 0.25 0.0 250.0 300.0 350.0 400.0 450.0 500.0 550.0 600.0 650.0 700.0 750.0 800.0 c:\spdata\tzirakis\phcho.uvd nm S23
Compound 2a a) 1 NMR (300 Mz, DCB-d 4 ) Me b) 13 C NMR (75 Mz, DCB-d 4 ) 195,513 150,447 149,944 145,933 145,782 145,510 145,471 144,905 144,892 144,728 144,238 144,181 143,963 143,915 143,312 143,197 142,932 141,767 141,223 141,128 140,656 140,600 140,552 140,255 140,213 140,118 139,100 138,623 134,589 134,511 132,130 131,074 129,053 128,716 128,625 128,521 128,380 126,215 125,884 125,554 75,887 56,748 20,408 CS2 200 175 150 125 100 75 50 25 S24
c) FT-IR (KBr) 2,60 2,4 2,2 2,0 1,8 1,6 %T 1,4 1,2 1,0 2915,06 1426,42 1008,13 801,26 578,28 0,8 0,6 1670,93 1510,82 1603,85 1232,54 871,74 0,4 0,2 0,0 1180,04 526,25-0,20 3000,0 2800 2400 2000 1800 1600 1400 1200 1000 800 600 400,0 cm-1 d) UV-vis (CCl 3 ) 1.6 ABS 1.4 1.2 1.0 0.8 0.6 0.4 0.2 0.0 250.0 300.0 350.0 400.0 450.0 500.0 550.0 600.0 650.0 700.0 750.0 800.0 c:\spdata\tzirakis\mephcho.uvd nm S25
Compound 3a a) 1 NMR (500 Mz, CDCl 3 /CS 2 ) Me b) 13 C NMR (75 Mz, CDCl 3 /CS 2 ) 195,961 164,138 151,771 151,361 147,018 146,838 146,486 146,424 146,305 146,290 145,762 145,750 145,544 145,501 144,716 144,555 143,347 142,794 142,739 142,720 142,259 142,138 142,033 141,814 141,757 141,710 140,677 140,201 136,212 135,816 132,450 128,406 114,507 77,583 77,366 77,160 76,737 58,374 55,658 175 150 125 S26 100 75
c) FT-IR (KBr) 8,50 8,0 7,5 7,0 6,5 6,0 5,5 5,0 2915,73 4,5 4,0 3,5 1014,78 %T 3,0 1460,01 845,38 2,5 1508,34 1419,97 871,97 729,30 2,0 1664,15 1571,45 1,5 1261,19 1,0 0,5 1597,41 0,0-0,5 1238,44 1170,15 526,20-1,0-1,5-2,00 3100,0 2800 2400 2000 1800 1600 1400 1200 1000 800 600 400,0 cm-1 d) UV-vis (CCl 3 ) 1.4 ABS 1.2 1.0 0.8 0.6 0.4 0.2 0.0 250.0 300.0 350.0 400.0 450.0 500.0 550.0 600.0 650.0 700.0 750.0 800.0 c:\spdata\tzirakis\meophcho.uvd nm S27
Compound 4a a) 1 NMR (500 Mz, CDCl 3 /CS 2 ) C= b) 13 C NMR (125 Mz, DCB-d 4 /CS 2 ) 197,161 189,607 152,007 149,873 147,446 147,244 146,944 146,544 146,439 146,294 145,826 145,763 145,601 145,513 145,447 144,762 144,339 143,350 143,078 142,834 142,708 142,204 142,000 141,848 141,670 141,561 141,280 140,766 140,473 140,164 139,159 136,311 135,671 129,670 77,586 57,169 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 S28
c) FT-IR (KBr) 3,00 2,5 2,0 1,5 2964,10 1503,42 1422,22 572,23 1697,57 698,68 1,0 522,21 %T 0,5 1261,67 0,0-0,5 1020,49 802,13-1,0 1093,60-1,50 3600,0 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 400,0 cm-1 d) UV-vis (CCl 3 ) 1.4 ABS 1.2 1.0 0.8 0.6 0.4 0.2 0.0 250.0 300.0 350.0 400.0 450.0 500.0 550.0 600.0 650.0 700.0 750.0 800.0 terephthaldehyde nm S29
Compound 5a a) 1 NMR (500 Mz, CDCl 3 /CS 2 ) 7,804 7,800 7,775 7,772 7,744 7,731 7,717 7,704 7,701 7,688 7,674 7,260 2,215 2,213 2,202 2,199 3.076 1.010 2.000 8.00 7.50 7.00 6.50 6.00 5.50 5.00 4.50 4.00 3.50 3.00 2.50 2.00 b) 13 C NMR (125 Mz, CDCl 3 /CS 2 ) 192,454 190,835 153,467 150,163 148,594 148,582 147,686 147,246 147,155 146,968 146,500 146,237 146,149 145,835 145,571 145,546 145,299 145,231 144,738 144,162 143,283 142,710 142,593 142,405 142,169 142,035 141,708 141,560 141,545 140,630 140,080 136,618 135,172 126,106 77,535 77,413 77,160 76,907 55,458 19,082 200 175 150 125 100 75 50 25 S30
c) FT-IR (KBr) 2,40 2,2 2,0 1,8 1,6 1,4 1,2 2848,53 897,54 %T 1,0 0,8 0,6 0,4 0,2 1620,10 1687,22 1431,06 1288,11 1258,99 1093,65 1054,16 957,45 806,42 767,92 574,20 553,47 0,0 525,83-0,2-0,4-0,50 3000,0 2800 2400 2000 1800 1600 1400 1200 1000 800 600 400,0 cm-1 d) UV-vis (CCl 3 ) 1.2 ABS 1.0 0.8 0.6 0.4 0.2 0.0 250.0 300.0 350.0 400.0 450.0 500.0 550.0 600.0 650.0 700.0 750.0 800.0 crotonaldehyde nm S31
Compound 6a a) 1 NMR (500 Mz, CDCl 3 /CS 2 ) 7,716 7,261 3,747 3,733 3,719 2,103 2,089 2,084 2,074 2,070 2,062 2,059 2,044 1,644 1,629 1,617 1,614 1,603 1,599 1,588 1,584 1,569 1,110 1,095 1,080 * * 3.07 2.09 2.07 2.00 0.96 8.00 7.50 7.00 6.50 6.00 5.50 5.00 4.50 4.00 3.50 3.00 2.50 2.00 1.50 1.00 0.50 0.00 b) 13 C NMR (75 Mz, CDCl 3 /CS 2 ) 203,499 153,481 150,234 147,568 147,280 147,158 147,007 146,535 146,257 146,195 146,183 145,860 145,585 145,568 145,348 145,261 144,766 144,174 143,325 142,760 142,656 142,413 142,222 142,074 141,774 141,613 141,520 140,687 140,189 136,425 135,132 78,704 77,582 77,160 76,737 55,808 39,922 26,988 22,770 14,301 * 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 * grease S32
c) FT-IR (KBr) 5,88 5,5 5,0 4,5 4,0 3,5 1184,51 3,0 1121,45 1052,28 573,84 %T 2,5 2,0 2851,91 1460,50 1429,43 766,02 553,61 1,5 2918,95 1,0 0,5 0,0 1719,85 527,60-0,5-0,70 3100,0 2800 2400 2000 1800 1600 1400 1200 1000 800 600 400,0 cm-1 d) UV-vis (CCl 3 ) 1.1 ABS 1.0 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0-0.1 250.0 300.0 350.0 400.0 450.0 500.0 550.0 600.0 650.0 700.0 750.0 800.0 c:\spdata\tzirakis\valerald.uvd nm S33
Compound 7a a) 1 NMR (500 Mz, CDCl 3 /CS 2 ) 7,589 7,366 7,363 7,349 7,329 7,314 7,298 7,229 7,226 7,223 7,212 7,200 7,197 7,195 4,138 4,129 4,127 4,120 4,114 4,109 4,089 4,084 4,078 4,070 4,068 4,060 3,899 3,885 3,872 3,857 3,852 3,844 3,825 3,812 1,592 1,579 3.073 2.098 1.038 1.094 4.041 0.925 8.00 7.50 7.00 6.50 6.00 5.50 5.00 4.50 4.00 3.50 3.00 2.50 2.00 1.50 b) 13 C NMR (125 Mz, CDCl 3 /CS 2 ) 202,465 153,440 153,305 149,755 149,555 147,561 147,523 147,332 147,126 147,063 146,583 146,557 146,301 146,247 146,228 146,213 145,886 145,869 145,844 145,642 145,632 145,548 145,391 145,340 145,290 145,249 144,795 144,218 144,196 143,344 143,327 143,126 142,788 142,685 142,669 142,426 142,387 142,245 142,113 141,800 141,782 141,662 141,600 141,538 140,695 140,662 140,198 140,088 136,683 136,502 135,184 135,118 128,837 127,113 126,875 78,950 77,583 77 76 160 737 200 175 150 125 100 75 50 25 S34
c) FT-IR (KBr) 2,56 2,4 2,2 2,0 1,8 1,6 1,4 1,2 2915,42 1509,70 1426,74 1181,95 575,35 %T 1,0 0,8 1712,32 753,65 696,25 0,6 0,4 0,2 0,0 526,48-0,2-0,4-0,60 3000,0 2800 2400 2000 1800 1600 1400 1200 1000 800 600 400 300,0 cm-1 d) UV-vis (CCl 3 ) 1.2 ABS 1.0 0.8 0.6 0.4 0.2 0.0 250.0 300.0 350.0 400.0 450.0 500.0 550.0 600.0 650.0 700.0 750.0 800.0 3-phenylbutyraldehyde nm S35
Compound 8a a) 1 NMR (500 Mz, CDCl 3 /CS 2 ) b) 13 C NMR (125 Mz, CDCl 3 /CS 2 ) 206,161 192,557 153,737 149,779 147,700 147,299 147,173 147,045 146,598 146,317 146,247 146,226 145,939 145,640 145,605 145,397 145,288 144,838 144,215 143,389 142,808 142,694 142,459 142,289 142,110 141,813 141,619 140,688 140,170 136,581 135,106 78,797 77,583 77,160 76,737 55,727 47,058 30,883 25,874 200 175 150 125 100 75 50 25 S36
c) FT-IR (KBr) 5,43 5,0 4,5 4,0 3,5 3,0 2,5 %T 2,0 1,5 1140,64 1094,16 765,98 729,82 553,82 1,0 0,5 2916,90 1446,69 1427,80 998,08 573,80 0,0-0,5-1,0 1711,29 527,38-1,50 3000,0 2800 2400 2000 1800 1600 1400 1200 1000 800 600 400,0 cm-1 d) UV-vis (CCl 3 ) 1.75 ABS 1.5 1.25 1.0 0.75 0.5 0.25 0.0 250.0 300.0 350.0 400.0 450.0 500.0 550.0 600.0 650.0 700.0 750.0 800.0 cyclohexanecarboxaldehyde nm S37
Compound 9a a) 1 NMR (500 Mz, CDCl 3 /CS 2 ) b) 13 C NMR (125 Mz, CDCl 3 /CS 2 ) 207,107 192,644 153,938 153,928 149,958 149,929 147,762 147,683 147,392 147,273 147,136 146,669 146,397 146,320 146,306 146,008 145,999 145,719 145,657 145,637 145,477 145,366 144,910 144,291 143,469 143,191 142,873 142,760 142,565 142,355 142,191 141,876 141,705 141,694 141,675 140,742 140,152 140,094 136,543 135,179 79,535 77,414 77,160 76,906 56,036 49,458 32,591 30,118 26,376 23,066 14,105 12,554 200 175 150 125 100 75 50 25 S38
c) FT-IR (KBr) 5,51 5,0 4,5 4,0 3,5 3,0 573,99 %T 2,5 1459,74 1426,94 1027,59 753,95 2,0 1,5 2916,66 1,0 0,5 1712,11 527,26 0,0-0,60 3000,0 2800 2400 2000 1800 1600 1400 1200 1000 800 600 410,0 cm-1 d) UV-vis (CCl 3 ) 1.2 ABS 1.0 0.8 0.6 0.4 0.2 0.0 250.0 300.0 350.0 400.0 450.0 500.0 550.0 600.0 650.0 700.0 750.0 800.0 2-ethylhexanal nm S39
Compound 9b a) 1 NMR (500 Mz, CDCl 3 /CS 2 ) 3,073 3,058 3,036 3,001 2,986 2,978 2,973 2,966 2,958 2,951 2,946 2,939 2,935 2,927 2,924 2,918 2,913 2,907 2,900 2,897 2,890 2,886 2,879 2,502 2,488 2,473 2,459 2,444 2,430 2,422 2,416 2,407 2,397 2,391 2,384 2,380 2,370 2,005 1,990 1,976 1,963 1,954 1,942 1,925 1,915 1,905 1,893, 1,876 1,867 1,861 1,855 1 843 828 696 679 641 548 132 117 3.085 3.170 2.193 1.077 1.089 2.082 2.031 1.015 3.00 2.75 2.50 2.25 2.00 1.75 1.50 1.25 S40
b) UV-vis (CCl 3 ) 1.4 ABS 1.2 1.0 0.8 0.6 0.4 0.2 0.0 250.0 300.0 350.0 400.0 450.0 500.0 550.0 600.0 650.0 700.0 750.0 800.0 2-ethylhexanal(2) nm S41
Compound 10a a) 1 NMR (500 Mz, DCB-d 4 ) 7,256 7,000 6,558 1,892 9.12 1.00 7.50 7.00 6.50 6.00 5.50 5.00 4.50 4.00 3.50 3.00 2.50 2.00 1.50 b) 13 C NMR (125 Mz, DCB-d 4 ) 210,282 152,192 150,941 147,315 147,174 147,100 146,346 146,280 146,183 145,925 145,713 145,450 145,404 145,360 144,663 144,368 143,231 142,658 142,595 142,060 142,003 141,964 141,750 141,681 141,566 140,511 139,767 136,563 136,373 132,520 130,366 130,163 129,961 127,525 127,327 127,128 75,849 60,533 49,002 27,876 210 ppm (t1) 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 S42
c) FT-IR (KBr) 5,25 5,0 4,5 4,0 1182,73 3,5 2946,43 1359,51 1426,18 1006,02 578,10 3,0 1474,33 1459,91 1056,19 879,76 %T 2,5 2,0 1,5 1697,50 1,0 526,26 0,50 3100,0 2800 2400 2000 1800 1600 1400 1200 1000 800 600 400,0 cm-1 d) UV-vis (CCl 3 ) 1.2 ABS 1.0 0.8 0.6 0.4 0.2 0.0 250.0 300.0 350.0 400.0 450.0 500.0 550.0 600.0 650.0 700.0 750.0 800.0 c:\spdata\tzirakis\pivalald.uvd nm S43
Compound 10b a) 1 NMR (500 Mz, CDCl 3 /CS 2 ) when the reaction of C 60 with 10 was performed at T = 5 10 ºC. (C 3 ) 3 C- 1,2-isomer (C 3 ) 3 C- 1,4-isomer C 60-1,2-isomer C 60-1,4-isomer a) 1 NMR (500 Mz, CDCl 3 /CS 2 ) when the reaction of C 60 with 10 was performed at -40 ºC. * * * * toluene S44
b) 13 C NMR (125 Mz, CDCl 3 /CS 2 ) (Mixture of 1,2 and 1,4-isomers, 5:1 molar ratio) 192,412 154,527 153,927 147,593 147,319 147,089 146,967 146,837 146,307 146,296 146,146 146,058 145,762 145,286 145,270 144,627 144,429 143,174 142,580 142,566 142,132 142,111 142,007 141,628 141,534 141,384 140,313 139,024 136,440 136,379 77,582 77,160 76,738 73,448 56,969 48,812 41,326 41,139 27,535 26,796 ppm (t1) 175 150 125 100 75 50 25 S45
c) FT-IR (KBr) 0,750 0,70 0,65 0,60 0,55 0,50 0,45 0,40 1094,33 903,81 0,35 0,30 583,09 %T 0,25 0,20 0,15 0,10 0,05 0,00 2959,42 2866,19 1511,62 1462,40 1427,42 1397,13 1369,61 1199,66 1188,54 764,01 729,85 573,22 553,87 527,30-0,05-0,10-0,15-0,190 3200,0 2800 2400 2000 1800 1600 1400 1200 1000 800 600 400,0 cm-1 d) UV-vis (CCl 3 ) 1.4 ABS 1.2 1.0 0.8 0.6 0.4 0.2 0.0 250.0 300.0 350.0 400.0 450.0 500.0 550.0 600.0 650.0 700.0 750.0 800.0 t-butyl nm S46
Compound 11a a) 1 NMR (500 Mz, DCB-d 4 /CS 2 ) 7,596 7,343 7,328 7,298 7,283 7,268 7,254 7,228 7,213 7,199 7,032 4,877 2.182 1.403 2.409 2.122 1.000 7.75 7.50 7.25 7.00 6.75 6.50 6.25 6.00 5.75 5.50 5.25 5.00 4.75 b) 13 C NMR (125 Mz, DCB-d 4 /CS 2 ) 200,903 153,564 150,073 147,788 147,556 147,355 147,290 146,822 146,541 146,476 146,452 146,112 145,946 145,880 145,615 145,524 145,046 144,441 143,580 143,315 143,030 142,926 142,666 142,502 142,361 142,046 141,959 141,779 140,926 140,539 137,020 135,404 133,874 132,720 129,266 79,147 56,246 46,369 200 ppm (t1) 175 150 125 100 75 50 S47
c) FT-IR (KBr) 6,40 6,0 5,5 5,0 4,5 %T 4,0 3,5 3,0 2915,64 1492,54 1425,68 1088,48 1037,45 702,61 574,56 2,5 751,65 2,0 1,5 1,0 1720,23 527,01 0,5 0,30 3000,0 2800 2400 2000 1800 1600 1400 1200 1000 800 600 400,0 cm-1 d) UV-vis (CCl 3 ) 1.2 ABS 1.0 0.8 0.6 0.4 0.2 0.0 250.0 300.0 350.0 400.0 450.0 500.0 550.0 600.0 650.0 700.0 750.0 800.0 phenylacetaldehyde nm S48
Compound 11b a) 1 NMR (500 Mz, DCB-d 4 ) 7,774 7,759 7,466 7,451 7,436 7,365 7,350 7,335 7,250 6,998 6,524 4,654 2.05 1.00 1.07 2.09 2.01 8.00 7.50 7.00 6.50 6.00 5.50 5.00 4.50 4.00 b) 13 C NMR (75 Mz, CDCl 3 /CS 2 ) S49
c) FT-IR (KBr) 4,50 4,0 3,5 %T 3,0 2,5 2,0 1451,79 1492,51 1460,08 1426,92 1259,01 1214,81 1180,91 1064,09 1023,96 807,30 760,07 744,13 722,07 662,00 546,07 475,08 512,06 697,37 1,5 575,15 1,0 0,5 525,36 0,00 1600,0 1500 1400 1300 1200 1100 1000 900 800 700 600 500 400,0 cm-1 d) UV-vis (CCl 3 ) 1.4 ABS 1.2 1.0 0.8 0.6 0.4 0.2 0.0 250.0 300.0 350.0 400.0 450.0 500.0 550.0 600.0 650.0 700.0 750.0 800.0 c:\spdata\tzirakis\phch2cho.uvd nm S50
Compound 12b a) 1 NMR (500 Mz, DCB-d 4 /CS 2 ) 7,761 7,747 7,443 7,428 7,413 7,333 7,319 7,304 7,253 7,015 6,576 4,651 4,637 4,623 4,609 2,376 2,362 3.084 1.006 1.037 1.071 2.107 2.000 8.00 7.50 7.00 6.50 6.00 5.50 5.00 4.50 4.00 3.50 3.00 2.50 2.00 b) 13 C NMR (125 Mz, DCB-d 4 /CS 2 ) 154,951 154,700 154,431 154,123 147,490 147,300 147,118 147,019 146,945 146,834 146,464 146,452 146,418 146,269 146,202 145,860 145,835 145,514 145,501 145,420 145,406 144,797 144,756 144,610 144,574 143,272 143,245 143,067 142,614 142,599 142,303 142,106 141,867 141,831 141,677 141,575 141,332 140,243 140,228 139,744 139,600 136,656 136,638 136,537 136,489 128,855 128,018 70,334 58,107 53,836 18,462 225 ppm (t1) 200 175 150 125 100 75 50 25 S51
c) FT-IR (KBr) 0,700 0,65 0,60 0,55 0,50 0,45 0,40 0,35 %T 0,30 0,25 0,20 0,15 0,10 2977,91 2921,06 1600,00 1450,74 1358,84 1182,97 1024,08 761,80 0,05 0,00 1426,88 552,45 579,73 699,75-0,05 526,54-0,10-0,15-0,20-0,25-0,300 3200,0 2800 2400 2000 1800 1600 1400 1200 1000 800 600 400,0 cm-1 d) UV-vis (CCl 3 ) 0.9 ABS 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0-0.1 250.0 300.0 350.0 400.0 450.0 500.0 550.0 600.0 650.0 700.0 750.0 800.0 2-phenylpropionaldehyde nm S52
Compound 13a a) 1 NMR (500 Mz, CDCl 3 /CS 2 ) b) 13 C NMR (125 Mz, CDCl 3 /CS 2 ) S53
c) FT-IR (KBr) 6,50 6,0 5,5 5,0 4,5 4,0 1182,76 %T 3,5 1429,37 1373,73 1054,50 577,11 3,0 2,5 1702,05 753,34 2,0 1,5 1,0 526,52 0,50 3000,0 2800 2400 2000 1800 1600 1400 1200 1000 800 600 405,0 cm-1 d) UV-vis (CCl 3 ) 1.6 ABS 1.4 1.2 1.0 0.8 0.6 0.4 0.2 0.0 250.0 300.0 350.0 400.0 450.0 500.0 550.0 600.0 650.0 700.0 750.0 800.0 cyclopropanecarboxaldehyde nm S54
Compound 14a a) 1 NMR (500 Mz, CDCl 3 /CS 2 ) 7,797 7,310 7,295 7,280 7,261 7,237 7,228 7,212 3,754 3,745 3,744 3,738 3,736 3,730 3,728 3,720 3,193 3,185 3,180 3,175 3,172 3,167 3,162 3,154 2,334 2,326 2,324 2,316 2,307 2,306 2,298 1,916 1,907 1,902 1,900 1,894 1,892 1,886 1,878 Ph 1.080 1.002 1.048 1.008 2.895 2.310 1.000 7.50 7.00 6.50 6.00 5.50 5.00 4.50 4.00 3.50 3.00 2.50 2.00 1.50 1.00 0.50 b) 13 C NMR (125 Mz, CDCl 3 /CS 2 ) 201,899 192,639 153,390 153,344 150,171 150,075 147,766 147,671 147,441 147,258 147,249 147,184 146,658 146,641 146,408 146,317 145,992 145,721 145,470 145,391 144,882 144,333 144,321 143,417 143,189 142,864 142,739 142,533 142,523 142,321 142,185 141,869 141,706 141,676 141,665 140,776 140,311 140,299 139,270 136,701 136,566 135,335 128,842 127,207 126,740 78,651 77,414 77,160 76,906 55,600 32,611 30,458 21,674 225 200 175 150 125 100 75 50 25 S55
c) FT-IR (KBr) 2,30 2,2 2,0 1,8 1,6 1,4 1,2 %T 1,0 0,8 0,6 2848,50 1390,93 1427,23 1180,73 1058,18 903,84 579,63 0,4 0,2 1698,13 1101,27 730,83 693,92 0,0-0,2 526,11-0,4-0,50 3000,0 2800 2400 2000 1800 1600 1400 1200 1000 800 600 400,0 cm-1 d) UV-vis (CCl 3 ) 1.4 ABS 1.2 1.0 0.8 0.6 0.4 0.2 0.0 250.0 300.0 350.0 400.0 450.0 500.0 550.0 600.0 650.0 700.0 750.0 800.0 phenyl-cyclopropanecarboxaldehyde nm S56
8. 1 and 13 C NMR Spectra of Methyl 4-Methoxybenzoate-d 3 a) 1 NMR (500 Mz, CDCl 3 ) 8,002 7,984 7,260 6,922 6,904 3,884 C 3 CD 3 2.994 2.000 2.034 8.00 7.50 7.00 6.50 6.00 5.50 5.00 4.50 4.00 b) 13 C NMR (500 Mz, CDCl 3 ) 166,602 163,231 131,428 122,444 113,442 77,415 77,160 76,905 54,885 54,710 54,535 54,360 54,185 54,010 53,835 51,591 55.00 54.75 54.50 54.25 54.00 53.75 150 125 100 75 50 S57
54.50 54.25 54.00 53.75 53.50 9. 1 and 13 C NMR Spectra of 4-Methoxybenzyl Alcohol-d 5 a) 1 NMR (500 Mz, CDCl 3 ) 7,282 7,264 6,889 6,872 D D CD 3 2.000 2.046 8.50 8.00 7.50 7.00 6.50 6.00 5.50 5.00 4.50 b) 13 C NMR (500 Mz, CDCl 3 ) 158,639 132,940 128,335 113,488 77,416 77,160 76,904 63,612 63,439 63,267 63,095 62,923 54,559 54,386 54,212 54,037 53,863 53,689 53,515 63.75 63.50 63.25 63.00 62.75 175 150 125 100 75 50 25 S58