EL DOCENTE Y LA COMPRENSIÓN LECTORA

1,2-Diphenoxyethane 123

Phenoxyacetic acid (60 mg, 0.4 mmol), and Pt-TiO2(250 mg, 3.1 mmol) were reacted in accordance with the general procedure. Following irradiation for 21 h the crude reaction mixture was purified by column chromatography on silica gel (eluent: 50% CH2Cl2in petrol 40/60) to yield123as a colourless solid (22.5 mg, 53%).1_{H NMR (400 MHz, CDCl}

3, 297 K):= 4.34 (s, 4H, CH2), 6.95-7.00 (m, 6H, ArH), 7.28-7.34 (m, 4H, ArH); 13_{C NMR (75 MHz, CDCl}

3, 298 K):= 66.5, 114.7, 121.1, 129.5, 158.7. Consistent with literature.[19]_{Analysis of the}1_{H NMR prior to chromatography revealed} phenoxyacetone (11% w.r.t. 123), phenol (6% w.r.t. 123) and 3-phenoxypropanenitrile (3% w.r.t.123). These data were consistent with literature.[20]

1,2-Bis(benzyloxy)ethane 128

Benzyloxyacetic acid (66 mg, 0.4 mmol), and Pt-TiO2(250 mg, 3.1 mmol) were reacted in accordance with the general procedure. Following irradiation for 21 hours the crude reaction mixture was purified by column chromatography on silica gel (eluent: CH2Cl2) to yield128as a colourless oil (18.6 mg, 53%). 1_{H NMR (400 MHz, CDCl}

3, 295 K): = 3.67 (s, 4H, OCH2) 4.59 (s, 4H, ArCH2), 7.27-7.39 (m, 10H, ArH);13_{C NMR (100 MHz, CDCl}

3, 296 K):= 69.5, 73.3, 127.6, 127.8, 128.4, 138.3. Consistent with literature.[21]

1-Adamantyl methyl ketone 129

Adamantane-1-carboxylic acid (115.3 mg, 0.64 mmol) and Pt-TiO2(410 mg, 5.12 mmol) were reacted in accordance with the general procedure. Following irradiation for 18 hours 129 was obtained as a yellow oil (24.8 mg, 22%) without further purification.1_{H NMR (400 MHz, CDCl}

3, 296 K):= 1.67 (d,J= 11.5 Hz, 3H, Hc), 1.74(d,J= 11.5 Hz, 3H, Hc’), 1.79 (d,J= 2.4 Hz, 6H, Ha), 2.03 (bm, 3H, Hb), 2.08 (s, 3H, CH3);13C NMR (75 MHz, CDCl3, 297 K):  = 24.7, 28.3, 37.0, 38.7, 214.7. Data consistent with literature.[22]

Photolysis reaction of phenylbutyric acid 130

Phenylbutyric acid (14.8 mg, 0.09 mmol) and Pt-TiO2 (60 mg, 0.75 mmol) were reacted in accordance with the general procedure. Following irradiation for 18 hours1_{H NMR and GC-MS} analysis revealed only starting material present.

Photolysis reaction of cyclohex-1-enylacetic acid 132

Cyclohex-1-enylacetic acid (13 mg, 0.09 mmol) and Pt-TiO2(60 mg, 0.75 mmol) in CD3CN (12 mL) were reacted in accordance with the general procedure. Following irradiation for 19 hours 1_{H NMR analysis wrt a CH}

2Br2 standard revealed: 1,2-di(cyclohex-1-en-1-yl)ethane 133 (0.02 mmol, 41%), 2'-methylene-[1,1'-bi(cyclohexan)]-1-ene 134 (0.01 mmol, 26%) and 2,2'- dimethylene-1,1'-bi(cyclohexane)135(0.01 mmol, 14%). Data consistent with literature.[23]

Photolysis reaction of (E)-5-phenylpent-3-enoic acid 136

(E)-5-Phenylpent-3-enoic acid (112.8 mg, 0.64 mmol) and Pt-TiO2 (410 mg, 5.12 mmol) were reacted in accordance with the general procedure for 19 hours. The reaction mixture was subjected to column chromatography on silica gel (eluent: 10% EtOAc in CH2Cl2) yielding a fraction containing five isomeric dimerised products (40.8 mg, 49 % combined). 1_{H NMR} analysis proved inconclusive but five compounds were observed by GC-MS (see pg 53-54 for full details). tR14.59 & 14.90 min:m/z(%) 262 (2), 171 (23), 158 (29), 131 (85), 91 (100), 79 (6), 65 (7). tR15.85 min:m/z(%) 262 (3), 171 (49), 131 (100), 115 (20), 91 (100), 77 (3), 67 (11). tR16.73, 16.81 & 16.87 min:m/z(%) 262 (2), 171 (41), 158 (28), 143 (5), 131 (100), 115 (27), 91 (58), 77 (5), 65 (3).

Bibenzyl 144

Phenylacetic acid (87 mg, 0.64 mmol), and Pt-TiO2 (410 mg, 5.12 mmol) were reacted in accordance with the general procedure. Following irradiation for 16 hours 144 was obtained as a colourless solid (50.6 mg, 87%) without further purification.1_{H NMR (500 MHz, CDCl}

3, 298 K):= 2.95 (s, 4H, CH2) 7.21- 7.24 (m, 6H, ArH), 7.30-7.33 (m, 4H, ArH);13_{C NMR (100 MHz, CDCl}

3, 296 K):= 38.0, 126.0, 128.4, 128.5, 141.8. Consistent with literature.[24]

Photolysis reaction of ethynylacetic acid 145

Ethynylacetic acid (7.9 mg, 0.09 mmol) and Pt-TiO2(60 mg, 0.75 mmol) were reacted in CD3CN (12 mL) in accordance with the general procedure. Following irradiation for 18 hours1_{H NMR} and GC-MS analysis revealed only starting material present.

84 Succinonitrile 148

Cyanoacetic acid (54.5 mg, 0.64 mmol) and Pt-TiO2 (410 mg, 5.12 mmol) were reacted in accordance with the general procedure. Following irradiation for 16 hours 1_{H NMR analysis revealed 148 (< 0.03 mmol, < 5%) wrt a CH}

2Br2 standard. Data consistent with literature.[25]

1,2-Bis(4-methoxyphenyl)ethane 150

4-Methoxyphenylacetic acid (106.4 mg, 0.64 mmol) and 0.1% (w/w) Pt-TiO2 (410mg, 5.12 mmol) were reacted in accordance with the general procedure. Following irradiation for 20 hours 150 was obtained as a colourless solid (65.3 mg, 84%) without further purification. 1_{H NMR} (500 MHz, CDCl3, 295 K):= 2.84 (s, 4H, CH2), 3.80 (s, 6H, OCH3), 6.83 (d,J= 8.6 Hz, 4H, ArH), 7.09 (d, J= 8.6 Hz, 4H, ArH); 13_{C NMR (75 MHz, CDCl}

3, 298 K): = 37.3, 55.3, 113.7, 129.4, 134.0, 157.8. Data consistent with literature.[26]

1,2-bis(4-(trifluoromethyl)phenyl)ethane 152

4-Trifluoromethylphenylacetic acid (204.2 mg, 0.64 mmol) and Pt- TiO2 (410mg, 5.12 mmol) were reacted in accordance with the general procedure. Following irradiation for 19 hours 152 was obtained as a colourless solid (75.6 mg, 74%) without further purification.1_{H NMR (500 MHz,} CDCl3, 293 K):= 3.00 (s, 4H, CH2), 7.27 (m, 4H, ArH), 7.55 (m, 4H, ArH);19F NMR (470 MHz, CDCl3, 293 K):= -62.6. Data consistent with literature.[27]

1,2-Bis(perfluorophenyl)ethane 154

2,3,4,5,6-Pentafluorophenylacetic acid (144.7 mg, 0.64 mmol), and Pt-TiO2 (410mg, 5.12 mmol) were reacted in accordance with the general procedure for 40 hours. The reaction mixture was subjected to column chromatography on silica gel (eluent: 20% CH2Cl2 in pentanes) to yield154as a colourless crystalline solid (61 mg, 53%).1_{H NMR (500 MHz, CDCl}

3, 295 K):= 3.02 (s, 4H, CH2);19F NMR (470 MHz, CDCl3, 295 K)= -144.3 (dd, 4F,J= 8.2, 22.6 Hz, Fc), -155.9 (t, 2F J = 21 Hz, Fa), -162.1 (td, 4F,J = 9.1, 13.3 Hz, Fb). 2,3,4,5,6-Pentafluoro

1,2-Di(thiophen-2-yl)ethane 157

2-Thiopheneacetic acid (27 mg, 0.19 mmol), and Pt-TiO2(120 mg, 1.5 mmol) were reacted in accordance with the general procedure. Following irradiation for 20 hours 157 was obtained as a colourless solid (15.3 mg, 83%) without further purification.1_{H NMR (300 MHz, CDCl}

3, 296 K):= 3.20 (s, 4H, CH2), 6.80 (d,J= 3.4 Hz, 2H, ArH), 6.91-6.94 (m, 2H, ArH), 7.14 (d,J= 5.2 Hz, 2H, ArH);13_{C NMR (100 MHz,} CDCl3, 296 K):= 32.2, 123.4, 124.7, 126.8, 143.7. Consistent with literature.[29]

1,2-Di(thiophen-3-yl)ethane 158

3-Thiopheneacetic acid (27 mg, 0.19 mmol), and Pt-TiO2(120 mg, 1.5 mmol) were reacted in accordance with the general procedure. Following irradiation for 20 hours 158 was obtained as a colourless solid (14.3 mg, 78%) without further purification.1_{H NMR (300 MHz, CDCl}

3, 296 K):= 2.96 (s, 4H, CH2), 6.93 (m, 4H, ArH), 7.24 (m, 2H, ArH); 13_{C NMR (100 MHz, CDCl}

3, 296 K):  = 31.3, 120.4, 125.3, 128.2, 142.1. Consistent with literature.[30]

1,2-Bis(benzo[b]thiophen-3-yl)ethane 160

Benzo[b]thiophen-3-ylacetic acid (76.9 mg, 0.4 mmol) and 0.1% (w/w) Pt-TiO2 (250 mg, 3.1 mmol) were reacted in accordance with the general procedure for 22 hours. The reaction mixture was subjected to column chromatography on silica gel (eluent: 20-40% CH2Cl2in pentanes) to yield160as a yellow oil (32.8 mg, 56%).1_{H NMR (300 MHz, CDCl}

3, 293 K):= 3.31 (s, 4H, CH2), 7.12 (s, 2H, ArH), 7.35-7.44 (m, 4H, ArH), 7.76-7.82 (m, 2H, ArH), 7.87-7.93 (m, 2H, ArH); 13_{C NMR (75} MHz, CDCl3, 295 K):= 28.3, 121.6, 121.7, 123.0, 124.0, 124.3, 136.0, 138.9, 140.5; LR-ESIMS:

m/z= 295 [MH]+_{; HR-ESIMS:m/z= 295.0610 (calcd. for C}

18H15S2, 295.0615). Benzo[b]thiophen- 3-ylacetic acid (3% wrt160) was also observed by NMR.

Photolysis reaction of Indole-3-acetic acid 161

Indole-3-acetic acid (70.1 mg, 0.4 mmol) and Pt-TiO2 (250 mg, 5.12 mmol) were reacted in accordance with the general procedure. Following irradiation for 21 hours1_{H NMR and GC-MS} analysis revealed only starting material present.

86 1,2-Di(naphthalen-2-yl)ethane 165

(Naphthalen-2-yl)acetic acid (58.3 mg, 0.31 mmol), and Pt-TiO2 (200 mg, 2.5 mmol) were reacted in accordance with the general procedure. Following irradiation for 52 hours 1_{H NMR analysis of} the resultant mixture revealed 165 (0.087 mmol, 56%). 2-methylnaphthalene (0.125 mmol, 40%) was also observed. These data are consistent with literature.[31]

1,2-Di(naphthalen-1-yl)ethane 166

Naphthalen-1-ylacetic acid (119.2 mg, 0.64 mmol) and Pt-TiO2(410 mg, 5.12 mmol) were reacted in accordance with the general procedure. Following irradiation for 39 h,1_{H NMR analysis of the resultant mixture} revealed 166 (0.18 mmol, 56%). 1-methylnaphthalene (0.19 mmol, 30%) was also observed. These data are consistent with literature.[32]

1,1,2,2-Tetraphenylethane 168

Diphenylacetic acid (84.9 mg, 0.4 mmol) and Pt-TiO2 (250mg, 3.1 mmol) were reacted in accordance with the general procedure. Following irradiation for 22 hours the reaction mixture was purified by column chromatography on silica gel (eluent 30% CH2Cl2 in petroleum 40/60) to yield168as a colourless solid (61 mg, 91%).1_{H NMR (300 MHz, CDCl}

3, 294 K): = 4.79 (s, 2H, CH), 7.00-7.05 (m, 4H, ArH), 7.09-7.20 (m, 16H, ArH); 13_{C NMR (75 MHz,} CDCl3, 295 K):= 56.4, 125.9, 128.2, 128.6, 143.5. Consistent with literature.[33]

9H-Fluorene 170

9H-fluorene-9-carboxylic acid (210.2 mg, 0.64 mmol) and Pt-TiO2 (410 mg, 5.12 mmol) were reacted in accordance with the general procedure for 40 hours. The reaction mixture was subjected to column chromatography on silica gel (eluent: 10% CH2Cl2 in pentanes) yielding a fraction containing two compounds. 1H NMR analysis revealed the title compound 170(0.53 mmol, 83%) along with 9,9'-bifluorene 171(0.02 mmol, 7%) with respect to a CH2Br2standard. Data was consistent with literature.[34]

Triphenylmethane 173

Triphenylacetic acid (184.5 mg, 0.64 mmol) and Pt-TiO2(410 mg, 5.12 mmol) were reacted in accordance with the general procedure. Following irradiation for 18 hours the reaction mixture was subjected to column chromatography on silica gel (eluent: 25% CH2Cl2 in pentanes) yielding a fraction containing two compounds. 1_{H NMR analysis revealed 173 (0.32 mmol, 50%) along with 9-phenyl-9H-} fluorene174 (0.17 mmol, 26%) with respect to a CH2Br2 standard. Data was consistent with literature.[35]

1,2-Difluorobibenzyl 179

-Fluorophenylacetic acid (98.6 mg, 0.64 mmol) and Pt-TiO2 (410 mg, 5.12 mmol) were reacted in accordance with the general procedure. Following irradiation for 21 hours a 1:1 mixture of the D/L andmesoisomers of179 was obtained as colourless oil (63.1 mg, 90% combined) without further purification. D/L isomer:1_{H {}19_{F} NMR (500 MHz, CDCl} 3, 293 K): = 5.61 (s, 2H, CHF), 7.11-7.13 (m, 4H, ArH), 7.26-7.28 (m, 6H, ArH);19_{F {}1_{H} NMR (470 MHz, CDCl} 3, 293 K):= -184.3.Mesoisomer:1H {19F} NMR (500 MHz, CDCl3, 293 K):= 5.68 (s, 2H, CHF), 7.17-7.19 (m, 4H, ArH), 7.33-7.34 (m, 6H, ArH);19_{F {}1_{H} NMR (470 MHz, CDCl}

3, 293 K):= -187.7. Data consistent with literature.[36]

1,1,2,2-Tetrafluorobibenzyl 181

,-Difluorophenylacetic acid (110.1 mg, 0.64 mmol) and Pt-TiO2 (410 mg, 5.12 mmol) were reacted in accordance with the general procedure for 20 hours. The reaction mixture was subjected to column chromatography on silica gel (eluent: 20% CH2Cl2in pentanes) to yield181as a colourless solid (5 mg, 3%).1H NMR (400 MHz, CDCl3, 295 K):= 7.39-7.51 (m, 10H, ArH);19F NMR (376 MHz, CDCl3, 296 K):= - 112.4. Data consistent with literature.[37]

Photolysis reaction of D/L Mandelic acid 182

D/L Mandelic acid (97.4 mg, 0.64 mmol) and Pt-TiO2 (410mg, 5.12 mmol) were reacted in accordance with the general procedure. Following irradiation for 18 hours1_{H NMR analysis of} the resultant mixture revealed benzaldehyde184(0.17 mmol, 27%). Benzyl alcohol183(0.07 mmol, 11%) was also observed. Spectral data consistent with literature.[38]

88 Photolysis reaction of 1-Phenylglycine 185

1-Phenylglycine (96.8 mg, 0.64 mmol) and Pt-TiO2 (410 mg, 5.12 mmol) were reacted in accordance with the general procedure. Following irradiation for 18 hours1_{H NMR analysis of} the resultant mixture revealed 191 (0.09 mmol, 14%). Benzaldehyde 184 (0.04 mmol, 11%) was also observed. Data consistent with literature.[38a, 39]

1,1,2,2-Tetraphenylethane-1,2-diol 189

Benzilic acid (91.3 mg, 0.4 mmol) and Pt-TiO2(250 mg, 3.1 mmol) were reacted in accordance with the general procedure for 18 hours. The reaction mixture was subjected to column chromatography on silica gel (eluent: 25% CH2Cl2 in pentanes) yielding a fraction containing two compounds. 1H NMR analysis revealed189(0.04 mmol, 20%) along with benzophenone188(0.27 mmol, 67%) with respect to a CH2Br2standard. Data were consistent with literature.[37]

N-Benzhydryl-1,1-diphenylmethanimine 191

1,1-Diphenylglycine (145.5 mg, 0.64 mmol) and Pt-TiO2 (410 mg, 5.12 mmol) were reacted in accordance with the general procedure for 17 hours. The reaction mixture was subjected to column chromatography on silica gel (eluent: 25% CH2Cl2in pentanes) to yield191as an off-white solid (83.5 mg, 74%)1_{H NMR (500 MHz, CDCl} 3, 295 K):  = 5.58 (s, 1H, NCH), 7.09-7.11 (m, 2H, ArH), 7.19-7.22 (m, 2H, ArH),7.27-7.30 (m, 4H, ArH), 7.34-7.40 (m, 7H, ArH), 7.42-7.45 (m, 3H, ArH), 7.77-7.79 (m, 2H, ArH); 13_{C NMR (75 MHz, CDCl} 3, 298 K):  = 70.0, 126.8, 127.7, 127.8, 128.1, 128.5, 128.6, 128.9, 130.2, 136.8, 139.9, 145.0, 167.0. Data consistent with literature.[40]