Synthesis of Bi, p-Quarter, p-Sexi and p-Octiphenyl

5.2 Synthesis

5.2.3 Synthesis of Bi, p-Quarter, p-Sexi and p-Octiphenyl

0¹⁰,0¹⁰-di(tert-butyl) ester (182)

O O

This compound was prepared as reported in the literature.²⁰⁹

2,2’-[[1,1’:4’,1”-Biphenyl]-3,3’-diylbis(oxy)]bis[acetic acid]

0¹,0¹⁰-di(2,3,5,6-tetrafluoro-4-iodobenzyl) ester (190)

O O

F F

I F F F

F I F

To a solution of182(25 mg, 60µmol) in DCM (1 ml), TFA (1 ml, 13 mmol) was added. The reaction mixture was stirred at rt for 1 h. The solvent and the side-products were evaporated first under nitrogen flux and then under high vacuum to give 186. This crude was dissolved in dry DMF (5 ml), DIPEA (400 µl, 2.4 mmol) was added and stirred at rt for 15 min. 156 (80 mg, 240 µmol) was added and the reaction mixture was stirred at 120 ^◦C under µW irradiation for 3 h. The solvent was then evaporated in vacuo, acidic water was added (20 ml, 0.1 M HCl) and extracted with DCM (3 x 20 ml).

The organic phases were dried over Na2SO4, concentrated in vacuo and the

5 Experimental Section 157

product was purified by PTLC (2 x, DCM, Rf: 0.30) to afford 190(38 mg, 75%) as a colorless solid. R_f (DCM): 0.45; IR (neat): 2930 (w), 2343 (w), 1766 (m), 1630 (w), 1600 (w), 1576 (w), 1474 (s), 1413 (w), 1368 (w), 1267 (m), 1173 (s), 1087 (w), 1051 (w), 975 (w), 919 (w), 801 (w), 776 (w), 694 (w), 642 (w); ¹H NMR (500 MHz; CDCl3): 7.34 (t, ³J = 7.9 Hz, 2H), 7.19 (br.d, ³J = 7.9 Hz, 2H), 7.08 (t, ³J = 2.1 Hz, 2H), 6.87 (dd,³J = 7.9, ⁴J

= 2.1 Hz, 2H), 5.37 (s, 4H), 4.73 (s, 4H); ¹³C NMR (126 MHz; CDCl₃):

168.2 (s), 157.9 (s), 147.1 (s, 2 x 2C), 144.6 (s, 2 x 2C), 142.3 (s), 129.9 (d), 120.9 (d), 114.4 (s), 113.7 (d), 113.5 (s), 74.1 (s, 2C), 65.2 (t, 2C), 54.4 (t, 2C); ¹⁹F NMR (282 MHz; CDCl3): -119.9 - -120.1 (m, 4F), -140.7 - -140.9 (m, 4F); MS (MALDI, DCTB): 917 (30, [M+K]⁺), 901 (100, [M+Na]⁺), 879 (70, [M+H]⁺).

2,2’-[[1,1’:4’,1”-Biphenyl]-3,3’-diylbis(oxy)]bis[acetic acid]

0¹,0¹⁰-di(2,3,4,5,6-pentafluorobenzyl) ester (194)

O O

F F

F F F F

F F F

To a solution of182(20 mg, 48µmol) in DCM (1 ml), TFA (1 ml, 13 mmol) was added. The reaction mixture was stirred at rt for 1 h. The solvent and the side-products were evaporated first under nitrogen flux and then under high vacuum to give186. This crude was dissolved in dry DMF (3 ml), DIPEA (163 µl, 960µmol) was added and stirred at rt for 15 min. 146(125 mg, 480µmol) was added and the reaction mixture was stirred at -10 ^◦C 1 h. The solvent was then evaporated in vacuo, water was added (15 ml) and extracted with DCM (3 x 20 ml). The organic phases were dried over Na2SO4, concentrated in vacuo and the product was purified by PTLC (DCM, Rf: 0.6) to afford

194(32 mg, quant.) as a colorless solid. Rf (DCM): 0.65; IR (neat): 1769 (m), 1658 (w), 1601 (w), 1577 (w), 1524 (m), 1506 (s), 1367 (w), 1310 (w), 1176 (m), 1132 (w), 1087 (w), 1056 (w), 960 (w), 941 (w), 776 (w), 694 (w); ¹H NMR (500 MHz; CDCl₃): 7.35 (t, ³J = 8.0 Hz, 2H), 7.21 - 7.20 (m, 2H), 7.08 (t, ⁴J = 2.3 Hz, 2H), 6.87 (dd,³J = 8.0, ⁴J =2.3 Hz, 2H), 5.35 (s, 4H), 4.72 (s, 4H); ¹³C NMR (126 MHz; CDCl3): 168.2 (s), 157,8 (s), 145.7 (s, 2 x 2C), 142.3 (s), 142.1 (s, 2 x 2C), 137.5 (s, 2 x 2C), 129.9 (d), 120.9 (d), 113.7 (d), 113.5 (d), 108.8 (s), 65.2 (t), 53.9 (t); ¹⁹F NMR (282 MHz; CDCl₃): -141.06 - -141.16 (m, 4F), -151.24 - -151.44 (m, 2F), -160.72 - -160.91 (m, 4F); MS (MALDI, DCTB): 685 (45, [M+Na]⁺), 663 (100, [M+H]⁺).

2,2’,2”,2”’-[[1,1’:4’,1”:4”,1”’-Quaterphenyl]-2”,3,3’,3”’-tetrayltetrakis(oxy)]

tetrakis[acetic acid] 0¹,0¹⁰,0¹⁰⁰,0¹⁰⁰⁰-tetra(tert-butyl) ester (183)

O O

This compound was prepared as reported in the literature.²⁰⁹

5 Experimental Section 159

2,2’,2”,2”’-[[1,1’:4’,1”:4”,1”’-Quaterphenyl]-2”,3,3’,3”’-tetrayltetrakis(oxy)]

tetrakis[acetic acid] 0¹,0¹⁰,0¹⁰⁰,0¹⁰⁰⁰-tetra(2,3,5,6-tetrafluoro-4-iodobenzyl) ester (191) was added. The reaction mixture was stirred at rt for 1 h. The solvent and the side-products were evaporated first under nitrogen flux and then under high vacuum to give187. This crude was dissolved in dry DMF (2 ml), DIPEA (84 µl, 494µmol) was added and stirred at rt for 15 min. 211(62 mg, 148µmol) in DMF (2 ml) was added and the reaction mixture was stirred at 80^◦C under an atmosphere of argon for 48 h. The solvent was then evaporated in vacuo, acidic water was added (25 ml, 0.1 M HCl) and extracted with DCM (3 x 25 ml). The organic phases were dried over Na₂SO₄, concentratedin vacuo and the product was purified by PTLC (2 x DCM, Rf: 0.20) to afford191 (6.5

(d), 130.0 (d), 126.8 (s), 120.8 (d), 120.7 (d), 114.5 (s, 2 x 2C), 113.8 (d),

tetrakis[acetic acid] 0¹,0¹⁰,0¹⁰⁰,0¹⁰⁰⁰-tetra(2,3,4,5,6-pentafluorobenzyl) ester (195) was added. The reaction mixture was stirred at rt for 1 h. The solvent and the side-products were evaporated first under nitrogen flux and then under high vacuum to give 187. This crude was dissolved in dry DMF (2 ml), DIPEA (117 µl, 688 µmol) was added and stirred at rt for 15 min. 146 (27 mg, 103 µmol) was added and the reaction mixture was stirred at 120 ^◦C under µW irradiation for 3 h. The solvent was then evaporated in vacuo, acidic water was added (25 ml, 0.1 M HCl) and extracted with DCM (3 x 25 ml).

The organic phases were dried over Na₂SO₄, concentrated in vacuo and the product was purified by PTLC (2 x DCM, Rf: 0.30) to afford 195 (12 mg, 80%) as a colorless solid. Rf (DCM): 0.40; IR (neat): 2923 (w), 1768 (m), 1657 (w), 1603 (w), 1523 (m), 1504 (s), 1437 (w), 1397 (w), 1309 (w), 1172

5 Experimental Section 161

(s), 1131 (m), 1057 (m), 965 (w), 940 (m), 824 (w), 780 (w), 737 (w), 697 (w), 658 (w), 611 (w); ¹H NMR (500 MHz; CDCl₃): 7.44 (d, ³J = 8.0 Hz, 2H), 7.37 (t,³J= 8.0 Hz, 2H), 7.29 - 7.25 (m, 2H), 7.24 - 7.20 (m, 2H), 7.13 (br.s, 2H), 7.02 (br.s, 2H), 6.89 (dd,³J = 8.0,⁴J= 2.1 Hz, 2H), 5.37 (s, 4H), 5.29 (s, 4H), 4.75 (s, 4H), 4.71 (s, 4H);¹³C NMR (126 MHz; CDCl3): 168.3 (s), 168.3 (s), 158.0 (s), 155.5 (s), 145.7 (s, 4 x 2C), 142.3 (s), 142.0 (s, b2 x 2C), 141.5 (s), 137.5 (s, 4 x 2C), 132.4 (d), 129.9 (d), 126.8 (s), 120.8 (d), 120.6 (d), 113.9 (d), 113.3 (d), 111.4 (d), 108.8 (s, 2 x 2C), 65.9 (t), 65.2 (t), 53.9 (t), 53.7 (t);¹⁹F NMR (282 MHz; CDCl₃): -141.5 - -141.7 (m, 8F), -151.6 - -152.1 (m, 4F), -161.1 - -161.4 (m, 8F); MS (MALDI, DCTB): 1362 (30, [M+K]⁺), 1346 (50, [M+Na]⁺), 1324 (100, [M+H]⁺).

2,2’,2”,2”’,2””,2””’-[[1,1’:4’,1”:4”,1”’:4”’,1””:4””,1””’-Sexiphenyl]-2”,2””,3,3’,3”’,3””’-sexiylhexakis(oxy)]hexakis[acetic acid]

0¹,0¹⁰,0¹⁰⁰,0¹⁰⁰⁰,0¹⁰⁰⁰⁰,0¹⁰⁰⁰⁰⁰-hexa(tert-butyl) ester (184)

O O O

O O O O O

O O

This compound was prepared with an adapted reported procedure.²¹⁰

was added. The reaction mixture was stirred at rt for 3 h. The solvent and the side-products were evaporated first under nitrogen flux and then under high vacuum to give 188. This crude was dissolved in dry DMF (3 ml), DIPEA (82 µl, 482 µmol) was added and stirred at rt for 15 min. 210 (30 mg, 82 µmol) was added and the reaction mixture was stirred at 120 ^◦C under µW irradiation for 3 h. The solvent was then evaporated in vacuo, acidic water was added (25 ml, 0.1 M HCl) and extracted with DCM (3 x 25 ml).

The organic phases were dried over Na₂SO₄, concentrated in vacuo and the product was purified by PTLC (2 x, 3 DCM runs, Rf: 0.15) to afford 192

5 Experimental Section 163 was added. The reaction mixture was stirred at rt for 3 h. The solvent and the side-products were evaporated first under nitrogen flux and then under high vacuum to give 188. This crude was dissolved in dry DMF (3 ml), DIPEA (82 µl, 482 µmol) was added and stirred at rt for 15 min. 146(20 mg, 77 µmol) was added and the reaction mixture was stirred at 120 ^◦C under µW irradiation for 3 h. The solvent was then evaporatedin vacuo, acidic water was added (20 ml, 0.1 M HCl) and extracted with DCM (3 x 20 ml). The organic phases were dried over Na2SO4, concentrated in vacuo and the product was purified by PTLC (2 x, 2 DCM runs, Rf: 0.20) to afford196(7.9 mg, quant-) as a colorless solid. Rf (DCM): 0.30; IR (neat): 3525 (w), 1762 (m), 1658

(w), 1603 (w), 1523 (m), 1504 (s), 1449 (w), 1396 (w), 1309 (w), 1187 (m), 1134 (m), 1087 (w), 1054 (m), 956 (w), 933 (w), 828 (w), 804 (w);¹H NMR (500 MHz; CDCl3): 7.46 (d, ³J = 7.9 Hz, 2H), 7.45 (d,³J = 7.9 Hz, 2H), 7.37 (t,³J = 7.9 Hz, 2H), 7.29-7.27 (m, 4H), 7.22 - 7.20 (m, 2H), 7.13 (br.s, 2H), 7.06 (br.s, 2H), 7.02 (br.s, 2H), 6.88 (dd, ³J = 7.9, 4J = 2.2 Hz, 2H), 5.36 (s, 4H), 5.29 (s, 8H), 4.74 (s, 4H), 4.71 (s, 8H); ¹³C NMR (126 MHz;

CDCl₃): 168.35 (s), 168.33 (s), 168.29 (s), 158.0 (s), 155.6 (s), 155.5 (s), 145.7 (s, 6 x 2C), 142.3 (s), 141.9 (s, 3 x 2C), 141.5 (s), 141.5 (s), 137.4 (s, 6 x 2C), 132.4 (d, 2 x 2C), 130.0 (d), 126.84 (s), 126.80 (s), 120.8 (d), 120.7 (d), 120.6 (d), 113.9 (d), 113.3 (d), 111.5 (d), 111.4 (d), 108.8 (s, 3 x 2C), 66.0 (t), 65.9 (t), 65.2 (t), 53.9 (t), 53.7 (t, 2 x 2C); ¹⁹F NMR (282 MHz;

CDCl3): -141.5 - -141.7 (m, 12F), -151.7 - -151.9 (m, 6F), -161.0 - -161.4 (m, 12F); MS (MALDI, DCTB): 2022 (20, [M+K]⁺), 2006 (35, [M+Na]⁺), 1984 (100, [M+H]⁺).

2,2’,2”,2”’,2””,2””’,2”””,2”””’-[[1,1’:4’,1”:4”,1”’:4”’,1””:4””,1””’:4””’,

1”””:4”””,1”””’-Octiphenyl]-2”,2””,2”””,3,3’,3”’,3””’,3”””’-octayloctakis(oxy)]octakis[acetic acid] 0¹,0¹⁰,0¹⁰⁰,0¹⁰⁰⁰,0¹⁰⁰⁰⁰,0¹⁰⁰⁰⁰⁰, 0¹⁰⁰⁰⁰⁰⁰,0¹^0000000 -octa(tert-butyl) ester (185)

O O O

O O O O O

O O

This compound was prepared with an adapted reported procedure.²¹¹

5 Experimental Section 165

2,2’,2”,2”’,2””,2””’,2”””,2”””’-[[1,1’:4’,1”:4”,1”’:4”’,1””:4””,1””’:4””’,

O 13 mmol) was added. The reaction mixture was stirred at rt for 3 h. The solvent and the side-products were evaporated first under nitrogen flux and then under high vacuum to give189. This crude was dissolved in dry DMF (3 ml), DIPEA (80µl, 470µmol) and Na₂SO₄ (anhydrous, 2g, 14 mmol) were added and stirred at rt for 15 min. 156(38 mg, 119 µmol) was added and the reaction mixture was stirred at 150 ^◦C under µW irradiation for 5 min.

To this reaction mixture,156(38 mg, 119µmol) was added and the reaction mixture was stirred at 160^◦C underµW irradiation for 5 min. To this mixture, 210 (44 mg, 120 µmol) was added and the reaction mixture was stirred at 170 ^◦C underµW irradiation for 5 min. The solvent was then evaporatedin vacuo, acidic water was added (30 ml, 0.1 M HCl) and extracted with DCM (3 x 30 ml). The organic phases were dried over Na2SO4, concentrated in vacuo and the product was purified by PTLC (2 x, 3 DCM runs, R_f: 0.15) to afford 193(4.2 mg, 30%) as a colorless solid. Rf (DCM): 0.15; IR (neat):

2927 (w), 1767 (m), 1639 (w), 1603 (w), 1476 (s), 1294 (w), 1265 (w), 1178 (m), 1048 (w), 964 (w), 903 (w), 802 (w), 638 (w); ¹H NMR (400 MHz;

CDCl3): 7.56 (d, ³J = 7.4 Hz, 2H), 7.52 (d,³J = 8.1 Hz, 4H), 7.44 - 7.40 0¹⁰⁰⁰⁰⁰⁰,0¹^0000000 -octa(2,3,4,5,6-pentafluorobenzyl) ester (197)

O mmol) was added. The reaction mixture was stirred at rt for 3 h. The solvent and the side-products were evaporated first under nitrogen flux and then under high vacuum to give189. This crude was dissolved in dry DMF (3 ml), DIPEA (80 µl, 470 µmol) and Na2SO4 (anhydrous, 2g, 14 mmol) were added and stirred at rt for 15 min. 146(20 mg, 77 µmol) was added and the reaction mixture was stirred at 150 ^◦C underµW irradiation for 30 min. The solvent was then evaporated in vacuo, acidic water was added (20 ml, 0.1 M HCl) and extracted with DCM (3 x 20 ml). The organic phases were dried over Na2SO4, concentratedin vacuo and the product was purified by PTLC (2 x,

5 Experimental Section 167

3 DCM runs, Rf: 0.25) to afford197(3.9 mg, 50%) as a colorless solid. Rf

(DCM): 0.15; IR (neat): 1763 (m), 1657 (w), 1603 (w), 1522 (m), 1508 (s), 1395 (w), 1270 (w), 1186 (m), 1133 (m), 1089 (w), 1054 (m), 933 (w), 826 (w), 802 (w), 614 (w);¹H NMR (500 MHz; CDCl₃): 7.50-7.46 (m, 6H), 7.38 (t,³J = 8.1 Hz, 2H), 7.31-7.29 (m, 6H), 7.25 - 7.21 (m, 2H), 7.14 (br.s, 2H), 7.10 - 7.08 (m, 4H), 7.03 (br.s, 2H), 6.90 (dd, ³J = 8.1,⁴J = 2.0 Hz, 2H), 5.38 (s, 4H), 5.32-5.31 (m, 12H), 4.75-4.73 (m, 16H); ¹⁹F NMR (282 MHz;

CDCl3): -137.9 - -138.1 (m, 16F), -148.1 - -148.3 (m, 8F), -157.5 - -157.7 (m, 16F); MS (MALDI, DCTB): 2665 (30, [M+Na]⁺), 2643 (100, [M+H]⁺).

5.3 Methods

Dans le document Anion transport with anion-π interactions and halogen bonds (Page 175-186)