Calix-Tris-Tröger s Bases A New Cavitand Family

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1 Supplementry Mteril (ESI) for Chemicl Communictions This journl is (c) The Royl Society of Chemistry 200 Clix-Tris-Tröger s Bses A ew Cvitnd Fmily Mrtin Vlík, Jn Čejk, Mrtin vlík, Vldimír Král, Bohumil Dolenský * Deprtment of Anlyticl Chemistry nd Deprtment of Solid Stte Chemistry, Institute of Chemicl Technology Prgue, Technická 5, Prh 6, , Czech Repulic. dolensk@vscht.cz C o n t e x t S2 S2 S3 S3 S4 S4 S5 S6 Preprtion of nitromide 2c Preprtion of minomide 3c Preprtion of hexmine 4c Preprtion of throne-1c Preprtion of clix-1c y distereiosomertion One-pot preprtion of throne-1 Preprtion of clix-1 y distereiosomertion Approximtion of cvity volume clcultion S1

2 Supplementry Mteril (ESI) for Chemicl Communictions This journl is (c) The Royl Society of Chemistry 200 E X P E R I M E T A L P A R T All 1 nd 13 C MR experiments were recorded t nd 5.46 Mz, respectively. Chemicl shifts δ (ppm) re referenced to the internl stndrd Me 4 Si for oth 1 nd 13 C MR spectr; the coupling constnts J re given in ertz (z). The correltion techniques g-sqc, g-cosy, 1D OESY (mixing time 600 ms) were recorded under common conditions. The g-mbc spectr were recorded with prmeters of 1 J C coupling 180 z (prmeter j1hx t Vrin Mercury MR mchine) nd n J C coupling 8 z (prmeter jnhx t Vrin Mercury MR mchine). The chemicl shifts nd coupling constnts for,, 8, 8, nd in clix-1 nd clix-1c were determined y simultion s six-spins system y MestRe-C (Mestrel Reserch, Spin). Crystllogrphic dt hve een deposited with the Cmridge Crystllogrphic Dt Centre s supplementry puliction nos. CCDC-6406 (clix-1c) nd CCDC (throne-1c). Copies of the dt cn e otined free of chrge on ppliction to CCDC, 12 Union Rod, Cmridge CB2 1EZ, UK (fx: (+44) ; e-mil: deposit@ccdc.cm.c.uk). The preprtions of compounds 2, 3, 4, throne-1, 2, 3 nd 4, nd unsuccessful ttempt of throne-1 preprtion were descried previously. [6] Preprtion of nitromide 2c 5-methoxy-2-nitroenzoic cid (12. g, 65.5 mmol) ws refluxed with SOCl 2 (40 ml) in toluene (50 ml) for 5 h. The voltile prt of rection mixture ws evported nd residue codestilted with toluene (2 20 ml). Residul rown oil ws dded to solution of 1,3,5-triminoenzene (2.02 g, 16.4 mmol) in pyridine (20 ml) nd DMF (40 ml). Rection mixture ws stirred 12 h t room temperture nd 1 h t 50 C. After cooling, 1 L of wter ws dded. The formed precipitte of 2c (6.10 g, 63% yield) ws filtered off, wshed with methnol (100 ml) nd dichlormethne (150 ml). Additionl prt of 2c (0.5 g, 8% yield) ws otined from the orgnic prt of the filtrte. 1 MR (DMSO-d 6 ): 3.2 (, s, OC 3 ),.20 (6, m),.8 (3, s), 8.15 (3, d, 8.5), 10.6 (3, s, ). 13 C APT MR (DMSO-d 6 ): 56.5 (OC 3 ), (C), (C), (C), (C), 135.6, , 13.41, , Elementl nlysis for C O 12 clcd: %C, 3.66 %, 12.2 %; found: %C, 3.3 %, %. Preprtion of minomide 3c A flsk ws chrged with 1.00 g (1.5 mmol) of 2c, 100 mg of Pd/C (10%), 50 ml of methnol, nd 10 ml of DMF. The mixture ws stirred over night under 2 tmosphere. The ctlyst ws filtrted off through cellite nd the filtrte ws concentrted in vcuo to otined 0.86 g of 3c (100% yield). 1 MR (DMSO-d 6 ): 3.2 (, s), (6, r s), 6.2 (3, d, 8.8), 6.8 (3, dd, 8.8, 2.8),.20 (3, d, 2.8),.81 (3, s), (3, r s). 13 C APT MR (DMSO-d 6 ): S2

3 Supplementry Mteril (ESI) for Chemicl Communictions This journl is (c) The Royl Society of Chemistry 200 (OC 3 ), 10.0 (C), (C), , 11.6 (C), 11.2 (C), 13.03, , 14.52, RMS (FAB + ) for C O 6 (M + ) clcd: ; found: , nd for C O 6 (M + ) clcd: ; found: Preprtion of hexmine 4c 3.5 M toluene solution of LA (18 ml, 63 mmol) ws slowly dded to 3c (1.30 g, 2.3 mmol) in dioxne (40 ml). Then the rection mixture ws refluxed for 14 h. The flsk ws plced into ice th nd 6 ml of wter, followed y ml of queous solution of O (15%) nd 10 ml of wter were cutiously dded. The mixture ws filtered nd the filtrte ws evported in vcuo to otin 1.12 g of 4c (3% yield). 1 MR (DMSO-d 6 ): 3.5 (, s), 3.1 (6, d, 5.5), 4.45 (6, r s), 5.30 (6, m), 6.54 (6, m), 6.6 (3, t, 1.6). 13 C APT MR (DMSO-d 6 ): (C 2 ), (OC 3 ), 8.64 (C), (C), (C), (C), , 13.80, , LRMS (FAB + ): for C O 3 (M + ) clcd: 52.2; found: Preprtion of throne-1c exmine 4c (1.21 g, 2.3 mmol) nd 1.00 g of prformldehyde were dded to trifluorocetic cid (145 ml). The rection mixture ws stirred 1 h t 50 C, then diluted with ice wter (1 L), nd conc. q. mmoni ws dded to p 14. The mixture ws extrcted with C 2 Cl 2 (3 150 ml). The orgnic prts were comined, wshed with rine, dried over 2 SO 4, nd evported in vcuo to dryness. By repeting column chromtogrphy on silic (C 2 Cl 2 /EtOAc/ethnol 250:250:12) 80 mg of y-product 5 (6% yield) 320 mg of crude Tris-TB throne-1c were otined. The crystlliztion of crude throne-1c from C 2 Cl 2 /cetone gve 240 mg (18% yield) of pure throne-1c. By-product 5: 1 MR (CDCl 3 ): 2.80 (3, s, C 3 ), 3.1 (3, s, OC 3 ), 3.3 (3, s, OC 3 ), 3.5 (3, s, OC 3 ), 3.1 (1, d, 16.), 3.5 (1, d, 10.8), 4.01 (1, d, 15.8), 4.02 (1, d, 13.3), 4.04 (1, d, 10.6), 4.13 (1, d, 12.), 4.18 (1, d, 15.6), 4.1 (1, d, 12.2), 4.28 (3, m), 4.46 (1, d, 16.), 4.4 (1, d, 1.1), 4.52 (1, d, 1.), 4.56 (1, d, 1.2), 4.5 (1, d, 16.6), 6.41 (1, d, 2.), 6.46 (1, d, 2.8), 6.50 (1, t, C 3 O 3 C OC ), 6.6 (1, s), 6.8 (4, m),.0 (1, d, 8.8),.11 (1, d, 8.8). 13 C OC 3 APT MR (CDCl 3 ): 38.3 (C 3 ), (C 2 ), (C 2 ), 55.2 (OC 3 ), (OC 3 ), (C 2 ), (OC 3 ), (C 2 ), 5.08 (C 2 ), 66.6 (C 2 ), 6.00 (C 2 ), 1.05 (C 2 ), (C), (C), (C), (C), (C), (C), 113. (C), (C), 11.8, 118., 123.5, (C), (C), , 128.5, , 140., 140.2, , 14.53, , , , RMS (FAB + ): for C O 3 (M + ) clcd: ; found: Bsed on these chrcteristics nd 2D MR spectr (g-cosy, g-sqc, g-mbc) the following structure ws deduced. S3

4 Supplementry Mteril (ESI) for Chemicl Communictions This journl is (c) The Royl Society of Chemistry 200 Throne-1c: 1 MR (CDCl 3 ): 3.60 (1, d, 16.8), 3.65 (3, s), 3.2 (3, s), 3.3 (3, s), 3.82 (1, d, 16.5), 3.88 (1, d, 16.), 4.08 (1, d, 12.8), 4.10 (1, d, 12.2), 4.16 (1, d, ~13), 4.18 (1, d, ~13), 4.1 (2, s), 4.2 (1, d, 1.4), 4.36 (1, d, 1.0), (5, m), 4.53 (1, d, 1.4), 4.56 (1, d, 1.0), 6.25 (1, d, 2.), 6.41 (1, d, 2.), 6.45 (1, d, 2.), 6.6 (1, dd, 8.8, 2.), 6.6 (1, dd, 8.8, 2.), 6.8 (3, dd, 8.8, 2.),.08 (1, d, 8.8),.12 (1, d, 8.8),.15 (3, d, 8.8). 13 C APT MR (CDCl 3 ): 54.6 (2 C 2 ), (2 C 2 ), (OC 3 ), (OC 3 ), (OC 3 ), 55.5 (C 2 ), 56.1 (C 2 ), 66.6 (C 2 ), 66.4 (C 2 ), 66. (C 2 ), (C), (2 C), (C), (C), (C), 11.4, , 11.02, (C), (C), (C), , , , , 140.4, 141.1, 143.4, (2 C), 155.2, 155., RMS (FAB + ): for C O 3 (M + ) clcd: ; found: Preprtion of clix-1c y distereiosomertion Throne-1c (54 mg) ws dissolved in 5 ml of TFA nd wrmed t 110 C for 15 h. The otined mixture of throne-1c nd clix-1c in rtio :3 ws seprted y preprtive TLC (Uniplte Silic Gel GF, 20 cm 20 cm 0.1 cm, with PA zone, C 2 Cl 2 /C 3 O :3). The distereoisomer throne-1c ws suject of next distereoisomeriztion. The collected portions of clix-1c from five isomeriztions gve 6 mg (11% yield). The single crystl for X-ry nlysis ws otined y crystliztion from mixture C 2 Cl 2 /C 3 O. The 1 nd 13 C chemicl shifts in MR spectr were ssigned sed on g-cosy, g-sqc, 12 OC 3 g-mbc nd 1D OEDIF spectr nlogously to ssignment on istb derivtives. [6c] Clix-1c: 1 MR (CDCl 3 ): 3.64 (, s, 12), 3.65 (3, d, 16.8, ), 4.18 (3, d, 1., ), 4.18 (3, d, 12.3, 8 or 8 ), 4.20 (3, d, 12.3, 8 or 8 ), 4.48 (3, d, 16.8, ), 4.66 (3, d, 1., ), 6.28 (3, d, 2., 6), 6.1 (3, dd, 8.8, 2., 2),.11 (3, d, 8.8, 3). 13 C MR (CDCl 3 ): 54.1 C, C12, 56.0 C, 66.3 C8, C6, C2, C 3 O C10, C3, C5, C4, C11, C1. RMS (FAB + ): for C O 3 (M + ) clcd: ; found: OC S4

5 Supplementry Mteril (ESI) for Chemicl Communictions This journl is (c) The Royl Society of Chemistry 200 One-pot preprtion of throne-1 A vil ws chrged with 86 mg (0.0 mmol) of 1,3,5-triminoenzene, 24 mg (2.32 mmol) of p-toluidine nd 1 mg (equiv. of 6.63 mmol of C 2 O) of prformldehyde, nd 4 ml of TFA ws dded. The vil ws closed with cup, nd the mixture ws vigorously stirred for 24 h in 60 C oil th. The mixture ws cool down nd diluted with 200 ml of wter, nd lklized y dding of 5 ml of conc. queous mmonium. The mixture ws extrcted with C 2 Cl 2 (2 x 20 ml). The orgnic prts were dried over MgSO 4 nd evported in vcuo to dryness. Repeting seprtion on preprtive TLC (C 2 Cl 2 /C 3 O 100:3) gve 8 mg (2% yield) of throne-1. The MR chrcteristics confirm the identity with the compound isolted previously. [6c] Throne-1: 1 MR (CDCl 3 ): 2.18 (3, s, C 3 ), 2.24 (6, m, 2C 3 ), 3.60 (1, d, 16.5), 3.3 (1, d, 16.8), 3.86 (1, d, 16.5), (15, m), 6.54 (1, s), 6.0 (1, s), 6.4 (1, s), (6, m). 13 C APT MR (CDCl 3 ): (C 3 ), 21.0 (C 3 ), 20.6 (C 3 ), 54.3 (C 2 ), (C 2 ), (C 2 ), 55.1 (C 2 ), (C 2 ), (C 2 ), 66.5 (2C 2 ), (C 2 ), 11.0 (C), (C), (C), (C), 124. (C), (C), (C), (C), 12.1 (C), (2C), (C), 12.0 (C), 12.8 (C), (C), (C), (C), (C), (C), (C), (C), 144. (C), (C), (C). RMS (FAB + ): for C (M + ) clcd: ; found: Preprtion of clix-1 y distereiosomertion Throne-1 (1 mg) ws dissolved in 2 ml of TFA nd wrmed t 110 C for 1 h. The otined mixture of throne-1 nd clix-1 in rtio :3 ws seprted y preprtive TLC (Uniplte Silic Gel GF, 20 cm 20 cm 0.1 cm, with PA zone, C 2 Cl 2 /C 3 O 2:2) to give out 1 mg of clix-1. The 1 nd 13 C chemicl shifts in MR spectr were ssigned sed on gcosy, gsqc, gmbc nd 1D OEDIF spectr nlogously to ssignment on istb derivtives. [6c] Clix-1: 1 MR (CDCl 3 ): 2.16 (, s, 12), 3.5 (3, d, , ), 4.16 (3, d, 12.4, 8 or 8 ), 4.20 (3, d, 12.4, 8 or C ), 4.21 (3, d, 16.6, ), 4.45 (3, d, 16., ), 4.65 (3, d, 1.6, ), 6.56 (3, d, 1.4, 6), 6.4 (3, dd, 8.1, 1., 2),.06 (3, d, 8.1, 3). 13 C MR (CDCl 3 ): 20.6 C12, C, C, 66.2 C8, C10, C3, C5, C6, C2, C1, C11, 145. C4. 3 C C 3 S5

clix-1c ws clculted from X-ry dt s the volume of truncted cone with following

The nitrogen toms of centrl enzene define lmost equilterl tringle with side 0.

The oxygen toms define lmost equilterl tringle with side 0.

6 Supplementry Mteril (ESI) for Chemicl Communictions This journl is (c) The Royl Society of Chemistry 200 Approximtion of cvity volume clcultion The volume of the clix-1c ws clculted from X-ry dt s the volume of truncted cone with following definition. The nitrogen toms of centrl enzene define lmost equilterl tringle with side 0.4 nm nd the circumscried circle d 1 = 0.65 nm. The oxygen toms define lmost equilterl tringle with side 0.85 nm nd the circumscried circle d 2 = 0.8 nm. The distnce of the tringle centroids is h = 0.55 nm. The dimensions must e decresed y vn der Wls dimeter; let s use correction y 0.16 nm. The volume of the free spce for guest is 0.08 nm 3. S6

Construction of right-handed-, left-handed- and racemic helical. coordination polymers. Enantioselective recognition via chiral.

Construction of right-handed-, left-handed- and racemic helical. coordination polymers. Enantioselective recognition via chiral. Construction of right-hnded-, left-hnded- nd rcemic helicl coordintion polymers. Enntioselective recognition vi chirl helicl crystls Kyung Hwn Prk, Te Hwn Noh, Yoon-Bo