Supporting Information for: Unusual para-substituent effects on the intramolecular hydrogen-bond in hydrazone-based switches

Transcription

1 Supporting Information for: Unusual para-substituent effects on the intramolecular hydrogen-bond in hydrazone-based switches Xin Su a, Märt Lõkov b, Agnes Kütt b, Ivo Leito b and Ivan Aprahamian a a Department of Chemistry, Dartmouth College, Hanover, New Hampshire 03755, USA. b Institute of Chemistry, University of Tartu, Ravila 14a, Tartu, Estonia. ivan.aprahamian@dartmouth.edu; ivo.leito@ut.ee Website:

2 Table of Contents 1 General S1 2 Synthesis S1 3 Summary of Analyzed Data S4 4 pk a Measurements Data S5 5 Analysis Plots S6 6 Single Crystal Diffraction S9 7 Computational Methods S13 8 NMR Spectra S18

3 1 General All reagents and starting materials were purchased from commercial sources and used as supplied unless otherwise indicated. All experiments were conducted in air unless otherwise noted. Column chromatography was performed on silica gel (SiliCycle, 60 Å, mesh). Deuterated solvents were purchased from Cambridge Isotope Laboratories, Inc. and used as received. NMR spectra were recorded on a Varian Mercury 300 MHz NMR spectrometer, with working frequencies of MHz for 1 H nuclei and MHz for 13 C nuclei, respectively. Chemical shifts are quoted in ppm relative to tetramethylsilane (TMS), using the residual solvent peak as the reference standard. Mass spectra were obtained either on a Shimadzu GCMS-QP2010S gas chromatograph/ EI mass spectrometer or on a Waters Quattro II ESI mass spectrometer. Melting points were measured on an Electrothermal Thermo Scientific IA9100X1 digital melting point instrument. The pk a measurements were conducted using a previously reported methodology. S1,S2 2 Synthesis Compound p-h was synthesized by following a reported procedure. S3 All other hydrazone derivatives were synthesized in a similar manner starting from the corresponding p-substituted anilines and ethyl-2-pyridyl acetate. Scheme S1: The synthesis and structures of the hydrazone derivatives with different parasubstituents on the phenyl ring. p-nme 2 : obtained as a red crystalline powder, yield 79%, m.p C; 1 H NMR (300 MHz, CD 3 CN) δ (s, N H), 8.68 (ddd, J= 5.0, 1.9, 1.0 Hz, H1), 8.19 (dt, J= 8.4, 1.0 Hz, H4), 7.87 (ddd, J= 8.4, 7.5, 1.9 Hz, H3), (m, H2 and H5), (d, J= 9.0 Hz, H6), 4.30 (qd, J= 7.1, 1.8 Hz, CH 2 ), 2.89 (s, N(CH 3 ) 2 ), 1.37 (t, J= 7.1 Hz, CH 3 ) S1

4 ppm; 13 C NMR (75 MHz, CD 3 CN) δ , , , , , , , , , , , , , 61.27, 41.14, ppm. MS (ESI): m/z found [M H + ] for C 17 H 21 N 4 O (calcd ). p-oh: obtained as a yellow powder, yield 82%, m.p C; 1 H NMR (300 MHz, CD 3 CN) δ (s, N H), 8.70 (d, J= 5.0 Hz, H1), 8.16 (d, J= 8.4 Hz, H4), (m, H3), 7.34 (dd, J= 6.5, 5.1 Hz, H2), 7.24 (d, J= 8.9 Hz, H5), 6.83 (d, J= 8.9 Hz, H6), 6.74 (s, OH), 4.31 (q, J = 7.1 Hz, CH 2 ), 1.37 (t, J = 7.1 Hz, CH 3 ) ppm; 13 C NMR (75 MHz, CD 3 CN) δ , , , , , , , , , , , , , 61.41, ppm. MS (ESI): m/z found [M H + ] for C 15 H 16 N 3 O (calcd ). p-onhex: obtained as bright yellow flakes, yield 89%, m.p C; 1 H NMR (300 MHz, CD 3 CN) δ (s, N H), (m, H1), 8.16 (d, J= 8.4 Hz, H4), 7.87 (ddd, J= 24.0, 12.6, 8.7 Hz, H3), (m, H2 and H5), 6.90 (dd, J= 10.3, 5.6 Hz, H6), 4.31 (q, J= 7.1 Hz, OCH 2 CH 3 ), 3.94 (dd, J= 9.0, 4.1 Hz, OCH 2 CH 2 ), (m, OCH 2 CH 2 ), (m, CH 2 CH 2 CH 2 CH 2 CH 3 and OCH 2 CH 3 ), 0.91 (dd, J= 9.6, 4.3 Hz, CH 2 CH 2 CH 3 ) ppm; 13 C NMR (75 MHz, CD 3 CN) δ , , , , , , , , , , , , 69.06, 61.43, 32.23, 29.92, 26.34, 23.24, 14.59, ppm. MS (EI): m/z found M + for C 21 H 27 N 3 O (calcd. 369). p-ome: obtained as a dark yellow powder, yield 69%, m.p C; 1 H NMR (300 MHz, CD 3 CN) δ (s, N H), 8.70 (ddd, J= 5.0, 1.8, 0.9 Hz, H1), 8.15 (dt, J= 8.3, 0.9 Hz, H4), 7.88 (ddd, J= 8.4, 7.6, 1.9 Hz, H3), (m, H2 and H5), 6.94 (d, J= Hz, H6), 4.31 (q, J= 7.1 Hz, CH 2 ), 3.77 (s, OCH 3 ), 1.37 (t, J= 7.1 Hz, CH 2 CH 3 ) ppm; 13 C NMR (75 MHz, CD 3 CN) δ , , , , , , , , , , , , , 61.46, 56.07, ppm. MS (EI): m/z found M + for C 16 H 17 N 4 O (calcd. 299). p-f: obtained as a bright yellow powder, yield 75%, m.p C; 1 H NMR (300 MHz, CD 3 CN) δ (s, N H), 8.71 (ddd, J= 5.0, 1.8, 1.0 Hz, H1), 8.12 (dt, J= 8.3, 1.0 Hz, H4), 7.90 (ddd, J= 8.4, 7.6, 1.9 Hz, H3), (m, H2 and H5), (m, H6), 4.33 S2

5 (qd, J = 7.1, 1.9 Hz, CH 2 ), 1.38 (t, J = 7.2 Hz, CH 3 ) ppm; 13 C NMR (75 MHz, CD 3 CN) δ , , , , , , , , , , , , , 61.65, ppm. MS (EI): m/z found M + for C 15 H 14 FN 3 O (calcd. 287). p-cl: obtained as a bright yellow powder, yield 81%, m.p C; 1 H NMR (300 MHz, CD 3 CN) δ (s, N H), 8.72 (ddd, J= 5.0, 1.9, 1.0 Hz, H1), 8.10 (dt, J= 8.3, 1.0 Hz, H4), (m, H3), (m, H2, H5 and H6), 4.32 (qd,j= 7.2, 4.2 Hz, CH 2 ), 1.36 (t, J= 7.2 Hz CH 3 ) ppm; 13 C NMR (75 MHz, CD 3 CN) δ , , , , , , , , , , , , , 61.77, ppm. MS (EI): m/z found M + for C 15 H ClN 3 O (calcd. 303) and C 15 H ClN 3 O (calcd. 305). p-br: obtained as a bright yellow powder, yield 83%, m.p C; 1 H NMR (300 MHz, CD 3 CN) δ (s, 1H), (m, H1), 8.10 (dt, J= 8.3, 1.0 Hz, H4), (m, H3), (m, H6), 7.39 (ddd, J= 7.5, 5.0, 1.1 Hz, H2), (m, H5), 4.33 (qd, J= 7.1, 2.8 Hz, CH 2 ), 1.37 (t, J = 7.2 Hz CH 3 ) ppm; 13 C NMR (75 MHz, CD 3 CN) δ , , , , , , , , , , , , , 61.80, ppm. MS (EI): m/z found M + for C 15 H BrN 3 O (calcd. 347) and C 15 H BrN 3 O (calcd. 350). p-mc: obtained as a bright yellow powder, yield 80%, m.p C; 1 H NMR (300 MHz, CD 3 CN) δ (s, N H), (m, H1), 8.07 (dt, J= 8.3, 1.0 Hz, 4H), (m, H3 and H5), (m, H2 and H6), 4.35 (qd, J = 7.1, 1.9 Hz, CH 2 ), 3.84 (s, OCH 3 ), 1.38 (t, J= 7.2 Hz, CH 2 CH 3 ) ppm; 13 C NMR (75 MHz, CD 3 CN) δ , , , , , , , , , , , , , 62.00, 52.37, ppm. MS (EI): m/z found M + for C 17 H 17 N 3 O (calcd. 327). p-cn: obtained as a bright yellow powder, yield 80%, m.p C; 1 H NMR (300 MHz, CD 3 CN) δ (s, N H), (m, H1), 8.06 (d, J= 8.3 Hz, H4), (m, H3), 7.65 (d, J= 7.7 Hz, H5), (m, H2 and H6), 4.35 (q, J= 7.1 Hz, CH 2 ), 1.38 (t, J= 7.1 Hz, CH 3 ) ppm; 13 C NMR (75 MHz, CD 3 CN) δ , , , , , , , , , , , , , , 62.09, ppm. MS (EI): m/z found M + for C 16 H 14 N 4 O (calcd. 294). S3

6 p-no 2 : obtained as a bright yellow powder, yield 77%, m.p C; 1 H NMR (300 MHz, CD 3 CN) δ (s, N H), 8.75 (ddd, J= 4.9, 1.8, 1.0 Hz, H1), (m, H6), 8.05 (dt, J= 8.2, 1.0 Hz, H4), (m, H3), (m, H2 and H5), 4.37 (dq, J= 14.2, 7.0 Hz, CH 2 ), 1.39 (t, J= 7.1 Hz, CH 3 ) ppm; 13 C NMR (75 MHz, CD 3 CN) δ , , , , , , , , , , , , , , 62.19, ppm. MS (EI): m/z found M + for C 15 H 14 N 4 O (calcd. 314). 3 Summary of Analyzed Data Table S1: A summary of Hammett constants, chemical shifts (CD 3 CN), N N distances and pk a values. σ p δ N H,Z /ppm δ N H,E /ppm δ H5 /ppm d(n N)/Å pk a p-nme (14) p-oh p-onhex (37) p-ome p-h (23) p-f p-cl (32) p-br (27) p-mc p-cn p-no (16) 10.2 S4

7 4 pk a Measurements Data Table S2: Results of the experimental pk a measurements. Base Reference base pk a pk a pk a pk a (B) (B) (RB) RB a pk a (RB) - pk a (B) (B) Assigned p-nme 2 2-Me-Pyridine ,6-Me2-Pyridine p-oh Pyridine Me-Pyridine p-onhex Pyridine Me-Pyridine p-ome 2-Me-Pyridine Pyridine p-h 4-MeO-Aniline Me-Aniline Pyridine p-f 4-MeO-Aniline Pyridine p-cl Pyridine MeO-Aniline p-br 4-MeO-Aniline Pyridine p-mc Aniline MeO-Aniline N,N-Me2-Aniline p-cn 2-Me-Aniline MeO-Aniline N,N-Me2-Aniline p-no 2 N,N-Me2-Aniline Me-Aniline a pk a values of reference bases were taken from Refs. S1 and S2. S5

8 5 Analysis Plots Figure S1: The plot of δ N H,Z of the different derivatives (Z configuration) vs. the corresponding σ p values, and the linear regression fitting results. Figure S2: The plot of δ N H,E of the different derivatives (E configuration) vs. the corresponding σ p values, and the linear regression fitting results. S6

9 Figure S3: The plot of δ H5 of the different derivatives vs. the corresponding σ p values, and the linear regression fitting results. Figure S4: The plot of the pk a s of the different derivatives vs. the corresponding σ p values, and the linear regression fitting results. S7

10 Figure S5: The plot of δ N H,E of the different derivatives (E configuration) vs. the corresponding pk a values. Figure S6: The plot of the predicted pk a values of the different derivatives vs. the corresponding experimental pk a values, and the linear regression fitting results. S8

11 6 Single Crystal Diffraction Data were collected using a Bruker CCD (charge coupled device) based diffractometer equipped with an Oxford Cryostream low-temperature apparatus operating at 173 K. Data were measured using ω and φ scans of 0.5 per frame for 30 s. The total number of images was based on results from the program COSMO S4 where redundancy was expected to be 4.0 and completeness of 100% out to 0.83 Å. Cell parameters were retrieved using APEX II software S5 and refined using SAINT on all observed reflections. Data reduction was performed using the SAINT software S6 which corrects for L p. Scaling and absorption corrections were applied using SADABS S7 multi-scan technique, supplied by George Sheldrick. The structures are solved by the direct method using the SHELXS-97 program and refined by least squares method on F 2, SHELXL-97, which are incorporated in SHELXTL-PC V S8 All non-hydrogen atoms are refined anisotropically. All hydrogens were calculated by geometrical methods and refined as a riding model. Figure S7: Ball-stick drawings of the crystal structures of p-nme 2 (a), p-onhex(b), p-cl(c), p-br(d) and p-no 2 (e). S9

12 Table S3: Crystal data and parameters for p-nme 2, p-onhex, p-cl, p-br and p-no 2. p-nme 2 p-onhex CCDC Empirical formula C 17 H 20 N 4 O 2 C 21 H 27 N 3 O 3 Formula weight Temperature 173(2) K 173(2) K Wavelength Å Å Crystal system Monoclinic Monoclinic Space group P2 1 /c P2 1 /c Unit cell dimensions a = (13) Å a = (7) Å α = 90 α = 90 b = (5) Å b = (5) Å β = (10) β = (3) c = (8) Å c = (2) Å γ = 90 γ = 90 Volume (2) Å (11) Å 3 Z 4 4 Density (calcd.) Mg m Mg m 3 Absorption coefficient mm mm 1 F Crystal size mm mm 3 θ range for data collection 2.15 to to Index ranges -22 h h 25-9 k 9-14 k l 13-7 l 7 Reflections collected Independent reflections 2925 [R int = ] 3505 [R int = ] Completeness to θ = % 96.7% Absorption correction Semi-empirical from equivalents Semi-empirical from equivalents Max. and min. transmission and and Refinement method Full-matrix least-squares on F 2 Full-matrix least-squares on F 2 Data / restraints / parameters 2925 / 0 / / 0 / 352 Goodness-of-fit on F Final R indices [I > 2σ(I)] R 1 = , ωr 2 = R 1 = , ωr 2 = R indices (all data) R 1 = , ωr 2 = R 1 = , ωr 2 = Largest diff. peak and hole and e Å and e Å 3 S10

13 (Continued) p-cl p-br CCDC Empirical formula C 15 H 14 ClN 3 O 2 C 15 H 14 BrN 3 O 2 Formula weight Temperature 173(2) K 173(2) K Wavelength Å Å Crystal system Orthorhombic Orthorhombic Space group P P Unit cell dimensions a = (4) Å a = (2) Å α = 90 α = 90 b = (7) Å b = (3) Å β = 90 β = 90 c = (2) Å c = (6) Å γ = 90 γ = 90 Volume (19) Å (7) Å 3 Z 4 4 Density (calcd.) Mg m Mg m 3 Absorption coefficient mm mm 1 F Crystal size mm mm 3 θ range for data collection 2.21 to to Index ranges -5 h 5-8 h 5-11 k k l l 19 Reflections collected Independent reflections 2590 [R int = ] 2644 [R int = ] Completeness to θ = % 100.0% Absorption correction Semi-empirical from equivalents Semi-empirical from equivalents Max. and min. transmission and and Refinement method Full-matrix least-squares on F 2 Full-matrix least-squares on F 2 Flack parameters -0.02(10) 0.000(9) Data / restraints / parameters 2590 / 0 / / 0 / 191 Goodness-of-fit on F Final R indices [I > 2σ(I)] R 1 = , ωr 2 = R 1 = , ωr 2 = R indices (all data) R 1 = , ωr 2 = R 1 = , ωr 2 = Largest diff. peak and hole and e Å and e Å 3 S11

14 (Continued) p-no 2 CCDC Empirical formula C 15 H 14 N 4 O 2 Formula weight Temperature Wavelength Crystal system Space group Unit cell dimensions 173(2) K Å Orthorhombic Pbca a = (5) Å α = 90 b = (15) Å β = 90 c = (17) Å γ = 90 Volume (4) Å 3 Z 8 Density (calcd.) Absorption coefficient Mg m mm 1 F Crystal size mm 3 θ range for data collection 1.79 to Index ranges -8 h 8-23 k l 28 Reflections collected Independent reflections 3134 [R int = ] Completeness to θ = % Absorption correction Semi-empirical from equivalents Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 3134 / 0 / 264 Goodness-of-fit on F Final R indices [I > 2σ(I)] R 1 = , ωr 2 = R indices (all data) R 1 = , ωr 2 = Largest diff. peak and hole and e Å 3 S12

15 7 Computational Methods Calculations were performed using density functional theory (DFT) with the B3LYP functional S9 as implemented in Gaussian 09. S10 Geometry optimizations and frequency analysis were performed using the G(d) basis set. NBO calculations were done using the B3LYP optimized structures. Table S4: A summary of the NBO calculated charge distributions on the N H and the pyridyl nitrogens in p-nme 2, p-h and p-no 2. N H Nitrogen Pyridyl Nitrogen p-nme p-h p-no Figure S8: Ball-and-stick drawing of the B3LYP/6-311+G(d) optimized structure of p-nme 2. The NBO calculated charge distribution is shown as well. S13

16 Figure S9: Ball-and-stick drawing of the B3LYP/6-311+G(d) optimized structure of p-h. The NBO calculated charge distribution is shown as well. Figure S10: Ball-and-stick drawing of the B3LYP/6-311+G(d) optimized structure of p-no2. The NBO calculated charge distribution is shown as well. S14

17 Table S5: Cartesian coordinates for the B3LYP/6-311+G(d) optimized structure of p-nme 2. O O N H N N N C C H C H C C H C H C H H H C H H H C C C H H C H H H C C H C H C H C H S15

18 Table S6: Cartesian coordinates for the B3LYP/6-311+G(d) optimized structure of p-h. O O N N H N C C C C H C H C H C H C H H C H H H C C H C H C H C H C H S16

19 Table S7: Cartesian coordinates for the B3LYP/6-311+G(d) optimized structure of p-no 2. O O O O N H N N N C C C H H C H H H C C H C H C H C H C C H C H C C H C H S17

20 8 NMR Spectra Figure S11: 1 H NMR spectrum of p-nme 2 in CD 3 CN at 294 K in the presence of the minor Z Figure S12: 13 C NMR spectrum of p-nme 2 in CD 3 CN at 294 K in the presence of the minor Z S18

21 Figure S13: 1 H NMR spectrum of p-oh in CD 3 CN at 294 K in the presence of the minor Z Figure S14: 13 C NMR spectrum of p-oh in CD 3 CN at 294 K in the presence of the minor Z S19

22 Figure S15: 1 H NMR spectrum of p-onhex in CD 3 CN at 294 K in the presence of the minor Z Figure S16: 13 C NMR spectrum of p-onhex in CD 3 CN at 294 K in the presence of the minor Z S20

23 Figure S17: 1 H NMR spectrum of p-ome in CD 3 CN at 294 K in the presence of the minor Z Figure S18: 13 C NMR spectrum of p-ome in CD 3 CN at 294 K in the presence of the minor Z S21

24 Figure S19: 1 H NMR spectrum of p-f in CD 3 CN at 294 K in the presence of the minor Z Figure S20: 13 C NMR spectrum of p-f in CD 3 CN at 294 K in the presence of the minor Z S22

25 Figure S21: 1 H NMR spectrum of p-cl in CD 3 CN at 294 K in the presence of the minor Z Figure S22: 13 C NMR spectrum of p-cl in CD 3 CN at 294 K in the presence of the minor Z S23

26 Figure S23: 1 H NMR spectrum of p-br in CD 3 CN at 294 K in the presence of the minor Z Figure S24: 13 C NMR spectrum of p-br in CD 3 CN at 294 K in the presence of the minor Z S24

27 Figure S25: 1 H NMR spectrum of p-mc in CD 3 CN at 294 K in the presence of the minor Z Figure S26: 13 C NMR spectrum of p-mc in CD 3 CN at 294 K in the presence of the minor Z S25

28 Figure S27: 1 H NMR spectrum of p-cn in CD 3 CN at 294 K in the presence of the minor Z Figure S28: 13 C NMR spectrum of p-cn in CD 3 CN at 294 K in the presence of the minor Z S26

29 Figure S29: 1 H NMR spectrum of p-no 2 in CD 3 CN at 294 K in the presence of the minor Z Figure S30: 13 C NMR spectrum of p-no 2 in CD 3 CN at 294 K in the presence of the minor Z S27

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31 R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, Ö. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, and D. J. Fox, Gaussian 09 Revision A.1, Gaussian Inc. Wallingford CT S29