Study of Cyclic Quaternary Ammonium Bromides by B3LYP Calculations, NMR and FTIR Spectroscopies
Abstract
:1. Introduction
2. Results and Discusion
2.1. Synthesis
2.2. B3LYP Calculations
Parameters | 1 | 2 | 3 |
---|---|---|---|
Energy (a.u) | -3495.20808 | -3453.27811 | -3413.96044 |
Dipol moment (Debye) | 13.4951 | 11.4097 | 11.4657 |
Bond length (Å) | |||
N+…Br- | 3.888 | 3.709 | 3.674 |
C(1)-H…Br- | 3.636 | 3.536 | 3.486 |
C(1’)-H…Br- | 3.686 | ||
C(4)-H…Br- | 3.551 | 3.570 | 3.616 |
C(4’)-H…Br- | 3.360 | 3.346 | |
N-C(1) | 1.535 | 1.538 | 1.532 |
N-C(1’) | 1.533 | 1.514 | 1.513 |
N-C(4) | 1.548 | 1.542 | 1.529 |
N-C(4’) | 1.531 | 1.551 | 1.543 |
Bond angle (o) | |||
N-C(1)-C(2) | 119.5 | 115.3 | 106.2 |
N-C(1’)-C(2’) | 116.9 | 114.2 | 106.2 |
N-C(4)-C(5) | 117.9 | 116.3 | 115.6 |
N-C(4’)-C(5’) | 120.2 | 119.9 | 118.6 |
Dihedral angle (o) | |||
N-C(1)-C(2)-C(3) | -70.3 | -49.5 | |
N-C(1’)-C(2’)-C(3’) | 88.6 | ||
N-C(1’)-C(2’)-C(3) | 57.8 | ||
N-C(1)-C(2)-C(2’) | -18.2 | ||
N-C(1’)-C(2’)-C(2) | 25.2 | ||
N-C(4)-C(5)-C(6) | -176.8 | -177.4 | -176.9 |
N-C(4’)-C(5’)-C(6’) | -176.5 | -172.3 | -170.0 |
2.3. FTIR and Raman Spectra Study
Raman | IR | IR(calc.) | INT | Proposed assignment |
---|---|---|---|---|
3437w | νOH | |||
2973m | 2956s | 3016 | 43.7 | νCH2 |
3013 | 62.3 | νCH2 | ||
3011 | 64.9 | νCH2 | ||
2999 | 23.3 | νCH2 | ||
2987 | 63.2 | νCH2 | ||
2974 | 18.6 | νCH2 | ||
2943 | 112 | νCH2 | ||
2926s | 2925s | 2934 | 61.4 | νCH2 |
2919 | 6.4 | νCH2 | ||
2864s | 2856s | 2914 | 200 | νCH2 |
2781vw | νCH2 | |||
2727vw | νCH2 | |||
2709vw | 2696vw | νCH2 | ||
2669vw | 2670vw | νCH2 | ||
1490vw | 1485m | 1501 | 21.9 | νCC |
1481 | 4.7 | |||
1448w | 1468m | 1467 | 8.0 | νCC |
1456 | 7.9 | |||
1452 | 2.3 | |||
1392w | 1396 | 1.5 | νCN | |
1377w | 1376 | 3.5 | νCN | |
1372 | 1.6 | |||
1358vw | 1360w | 1354 | 4.9 | νCC, βCH2 |
1349vw | 1338w | 1344 | 1.4 | βCH2 |
1321 | 2.8 | |||
1313vw | 1310w | 1308 | 2.7 | βCH2 |
1295 | 1.6 | |||
1280vw | 1277w | 1281 | 3.4 | νCC |
1263vw | 1251vw | 1264 | 2.8 | νCC |
1245 | 0,81 | |||
1217vw | 1218vw | 1205 | 0.63 | νCC |
1186 | 1.3 | |||
1141vw | 1141vw | 1169 | 3.3 | νCN |
1115vw | 1115vw | 1115 | 2.4 | νCN |
1087vw | 1088w | 1075 | 15.3 | γCH2 |
1069vw | 1068vw | 1055 | 1.6 | γCH2 |
1048vw | 1047vw | 1029 | 3.8 | βCH2 |
1014vw | 1007w | 1014 | 2.9 | βCCC |
960vw | 962w | 997 | 2.6 | βCCC |
930vw | 930vw | 944 | 2.0 | βCCC |
933 | 9.7 | |||
865vw | 875w | 878 | 13.7 | βCCC |
846vw | 847vw | 853 | 4.6 | βCCC |
831vw | 832w | βCCC | ||
803vw | 800vw | 788 | 2.5 | βCCC |
767vw | 765vw | 742 | 19.5 | βCCC |
741vw | 738w | βCCC | ||
723w | 714 | 4.0 | βCCC | |
706vw | βCCC | |||
659vw | 651vw | 616 | 1.8 | βCNC |
580vw | 578vw | βNCC | ||
542vw | 538vw | βCCC | ||
498vw | 499vw | 499 | 3.8 | γCCC |
403vw | 403vw | 439 | 1.5 | γCCC |
375vw | 346 | 1.3 | Lattice mode | |
360vw | Lattice mode | |||
330vw | Lattice mode | |||
303vw | Lattice mode | |||
288vw | 224 | 1.2 | Lattice mode | |
201vw | 123 | 4.1 | Lattice mode | |
86vw | 91 | 0.59 | Lattice mode | |
51 | 2.5 |
2.4. 1H-NMR and 13C-NMR Spectra
δ exp | δcalc | σcalc | δexp | δcalc | σcalc | ||
---|---|---|---|---|---|---|---|
C(1) | 63.1 | 57.4 | 118.0 | H(1) | 3.70 | 3.85 | 27.44 |
C(2) | 22.2 | 23.3 | 155.4 | H(2) | 2.01 | 1.62 | 30.27 |
C(3) | 27.3 | 21.7 | 157.1 | H(3) | 1.79 | 2.06 | 29.72 |
C(4) | 61.3 | 64.6 | 110.1 | H(4) | 3.45 | 3.25 | 28.20 |
C(5) | 22.6 | 25.7 | 152.7 | H(5) | 1.71 | 1.59 | 30.32 |
C(6) | 26.4 | 27.1 | 151.2 | H(6) | 1.27 | 1.23 | 30.77 |
C(7) | 29.1 | 30.3 | 147.7 | H(7) | 1.27 | 1.33 | 30.65 |
C(8) | 29.0 | 30.3 | 147.7 | H(8) | 1.27 | 1.31 | 30.67 |
C(9) | 31.6 | 32.2 | 145.6 | H(9) | 1.27 | 1.27 | 30.72 |
C(10) | 22.6 | 24.1 | 154.5 | H(10) | 1.27 | 1.34 | 30.63 |
C(11) | 14.0 | 12.4 | 167.3 | H(11) | 0.88 | 1.05 | 31.00 |
a | -0.9113 | a | -0.7865 | ||||
b | 164.9046 | b | 25.4318 | ||||
r2 | 0.9622 | r2 | 0.9609 |
δ exp | δcalc | σcalc | δexp | δcalc | σcalc | ||
---|---|---|---|---|---|---|---|
C(1) | 58.9 | 54.8 | 129.6 | H(1) | 3.78 | 3.28 | 27.90 |
C(2) | 20.0 | 20.5 | 167.8 | H(2) | 1.90 | 1.67 | 29.95 |
C(3) | 26.4 | 20.5 | 167.8 | H(3) | 1.90 | 1.47 | 30.23 |
C(4) | 58.1 | 61.0 | 122.7 | H(4) | 3.46 | 3.88 | 27.12 |
C(5) | 21.7 | 23.2 | 161.8 | H(5) | 1.65 | 1.77 | 29.84 |
C(6) | 22.5 | 25.7 | 162.1 | H(6) | 1.27 | 1.42 | 30.30 |
C(7) | 29.0 | 29.2 | 158.1 | H(7) | 1.27 | 1.33 | 30.41 |
C(8) | 28.9 | 29.2 | 158.1 | H(8) | 1.27 | 1.37 | 30.36 |
C(9) | 31.6 | 30.7 | 156.5 | H(9) | 1.27 | 1.30 | 30.45 |
C(10) | 20.6 | 23.1 | 164.9 | H(10) | 1.27 | 1.39 | 30.33 |
C(11) | 14.0 | 13.6 | 175.5 | H(11) | 0.88 | 1.02 | 30.81 |
a | 170.9303 | a | 24.0232 | ||||
b | -0.8962 | b | -0.7758 | ||||
r2 | 0.9640 | r2 | 0.9168 |
δ exp | δcalc | σcalc | δexp | δcalc | σcalc | ||
C(1) | 62.9 | 61.9 | 126.0 | H(1) | 3.85 | 3.69 | 27.57 |
C(2) | 21.8 | 18.6 | 169.5 | H(2) | 2.31 | 1.77 | 29.81 |
C(4) | 59.4 | 59.7 | 128.2 | H(4) | 3.43 | 3.32 | 28.00 |
C(5) | 23.4 | 24.2 | 163.9 | H(5) | 1.70 | 2.43 | 29.04 |
C(6) | 26.3 | 27.5 | 160.6 | H(6) | 1.27 | 1.30 | 30.49 |
C(7) | 29.0 | 29.2 | 158.9 | H(7) | 1.27 | 1.26 | 30.24 |
C(8) | 28.9 | 30.2 | 157.8 | H(8) | 1.27 | 1.25 | 30.41 |
C(9) | 31.5 | 31.1 | 156.9 | H(9) | 1.27 | 1.40 | 30.40 |
C(10) | 22.5 | 23.3 | 164.8 | H(10) | 1.27 | 1.18 | 30.35 |
C(11) | 14.0 | 12.5 | 175.6 | H(11) | 0.88 | 0.91 | 30.80 |
a | 187.2433 | a | 27.4355 | ||||
b | -0.9949 | b | -0.8611 | ||||
r2 | 0.9920 | r2 | 0.9049 |
3. Conclusions
4. Experimental
4.1. General
4.2. Computational Details
4.3. General procedure for the synthesis of N,N-dioctylcycloalkylammonium salts 1-3
Acknowledgments
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Brycki, B.; Szulc, A.; Kowalczyk, I. Study of Cyclic Quaternary Ammonium Bromides by B3LYP Calculations, NMR and FTIR Spectroscopies. Molecules 2010, 15, 5644-5657. https://doi.org/10.3390/molecules15085644
Brycki B, Szulc A, Kowalczyk I. Study of Cyclic Quaternary Ammonium Bromides by B3LYP Calculations, NMR and FTIR Spectroscopies. Molecules. 2010; 15(8):5644-5657. https://doi.org/10.3390/molecules15085644
Chicago/Turabian StyleBrycki, Bogumił, Adrianna Szulc, and Iwona Kowalczyk. 2010. "Study of Cyclic Quaternary Ammonium Bromides by B3LYP Calculations, NMR and FTIR Spectroscopies" Molecules 15, no. 8: 5644-5657. https://doi.org/10.3390/molecules15085644