Synthesis and Spectroscopic Characterisation of N-Alkyl Quaternary Ammonium Salts Typical Precursors of Cyanines
Abstract
:Introduction
Results and Discussion
Conclusions
Experimental
General
Synthesis of quaternary ammonium salts 6-10
Salt | Yield (%) | m.p. (ºC) (Lit.) | FTIR λmax (cm-1) | HR FAB-MS m/z found (M. formula: calcd.) |
---|---|---|---|---|
6a | 78 | 198-199 (219)[14] | 2970, 2915, 1578, 1513, 1445, 1330, 779 | 178.068281 (C10H12NS: 178.069046) |
6b | 59 | 152-153 | 2957, 2908, 2861, 1578, 1521, 1461, 1442, 1333, 768 | 220.115129 (C13H18NS: 220.115997) |
6c | 44 | 125-126 | 2956, 2925, 2871, 2853, 1579, 1520, 1459, 1440, 1338, 763 | 234.130630 (C14H20NS: 234.131647) |
6d | 39 | 111-112 | 2921, 2859, 1581, 1517, 1464, 1441, 1336, 770 | 290.194478 (C18H28NS: 290.194247) |
7a | 69 | 212-213 (212)[15] | 2971, 2920, 1579, 1509, 1445, 1320, 1191, 777 | 224.015196/226.014502 (C10H12N78Se: 224.014278; C10H12N80Se: 226.013495) |
7b | 47 | 163-164 | 2952, 2920, 2864, 1576, 1515, 1441, 1369, 1326, 1188, 770 | 266.060980/268.060429 (C13H18N78Se: 266.061229; C13H18N80Se: 268.060445) |
7c | 40 | 132-133 | 2953, 2932, 2858, 1578, 1516, 1457, 1440, 1325, 1185, 757 | 280.077788/282.076779 (C14H20N78Se: 280.076879; C14H20N80Se: 282.076095) |
7d | 25 | 140-141 | 2921, 2852, 1579, 1514, 1457, 1442, 1324, 1189, 757 | 336.139687/338.139261 (C18H28N78Se: 336.139479; C18H28N80Se: 338.138696) |
8a | 58 | 195-197 (195-197)[16] | 2979, 1599, 1461, 1389, 766 | 162.091907 (C10H12NO: 162.091889) |
8b | 41 | 103-105 | 2953, 2933, 2867, 1588, 1461, 1392, 765 | 204.139504 (C13H18NO: 204.138839) |
8c | 35 | 90-91 | 2954, 2921, 2852, 1590, 1462, 1390, 766 | 218.154355 (C14H20NO: 218.154489) |
8d | 28 | 83-85 | 2921, 2852, 1589, 1461, 1391, 765 | 274.217316 (C18H28NO: 274.217090) |
9a | 59 | 226-228 | 2972, 1635, 1459, 1437, 773 | 188.144234 (C13H18N: 188.143925) |
9b | 50 | 138-139 | 2953, 2935, 2867, 1626, 1463, 769 | 230.191539 (C16H14N: 230.190875) |
9c | 46 | 146-147 | 2967, 2933, 2856, 1623, 1467, 1455, 769 | 224.207536 (C17H26N: 224.206525) |
9da) | 46b) | viscous oil | 2925, 2856, 1625, 1607, 1461, 765 | 300.268937 (C21H34N: 300.269125) |
10a | 73 | 238-239 (237-39)[17] | 2994, 2925, 1603, 1521, 1436, 1363, 1344, 1150, 828, 786 | 172.113046 (C12H14N: 172.112625) |
10b | 65 | 156-157 | 2947, 2931, 2869, 1603, 1523, 1428, 1367, 1347, 1172, 781 | 214.160311 (C15H20N: 214.159575) |
10c | 46 | 129-130 | 2948, 2913, 2868, 2826, 1604, 1524, 1428, 1373,1359, 825, 779 | 228.175540 (C16H22N: 228.175225) |
10d | 37 | 118-120 | 2917, 2853, 1609, 1522, 1472, 1424, 1365, 816, 778 | 284.238820 (C20H30N: 284.237825) |
Salt | δ (ppm), multiplicity, J (Hz) (Lit. value)[reference] | |||||||
---|---|---|---|---|---|---|---|---|
N-ethyl (N-CH2aCH3b) | ||||||||
CH2a | CH3b | 2-CH3 | C(CH3)2 | |||||
6aa) | 4.78, q, 7.0 (4.74)[4] | 1.46, t, 7.0 (1.49) [4] | 3.23, s (3.22)[4] | - | ||||
7aa) | 4.74, q, 7.0 (4.63)[4] | 1.44, t, 7.0 (1.40)[4] | 3.24, s (3.15)[4] | - | ||||
8aa),b) | 4.73, q, 7.5 (4.60)[4] | 1.63, t, 7.5 (1.51)[4] | 3.36, s (3.12)[4] | - | ||||
9aa) | 4.50, q, 7.0 (4.63)[4]c) | 1.44, t, 7.0 (1.66)[4]c) | 2.84, s (3.10)[4]c) | 1.53, s | ||||
10d) | 5.01, q, 7.0 (4.95)[4] (5.03)[5] | 1.54, t, 7.0 (1.52)[4] (1.54)[5] | 3.13, s (3.10)[4] (3.15)[5] | - | ||||
N-pentyl (N-CH2aH2bCH2cCH2dCH3e) | ||||||||
CH2a | CH2b | CH2c | CH2d | CH3e | 2-CH3 | C(CH3)2 | ||
6bd) | 4.72, t, 7.5 | 1.86, qt, 8.0 | 1.40-1.46, m | 1.35, sext, 7.5 | 0.89, t, 7.0 | 3.23, s | - | |
7be) | 4.68, t, 8.0 | 1.82, qt, 8.0 | 1.25-1.47, m | 0.86, t, 7.0 | 3.25, s | - | ||
8ba),b) | 4.69, t, 8.0 | 2.00, qt, 7.5 | 1.34-1.44, m | 0.87, t, 7.0 | 3.38, s | - | ||
9ba) | 4.45, t, 7.5 | 1.84, qt, 7.5 | 1.30-1.44, m | 0.88, t, 7.0 | 2.84, s | 1.55, s | ||
10bd) | 4.92, t, 8.0 | 1.90, qt, 8.0 | 1.55, qt, 7.5 | 1.40, sext, 7.5 | 0.92, t, 7.0 | 3.12, s | - | |
N-hexyl (N-CH2aCH3bCH2cCH2dCH2eCH3f) | ||||||||
CH2a | CH2b | CH2c | CH2d | CH2e | CH3f | 2-CH3 | C(CH3)2 | |
6ca) | 4.71, t, 8.0 | 1.84, qt, 8.0 | 1.44, qt, 7.5 | 1.26-1.34, m | 0.87, t, 7.0 | 3.22, s | - | |
7ca) | 4.67, t, 8.0 | 1.83, qt, 8.0 | 1.44, qt, 7.5 | 1.25-1.35, m | 0.87, t, 7.0 | 3.22, s | - | |
8ca),b) | 4.66, t, 7.5 | 1.99, qt, 7.5 | 1.43, qt, 7.5 | 1.24-1.33, m | 0.83, t, 7.0 | 3.36, s | - | |
9ca) | 4.46, t, 8.0 | 1.83, qt, 8.0 | 1.42, qt, 7.5 | 1.24-1.34, m | 0.86, t, 7.0 | 2.86, s | 1.54, s | |
10ca) | 4.91, t, 8.0 | 1.88, qt, 8.0 | 1.56, qt, 7.5 | 1.29-1.37, m | 0.89, t, 7.0 | 3.12, s | - | |
N-decyl (N-CH2aCH2bCH2cCH2dCH2eCH2fCH2gCH2hCH2iCH3j) | ||||||||
CH2a | CH2b | CH2c | CH2d | CH2e-i | CH3j | 2-CH3 | C(CH3)2 | |
6dd) | 4.72, t, 8.0 | 1.84, qt, 8.0 | 1.44, qt, 7.5 | 1.32, qt, 7.0 | 1.25-1.28, m | 0.85, t, 7.0 | 3.24, s | - |
7da) | 4.67, t, 8.0 | 1.81, qt, 8.0 | 1.43, qt, 7.5 | 1.20-1.32, m | 0.84, t, 7.0 | 3.22, s | - | |
8da),b) | 4.70, t, 7.5 | 2.00, qt, 7.5 | 1.44, qt, 7.5 | 1.33, qt, 7.0 | 1.22-1.28, m | 0.85, t, 7.0 | 3.39, s | - |
9da) | 4.46, t, 7.5 | 1.83, qt, 7.5 | 1.41, qt, 7.0 | 1.22-1.32, m | 0.83, t, 6.5 | 2.86, s | 1.54, s | |
10dd) | 4.91, t, 8.0 | 1.88, qt, 8.0 | 1.56, qt, 7.5 | 1.36, qt, 7.0 | 1.26-1.28, m | 0.86, t, 7.0 | 3.11, s | - |
Salt | δ (ppm), multiplicity, J (Hz) (Lit. value)[reference] | |||||
---|---|---|---|---|---|---|
benzothiazolium | 4-H | 5-H | 6-H | 7-H | ||
6aa) | 8.35, d, 8.0 (8.28)[4] | 7.89, dt, 7.5; 1.0 (7.86)[4] | 7.80, dt, 7.5; 1.0 (7.77)[4] | 8.42, d, 8.0 (8.39)[4] | ||
6bb) | 8.36, d, 8.5 | 7.90, dt, 7.5; 1.0 | 7.81, dt, 7.5; 1.0 | 8.47, d, 8.0 | ||
6ca) | 8.34, d, 8.5 | 7.89, dt, 8.0; 1.0 | 7.80, t, 7.5 | 8.46, d, 8.0 | ||
6db) | 8.36, d, 8.5 | 7.81, dt, 7.5; 1.0 | 7.90, dt, 8.0; 1.0 | 8.48, dd, 8.0; 1.0 | ||
benzoselenazolium | 4-H | 5-H | 6-H | 7-H | ||
7aa) | 8.31, d, 8.0 (8.18)[4] | 7.82, dt, 7.5; 1.0 (7.71)[4] | 7.72, dt, 7.5; 1.0 (7,61)[4] | 8.51, dd, 8.0; 1.0 (8.36)[4] | ||
7bc) | 8.31, d, 8.0 | 7.81, t, 7.5 | 7.70, t, 7.5 | 8.54, d, 8.0 | ||
7ca) | 8.30, d, 8.0 | 7.83, dt, 7.5; 1.0 | 7.72, dt, 7.5; 1.0 | 8.45, dd, 8.0; 1.0 | ||
7da) | 8.30, d, 8.0 | 7.82, dt, 7.5; 1.0 | 7.72, dt, 7.5; 1.0 | 8.48, dd, 8.0; 1.0 | ||
benzoxazolium | 4-H | 5-H | 6-H | 7-H | ||
8aa),d) | 7.80-7.78, m (8.09)[4] | 7.68-7.65, m (7.74)[4] (7.75)[4] | 7.98-7.96, m (8.16)[4] | |||
8ba),d) | 7.83-7.81, m | 7.71-7.68, m | 7.92-7.90, m | |||
8ca),d) | 7.90-7.88, m | 7.69-7.67, m | 7.82-7.80, m | |||
8da),d) | 7.91-7.89, m | 7.72-7.67, m | 7.84-7.81, m | |||
indolium | 4-H | 5-H | 6-H | 7-H | ||
9aa) | 7.96-7.99, m (8.00)[4]e) | 7.62-7.64, m (7.79)[4]e) | 7.84-7.86, m (7.93)[4]e) | |||
9ba) | 7.96-7.98, m | 7.60-7.65, m | 7.82-7.86, m | |||
9ca) | 7.97-8.00, m | 7.60-7.65, m | 7.83-7.86, m | |||
9da) | 7.98-8.00, m | 7.60-7.64, m | 7.84-7.87, m | |||
quinolinium | 3-H | 4-H | 5-H | 6-H | 7-H | 8-H |
10ab) | 8.14, d, 8.5 (8.14)[5] | 9.12, d, 8.5 (9.13)[5] | 8.43, dd, 8.0; 1.0 (8.27)[5] | 8.00, t, 7.5 (8.03)[5] | 8.25, dt, 8.0; 1.0 (8.10)[5] | 8.63, d, 9.0 (8.64)[5] |
10bb) | 8.14, d, 8.5 | 9.11, d, 8.5 | 8.42, dd, 8.0; 1.0 | 8.00, t, 7.5 | 8.24, dt, 8.0; 1.0 | 8.59, d, 9.0 |
10ca) | 8.13, d, 8.5 | 9.11, d, 8.5 | 8.41, dd, 8.0; 1.0 | 7.99, t, 7.5 | 8.23, dt, 8.0; 1.0 | 8.59, d, 9.0 |
10db) | 8.12, d, 8.5 | 9.10, d, 8.5 | 8.41, dd, 8.0; 1.0 | 8.00, t, 7.5 | 8.23, dt, 8.0; 1.0 | 8.59, d, 9.0 |
Salt | δ (ppm) (Lit. value)[reference] | |||||||
---|---|---|---|---|---|---|---|---|
N-ethyl (N-CaH2CbH3) | ||||||||
CaH2 | CbH3 | 2-CH3 | C(CH3)2 | |||||
6aa) | 44.7 | 13.2 | 16.8 | - | ||||
7aa) | 45.6 | 13.0 | 19.5 | - | ||||
8aa),b) | 44.4 | 14.0 | 16.7 | - | ||||
9aa) | 43.0 | 12.6 | 13.7 | 21.8 | ||||
10a) | 47.1 (47.26)[5] | 13.3 (13.43)[5] | 22.3 (22.44)[5] | - | ||||
N-pentyl (N-CaH2CbH2CcH2CdH2CeH3) | ||||||||
CaH2 | CbH2 | CcH2 | CdH2 | CeH3 | 2-CH3 | C(CH3)2 | ||
6bc) | 49.2 | 28.1 | 27.6 | 21.8 | 13.8 | 17.1 | - | |
7bc) | 50.1 | 28.0 | 27.4 | 21.8 | 13.8 | 19.9 | - | |
8ba),b) | 49.1 | 28.6 | 27.9 | 22.0 | 13.7 | 16.7 | - | |
9ba) | 47.3 | 27.8 | 26.7 | 21.5 | 13.5 | 13.8 | 21.8 | |
10bc) | 51.5 | 28.0 | 27.8 | 21.8 | 13.9 | 22.7 | - | |
N-hexyl (N-CaH2CbH2CcH2CdH2CeH2CfH3) | ||||||||
CaH2 | CbH2 | CcH2 | CdH2 | CeH2 | CfH3 | 2-CH3 | C(CH3)2 | |
6ca) | 49.1 | 30.6 | 27.7 | 25.4 | 21.8 | 13.8 | 16.8 | - |
7ca) | 50.0 | 30.6 | 27.6 | 25.4 | 21.9 | 13.8 | 19.5 | - |
8ca),b) | 49.0 | 31.0 | 28.1 | 26.3 | 22.2 | 13.8 | 16.7 | - |
9ca) | 47.5 | 30.6 | 27.1 | 25.4 | 21.9 | 13.7 | 14.0 | 21.7 |
10ca) | 51.3 | 30.6 | 27.9 | 25.4 | 21.9 | 13.7 | 22.4 | - |
N -decyl (N-CaH2CbH2CcH2CdH2CeH2CfH2CgH2ChH2CiH2CjH3) | ||||||||
CaH2 | CbH2 | CcH2 | Cd-iH2 | CjH3 | 2-CH3 | C(CH3)2 | ||
6dc) | 49.3 | 31.2 | 28.9 | 28.7, 28.6, 27.8, 25.9, 22.1 | 13.9 | 17.3 | - | |
7da) | 50.0 | 31.1 | 28.7 | 28.5, 28.4, 27.5, 25.7, 21.9 | 13.8 | 19.6 | - | |
8da),b) | 49.2 | 31.7 | 29.3 | 29.2, 29.1, 28.9, 28.2, 26.7, 22.5 | 14.0 | 16.7 | - | |
9da) | 47.6 | 31.1 | 28.7 | 28.5, 28.4, 27.1, 25.7 | 13.8, 14.1 | 21.9 | ||
10dc) | 51.5 | 31.3 | 28.9 | 28.7, 28.6, 28.1, 25.9, 22.1 | 14.0 | 22.6 | - |
Salt | δ (ppm) (Lit. value)[reference] | |||||||||
---|---|---|---|---|---|---|---|---|---|---|
benzothiazolium | 2-C | 3a-C | 4-C | 5-C | 6-C | 7-C | 7a-C | |||
6aa) | 176.7 | 140.4 | 116.6 | 129.3 | 127.9 | 124.6 | 129.9 | |||
6bb) | 177.0 | 140.8 | 116.9 | 129.4 | 128.1 | 124.7 | 129.1 | |||
6ca) | 176.9 | 140.7 | 116.8 | 129.3 | 128.0 | 124.6 | 129.0 | |||
6db) | 176.8 | 140.7 | 116.9 | 129.3 | 128.0 | 124.7 | 129.0 | |||
benzoselenazolium | 2-C | 3a-C | 4-C | 5-C | 6-C | 7-C | 7a-C | |||
7aa) | 187.9 | 141.4 | 118.1 | 128.6 | 127.5 | 127.6 | 131.8 | |||
7bb) | 188.0 | 141.8 | 118.4 | 128.7 | 127.6 | 127.7 | 131.8 | |||
7ca) | 188.1 | 141.8 | 118.4 | 128.7 | 127.3 | 127.7 | 131.8 | |||
7da) | 188.0 | 141.7 | 118.3 | 128.6 | 127.3 | 127.6 | 131.8 | |||
benzoxazolium | 2-C | 3a-C | 4-C | 5-C | 6-C | 7-C | 7a-C | |||
8aa),c) | 167.0 | 147.8 | 113.2 | 129.1 | 128.3 | 114.5 | 129.2 | |||
8ba),c) | 167.3 | 147.9 | 113.3 | 129.3 | 128.4 | 114.5 | 129.6 | |||
8ca),c) | 167.2 | 147.8 | 113.3 | 129.3 | 128.4 | 114.4 | 129.6 | |||
8da),c) | 167.3 | 147.9 | 113.3 | 129.3 | 128.4 | 114.5 | 129.7 | |||
indolium | 2-C | 3-C | 3a-C | 4-C | 5-C, 6-C | 7-C | 7a-C | |||
9aa) | 196.0 | 54.0 | 141.8 | 115.2 | 128.8, 129.3 | 123.4 | 140.6 | |||
9ba) | 196.3 | 54.1 | 141.8 | 115.2 | 128.7, 129.2 | 123.3 | 141.0 | |||
9ca) | 196.3 | 54.0 | 141.7 | 115.4 | 128.8, 129.3 | 123.4 | 141.0 | |||
9da) | 196.2 | 54.0 | 141.7 | 115.4 | 128.8, 129.3 | 123.4 | 140.9 | |||
quinolinium | 2-C | 3-C | 4-C | 4a-C | 5-C | 6-C | 7-C | 8-C | 8a-C | |
10aa) | 160.4 (160.40)[5] | 125.4 (125.49)[5] | 145.5 (145.51)[5] | 128.1 (128.25)[5] | 130.5 (118.75)[5] | 128.9 (128.98)[5] | 135.2 (135.26)[5] | 118.7 (130.57)[5] | 137.9 (138.07)[5] | |
10bd) | 160.5 | 125.6 | 145.6 | 128.2 | 130.6 | 129.0 | 135.3 | 119.0 | 138.2 | |
10ca) | 160.4 | 125.4 | 145.5 | 128.1 | 130.4 | 128.9 | 135.2 | 118.8 | 138.1 | |
10dd) | 160.6 | 125.6 | 145.6 | 128.2 | 130.6 | 129.0 | 135.3 | 119.0 | 138.2 |
Acknowledgements
References
- Hamer, F. M. The Cyanine Dyes and Related Compounds - The Chemistry of Heterocyclic Compounds; Weissberger, A., Ed.; Interscience Publishers: New York, 1971; Vol. 18. [Google Scholar]
- Zollinger, H. Color Chemistry - Synthesis, Properties and Applications of Organic Dyes and Pigments; VCH Publishers Inc.: Weinheim, 1991; pp. 65–69. [Google Scholar]
- Sturmer, D. M.; Heseltine, D. W. Sensitizing and Desensitizing Dyes – The Theory of the Photographic Processes; James, T. H., Ed.; Macmillan Co.: New York, 1977; pp. 205–220. [Google Scholar]
- Kleinpeter, Von E.; Borsdorf, R.; Dietz, F. Zur reaktivität der 2-methylcycloammoniumsalze. J. Prakt. Chem. 1973, 315, 600–610. [Google Scholar]
- Jaroszewska, J.; Wawer, I. Oszczapowicz, 13C and 1H NMR spectral studies of N-alkylmethylquinolinium salts. J. Org. Magn. Reson. 1984, 22, 323–327. [Google Scholar]
- Narayanan, N.; Strekowski, L.; Patonay, G. A new method for the synthesis of heptamethine cyanine dyes: synthesis of new near-infrared fluorescent labels. J. Org. Chem. 1995, 60, 2391–95. [Google Scholar]
- Li, M.; Pacey, G. E. Spectrophotometric determination of trace water in organic solvents with a near infrared absorbing dye. Talanta 1997, 44, 1948–1958. [Google Scholar]
- Patonay, G.; Antoine, M. D.; Devanathan, S.; Strekowski, L. Near-infrared probe for determination of solvent hydrophobicity. Appl. Spectrosc. 1991, 45, 457–461. [Google Scholar]
- Samat, A. M.; Guglielmetti, R. J.; Martin, G. J. Etude des formes fermées et ouverts de spiropyrannes benzothiazoliniques en RMN 13C et 1H par transformée de Fourier. Org. Magn. Reson. 1976, 8, 62–73. [Google Scholar]
- Benassi, R.; Grandi, R.; Pagnoni, U. M.; Taddei, F. Study of the effect of N-protonation and N-methylation on the 1H and 13C chemical shifts of the six-membered ring in benzoazoles and 2-substituted N,N-dimethylamino derivatives. Magn. Reson. Chem. 1986, 24, 415–420. [Google Scholar]
- Muñoz, M. A.; Carmona, C.; Hidalgo, J.; Balón, M. On the protonation site of Rauwolfia alkaloids in highly concentrated sulphuric acid solutions. Heterocycles 1989, 29, 1343–1348. [Google Scholar]
- Reichardt, C.; Engel, H.-D. Eine verbesserte methode zur herstellung von 1,3,3-trialkyl-2-alkylineneindolinen. Chem. Ber. 1988, 121, 1009–1111. [Google Scholar]
- Pretsch, E.; Clerc, T.; Seibl, J.; Simson, W. Tables of Spectral Data for Structure Determination of Organic Compounds; Springer-Verlag: Berlin, 1989. [Google Scholar]
- Beilstein, II. 27, 21d.
- Beilstein, II. 27, 23f.
- Beilstein, II. 27, 20c.
- Beilstein, IV. 20, 3459.
- Sample Availability: Available from the authors.
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Pardal, A.C.; Ramos, S.S.; Santos, P.F.; Reis, L.V.; Almeida, P. Synthesis and Spectroscopic Characterisation of N-Alkyl Quaternary Ammonium Salts Typical Precursors of Cyanines. Molecules 2002, 7, 320-330. https://doi.org/10.3390/70300320
Pardal AC, Ramos SS, Santos PF, Reis LV, Almeida P. Synthesis and Spectroscopic Characterisation of N-Alkyl Quaternary Ammonium Salts Typical Precursors of Cyanines. Molecules. 2002; 7(3):320-330. https://doi.org/10.3390/70300320
Chicago/Turabian StylePardal, A. C., S. S. Ramos, P. F. Santos, L. V. Reis, and P. Almeida. 2002. "Synthesis and Spectroscopic Characterisation of N-Alkyl Quaternary Ammonium Salts Typical Precursors of Cyanines" Molecules 7, no. 3: 320-330. https://doi.org/10.3390/70300320