Effect of the Position of Reaction-Site in Amphipathic-Type Thioester in Aqueous Amidation Reaction
ABSTRACT
Amphipathic-type thioesters CH3(CH2)mCOS(CH2)nCOONa (m + n = 12) were synthesized and their reaction with various alkylamines was examined. Compounds having thioester moiety close to carboxylate (m = 10, n = 2) afforded the corresponding amides in good yields, while the substrate having thioester moiety distant from carboxylate (m = 2, n = 10) afforded the amides in relatively low yield. In all cases, the difference in yield due to the chain length of amine was not observed. The results indicated that the reaction took place effectively near the surface of micelle. However, the reaction was found to occur not only on micelle surface but also in solution.
Amphipathic-type thioesters CH3(CH2)mCOS(CH2)nCOONa (m + n = 12) were synthesized and their reaction with various alkylamines was examined. Compounds having thioester moiety close to carboxylate (m = 10, n = 2) afforded the corresponding amides in good yields, while the substrate having thioester moiety distant from carboxylate (m = 2, n = 10) afforded the amides in relatively low yield. In all cases, the difference in yield due to the chain length of amine was not observed. The results indicated that the reaction took place effectively near the surface of micelle. However, the reaction was found to occur not only on micelle surface but also in solution.
Cite this paper
Otomo, I. and Kuroda, C. (2015) Effect of the Position of Reaction-Site in Amphipathic-Type Thioester in Aqueous Amidation Reaction. Advances in Chemical Engineering and Science, 5, 311-316. doi: 10.4236/aces.2015.53032.
Otomo, I. and Kuroda, C. (2015) Effect of the Position of Reaction-Site in Amphipathic-Type Thioester in Aqueous Amidation Reaction. Advances in Chemical Engineering and Science, 5, 311-316. doi: 10.4236/aces.2015.53032.
References
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http://dx.doi.org/10.1021/ja0169318
[1] (a) Lindström, U.M. (2007) Organic Reactions in Water. Blackwell Publishing, Oxford.
http://dx.doi.org/10.1002/9780470988817
(b) Li, C.-J. (1993) Organic Reactions in Aqueous Media—With a Focus on Carbon-Carbon Bond Formation. Chemical Reviews, 93, 2023-2035.
http://dx.doi.org/10.1021/cr00022a004
(c) Li, C.-J. and Chen, L. (2006) Organic Chemistry in Water. Chemical Society Reviews, 35, 68-82.
http://dx.doi.org/10.1039/B507207G
(d) Lindström, U.M. (2002) Stereoselective Organic Reactions in Water. Chemical Reviews, 102, 2751-2772.
http://dx.doi.org/10.1021/cr010122p
(e) Kobayashi, S. (2013) The New World of Organic Reactions in Water. Pure and Applied Chemistry, 85, 1089-1101.
http://dx.doi.org/10.1351/PAC-CON-12-10-11 [2] (a) Breslow, R. (1991) Hydrophobic Effects on Simple Organic Reactions in Water. Accounts of Chemical Research, 24, 159-164.
http://dx.doi.org/10.1021/ar00006a001
(b) Breslow, R., Groves, K. and Mayer, M.U. (1998) The Hydrophobic Effect as a Mechanistic Tool. Pure and Applied Chemistry, 70, 1933-1938.
http://dx.doi.org/10.1351/pac199870101933
(c) Otto, S. and Engberts, J.B.F.N. (2003) Hydrophobic Interactions and Chemical Reactivity. Organic and Biomolecular Chemistry, 1, 2809-2820.
http://dx.doi.org/10.1039/b305672d [3] (a) Kawabata, Y. and Kinoshita, M. (1974) Studies on Functional Micelles, 1—Preparation of Cyclic Dipeptides from Phenylalanine S-Dodecyl Ester. Makromolekulare Chemie, 175, 105-110.
http://dx.doi.org/10.1002/macp.1974.021750112
(b) Kawabata, Y. and Kinoshita, M. (1975) Studies on Functional Micelles, 2—Micellar Effect on the Preparation of Cyclic Dipeptide from Thioalanine S-Dodecyl Ester. Makromolekulare Chemie, 176, 49-56.
http://dx.doi.org/10.1002/macp.1975.021760105 [4] (a) Kawabata, Y. and Kinoshita, M. (1975) Studies on Functional Micelles, 4—Effect of Alkyl Chain Length on the Micellar Reaction of Thioalanine S-Alkyl Esters. Makromolekulare Chemie, 176, 2797-2805.
http://dx.doi.org/10.1002/macp.1975.021761002
(b) Kawabata, Y. and Kinoshita, M. (1975) Studies on Functional Micelles, 5—Solvent and Salt Effects on the Micellar Condensation of Thioalanine S-Alkyl Esters. Makromolekulare Chemie, 176, 2807-2814.
http://dx.doi.org/10.1002/macp.1975.021761003 [5] Kunieda, N., Watanabe, M., Okamoto, K. and Kinoshita, M. (1981) Polycondensation of Thioglycine S-Dodecyl Ester Hydrobromide in Water. Makromolekulare Chemie, 182, 211-214.
http://dx.doi.org/10.1002/macp.1981.021820122 [6] Torihata, A. and Kuroda, C. (2010) Hydrophobic Effect and Substrate Specificity in Reaction of Thioester and Amine in Water. Bulletin of the Chemical Society of Japan, 83, 1534-1538.
http://dx.doi.org/10.1246/bcsj.20100143 [7] Torihata, A. and Kuroda, C. (2011) Reaction of Amphipathic-Type Thioester and Amine with Hydrophobic Effect in Water. Synlett, 2035-2038. [8] Kurooka, S., Hashimoto, M., Tomita, M., Maki, A. and Yoshimura, Y. (1976) Relationship between the Structures of S-Acyl Thiol Compounds and Their Rates of Hydrolysis by Pancreatic Lipase and Hepatic Carboxylic Esterase. Journal of Biochemistry, 79, 533-541. [9] Dellaria Jr., J.F., Nordeen, C. and Swett, L.R. (1986) The Facile and Efficient Preparation of Phenolic and Thiol Esters. Synthetic Communications, 16, 1043-1048.
http://dx.doi.org/10.1080/00397918608056346 [10] (a) Lu, Y., Tanasova, M., Borhan, B. and Reid, G.E. (2008) Ionic Reagent for Controlling the Gas-Phase Fragmentation Reactions of Cross-Linked Peptides. Analytical Chemistry, 80, 9279-9287.
http://dx.doi.org/10.1021/ac801625e
(b) Jessing, M., Brandt, M., Jensen, K.J., Christensen, J.B. and Boas, U. (2006) Thiophene Backbone Amide Linkers, a New Class of Easily Prepared and Highly Acid-Labile Linkers for Solid-Phase Synthesis. Journal of Organic Chemistry, 71, 6734-6741.
http://dx.doi.org/10.1021/jo060687r [11] Mathias, L.J. and Johnson, C.G. (1991) Solid-State NMR Investigation of Nylon 12. Macromolecules, 24, 6114-6122.
http://dx.doi.org/10.1021/ma00023a011 [12] Tomioka, K., Sumiyoshi, T., Narui, S., Nagaoka, Y., Iida, A., Miwa, Y., Taga, T., Nakano, M. and Handa, T. (2001) Molecular Assembly and Gelating Behavior of Didodecanoylamides of α,ω-Alkylidenediamines. Journal of the American Chemical Society, 123, 11817-11818.
http://dx.doi.org/10.1021/ja0169318