Synthesis of Bis(N-acylamidines) from Amidines and N-Acylbenzotriazoles

Abstract

Bis(N-acylamidines) 7, linked by a spacer connected to the carboxyl groups, were synthesized in moderate to good yields from bis(N-acylbenzotriazoles) 6 and amidines 2. In contrast, the corresponding bis(carboxylic acid) chlorides were not well suited for the synthesis of the compounds 7. 2-Aminothiazole gave the bis-amide 8, where the amidine moieties are part of heterocyclic ring systems. Furthermore, the reaction of a bis-amidine 9 with two equivalents of N-benzoylbenzotriazole (10) gave the bifunctional N-acylamidine 11, linked to the spacer at the amidine carbon atoms. All substances were thoroughly characterized including nine X-ray diffraction studies.

Key words

acylation - amidines - ligands - N-acylbenztriazoles - supramolecular chemistry

References

• 1a Eberhardt JK. Glaser T. Hoffmann RD. Fröhlich R. Würthwein E.-U. Eur. J. Inorg. Chem.  2005,  1175 
• 1b Eberhardt JK. Fröhlich R. Würthwein E.-U. J. Org. Chem.  2003,  68:  6690 
• 1c Eberhardt K.-K, and Würthwein E.-U. inventors; German Patent,  102 56 854 A1.  , BASF AG, ; Chem. Abstr. 2004, 141, 46414
• 2a Ley H. Werner F. Ber. Dtsch. Chem. Ges.  1913,  46:  4040 
• 2b Oehme G. Pracejus H. Z. Chem.  1969,  9:  140 
• 2c Bart JCJ. Bassi IW. Calcaterra M. Pieroni M. Inorg. Chim. Acta  1978,  28:  201 
• 3 Lee I.-M. Characteristics and Applications of Metal Complexes with β-Ketoiminate Ligands, In Focus on Organometallic Chemistry Research   Casto MA. Nova Science Publishers, Inc.; New York: 2005.  Chap. 5. p.133 
• 4 Böhm V, Röper M, Würthwein E.-U, Wigbers C, Chabanas M, Teles J.-H, and Altenhoff AG. inventors; German Patent,  102008000077K1.  , BASF AG, ; Chem. Abstr. 2008, 149, 238276
• 5 Pinner A. Ber. Dtsch. Chem. Ges.  1889,  22:  1600 
• 7 In analogy to a procedure by Cooper et al.: Cooper FC. Partridge MW. Org. Synth.  1956,  36:  64 
• 8 Chua S.-O. Cook MJ. Katritzky AR. J. Chem. Soc., Perkin Trans. 2  1974,  546 
• 9a

  Hack, V. unpublished results.

• 9b See: Hack V. Diploma Thesis   University of Münster; Germany: 2007. Carpino L. A.; J. Am. Chem. Soc.; 1993, 115: 4397
• 10 Carpino LA. J. Am. Chem. Soc.  1993,  115:  4397 
• 11 Katritzky AR. Suzuki K. Wang Z. Synlett  2005,  1656 
• 12a Katritzky AR. Zhang Y. Singh SK. Synthesis  2003,  2795 
• 12b Katritzky AR. Meher NK. Cai CS. Sandeep K. Rev. Soc. Quim. Mexico  2004,  4:  275 ; Chem. Abstr. 2005, 143, 26540
• 13 Müller U. Anorganische Strukturchemie   3rd ed.:  B. G. Teubner; Stuttgart: 1996. 
• 15 COLLECT   Nonius B. V.; Delft: 1998. 
• 16 Otwinowski Z. Minor W. Methods Enzymol.  1997,  276:  307 
• 17 Otwinowski Z. Borek D. Majewski W. Minor W. Acta Crystallogr., Sect. A  2003,  59:  228 
• 18 Sheldrick GM. Acta Crystallogr., Sect A  1990,  46:  467 
• 19 Sheldrick GM. Acta Crysallogr., Sect. A  2008,  64:  112 
• 20 Keller E. SCHAKAL 97   University of Freiburg; Germany: 1997. 
• 21 Cooper FC. Partridge MW. J. Chem. Soc.  1953,  255 
• 22 Mahadik ST. Sunthankar SV. Indian J. Chem.  1975,  13:  1369 

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Wigbers, C.; Prigge, J.; Fröhlich, R.; Chi, L.; Mu, Z.; Würthwein, E.-U. manuscript in preparation.

14

Data sets were collected with a Nonius KappaCCD diffractometer. Programs used: data collection COLLECT;^¹5 data reduction Denzo-SMN,^¹6 absorption correction Denzo,^¹7 structure solution SHELXS-97,^¹8 structure refinement SHELXL-97,^¹9 graphics SCHAKAL.^²0 CCDC 755612-755620 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: [phone], E-mail: [e-mail]].