Structural Aspects of Thermally Cleavable Adducts Derived from the Reaction of Imidazolines with Isocyanates

Andreas Laue; Andrea Preuß; Manuel Heck; Mandy Martin; Marcus Binner; Tobias Rüffer; Susann Anders; Carsten Werner; Lothar Kroll; Heinrich Lang; Stefan Spange

doi:10.1055/s-0035-1562626

Synthesis, Inhaltsverzeichnis

Synthesis 2016; 48(24): 4431-4442
DOI: 10.1055/s-0035-1562626

paper

Structural Aspects of Thermally Cleavable Adducts Derived from the Reaction of Imidazolines with Isocyanates

Andreas Laue

^aTechnische Universität Chemnitz, Institute of Chemistry, Polymer Chemistry, 09107 Chemnitz, Germany eMail: stefan.spange@chemie.tu-chemnitz.de

,

Andrea Preuß

^aTechnische Universität Chemnitz, Institute of Chemistry, Polymer Chemistry, 09107 Chemnitz, Germany eMail: stefan.spange@chemie.tu-chemnitz.de

,

Manuel Heck

^aTechnische Universität Chemnitz, Institute of Chemistry, Polymer Chemistry, 09107 Chemnitz, Germany eMail: stefan.spange@chemie.tu-chemnitz.de

,

Mandy Martin

^aTechnische Universität Chemnitz, Institute of Chemistry, Polymer Chemistry, 09107 Chemnitz, Germany eMail: stefan.spange@chemie.tu-chemnitz.de

,

Marcus Binner

^bLeibniz Institute of Polymer Research Dresden, Hohe Strasse 6, 01069 Dresden, Germany

,

Tobias Rüffer

^cTechnische Universität Chemnitz, Institute of Chemistry, Inorganic Chemistry, 09107 Chemnitz, Germany

,

Susann Anders

^dTechnische Universität Chemnitz, Faculty of Mechanical Engineering, Department of Lightweight Structures and Polymer Technology, 09107 Chemnitz, Germany

,

Carsten Werner

^bLeibniz Institute of Polymer Research Dresden, Hohe Strasse 6, 01069 Dresden, Germany

,

Lothar Kroll

^dTechnische Universität Chemnitz, Faculty of Mechanical Engineering, Department of Lightweight Structures and Polymer Technology, 09107 Chemnitz, Germany

,

Heinrich Lang

^cTechnische Universität Chemnitz, Institute of Chemistry, Inorganic Chemistry, 09107 Chemnitz, Germany

,

Stefan Spange*

^aTechnische Universität Chemnitz, Institute of Chemistry, Polymer Chemistry, 09107 Chemnitz, Germany eMail: stefan.spange@chemie.tu-chemnitz.de

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Abstract

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Abstract

The reaction of isocyanates with substituted imidazolines and the thermally induced cleavage of the resulting adducts are presented. For this purpose, reactions of various isocyanates [ethyl isocyanate, p-methylphenyl isocyanate, phenyl isocyanate, p-(trifluoromethyl)phenyl isocyanate] with 1-alkylimidazoline derivatives have been studied as a function of the substituent at the 2-position of the imidazoline ring. Three equivalents of isocyanate react with one equivalent of 1-ethylimidazoline to give a stoichiometric well-defined adduct. However, 1-ethyl-2-isopropylimidazoline reacts with isocyanates at 0 °C in another way, with formation of 2:1 adducts which belong to the family of 1,3-diphenyltetrahydroimidazo[1,2-a][1,3,5]triazine-2,4(1H,3H)-diones. The reaction of 1-ethyl-2-methylimidazoline with aromatic isocyanates at 0 °C also leads to 2:1 adducts, in this case of a malonamide type, which can react at 60 °C with an additional isocyanate equivalent to give the known pyrimidinediones. Thermal analysis (TG-MS/DSC) and trapping reactions with nucleophilic reagents, such as diphenylamine, show the release of isocyanate during the thermally induced cleavage reaction. Thus, blocked isocyanates are available by the reaction of isocyanates with 1-ethylimidazoline or 1-ethyl-2-isopropylimidazoline.

Key words

blocked isocyanates - imine bases - isocyanates - imidazolines - amidine/isocyanate adducts

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Referenzen

References
1 Wurtz A. Justus Liebigs Ann. Chem. 1849; 71: 326
2 Bayer O. DRP 728981, 1937
3 Bayer O. Angew. Chem. 1947; A59: 257
4 Delebecq E, Pascault JP, Boutevin B, Ganachaud F. Chem. Rev. 2013; 113: 80
5 Huard K, Bagley SW, Menhaji-Klotz E, Préville C, Southers JA, Smith AC, Edmonds DJ, Lucas JC, Dunn MF, Allanson NM, Blaney EL, Garcia-Irizarry CN, Kohrt JT, Griffith DA, Dow RL. J. Org. Chem. 2012; 77: 10050
6 Tabarki MA, Besbes R. Tetrahedron Lett. 2015; 56: 1837
7 Rigby JH, Sidique S. Org. Lett. 2007; 9: 7
8 Dong X.-F, Fan J, Shi X.-Y, Liu K.-Y, Wang P.-M, Wei J.-F. J. Organomet. Chem. 2015; 779: 55
9 Polenz I, Laue A, Uhrin T, Rüffer T, Lang H, Schmidt FG, Spange S. Polym. Chem. 2014; 5: 6678
10 Wicks DA, Wicks ZW. Prog. Org. Coat. 1999; 36: 148
11 Wicks DA, Wicks ZW. Prog. Org. Coat. 2001; 41: 1
12 Wicks DA, Wicks ZW. Prog. Org. Coat. 2001; 43: 131
13 Wicks ZW. Jr. Prog. Org. Coat. 1981; 9: 3
14 Wicks ZW. Jr. Prog. Org. Coat. 1975; 3: 73
15 Kostyk BW, Wicks ZW. Jr. J. Polym. Sci., Part A: Polym. Chem. 1979; 17: 2423
16 Kothandaraman H, Thangavel R. J. Polym. Sci., Part A: Polym. Chem. 1993; 31: 2653
17 Mühlebach A. J. Polym. Sci., Part A: Polym. Chem. 1994; 32: 753
18 Subramani S, Park YJ, Lee YS, Kim JH. Prog. Org. Coat. 2003; 48: 71
19 Subramani S, Cheong IW, Kim JH. Prog. Org. Coat. 2004; 51: 329
20 Bode S, Enke M, Görls H, Hoeppener S, Weberskirch R, Hager MD, Schubert US. Polym. Chem. 2014; 5: 2574
21 Laas H, Halpaap R, Pedain J. J. Prakt. Chem. 1994; 336: 185
22 Querat E, Tighzert L, Pascault JP, Dušek K. Angew. Makromol. Chem. 1996; 242: 1
23 Ulrich H, Tucker B, Richter R. J. Org. Chem. 1978; 43: 1544
24 Ulrich H. Acc. Chem. Res. 1969; 2: 186
25 Ulrich H. Chemistry and Technology of Isocyanates . John Wiley & Sons Ltd; Chichester: 1996
26 Richter R. Tetrahedron Lett. 1968; 5037
27 Giesecke H, Hocker J. Synthesis 1977; 806
28 Tietz H, Rademacher O, Zahn G. Eur. J. Org. Chem. 2000; 2105
29 Bernstein IL. J. Allergy Clin. Immunol. 1982; 70: 24
30 Ye G, Henry WP, Chen C, Zhou A, Pittman CU. Tetrahedron Lett. 2009; 50: 2135
31 Ye G, Chatterjee S, Li M, Zhou A, Song Y, Barker BL, Chen C, Beard DJ, Henry WP, Pittman CU. Tetrahedron 2010; 66: 2919
32 Ulrich H, Richter R. Justus Liebigs Ann. Chem. 1971; 743: 10
33 Fukuda H, Oda M, Taketa T, Endo T. Macromolecules 2000; 33: 6211
34 Schwetlick H. Organikum . Wiley-VCH; Weinheim: 2009
35 Çetinkaya B, Çetinkaya E, Hitchcock PB, Lappert MF, Özdemir I. J. Chem. Soc., Dalton Trans. 1997; 1359
36 Gruseck U, Heuschmann M. Chem. Ber. 1987; 120: 2053
37 Perillo I, Lamdan S. J. Heterocycl. Chem. 1970; 7: 791
38 Salerno A, Perillo I. Molecules 2005; 10: 435

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