16395-80-5

The present invention relates to novel compounds and compositions and the use of them for the control of fungal and bacterial pathogens, insect pests, acari, nematodes and other invertebrate pests including, but not limited to post-harvest and soil diseases, building mold remediation, and seed and grain sanitation.

The use of simple calix[4]arenes for chemical conversion of NO2/ N2O4 gases is demonstrated in solution and in the solid state. Upon reacting with these gases, calixarenes 1 encapsulate nitrosonium (NO+) cations within their cavities with the formation of stable calixarene-NO+ complexes 2. These complexes act as encapsulated nitrosating reagents; cavity effects control their reactivity and selectivity. Complexes 2 were effectively used for nitrosation of secondary amides 5, including chiral derivatives. Unique size-shape selectivity was observed, allowing for exclusive nitrosation of less crowded N-Me amides 5a-e (up to 95% yields). Bulkier N-Alk (Alk > Me) substrates 5 did not react due to the hindered approach to the encapsulated NO+ reagents. Robust, silica gel based calixarene material 3 was prepared, which reversibly traps NO 2/ N2O4 with the formation of NO +-storing silica gel 4. With material 4, similar size-shape selectivity was observed for nitrosation. The N-Me-N-nitroso derivatives 6d,e were obtained with ～30% yields, while bulkier amides were nitrosated with much lower yields (+ species, which can be generated by a number of NOx gases, these supramolecular reagents and materials may be useful for NOx entrapment and separation in the environment and biomedical areas.

(Matrix presented) A novel class of stable, mild, and size-shape-selective nitrosating agents for secondary amides is introduced. These are based on reversible entrapment and release of reactive nitrosonium species by calix[4]arenes. The NO+ encapsulation controls the reaction selectivity.