1. 1,3-Dipolar cycloaddition of diaryldiazomethanes across N-ethoxy-carbonyl-N-(2,2,2-trichloroethylidene)amine and reactivity of the resulting 2-azabutadienes towards thiolates and cyclic amides
- Author
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Michael Knorr, Rodolphe Kinghat, Abderrahim Khatyr, Kabula Ciamala, Gérard Schmitt, Sandrine Jacquot-Rousseau, Yoann Rousselin, Marek M. Kubicki, Univers, Transport, Interfaces, Nanostructures, Atmosphère et environnement, Molécules (UMR 6213) (UTINAM), Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université de Franche-Comté (UFC), and Université Bourgogne Franche-Comté [COMUE] (UBFC)-Université Bourgogne Franche-Comté [COMUE] (UBFC)
- Subjects
Chemistry(all) ,Stereochemistry ,General Chemical Engineering ,1,2,4-Triazoline ,Crystal structure ,010402 general chemistry ,01 natural sciences ,Medicinal chemistry ,chemistry.chemical_compound ,Thioether ,Nucleophile ,[CHIM]Chemical Sciences ,Reactivity (chemistry) ,Cycloaddition ,ComputingMilieux_MISCELLANEOUS ,2-Azabutadienes ,010405 organic chemistry ,General Chemistry ,0104 chemical sciences ,3. Good health ,chemistry ,1,3-Dipolar cycloaddition ,Azomethine ylides ,Chemical Engineering(all) ,Alkoxy group ,Piperidine ,Copper ,Macrocyclic complex - Abstract
1,3-dipolar cycloaddition of diaryldiazomethanes Ar2C N2 across Cl3C–CH N–CO2Et 1 yields Δ3-1,2,4-triazolines 2. Thermolysis of 2 leads, via transient azomethine ylides 3, to diaryldichloroazabutadienes [Ar(Ar')C N–CH CCl2] 4. Treatment of 4a (Ar = Ar' = C6H5) and 4c (Ar = Ar' = p-ClC6H4) with NaSR in DMF yields 2-azabutadienes [Ar2C N–C(H) C(SR)2] 5. In contrast, nucleophilic attack of NaStBu on 4 affords azadienic dithioethers [Ar2C N–C(StBu) C(H)(StBu)] (7a Ar = C6H5; 7b Ar' = p-ClC6H4). The reaction of 4a with NaSEt conducted in neat EtSH produces [Ph2C N–C(H)(SEt)–CCl2H] 8, which after dehydrochloration by NaOMe and subsequent addition of NaSEt is converted to [Ph2C N–C(SEt) C(H)(SEt)] 7c. Upon the reaction of 4c with NaSiPr, the intermediate dithioether [(p-ClC6H4)2C N–CH C(SiPr)2] 5k is converted to tetrakisthioether [(p-iPrSC6H4)2C N–CH C(SiPr)2] 6. Treatment of 4a with the sodium salt of piperidine leads to [Ph2C N–CH C(NC5H10)2] 10. The coordination of 6 on CuBr affords the macrocyclic dinuclear Cu(I) complex 11. The crystal structures of 5i, 7a,b, 10 and 11 have been determined by X-ray diffraction.
- Published
- 2016