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 |
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Institution: | 1. Institut UTINAM UMR CNRS 6213, Université de Franche-Comté, 16 Route de Gray, 25030 Besançon, France;2. Institut de Chimie Moléculaire de l''Université de Bourgogne UMR 6302, Université de Bourgogne, 9 Avenue A. Savary, 21078 Dijon, France |
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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. |
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Keywords: | 2-Azabutadienes Cycloaddition 1 2 4-Triazoline Azomethine ylides Thioether Macrocyclic complex Copper |
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