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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
- Source :
- Comptes Rendus Chimie, Comptes Rendus Chimie, Elsevier, 2016, 19, pp.320-332. ⟨10.1016/j.crci.2015.09.017⟩
- Publication Year :
- 2016
- Publisher :
- Elsevier BV, 2016.
-
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.
- 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
Subjects
Details
- ISSN :
- 16310748
- Volume :
- 19
- Database :
- OpenAIRE
- Journal :
- Comptes Rendus Chimie
- Accession number :
- edsair.doi.dedup.....8976070b7fed2549a23ed4acc9170240