Preparation of Phenyl Cyanate and Its Utilization for the Synthesis of α,β-Unsaturated Nitriles

The Curtius Rearrangement of Acyl Azides Revisited – Formation of Cyanate (R–O–CN)

“…[14] Matrix Isolation Procedure: A gaseous mixture of argon and benzoyl azide (ratio Ϸ 1000:1) is deposited slowly onto a CsBr window at 20 K. The matrix is irradiates with a 254-nm low-pressure mercury lamp (75 W; Graentzel, Karlsruhe, Germany) for 5 to 20 min (depending on the amount of azide), which leads to the complete decomposition of the azide and the formation of phenyl isocyanate, phenyl cyanate and singlet benzoylnitrene. Prolonged photolysis for 2-5 min with 308 nm excimer lamp (50 mW/cm 2 ; Ushio, Singapore) results in larger amounts of phenyl isocyanate, while the amount of phenyl cyanate increases slightly.…”

Structure−Activity Relationships of a Series of Pyrrolo[3,2-d]pyrimidine Derivatives and Related Compounds as Neuropeptide Y5 Receptor Antagonists

“…Alternatively, the substituted pyrroles 25 were prepared by the reaction of diethyl aminomalonate (24) with sodium ethoxide and substituted cyanoacetylenes 23. 42 With a variety of 5-substituted 3-amino-1H-pyrrole-2-carboxylates (25) in hand, several analogues with modifications at the R 1 position (see general structure 2) were prepared. Derivatives wherein R 1 is an alkyl group were prepared by treating pyrroles 25 with an alkyl cyanide in anhydrous hydrochloric acid at room temperature followed by heating with sodium hydroxide to give alcohol intermediates 26.…”

Copper‐Catalyzed Stereoselective Hydroarylation of 3‐Aryl‐2‐ propynenitriles with Arylboronic Acids

“…The literature precedents require the toxic cyanide nucleophile CuCN [8] or cyano electrophiles such as BrCN [9] or PhOCN. [10] Therefore, we used diethyl cyanomethylphosphonate as a less toxic nitrile precursor. According to a previous report, [11] pmethoxy-, 3,4-dimethoxy-, and 3,5-dimethoxy-substituted benzaldehydes were treated with an iodinated Horner-Emmons reagent in situ prepared from cyanomethylphosphonate in THF to yield 2-iodoacrylonitriles 2a-c in 82%, 76%, and 72% yields, respectively.…”