Chemistry of stable iminopropadienones, RN=C=C=C=O.

The synthesis, spectroscopic properties, and chemical reactions of the stable (neopentylimino)-, (mesitylimino)-, and (o-tert-butylphenylimino)propadienones (6) are reported. Nucleophilic addition of amines affords the malonic amidoamidines 7 and 8. 3,5-Dimethylpyrazole reacts analogously to form 9b. Addition of 1,2-dimethylhydrazine produces pyrazolinones 10-12. Addition of N,N'-dimethyldiaminoethane, -propane, and -butane gives diazepine, diazocine, and diazonine derivatives 13-15, respectively (X-ray structures of 13c, 14a, and 15a are available). The mesoionic pyridopyrimidinium olates 18 are obtained by addition of 2-(methylamino)pyridine (X-ray structure of 18b available). Primary 2-aminopyridines afford the pyridopyrimidininones 20-29 and 31 (X-ray structure of 21a available), and 2-aminopyrimidines and 2-aminopyrazine afford pyrimidopyrimidinones and pyrazinopyrimidinones 33-35. Pyrimidoisoquinolinone 36 results from 1-aminoisoquinoline and pyridoquinolinone 40 from 8-aminoquinoline. 2-Aminothiazoline and 2-aminothiazole afford thiazolopyrimidinone derivatives 41-43 (X-ray structure of 43a available).

Aryliminopropadienone-C-Amidoketenimine- Amidinoketene-2-Aminoquinolone Cascades and the Ynamine-Isocyanate Reaction.

Imidoylketenes 11 and oxoketenimines 12 are generated by flash vacuum thermolysis of Meldrum's acid derivatives 9, pyrrolediones 17 and 18, and triazole 19 and are observed by IR spectroscopy. Ketenimine-3-carboxylic acid esters 12a are isolable at room temperature. Ketenes 11 and ketenimines 12 undergo rapid interconversion in the gas phase, and the ketenes cyclize to 4-quinolones 13. When using an amine leaving group in Meldrum's acid derivatives 9c, the major reaction products are aryliminopropadienones, ArN=C=C=C=O (15). The latter react with 1 equiv of nucleophile to produce ketenimines 12 and with 2 equiv to afford malonic acid imide derivatives 16. N-Arylketenimine-C-carboxamides 12c cyclize to quinolones 13c via the transient amidinoketenes 11c at temperatures of 25-40 degrees C. This implies rapid interconversion of ketenes and ketenimines by a 1,3-shift of the dimethylamino group, even at room temperature. This interconversion explains previously poorly understood outcomes of the ynamine-isocyanate reaction. The solvent dependence of the tautomerism of 4-quinolones/4-quinolinols is discussed. Rotational barriers of NMe(2) groups in amidoketenimines 12c and malonioc amides and amidines 16 (24) are reported.

Cyanoketene and Iminopropadienones.

Cyanoketene (8) is generated in high yields on flash vacuum thermolysis (FVT) of suitably substituted Meldrum's acid derivatives (5-[(alkylamino)(methylthio or alkylamino)methylene]-2,2-dimethyl-1,3-dioxane-4,6-diones) (3e-j), and also on FVT of cyanoacetic acid derivatives 9e,f,g,j,k,m. The major reaction pathway from 3 proceeds via ketenimines 6 and (alkylimino)propadienones 7, the latter undergoing a retro-ene reaction to 8. A minor pathway is via imidoylketenes 4e,h and oxoketenimines 5e,h, which undergo retro-ene reactions to 9. All intermediates were characterized by Ar matrix FTIR and tandem mass spectrometry (collisional activation MS). Trapping of 4, 5, and 8 with nucleophiles is also reported. The preference of 1,3-X shifts over 1,5-H shifts in imidoylketenes 12 (X = SMe or NMe(2)) is corroborated by the calculated activation barriers. Neat cyanoketene is highly reactive, reacting at or below 80 K, and this is attributed to the availability of a low-lying ketene LUMO. The IR spectrum of cyanoketene (Ar, 14 K) is dominated by two absorptions at 2163 (s; C=C=O) and 2239 (w; CN) cm(-)(1) in excellent agreement with density functional (B3-LYP/6-31G) and ab initio (QCISD/6-31G) calculations.