90814-65-6

Upstream product

• 3463-27-2 1-methyl-5-phenyl-1H-pyrazole 
• 614-16-4 Benzoylacetonitrile 
• 74-89-5 methylamine 
• 624-90-8 methyl azide 
• 24840-05-9 (Z)-cinnamonitrile 
• 4360-47-8 cinnamonitrile 
• 12083-72-6 4-amino-3-methyl-2-phenylthiazolium chloride 

Downstream Products

• 1360588-13-1 C₂₉H₂₅BN₄ 
• 1360588-17-5 msv100105O₁ 
• 124413-21-4 2-cyano-3-methylaminothiocinnamaldehyde 

Relevant academic research and scientific papers

Four-coordinate organoboron compounds from β-enaminonitriles and diazonium salts

β-Enaminonitriles react with substituted benzenediazonium tetraphenylborates to form 1,2,4,3λ4-triazaborines or 1,3,2λ4-oxazaborines. The formation of either the first or the second product is affected by the reaction conditions, esp

Photochemistry of Phenyl-Substituted 1-Methylpyrazoles

Direct irradiation of 1-methyl-4-phenylpyrazole (2) in methanol results in regiospecific phototransposition to 1-methyl-4-phenylimidazole (4) and in photocleavage to (E)/(Z)-3-(N-methylamino)-2-phenylpropenenitrile (5) and (E)/(Z)-2-(N-methylaimno)-1-phenylethenyl isocyanide (6). Deuterium labeling confirms that the phototransposition occurs via the P4 permutation pathway. Separate experiments show that 5 and 6 undergo (Z) → (E) isomerization and photocyclization to imidazole 4. Quantum yields for these reactions show that the sequence 2 → 6 → 4 is a major pathway for the P4 phototransposition of 2 → 4. Isocyanides were also detected as intermediates in the P4 phototransposition of a variety of other pyrazoles confirming the generality of this pathway in pyrazole photochemistry. Direct irradiation of 1-methyl-5-phenylpyrazole (3) resulted in the formation of 1-methyl-5-phenylimidazole (7), 1-methyl-2-phenylimidazole (8), and 1-methyl-4-phenylimidazole (4). Deuterium labeling revealed that these products were formed by P4, P6, and P7 permutation pathways, respectively. (E)/(Z)-3-(N-methylamino)-3-phenylpropenenitrile (9) and (E)/(Z)-2-(N-methylamino)-2-phenylethenyl isocyanide (10) photocleavage products were also formed in this reaction. Irradiation of 3 in furan solvent did not result in phototransposition but led to the formation of endo and exo adducts formed by Diels-Alder reaction of furan with 4-phenyl-5-methyl-1,5-diazabicyclo[2.1.0]pent-2-ene. This constitutes the first direct evidence for the formation of a 1,5-diazabicyclo[2.1.0]hex-2-ene from photolysis of a pyrazole and is consistent with the electrocyclic ring closure - heteroatom migration mechanism suggested for the P6 and P7 phototranspositions.

REACTION DU METHYLAZIDE AVEC DES OLEFINES CINNAMIQUES, CROTONIQUES ET ACRYLIQUES. ETUDE DES COMPOSES OBTENUS

Methylazide reacts with the title olefines and gives expected 1,2,3-triazolines in equilibrium with corresponding amino dizao compounds.Because this equilibrium, E and Z olefines gives the same result, and the addition do not seem stereospecific.Thermolys

PHOTOCHEMICAL AND THERMAL REACTIONS OF HETEROCYCLES. PART 5. PRODUCTS VIA TRANSIENT QUASIANTIAROMATIC AZETINE INTERMEDIATES GENERATED BY DESULPHURISATION OF PHOTOCHEMICAL INTERMEDIATES FROM A THIAZOLIUM-4-OLATE AND 4-AMINOTHIAZOLIUM SALTS

Irradiation of the mesoionic triphenylthiazolium-4-olate (3) in the presence of tributylphosphine gave the quinolinone (7).This result was interpreted as arising via desulphurisation of the bicyclic intermediate (4) to the azetone (5), followed by its isomerisation to the ketene (6) and internal trapping.Similar irradiation of the 4-aminothiazolium salts (15) gave enamino nitriles (17) and benzoylacetonitrile (16).They are probably formed by isomerisation and hydration of the hitherto unknown quasiantiaromatic 2-imino-1,2-dihydroazete intermediates (20), which in turn are generated by desulphurisation of the bicyclic photochemical intermediates (19).

Interception of Photochemical Intermediates of Thiazole Derivatives. Formation and Isomerisation of Iminoazetine and Azetinone Intermediates

Irradiation of 4-aminothiazolium salts (7) in the presence of tributylphosphine gave enaminonitriles (9) and benzoylacetonitrile (8) by isomerisation and hydration of the iminoazetine intermediates (11), while a similar irradiation of the mesoionic triphenylthiazolium-4-olate (1) gave the quinolinol (5) by isomerisation of the azetinone intermediate (3).