7206-60-2

Upstream product

• 67-56-1 methanol 
• 938-81-8 N-nitrosoacetanilide 
• 127-09-3 sodium acetate 
• 71-43-2 benzene 
• 275-51-4 azulene 
• 33654-47-6 1-Cyano-3-phenylazulen 
• 33681-73-1 Ethyl-3-phenylazulen-1-carboxylat 
• 110-00-9 furan 
• 536-74-3 phenylacetylene 
• 6908-73-2 (E)-1-styrylpyrrolidine 
• 4481-35-0 cyclohepta[b]furan-2(2H)-one 
• 100-63-0 phenylhydrazine 
• 35043-92-6 cis-5,8,9,10-tetrahydronaphtho-1,4-quinone 
• 591-50-4 iodobenzene 

Downstream Products

• 1365097-62-6 C₂₄H₁₇N 

Relevant academic research and scientific papers

Azulene Functionalization by Iron-Mediated Addition to a Cyclohexadiene Scaffold

The functionalization of azulenes via reaction with cationic η5-iron carbonyl diene complexes under mild reaction conditions is demonstrated. A range of azulenes, including derivatives of naturally occurring guaiazulene, were investigated in reactions with three electrophilic iron complexes of varying electronic properties, affording the desired coupling products in 43-98% yield. The products were examined with UV-vis/fluorescence spectroscopy and showed interesting halochromic properties. Decomplexation and further derivatization of the products provide access to several different classes of 1-substituted azulenes, including a conjugated ketone and a fused tetracycle.

Preparation of 1-arylazulenes through regioselective photoarylation of azulene with aryl iodides

Photoirradiation of aryl iodide in the presence of azulene has been shown to be a useful method for regioselective arylation of azulene at the electron rich 1-position.

Ring expansion-annulation strategy for the synthesis of substituted azulenes and oligoazulenes. 2. Synthesis of azulenyl halides, sulfonates, and azulenylmetal compounds and their application in transition-metal-mediated coupling reactions

A "ring expansion-annulation strategy" for the synthesis of substituted azulenes is described based on the reaction of β'-bromo- α-diazo ketones with rhodium carboxylates. The key transformation involves an intramolecular Buechner reaction followed by β-elimination of bromide, tautomerization, and in situ trapping of the resulting 1-hydroxyazulene as a carboxylate or triflate ester. Further synthetic elaboration of the azulenyl halide and sulfonate annulation products can be achieved by employing Heck, Negishi, Stille, and Suzuki coupling reactions. Reaction of the azulenyl triflate 84 with pinacolborane provides access to the azulenylboronate 91, which participates in Suzuki coupling reactions with alkenyl and aryl iodides. The application of these coupling reactions to the synthesis of biazulenes, terazulene 101, and related oligoazulenes is described, as well as the preparation of the azulenyl amino acid derivative 110.

A ring expansion-annulation strategy for the synthesis of substituted azulenes. Preparation and suzuki coupling reactions of 1-azulenyl triflates

(matrix presented) A new strategy for the synthesis of substituted azulenes is reported, based on the reaction of β′-bromo-α-diazo ketones with rhodium carboxylates The key transformation involves intramolecular addition of a rhodium carbenoid to an arene π-bond, electrocyclic ring opening, β-elimination, tautomerization, and trapping to produce 1-hydroxyazulene derivatives. The synthetic utility of the method is enhanced by the ability of the triflate derivatives to participate in Suzuki coupling reactions, as illustrated in a synthesis of the antiulcer drug egualen sodium (KT1-32).

First intermolecular palladium catalyzed arylation of an unfunctionalized aromatic hydrocarbon

Azulene is arylated by iodobenzene and by 4-nitro-chlorobenzene under palladium catalysis at the electron-rich 1-position.

A divergent method for preparing 1-aryl- and 1,3-diarylazulenes from ethyl 3-(cyclohepta-1,3,5-trien-1-yl)-3-oxopropionate

The 3-aryl substituted 1,2,3,8-tetrahydroazulen-1-ones 3, prepared by the Knoevenagel condensation of ethyl 3-(cyclohepta-1,3,5-trien-1-yl)-3- oxopropionate (6) with arylaldehydes and subsequent Nazarov cyclization, were efficiently transformed into 1-aryl- and 1,3-diarylazulenes in a few steps.

ARYLATION OF AZULENE

In the reaction of azulene with phenylhydrazine and an oxidizing agent (Cu(2+)) a mixture of 1-phenylazulene (28percent) with 2-, 4-, and 6-phenylazulenes (27percent in total) is formed; a series of para-substituted phenylazulenes and α-naphthylazulenes were obtained in a similar way.If p-nitrophenylhydrazine is used, selective arylation of azulene (at position 1) and also of dimethylaniline (at the ortho and para positions) occurs.An excess of the oxidizing agent (Cu(2+)) increases and an excess of the reducing agent (arylhydrazine) reduces the selectivity of arylation.Some of the obtained arylazulenes can be used as dichroic coloring additives for liquid crystals.

Stereo- and Regio-specific Photochemical Cycloaddition of Furan to Benzonitrile and Phenylacetylene

Benzonitrile and phenylacetylene undergo exclusive regio- and stereo-specific 2,6-, 2',5'-photocycloaddition of furan: excited state interaction between the substituent and furan is considered to orient the addends and direct the reaction of this specific mode of attack.

THE FACILE SYNTHESIS OF 1- AND 2-ALKYLAZULENES BY THE REACTIONS OF 2H-CYCLOHEPTAFURAN-2-ONES WITH ENAMINES OF ALDEHYDES AND ACYCLIC KETONES

The reactions of 2H-cycloheptafuran-2-one and its 3-cyano derivatives with enamines derived from aldehydes and acyclic ketones were investigated.On the reactions, 1- and 2-alkylazulenes were easily synthesized.