6383-11-5Relevant articles and documents
Photoinduced α-Cleavage of 2-Azido-2-phenyl-1,3-indandione at Cryogenic Temperatures
Abe, Manabu,Banerjee, Upasana,Gudmundsdottir, Anna D.,Karney, William L.,Krause, Jeanette A.,Sarkar, Sujan K.
supporting information, p. 7885 - 7890 (2020/11/02)
To expand the utility of α-cleavage at cryogenic temperatures, we investigated the photoreactivity of 2-azido-2-phenyl-1,3-indandione (1). EPR spectroscopy revealed that irradiating 1 in 2-methyltetrahydrofuran (mTHF) matrices forms alkylnitrene 32, which has zero-field splitting parameters (D/hc = 1.5837 cm-1 E/hc = 0.0039 cm-1) typical of an alkylnitrene. IR spectroscopy demonstrated that irradiating 1 in argon matrices results in the concurrent formation of 32, imine 3, benzocyclobutenedione 4, and benzonitrile 5.
High-Intensity Laser-Jet Photochemistry: Formation of Benzocyclobutenedione from 1,2,3-Indantrione via Transient Targeting
Adam, Waldemar,Patterson, Wesley S.
, p. 7769 - 7773 (2007/10/03)
The photochemistry of 1,2,3-indantrione (1) under high-intensity (laser-jet) conditions has been investigated.Irradiation of trione 1 in a benzene solution under laser-jet conditions produces a complex mixture in which benzocyclobutenedione (2) is observed to be the sole high-intensity product (ca. 11percent yield, six cycles, 3..5 W MLUV argon ion laser) as compared to conventional irradiation (dispersed laser beam, 20 min, 3.5 W MLUV argon ion laser).Under similar conditions, dione 2 was not observed to undergo photolysis in the laser-jet (mass balance ca. 90percent).Additionally, phthalic anhydride, (E)-1,1'-bis-isobenzofuranylidene-3,3'-dione ((E)-4), and 2-benzopyrano-benzopyran-6,12-dione (5) were identified also in both the laser-jet and conventional irradiations of both trione 1 and dione 2.In view of the previously reported product studies, it is proposed that the formation of dione 2 under laser-jet conditions occurs by a photochemical electrocyclization of the intermediary cyclohexadiene-1,2-bisketene (B).The decarbonylation of trione 1 to bisketene B and the electrocyclization of the transient bisketene B to dione 2 constitute an unprecedented sequential multiple-photon transformation of polyketones in solution, which has been uncovered through product studies by using the novel laser-jet technique.
Thermolysis of Thiophenedicarboxylic Acid Anhydrides as a Route to Five-Membered Hetarynes
Reinecke, Manfred G.,Newsom, James G.,Chen, Lao-Jer
, p. 2760 - 2769 (2007/10/02)
Flow vacuum thermolysis (FVT) of the anhydrides of thiophene-2,3- (5) and -3,4-dicarboxylic acid (6) and of thianaphthene-2,3-dicarboxylic acid (7) in the presence of thiophene, 1,3-cyclohexadiene, or benzene gave thianthrene (15a), presumably by aromatization of an intermadiate Diels-Alder adduct of the diene traps and the aryne 2,3-didehydrothiophene (8).A similar rationale explains the formation of dibenzothiophene from 7 and thiophene, the four monomethylthianaphthenes 22-25 from 5 and cyclopentadiene, 5,6-dimethylthianaphthene (15f) from 5 and 2,3-dimethylbutadiene, and a mixture of hydroxythianaphthenes (15d) from 5 and furan.The latter reaction also produces a mixture of isomeric cyclopentanothiophenes (19) which probably arise by decarbonylation of 15d.An FVT reaction of 5 with propyne as the trap gave a mixture of allenyl-(28) and propynylthiophenes 29 which probably arise by an ene reaction of the trap and the aryne 8.Decomposition of the anhydrides 5 and 6 in molten anthracene led only to Friedel-Crafts products such as thienylanthracenes 33 and quinones 34 from 5 and 39 and 40 from 6.The diene reactivity of thiophene 13a in the gas phase was demonstrated by the formation of naphthalene from its reaction with benzyne generated from the thermolysis of indanetrione and by the formation of indene from 13a plus cyclopentadiene.Possible, but improbable, interpretations of the FVT results without invoking a five-membered hetaryne intermediate are considered.
