Reactivity of dehydrometallophthalocyanines and -porphyrazines.
The zinc dehydrophthalocyanine 2 and zinc dehydrobenzoporhyrazine 8 a were generated from the 1N-aminobenzotriazole-annulated zinc phtalocyanine 1 and zinc benzoporhyrazine 8, respectively, by oxidation with Pb(OAc)(4) in different solvents, for example, diethyl ether, tetrahydrofuran, acetic acid, and benzene. The reactivity of 2 and 8 a was studied in detail. These species not only easily undergo Diels-Alder additions with dienes, but also the used solvents can be added. Among the addition products with solvents ethoxy-, acetoxy-, acetoxybutyloxy-substituted and barrelen-fused phthalocyanines and benzoporpyrazines were isolated. No products resulting from the dimerization of two dehydro species were observed either for 2 or 8 a. Analysis of the reaction products in comparison with those obtained by oxidation of 1-aminobenzotriazole 15 under similar conditions proves a higher reactivity (electrophilicity) of the dehydro-PcZn 2 and dehydro-PzZn 8 a in comparison with unsubstituted benzyne towards the solvents used, such as diethyl ether and benzene.
Vagin
Sergei I
SI
Institut für Organische Chemie, Universität Tübingen, Auf der Morgenstelle 18, 72076 Tübingen, Germany. sergej.vagin@uni-tuebingen.de
Frickenschmidt
Antje
A
Kammerer
Bernd
B
Hanack
Michael
M
D002384:Catalysis; D007211:Indoles / Q000138:chemical synthesis* / Q000737:chemistry; D054833:Isoindoles; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D010084:Oxidation-Reduction; D013237:Stereoisomerism; D015032:Zinc / Q000737:chemistry*
D007211:Indoles; D054833:Isoindoles; D009942:Organometallic Compounds; C518153:zinc dehydrobenzoporhyrazine; D015032:Zinc; C008261:lead acetate; C013647:phthalocyanine