TY - JOUR
T1 - A facile and regioselective synthesis of trans-heterofunctionalized porphyrazine derivatives
AU - Forsyth, Timothy P.
AU - Bradley G Williams, D.
AU - Montalban, Antonio Garrido
AU - Stern, Charlotte L.
AU - Barrett, Anthony G.M.
AU - Hoffman, Brian M.
PY - 1998/1/23
Y1 - 1998/1/23
N2 - New methodology was developed for the selective synthesis of regiochemically defined porphyrazines of the form M[pz(A2;B2)] (shown in Chart 1) where A and B represent peripheral functionalization attached to the β-positions of the pyrroles. Specifically, phthalonitriles or derivatives thereof with sterically bulky groups in positions 3 and 6, in particular 4,7- bis(isopropyloxy)-1,3-diiminoisoindoline (3) act as a 'trans director' when macrocyclized with heteroatom-appended maleonitriles under Linstead conditions, the result being preferential formation of the trans- M[pz(A2;B2)] pigment where A = SR, NMe2, OR, as well as R (shown in Chart 2). Linstead crossover macrocyclization of 3 with 4, 11, 15, and 18 gave pigments 10, 14, 17, and 19, respectively. These pigments were characterized by 1H NMR, 13C NMR, UV-visible spectroscopy, mass spectrometry, microanalysis, and 17 was characterized by single-crystal X-ray analysis.
AB - New methodology was developed for the selective synthesis of regiochemically defined porphyrazines of the form M[pz(A2;B2)] (shown in Chart 1) where A and B represent peripheral functionalization attached to the β-positions of the pyrroles. Specifically, phthalonitriles or derivatives thereof with sterically bulky groups in positions 3 and 6, in particular 4,7- bis(isopropyloxy)-1,3-diiminoisoindoline (3) act as a 'trans director' when macrocyclized with heteroatom-appended maleonitriles under Linstead conditions, the result being preferential formation of the trans- M[pz(A2;B2)] pigment where A = SR, NMe2, OR, as well as R (shown in Chart 2). Linstead crossover macrocyclization of 3 with 4, 11, 15, and 18 gave pigments 10, 14, 17, and 19, respectively. These pigments were characterized by 1H NMR, 13C NMR, UV-visible spectroscopy, mass spectrometry, microanalysis, and 17 was characterized by single-crystal X-ray analysis.
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U2 - 10.1021/jo971683c
DO - 10.1021/jo971683c
M3 - Article
AN - SCOPUS:15444342060
SN - 0022-3263
VL - 63
SP - 331
EP - 336
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
IS - 2
ER -