Sapphyrins, derivatives and syntheses
AssigneeBoard of Regents, The University of Texas System
InventorsJonathan L. Sessler, Michael J. Cyr
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Abstract
The present invention involves, in addition to many unique substituted sapphyrins, a novel method for synthesizing sapphyrins with good efficiency and high yield. An improved 9-step synthesis of substituted sapphyrins, e.g., the two C.sub.2 symmetric sapphyrins, compounds 2 and 4 of FIG. 1C, is described herein. This synthesis involves as an important step the condensation between a tripyrrane diacid and a diformyl bipyrrole. The key tripyrrane component is prepared in three high-yield steps from readily available pyrrolic precursors and the bipyrrole portion is prepared in four steps from ethyl 3-methyl-4-methylpyrrole-2-carboxylate in roughly 33% yield overall.
Claims15
A sapphyrin compound of the formula:
- ##STR1## wherein at least one of D.sub.a, D.sub.b, D.sub.c, D.sub.d, D.sub.e, and D.sub.f is an alkyl and at least one is an alkyl with an amino, hydroxyl, carboxyl, cyanate, isocyanate, thiocyanate, sulfhydryl, nitrile, iodide, or sulfonic substituent.
A sapphyrin compound of the formula:
- ##STR2## wherein at least one of D.sub.a, D.sub.b, D.sub.c, D.sub.d, D.sub.e, and D.sub.f is an alkyl and at least one is an alkyl with a hydroxyl substituent.
A sapphyrin compound of the formula:
- ##STR3## wherein at least one of D.sub.a, D.sub.b, D.sub.c, D.sub.d, D.sub.e, and D.sub.f is an alkyl and at least one is an alkyl with an amino substituent.
A sapphyrin compound of the formula:
- ##STR4## wherein at least one of D.sub.a, D.sub.b, D.sub.c, D.sub.d, D.sub.e, and D.sub.f is an alkyl and at least one is an alkyl with a carboxyl substituent.
A sapphyrin compound of the formula:
- ##STR5## wherein at least one of D.sub.a, D.sub.b, D.sub.c, D.sub.d, D.sub.e, and D.sub.f is an alkyl and at least one is an alkyl with an alkenyl, aryl, alkynyl, cycloalkyl, fluoride, chloride or bromide substituent.
A sapphyrin compound of the formula:
- ##STR6## where D.sub.a, D.sub.e and D.sub.f are ethyl;
- D.sub.b and D.sub.c aremethyl;
- and D.sub.d is CH.sub.2 CO.sub.2 ET.
A sapphyrin compound of the formula:
- ##STR7## wher D.sub.a, D.sub.e and D.sub.f are ethyl;
- D.sub.b and D.sub.c are methyl;
- and D.sub.d is CH.sub.2 CO.sub.2 H.
A sapphyrin compond of the formula:
- ##STR8## where D.sub.a, D.sub.e and D.sub.f are ethyl;
- D.sub.b and D.sub.c are methyl;
- one D.sub.d is CH.sub.2 CO.sub.2 H and one is CH.sub.2 CO.sub.2 Et.
9,18-Di(carboxymethyl)-4,13,14,23-tetraethyl -3,8,19,24-tetramethyl-25,26,27,28,29-pentazahexacyclo {20.2.1.1.sup.2,5.1.sup.7,10.1.sup.12,15.1.sup.17,20 }nonacosa-2,4,6,8,10(28),11,13,15,17(26), 18,20,22,24-tridecaene.
9-Carboxymethyl-18-ethoxycarbonylmethyl-4,13,14,23-tetraethyl- 3,8,19,24-tetramethyl-25,26,27,28,29-pentazahexacyclo{20 2.1.1.sup.2,5.1.sup.7,10.1.sup.12,15.1.sup.17,20 }nonacosa-2,4,6,8,10(28),11,13,15,17(26),18,20,22,24-tridecaene.
9,18-Di(ethoxycarbonylmethyl)-4,13,14,23-tetraethyl -3,8,19,24-tetramethyl-25,26,27,28,29-pentazahexacyclo{20.2.1.1.sup.2,5.1. sup.7,10.1.sup.12,15.1.sup.17,20 }nonacosa-2,4,6,8,10(28),11,13,15,17(26), 18,20,22,24-tridecaene.
8,12,13,17-Tetraethyl-7,18-dimethyldioxosapphyrin.
Gadolinium pentavalently coordinated to 8,12,13,17-tetraethyl-7,18-dimethyldioxosapphyrin.
8,17-diethoxycarbonylmethyl-12,13-diethyl-7,18-dimethyldioxosapphyrin.
Gadolinium pentavalently coordinated to 8,17-diethoxycarbonylmethyl-12,13-diethyl -7,18-dimethyldioxosapphyrin.
Dependencies are inferred from the claim text.