Improved Protocols for the Synthesis and Halogenation of Sterically Hindered Metalloporphyrins

Chorghade, Mukund S.; Dolphin, David; Dupre, Daniel; Hill, David R.; Lee, E. C.; Wijesekera, Tilak P.

doi:10.1055/s-1996-4401

Cited by 43 publications

(26 citation statements)

References 6 publications

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“…Here such parameters as the solvent, rate of addition of the reagents, and reaction time were varied. Comparative analysis and modification of the various bromination procedures were used during the production of octabrominated zinc meso-tetrakis(2,6-dichlorophenyl)porphyrinate 39 from the β-unsubstituted porphyrin 40 [94] (Table 2). …”

Section: 31mentioning

confidence: 99%

Bromination of porphyrins (Review)

Chumakov

Khoroshutin

Anisimov

et al. 2009

Chem Heterocycl Comp

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Section: 31mentioning

confidence: 99%

Bromination of porphyrins (Review)

Chumakov

Khoroshutin

Anisimov

et al. 2009

Chem Heterocycl Comp

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“…CuT(3ʼ,5ʼ-DMP)PBr 16 Synthesis of H 2 T(3ʼ,5ʼ-DMP)PBr 16 . It was obtained by acid demetallation reaction of CuT(3ʼ,5ʼ-DMP)PBr 16 complex.…”

Section: Synthesis Of Highly Brominated Porphyrinsmentioning

confidence: 99%

“…The yield of the isolated product was found to be 0.160 g (90%). 1 Synthesis of ZnT(3ʼ,5ʼ-DMP)PBr 16 . To a solution of H 2 T(3ʼ,5ʼ-DMP)PBr 16 (0.10 g, 0.048 mmol) in minimum amount of CHCl 3 , Zn(OAc) 2 .…”

Section: Synthesis Of Highly Brominated Porphyrinsmentioning

confidence: 99%

“…Numerous porphyrins with polyhalogen substituents at the periphery of the macrocycle have been reported in the literature [1]. The interests in this class of perhaloporphyrins are four fold: (1) synthetic utility [4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21], (2) interesting physicochemical properties [10,, (3) robust catalysts for the oxidative transformation of organic substrates [6,[60][61][62][63][64][65][66][67][68][69][70][71][72], (4) useful precursors for the synthesis of a variety of other synthetically difficult or inaccessible porphyrins [73][74][75][76][77][78][79][80][81][82][83]…”

Section: Introductionmentioning

confidence: 99%

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Highly brominated porphyrins: synthesis, structure and their properties

Bhyrappa

Bhavana

Vittal

2003

J. Porphyrins Phthalocyanines

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This article reports the first perbromination of β-pyrrole and meso-phenyl groups of the 5,10,15,20-tetrakis(3ʼ,5ʼ-dimethoxyphenyl)porphinato copper(II) to generate highly brominated porphyrin, 2, 3,7,8,12,13,17,18-octabromo-5,10,15,20-tetrakis(2ʼ,6ʼ-dibromo-3ʼ,5ʼ-dimethoxyphenyl)-porphinato copper(II), CuT(3ʼ,5ʼ-DMP)PBr 16 complex. Its crystal structure exhibited unusual five-coordination geometry with saddle shaped conformation of the porphyrin core. H 2 T(3ʼ,5ʼ-DMP)PBr 16 and its metal complexes exhibited large anodic shift of oxidation potentials with marginal changes in reduction potentials relative to their corresponding octabromotetraphenylporphyri n, MTPPBr 8 derivatives. The enhanced electron deficiency of the ZnT(3ʼ,5ʼ-DMP)PBr 16 complex was probed by axial ligation of various Lewis bases with differing pK a values. The ZnT(3ʼ,5ʼ-DMP)PBr 16 complex exhibited decrease in equilibrium constants for the ligation of bases relative to sterically unhindered ZnTPPBr 8 . This has been ascribed to the sterics induced by the bulky ortho-bromo phenyl substituents that prevents the facile binding of Lewis bases to the Zn(II)-center.

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“…Cl 8 TPPFeCl was synthesized in our laboratory as reported. 19) The apparent valence of iron atom is ϩ3 in all porphyrins. Hydrogen peroxide (H 2 O 2 ) and meta-chloroperbenzoic acid (mCPBA) were purchased from Wako (Japan) and Sigma-Aldrich Japan Co., Ltd. (Tokyo, Japan), respectively, and other reagents were of the purest grade (99%) from Nacalai Tesque, Inc. (Kyoto, Japan).…”

Section: Chemicals Trans-permethrin (I) [3-phenoxybenzyl (1rs)-transmentioning

confidence: 99%

Iron-Porphyrin catalyzed oxidation of permethrin and fenvalerate

Fukushima

Katagi

2009

J. Pestic. Sci.

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Biomimetic oxidation of a trans isomer of permethrin, fenvalerate, together with the corresponding chrysanthemic acid and alcohol moieties was conducted using catalytic amounts of six iron-porphyrins having different substituents, not only at b-and meso-positions but also the axial ligand of iron in the presence of hydrogen peroxide or meta-chloroperbenzoic acid as an oxidant. The several degradation products via cleavage of ester and ether linkages and hydroxylation were identified and some were found to be in vivo metabolites previously reported in plants, animal and insects. The introduction of electron-withdrawing substituents at b-and mesopositions of a porphyrin ring resulted in higher conversion and the weak electron donor as the axial ligand of iron was found to increase the oxidative reactivity of porphyrin. ©Pesticide Science Society of Japan Keywords: biomimetic oxidation, fenvalerate, iron-porphyrin, permethrin. Materials and Methods Chemicals. trans-Permethrinand their potential degradates were synthesized in our laboratory by the reported methods.9-13) 14 C-I and II were prepared in our laboratory according to the reported procedures 14,15) and their radio-chemical purities were determined to be greater than 98% by HPLC. The specific activity of 14 C-I labeled at 1-position of the cyclopropyl ring and those of 14 C-II uniformly labeled at chlorophenyl and phenoxyphenyl rings were 5.06, 11.2 and 10.5 MBq mg Ϫ1 , respectively. The 14 C-derivatives corresponding to the alcohol moieties, PBalc and PBacid as well as the chrysanthemic acid derivatives of I were prepared during the synthesis of 14 C-I and II. 14 C-labeled CRA was also synthesized by the reported method.16) Abbreviations and the structure of reference standards employed in this study are presented in Table I. Other than the above reference standards, mono-hydroxylated compounds 9,17) of I, II, PBalc, PBacid and t-Cl 2 CA, oxidized compounds at the alkenyl methyl group of CRA 18) , carboxy and amide derivatives of II and dePh-II 13) , 2,3-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid and phenoxymandelic acid were used for HPLC and TLC analyses, but were not detected and are not listed in Table 1. The six iron porphyrins (Fig. 2) having different substituents at b-and meso-positions of the ring and an axial ligand were used. F 20 TPPFeCl and 4OMeTPPFeCl from Sigma-Aldrich Japan Co., Ltd. (Tokyo, Japan), F 20 Br 8 TPPFeCl from Wako Pure Chemical Industries, Ltd. (Osaka, Japan), and F 20 Br 8 -TPPFeNO 3 and F 20 Br 8 TPPFeCF 3 SO 3 from Funakoshi Co., Ltd. (Tokyo, Japan) were respectively purchased and used without further purification. Cl 8 TPPFeCl was synthesized in our laboratory as reported.19) The apparent valence of iron atom is ϩ3 in all porphyrins. Hydrogen peroxide (H 2 O 2 ) and meta-chloroperbenzoic acid (mCPBA) were purchased from Wako (Japan) and Sigma-Aldrich Japan Co., Ltd. (Tokyo, Japan), respectively, and other reagents were of the purest grade (99%) from Nacalai Tesque, Inc. (Kyoto, Japan). Biomimetic OxidationEach radio...

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Improved Protocols for the Synthesis and Halogenation of Sterically Hindered Metalloporphyrins

Abstract: Improved procedures are described for the synthesis of meso~tetra• kis(2,6-dichlorophcnyl)porphyrin and for subsequent perhalogcnation of the porphyrin ring.

Cited by 43 publications

References 6 publications

Bromination of porphyrins (Review)

Bromination of porphyrins (Review)

Highly brominated porphyrins: synthesis, structure and their properties

Iron-Porphyrin catalyzed oxidation of permethrin and fenvalerate

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