Positive Halogens Attached to Carbon in the Aromatic Series. Ii. Iodine Derivatives of Meta-Phenylenediamine and of Resorcinol

Nicolet, Ben H.; Sampey, John R.

doi:10.1021/ja01406a020

Cited by 18 publications

(7 citation statements)

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“…Uniformly ring labeled [14C]resorcinol (55 mCi/mmol) was purchased from American Radiolabeled Chemicals Inc. (St. Louis, MO). 2-Iodoresorcinol, 2,6-diiodoresorcinol 2,4,6-triiodophloroglucinol (Weil, 1976), and 4,6-diiodoresorcinol (Nicolet & Samprey, 1927) were synthesized and purified by the methods indicated. All other chemicals used were of analytical grade from commercial sources.…”

Section: Methodsmentioning

confidence: 99%

Mechanism-Based Inactivation of Lactoperoxidase and Thyroid Peroxidase by Resorcinol Derivatives

Divi¹,

Doerge²

1994

Biochemistry

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Humans are exposed to resorcinol derivatives in the environment through ground water, foods, food additives, drugs, and hair dyes. Epidemiological studies have linked human exposure to phenolic compounds with the thyroid disorder, goiter. The results presented here demonstrate the suicide (mechanism-based) inactivation of thyroid peroxidase (TPO) and the closely related lactoperoxidase (LPO) by resorcinol derivatives. The evidence for this mechanism includes irreversible, hydrogen peroxide-dependent loss of enzymatic activity by kinetics consistent with a suicide mechanism, concomitant with changes in the visible spectrum of the prosthetic heme group and covalent binding of resorcinol (ca. 10 mol/mol of lactoperoxidase inactivated). The inactivation was specific for thyroid peroxidase and lactoperoxidase since the activity of horseradish peroxidase, myeloperoxidase, chloroperoxidase, or the pseudoperoxidase, metmyoglobin, was unaffected by incubation with resorcinol. The enzymatic oxidation of resorcinol by lactoperoxidase was linked to inactivation since the same products were observed spectrally, albeit at a much lower level, as were observed with horseradish peroxidase. The results are consistent with thyroid peroxidase- and lactoperoxidase-catalyzed oxidation of resorcinol derivatives to reactive radical species that covalently bind to amino acid residues unique to these two enzymes. The oxidation of thyroid peroxidase and lactoperoxidase by hydrogen peroxide produces catalytic intermediates containing unpaired electron density on amino acid residues similar to that seen with cytochrome c peroxidase. These results provide an explanation for the potency of resorcinol derivatives in the inhibition of LPO and TPO and the goitrogenic responses observed in humans and animals. The widespread occurrence of resorcinol derivatives in the environment suggests that exposure to these compounds may cause thyroid dysfunction in humans.

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Section: Methodsmentioning

confidence: 99%

Mechanism-Based Inactivation of Lactoperoxidase and Thyroid Peroxidase by Resorcinol Derivatives

Divi¹,

Doerge²

1994

Biochemistry

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“…184). Mention must be made, however, of certain classes of compounds which are "positive" halogen carriers, examples of which appear in the tabular survey: certain ketones, diketones, and carboxylic compounds bearing -halogen atoms (67, 136); 1-halogenoalkynes (93,137,192); certain aromatic compounds containing activated halogen atoms (70,120,130,131,132,134,135,203); halogenonitromethanes (28,81,117,118,166,167,169); halogenoacetylmethanes (29); halogenocyanomethanes (27,28); halogenonitrosomethanes (30); trifluorohalogenomethanes (12); halogenomethanes (87, 91, 129, 141); certain trivalent nitrogen compounds containing halogen (58,168,175,183,205); nitroxyl chloride (nitryl chloride) (15, 142). Most of the above compounds contain oxygen.…”

Section: Other Halogenating Agentsmentioning

confidence: 99%

Organic Hypohalites.

Anbar¹,

Ginsburg²

1954

Chem. Rev.

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“…spectrum clearly indicated the alternative 2-acetyldibenzofuran structure (9). Professor Hogberg informed us that he had also isolated (9) in one experiment conducted at room temperature rather than 0 "C. The second product, isolated in 16% yield, proved to be a phenolic diacetyl derivative and is assigned structure (10). This compound had previously been reported from Friedel-Crafts acetylation of ruscodibenzofuran and the reported spectrometric data was in excellent agrzcment.…”

mentioning

confidence: 88%

“…Professor Hogberg informed us that he had also isolated (9) in one experiment conducted at room temperature rather than 0 "C. The second product, isolated in 16% yield, proved to be a phenolic diacetyl derivative and is assigned structure (10). spectrum clearly indicated the alternative 2-acetyldibenzofuran structure (9).…”

mentioning

confidence: 99%