2,6-Pyridinedicarbothioic acid

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2,6-Pyridinedicarbothioic acid
2,6-Pyridinedicarbothioicacid.svg
2,6-Pyridinedicarbothioic acid 3D ball.png
Names
IUPAC name
2,6-Pyridinedicarbothioic acid
Preferred IUPAC name
Pyridine-2,6-bis(carbothioic S-acid)
Other names
PDTC, dithiopyridinedicarbothioic acid
Identifiers
3D model (JSmol)
ChemSpider
PubChem CID
UNII
  • InChI=1S/C7H5NO2S2/c9-6(11)4-2-1-3-5(8-4)7(10)12/h1-3H,(H,9,11)(H,10,12) Yes check.svgY
    Key: SSRIAMRLMUFTNV-UHFFFAOYSA-N Yes check.svgY
  • C1=CC(=NC(=C1)C(=O)S)C(=O)S
  • O=C(S)c1nc(C(=O)S)ccc1
Properties
C7H5O2S2
Molar mass 185.24 g·mol−1
AppearanceWhite crystalline solid
Density 1.415 g/cm3
Melting point 97 to 99 °C (207 to 210 °F; 370 to 372 K)
Boiling point 404.4 °C (759.9 °F; 677.5 K)
1000 g/L (5.02 mol/L)
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
acidic
Flash point 198.4 °C (389.1 °F; 471.5 K)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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2,6-Pyridinedicarbothioic acid (PDTC) is an organosulfur compound that is produced by some bacteria. It functions as a , a low molecular weight compound that scavenges iron. Siderophores solubilize compounds by forming strong complexes. PDTC is secreted by the soil bacteria Pseudomonas stutzeri and Pseudomonas putida . [1]

Contents

Synthesis and biosynthesis

PDTC can be synthesized in the laboratory by treating the diacid dichloride of pyridine-2,6-dicarboxylic with H2S in pyridine:

NC5H3(COCl)2 + 2 H2S + 2 C5H5N → [C5H5NH+][HNC5H3(COS)2] + [C5H5NH]Cl

This route produces the pyridinium salt of pyridinium-2,6-dicarbothioate. Treatment of this orange-colored salt with sulfuric acid gives colorless PDTC, which can then be extracted with dichloromethane. [2]

The biosynthesis of PDTC remains unclear although some insights can be deduced from the genetics. [3] It is suggested that Pseudomonas stutzeri may have acquired at least one of the genes by lateral transfer from mycobacteria. [4] In a proposed biosynthetic sequence pyridine-2,6-dicarboxylic acid, a known bacterial metabolite, [4] is activated as its bis-adenosine monophosphate (AMP) derivative. The sulfur donor and its activation remain uncertain. [5]

Coordination chemistry

Structure of Fe(III) complex with two 2,6-pyridinedicarbothioate ligands. Color code: yellow = S, blue = N and Fe, gray = C, red = O. CSD CIF CUHGUH.png
Structure of Fe(III) complex with two 2,6-pyridinedicarbothioate ligands. Color code: yellow = S, blue = N and Fe, gray = C, red = O.

PDTC binds to both Fe2+ and Fe3+. The ferric complex is brown, whereas the ferrous complex is blue. In the presence of air, the ferrous complex oxidizes to the ferric compound. [7] It is iron selective [4] as only the Fe complex is soluble in water. PDTC is produced mainly during the exponential phase of bacterial growth. The conditions at which Pseudomonas produces PDTC is 25 °C, pH=8 and sufficient aeration. [5]

See also

Related Research Articles

<span class="mw-page-title-main">Pyridine</span> Heterocyclic aromatic organic compound

Pyridine is a basic heterocyclic organic compound with the chemical formula C5H5N. It is structurally related to benzene, with one methine group (=CH−) replaced by a nitrogen atom (=N−). It is a highly flammable, weakly alkaline, water-miscible liquid with a distinctive, unpleasant fish-like smell. Pyridine is colorless, but older or impure samples can appear yellow, due to the formation of extended, unsaturated polymeric chains, which show significant electrical conductivity. The pyridine ring occurs in many important compounds, including agrochemicals, pharmaceuticals, and vitamins. Historically, pyridine was produced from coal tar. As of 2016, it is synthesized on the scale of about 20,000 tons per year worldwide.

Chromic acid is jargon for a solution of formed by the addition of sulfuric acid to aqueous solutions of dichromate. It consists at least in part of chromium trioxide.

<span class="mw-page-title-main">Pyridinium</span> Chemical compound

Pyridinium refers to the cation [C5H5NH]+. It is the conjugate acid of pyridine. Many related cations are known involving substituted pyridines, e.g. picolines, lutidines, collidines. They are prepared by treating pyridine with acids.

<span class="mw-page-title-main">Siderophore</span> Iron compounds secreted by microorganisms

Siderophores (Greek: "iron carrier") are small, high-affinity iron-chelating compounds that are secreted by microorganisms such as bacteria and fungi. They help the organism accumulate iron. Although a widening range of siderophore functions is now being appreciated, siderophores are among the strongest (highest affinity) Fe3+ binding agents known. Phytosiderophores are siderophores produced by plants.

<span class="mw-page-title-main">Pyridinium chlorochromate</span> Chemical compound

Pyridinium chlorochromate (PCC) is a yellow-orange salt with the formula [C5H5NH]+[CrO3Cl]. It is a reagent in organic synthesis used primarily for oxidation of alcohols to form carbonyls. A variety of related compounds are known with similar reactivity. PCC offers the advantage of the selective oxidation of alcohols to aldehydes or ketones, whereas many other reagents are less selective.

<span class="mw-page-title-main">Dimethyl sulfide</span> Chemical compound

Dimethyl sulfide (DMS) or methylthiomethane is an organosulfur compound with the formula (CH3)2S. The simplest thioether, it is a flammable liquid that boils at 37 °C (99 °F) and has a characteristic disagreeable odor. It is a component of the smell produced from cooking of certain vegetables, notably maize, cabbage, beetroot, and seafoods. It is also an indication of bacterial contamination in malt production and brewing. It is a breakdown product of dimethylsulfoniopropionate (DMSP), and is also produced by the bacterial metabolism of methanethiol.

<span class="mw-page-title-main">Phosphorus pentasulfide</span> Chemical compound

Phosphorus pentasulfide is the inorganic compound with the formula P2S5 (empirical) or P4S10 (molecular). This yellow solid is the one of two phosphorus sulfides of commercial value. Samples often appear greenish-gray due to impurities. It is soluble in carbon disulfide but reacts with many other solvents such as alcohols, DMSO, and DMF.

<span class="mw-page-title-main">Sulfur dichloride</span> Chemical compound

Sulfur dichloride is the chemical compound with the formula SCl2. This cherry-red liquid is the simplest sulfur chloride and one of the most common, and it is used as a precursor to organosulfur compounds. It is a highly corrosive and toxic substance, and it reacts on contact with water to form chlorine-containing acids.

<span class="mw-page-title-main">Collins reagent</span> Chemical compound

Collins reagent is the complex of chromium(VI) oxide with pyridine in dichloromethane. This metal-pyridine complex, a red solid, is used to oxidize primary alcohols to the corresponding aldehydes and secondary alcohols to the corresponding ketones. This complex is a hygroscopic orange solid.

<span class="mw-page-title-main">Cornforth reagent</span> Chemical compound

The pyridinium dichromate(PDC) or Cornforth reagent is a pyridinium salt of dichromate with the chemical formula [C5H5NH]2[Cr2O7]. This compound is named after the Australian-British chemist Sir John Warcup Cornforth (b. 1917) who introduced it in 1962. The Cornforth reagent is a strong oxidizing agent which can convert primary and secondary alcohols to aldehydes and ketones respectively. In its chemical structure and functions it is closely related to other compounds made from hexavalent chromium oxide, such as pyridinium chlorochromate and Collins reagent. Because of their toxicity, these reagents are rarely used nowadays.

Pseudomonas balearica is a Gram-negative, rod-shaped, nonfluorescent, motile, and denitrifying bacterium. It is an environmental bacterium that has been mostly isolated from polluted environments all over the world. Many of the isolates have demonstrated capabilities to degrade several compounds. Some of the strains are naphthalene degraders and one strain isolated in New Zealand has demonstrated the potential to oxidize inorganic sulfur compounds to tetrathionate. Based on 16S rRNA analysis, P. balearica has been placed in the P. stutzeri group.

<i>Pseudomonas stutzeri</i> Species of bacterium

Pseudomonas stutzeri is a Gram-negative soil bacterium that is motile, has a single polar flagellum, and is classified as bacillus, or rod-shaped. While this bacterium was first isolated from human spinal fluid, it has since been found in many different environments due to its various characteristics and metabolic capabilities. P. stutzeri is an opportunistic pathogen in clinical settings, although infections are rare. Based on 16S rRNA analysis, this bacterium has been placed in the P. stutzeri group, to which it lends its name.

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<span class="mw-page-title-main">MOCS3</span> Protein-coding gene in the species Homo sapiens

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Oxidation with chromium(VI) complexes involves the conversion of alcohols to carbonyl compounds or more highly oxidized products through the action of molecular chromium(VI) oxides and salts. The principal reagents are Collins reagent, PDC, and PCC. These reagents represent improvements over inorganic chromium(VI) reagents such as Jones reagent.

<span class="mw-page-title-main">Pyoverdine</span> Chemical compound

Pyoverdines are fluorescent siderophores produced by certain pseudomonads. Pyoverdines are important virulence factors, and are required for pathogenesis in many biological models of infection. Their contributions to bacterial pathogenesis include providing a crucial nutrient, regulation of other virulence factors, supporting the formation of biofilms, and are increasingly recognized for having toxicity themselves.

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References

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  2. Hildebrand, U.; Ockels, W.; Lex, J.; Budzikiewicz, H. (1983). "Zur Struktur Eines 1:1-Adduktes von Pyridin-2,6-Dicarbothiosäure und Pyridin". Phosphorus and Sulfur and the Related Elements. 16 (3): 361–364. doi:10.1080/03086648308080490.
  3. Cortese, Marc S; Caplan, Allan B; Crawford, Ronald L (2002). "Structural, functional, and evolutionary analysis of moeZ, a gene encoding an enzyme required for the synthesis of the Pseudomonas metabolite, pyridine-2,6-bis(thiocarboxylic acid)". BMC Evolutionary Biology. 2: 8. doi: 10.1186/1471-2148-2-8 . PMC   115864 . PMID   11972321.
  4. 1 2 3 Cortese, Marc S.; Paszczynski, Andrzej; Lewis, Thomas A.; Sebat, Jonathan L.; Borek, Vladimir; Crawford, Ronald L. (2002). "Metal chelating properties of pyridine-2,6-bis(thiocarboxylic acid) produced by Pseudomonas spp. And the biological activities of the formed complexes". BioMetals. 15 (2): 103–120. doi:10.1023/A:1015241925322. PMID   12046919. S2CID   5545637.
  5. 1 2 Budzikiewicz, H. (2003). "Heteroaromatic monothiocarboxylic acids from Pseudomonas spp". Biodegradation. 14 (2): 65–72. doi:10.1023/A:1024012015127. PMID   12877462. S2CID   29898226.
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  7. Ockels, W., Roemer, A., Budzikiewicz, H., Korth, H., Pulverer, G., "Bacterial constituents. II. An iron(II) complex of pyridine-2,6-di-(monothiocarboxylic acid) - a novel bacterial metabolic product", Tetrahedron Lett. 1978, 3341. doi : 10.1016/S0040-4039(01)85634-3