New Reagents for the Reductive Quenching of Ozonolysis Reactions

Appell, Robert B.; Tomlinson, Ian A.; Hill, Ian R.

doi:10.1080/00397919508015494

Cited by 21 publications

(10 citation statements)

References 9 publications

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“…Some of the influence of solvent dependency described (27) in the ozonization of fatty substrates appears to have been minimized in the present work by operating at low temperature. Although a variety of methods have been described (28) for the reduction of the trioxane, we found it convenient to use either catalytic hydrogenation with hydrogen at atmospheric pressure in ethyl acetate containing 5% palladium-carbon or chemical reduction in acetic acid containing zinc, both of which methods gave comparable yields. Spectroscopic monitoring of ozonide formation by 1 H NMR examination indicated a broad band at δ 5.10 characteristic of the trioxane ring hydrogens (29).…”

Section: Resultsmentioning

confidence: 99%

Ozonization of phenols from Anacardium occidentale (cashew)

Graham

Tyman

2002

J Americ Oil Chem Soc

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The phenolic lipid components cardanol and cardol, obtained from heat-processed technical cashew nutshell liquid from Anacardium occidentale, and anacardic acid from the natural product, each containing monoene, diene, and triene constituents, were ozonized. The ozonides were reduced chemically and catalytically to give 8-(3-hydroxyphenyl)octanal, 8-(3,5-dihydroxyphenyl)octanal, and 8-(3-hydroxy-2-carboxyphenyl)octanal, respectively, together with formaldehyde, malondialdehyde, butanal, and heptanal in each case. Reduction of the 8-(3-hydroxphenyl)octanal, which was synthesized from 3-benzyloxybenzaldehyde, gave 3-octylphenol. Oxidation of the aldehyde with potassium permanganate gave 8-(3-hydroxyphenyl)octanoic acid, and reduction with sodium borohydride yielded 8-(3-hydroxyphenyl)octanol. For comparison, the transdiols of cardanol were prepared by treatment of cardanol with peroxyformic acid and cleaved by periodate oxidation to give an alternative route to 8-(3-hydroxyphenyl)octanal but in lower yield. Likewise, the cis-diols were obtained with potassium permanganate and cleaved without isolation to give the same product in lower yield compared with ozonization.

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Section: Resultsmentioning

confidence: 99%

Ozonization of phenols from Anacardium occidentale (cashew)

Graham

Tyman

2002

J Americ Oil Chem Soc

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“…Data were evaluated using the NIST Mass Spectral Search program. 3 Isolation of RNA and RT-PCR-Total RNA was isolated from V. paradoxus strain TBEA6 by using the Qiagen RNeasy-Kit according to the manufacturer's instructions. RT-PCR was performed using the Qiagen "One step RT-PCR" Kit according to the manufacturer's instructions.…”

Section: Isolation Of Strains Capable Of Using Tdp As Sole Source Ofmentioning

confidence: 99%

“…Experiment with rats showed that TDP was rapidly adsorbed after oral intake and excreted in the urine (2). In technical applications esters of TDP are important stabilizers of polyolefins (1), and polymer-bound TDP is used to replace methyl sulfide for the reductive quenching of ozonolysis reactions (3). Recently, the biotechnological production of medium-and long-chain dialkyl 3,3-thiodipropionate antioxidants by a lipase-catalyzed esterification of 3,3-thiodipropionic acid in the absence of solvents was reported.…”

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confidence: 99%

3-Mercaptopropionate Dioxygenase, a Cysteine Dioxygenase Homologue, Catalyzes the Initial Step of 3-Mercaptopropionate Catabolism in the 3,3-Thiodipropionic Acid-degrading Bacterium Variovorax paradoxus

Bruland

Wübbeler

Steinbüchel

2009

Journal of Biological Chemistry

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The thioether 3,3-thiodipropionic acid can be used as precursor substrate for biotechnological synthesis of 3-mercaptopropionic acid-containing polythioesters. Therefore, the hitherto unknown catabolism of this compound was elucidated to engineer novel and improved polythioester biosynthesis pathways in the future. Bacteria capable of using 3,3-thiodipropionic acid as the sole source of carbon and energy for growth were enriched from the environment. From eleven isolates, TBEA3, TBEA6, and SFWT were morphologically and physiologically characterized. Their 16 S rDNAs and other features affiliated these isolates to the ␤-subgroup of the proteobacteria. Tn5::mob mutagenesis of isolate Variovorax paradoxus TBEA6 yielded ten mutants fully or partially impaired in growth on 3,3-thiodipropionic acid. Genotypic characterization of two 3,3-thiodipropionic acid-negative mutants demonstrated the involvement of a bacterial cysteine dioxygenase (EC 1.13.11.22) homologue in the further catabolism of the 3,3-thiodipropionic acid cleavage product 3-mercaptopropionic acid. Detection of 3-sulfinopropionate in the supernatant of one of these mutants during cultivation on 3,3-thiodipropionic acid as well as in vivo and in vitro enzyme assays using purified protein demonstrated oxygenation of 3-mercaptopropionic acid to 3-sulfinopropionate by this enzyme; cysteine and cysteamine were not used as substrate. Beside cysteine dioxygenase and cysteamine dioxygenase, this 3-mercaptopropionic acid dioxygenase is the third example for a thiol dioxygenase and the first report about the microbial catabolism of 3-mercaptopropionic acid. Insertion of Tn5::mob in a gene putatively coding for a family III acyl-CoAtransferase resulted in the accumulation of 3-sulfinopropionate during cultivation on 3,3-thiodipropionic acid, indicating that this compound is further metabolized to 3-sulfinopropionylCoA and subsequently to propionyl-CoA.The thioether 3,3-thiodipropionic acid (TDP) 2 and its ester are effective non-toxic antioxidants (1), and they are therefore widely used as antioxidant and stabilizer in food, for food packaging, and for various technical applications. Experiment with rats showed that TDP was rapidly adsorbed after oral intake and excreted in the urine (2). In technical applications esters of TDP are important stabilizers of polyolefins (1), and polymer-bound TDP is used to replace methyl sulfide for the reductive quenching of ozonolysis reactions (3). Recently, the biotechnological production of medium-and long-chain dialkyl 3,3-thiodipropionate antioxidants by a lipase-catalyzed esterification of 3,3-thiodipropionic acid in the absence of solvents was reported. In contrast to the chemical production of TDP ester, the biotechnological process does not require any materials with deleterious effects on health and environment (4). Another biotechnological process using TDP as primary product is the microbial production of polythioesters (PTEs) (5). In addition to 3-mercaptopropionic acid Ralstonia eutropha is able to use the organo sul...

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“…4,49-Dithiodibutyric acid (DTDB), 3,39-dithiodipropionic acid (DTDP) and 3,39-thiodipropionic acid (TDP) are deployed in many different areas of research (Appel et al, 1995;Codognoto et al, 2007;Jang & Keng, 2006;Kanayama & Kitano, 2000;Saxena & Gupta, 1984;Scott, 1968;Tsutsumi et al, 1998;Tuan & Phillips, 1997). However, the biotechnological significance of these organic sulphur compounds (OSCs) is their application in studies for the improvement of polythioester (PTE) production (Lütke-Eversloh & Steinbüchel, 2003).…”

Section: Introductionmentioning

confidence: 99%

Biodegradation of the xenobiotic organic disulphide 4,4′-dithiodibutyric acid by Rhodococcus erythropolis strain MI2 and comparison with the microbial utilization of 3,3′-dithiodipropionic acid and 3,3′-thiodipropionic acid

et al. 2010

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Application of the non-toxic 3,3′-thiodipropionic acid (TDP) and 3,3′-dithiodipropionic acid (DTDP) as precursors for the microbial production of polythioesters (PTEs), a class of biologically persistent biopolymers containing sulphur in the backbone, was successfully established previously. However, synthesis of PTEs containing 4-mercaptobutyrate (4MB) as building blocks could not be achieved. The very harmful 4MB is not used as a PTE precursor or as the carbon source for growth by any known strain. As a promising alternative, the harmless oxidized disulfide of two molecules of 4MB, 4,4′-dithiodibutyric acid (DTDB), was employed for enrichments of bacterial strains capable of biodegradation. Investigation of novel precursor substrates for PTEs and comparison of respective strains growing on TDP, DTDP and DTDB as sole carbon source was accomplished. A broad variety of bacteria capable of using one of these organic sulphur compounds were isolated and compared. TDP and DTDP were degraded by several strains belonging to different genera, whereas all DTDB-utilizing strains were affiliated to the species Rhodococcus erythropolis. Transposon mutagenesis of R. erythropolis strain MI2 and screening of 7500 resulting mutants yielded three mutants exhibiting impaired growth on DTDB. Physiological studies revealed production of volatile hydrogen sulphide and accumulation of significant amounts of 4MB, 4-oxo-4-sulphanylbutanoic acid and succinic acid in the culture supernatants. Based on this knowledge, a putative pathway for degradation of DTDB was proposed: DTDB could be cleaved into two molecules of 4MB, followed by an oxidation yielding 4-oxo-4-sulphanylbutanoic acid. A putative desulphydrase probably catalyses the abstraction of sulphur, thereby generating succinic acid and hydrogen sulphide.

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New Reagents for the Reductive Quenching of Ozonolysis Reactions

Cited by 21 publications

References 9 publications

Ozonization of phenols from Anacardium occidentale (cashew)

Ozonization of phenols from Anacardium occidentale (cashew)

3-Mercaptopropionate Dioxygenase, a Cysteine Dioxygenase Homologue, Catalyzes the Initial Step of 3-Mercaptopropionate Catabolism in the 3,3-Thiodipropionic Acid-degrading Bacterium Variovorax paradoxus

Biodegradation of the xenobiotic organic disulphide 4,4′-dithiodibutyric acid by Rhodococcus erythropolis strain MI2 and comparison with the microbial utilization of 3,3′-dithiodipropionic acid and 3,3′-thiodipropionic acid

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