3588-17-8

Usage

Uses

Used in Occupational Health Monitoring:
trans,trans-Muconic acid is used as a biomarker for assessing the exposure levels of workers to benzene, a hazardous chemical substance. This helps in monitoring the health risks associated with benzene exposure and ensuring the safety of workers in various industries.

Purification Methods

Crystallise the diacid from H2O. [Beilstein 2 IV 2298.]

InChI:InChI=1/C6H6O4/c7-5(8)3-1-2-4-6(9)10/h1-4H,(H,7,8)(H,9,10)/p-2/b3-1+,4-2+

Upstream product

• 110-86-1 pyridine 
• 131543-46-9 Glyoxal 
• 141-82-2 malonic acid 
• 67969-40-8 (2E,4E)-6-oxohepta-2,4-dienal 
• 18409-46-6 (E,E)-muconaldehyde 
• 1119-43-3 (E,E)-hexa-2,4-dienedioic acid dimethyl ester 
• 869-10-3 diethyl 2,5-dibromoadipate 
• 60-29-7 diethyl ether 
• 62-53-3 aniline 
• 623-47-2 propynoic acid ethyl ester 
• 141-05-9 Diethyl maleate 
• 120-80-9 benzene-1,2-diol 
• 623-91-6 diethyl Fumarate 
• 159026-02-5 7-oxo-octa-2,4-dienedioic acid 

Downstream Products

• 6032-74-2 diethyl (2E,4E)-2,4-hexadienedioate 
• 1441-57-2 diethylmuconate 
• 526-99-8 meso-galactaric acid 
• 87-73-0 DL-idaric acid 
• 4436-74-2 hex-3-ene-1,6-dicarboxylic acid 
• 65682-02-2 (2E,4E)-1,6-diphenyl-2,4-hexadiene-1,6-dione 
• 14032-80-5 1-oxo-1-phenyl-hexadien-(2t.4t)-oic acid-⁽⁶⁾ 
• 98461-40-6 hexa-2,4-dienedioic acid dimenthyl ester 
• 107412-24-8 5-formyl-cyclohex-2-ene-1,4-dicarboxylic acid diethyl ester 
• 96581-72-5 hexa-2t,4t-dienedioic acid dibenzhydryl ester 
• 6154-11-6 trans-trans-Muconsaeure-diphenylester 
• 133-37-9 DL-tartaric acid 
• 144-62-7 oxalic acid 
• 64-18-6 formic acid 

Relevant academic research and scientific papers

Molecular design and polymer structure control based on polymer crystal engineering. Topochemical polymerization of 1,3-diene mono- and dicarboxylic acid derivatives bearing a naphthylmethylammonium group as the countercation

The topochemical polymerization of the alkylammonium salts of (Z,Z)-, (E,Z)-, and (E,E)-1,3-diene mono- or dicarboxylic acids, i.e., of the muconic and sorbic acid derivatives, is described from the viewpoint of polymer crystal engineering. Not only the (Z,Z)- but also the (E,E)-derivatives polymerize to give a high molecular weight polymer in the crystalline state under UV irradiation when a naphthylmethylammonium moiety is introduced to these monomers as the countercation. NMR spectroscopy confirms the formation of the stereoregular meso- or erythro-diisotactic-trans-2,5-polymer during the polymerization, irrespective of the configuration of the monomers and the structure of the substituents. The single-crystal structure analysis of the naphthylmethylammonium salt of sorbic acid reveals the stacking of the diene moieties in the columns formed in the crystals, favorable for the topochemical polymerization. The photopolymerization reactivity and the stereochemistry of the resulting polymers are determined by the molecular packing in the crystals during the topochemical polymerization of the diene monomers.

Copper and iron hydroxides as new catalysts for redox reactions in aqueous solutions

Supported or colloidal CuII and FeIII hydroxides catalyse the oxidation of catechol to a muconic acid derivative and of benzene to phenol in aqueous hydrogen peroxide solutions at ambient temperature.

Muconic acid production from methane using rationally-engineered methanotrophic biocatalysts

Here, we demonstrate bioconversion of methane to muconic acid, a dicarboxylic acid that can be upgraded to an array of platform chemicals, by three gammaproteobacterial methanotrophs. All engineered methanotrophs expressing a heterologous dihydroxyshikimate dehydratase, protocatechuate decarboxylase, and catechol dioxygenase produced muconic acid from methane, with the highest titer (12.4 mg MA per L), yield (2.8 mg MA per g CH4), and specific productivity (1.2 mg MA per g dcw, 48 hr) synthesized by Methylotuvimicrobium buryatense, Methylococcus capsulatus, and Methylotuvimicrobium alcaliphilium, respectively. Methylotuvimicrobium alcaliphilum genome-scale model-guided strain engineering predicted that disruption of the pyruvate dehydrogenase or shikimate dehydrogenase would significantly enhance flux to the heterologous muconic acid pathway in this organism. However, knock-out of these targets caused a growth defect, and coupled with similar muconic acid titers (～1 mg L-1), resulted in minimal flux enhancement to muconic acid in these genetically-modified strains. The shikimate dehydrogenase mutant's ability to grow without aromatic amino acid supplementation revealed that M. alcaliphilum likely encodes an unidentified enzyme or pathway with shikimate biosynthetic capacity, which prevents maximal flux through the synthetic muconic acid pathway. This study expands the suite of products that can be generated from methane using methanotrophic biocatalysts, lays the foundation for green production of muconic acid-derived polymers from methane, and highlights the need for further analysis of methanotroph biosynthetic potential to guide refinement of metabolic models and strain engineering.

N,N,O-Coordinated tricarbonylrhenium precatalysts for the aerobic deoxydehydration of diols and polyols

Rhenium complexes are well known catalysts for the deoxydehydration (DODH) of vicinal diols (glycols). In this work, we report on the DODH of diols and biomass-derived polyols using L4Re(CO)3as precatalyst (L4Re(CO)3= tricarbonylrhenium 2,4-di-tert-butyl-6-(((2-(dimethylamino)ethyl)(methyl)amino)methyl)phenolate). The DODH reaction was optimized using 2 mol% of L4Re(CO)3as precatalyst and 3-octanol as both reductant and solvent under aerobic conditions, generating the active high-valent rhenium speciesin situ. Both diol and biomass-based polyol substrates could be applied in this system to form the corresponding olefins with moderate to high yield. Typical features of this aerobic DODH system include a low tendency for the isomerization of aliphatic external olefin products to internal olefins, a high butadiene selectivity in the DODH of erythritol, the preferential formation of 2-vinylfuran from sugar substrates, and an overall low precatalyst loading. Several of these features indicate the formation of an active species that is different from the species formed in DODH by rhenium-trioxo catalysts. Overall, the bench-top stable and synthetically easily accessible, low-valent NNO-rhenium complex L4Re(CO)3represents an interesting alternative to high-valent rhenium catalysts in DODH chemistry.

Solvent-driven isomerization of: cis, cis -muconic acid for the production of specialty and performance-advantaged cyclic biobased monomers

The quest for green plastics calls for new routes to aromatic monomers using biomass as a feedstock. Suitable feedstock molecules and conversion pathways have already been identified for several commodity aromatics through retrosynthetic analysis. However, this approach suffers from some limitations as it targets a single molecule at a time. A more impactful approach would be to target bioprivileged molecules that are intermediates to an array of commodity and specialty chemicals along with novel compounds. Muconic acid (MA) has recently been identified as a bioprivileged intermediate as it gives access to valuable aliphatic and cyclic diacid monomers including terephthalic acid (TPA), 1,4-cyclohexanedicarboxylic acid (CHDA), and novel monounsaturated 1,4-cyclohexenedicarboxylic acids (CH1DA, CH2DA). However, accessing these cyclic monomers from MA requires to first isomerize biologically-produced cis,cis-MA to Diels-Alder active trans,trans-MA. A major impediment in this isomerization is the irreversible ring closing of MA to produce lactones. Herein, we demonstrate a green solvent-mediated isomerization using dimethyl sulfoxide and water. The mechanistic understanding achieved here elucidates the role of low concentrations of water in reducing the acidity of the system, thereby preventing the formation of lactones and improving the selectivity to trans,trans-MA from less than 5% to over 85%. Finally, a Diels-Alder reaction with trans,trans-MA is demonstrated with ethylene. The monounsaturated cyclic diacid obtained through this reaction (CH1DA) can be converted in a single step into TPA and CHDA, or can be directly copolymerized with adipic acid and hexamethylenediamine to tailor the thermal and mechanical properties of conventional Nylon 6,6.

Preparation method of gamma-substituted hexadienoic acid

The invention relates to a preparation method of gamma-substituted hexadienoic acid. The method is characterized by comprising the following steps: (1) at -10-40 DEG C, adding a solvent, a catalyst and a catalytic assistant into a reaction vessel, stirring, introducing oxygen, adding 1-(2-furyl)-1-alkyl methanol, controlling the molar ratio of the catalyst to the catalytic assistant to the 1-(2-furyl)-1-alkyl methanol at 0.0001-5:0.0001-3:100, reacting at 0-200 DEG C under 0.1-20 MPa for 1-74 h, wherein the solvent is a mixed solution composed of a water phase and an organic phase according toa volume ratio of 1:0.01-3, the water phase is a phosphate acidic solution, the organic phase is a reaction inert solvent, the catalyst is a palladium compound, and the catalytic assistant is an amine or phosphine compound; and (2) cooling the reaction vessel to room temperature, adding an organic solvent, extracting, and carrying out reduced pressure distillation on the organic phase. The methodhas the advantages that the defect of technical economy in an existing synthesis route is overcome, the technological process is simplified, consumption and emission are reduced, energy consumption and cost are reduced, and the method is suitable for industrial production for increasing productivity.

POLYMERS FROM MUCONIC ACID ISOMERS AND ITS DERIVATIVES

This invention relates to a process for preparing succinic acid and succinate ester from a succinic acid salt in fermentation broth. In the first stage of this invention, renewable carbon resources are utilized to produce succinic acid through biological fermentation. The succinic acid salt in the fermentation process is subjected to double displacement reaction with a strong acid leading to release of succinic acid. Succinic acid is recovered by fractional crystallization integrated with simulated moving bed chromatography to produce succinic acid and succinate ester.

Ionic liquid-mediated deoxydehydration reactions: Green synthetic process for bio-based adipic acid

A novel recyclable Re-catalyzed deoxydehydration (DODH) reaction was developed with an ionic liquid (IL) as a reaction medium for an efficient synthesis of adipic acid (1), one of the commercially important dicarboxylic acids, from biomass galactaric acid. The carefully designed solubility of ILs allowed a homogeneous DODH reaction to produce muconate 3 in excellent yields, a key intermediate for 1. Use of the IL also enabled an efficient separation of the DODH product 3 from the reaction mixture by simple decantation. The recovered IL layer containing the expensive Re catalyst was reused up to four times, yielding 3 without much decrease in yields. The target compound 1 was also produced in an excellent yield with the catalytic hydrogenation of 3 followed by the acidic hydrolysis. Thus, the overall process for bio-based adipic acid would become much more cost-effective, eco-friendly, and industrially viable, which could be applied to various biomass conversions.

Synthesis of SiO2 coated zero-valent iron/palladium bimetallic nanoparticles and their application in a nano-biological combined system for 2,2′,4,4′-tetrabromodiphenyl ether degradation

Polybrominated diphenyl ethers (PBDEs) are emerging persistent organic pollutants and the degradation of PBDEs is still a significant challenge owing to their extreme persistence and toxicity. In this study, the remediation of 2,2′,4,4′-tetrabromodiphenyl ether (BDE47) was investigated by employing a nano-biological combined system with SiO2-coated zero-valent iron/palladium bimetallic nanoparticles (SiO2-nZVI/Pd) as a reductant and Pseudomonas putida as a biocatalyst. The SiO2-nZVI/Pd exhibited much lower toxicity to the P. putida strain and higher reactivity in debromination than nZVI/Pd. The strain could grow well when the dosage was up to 1.0 g L-1. During the combined process, BDE47 (5 mg L-1) was completely debrominated to diphenyl ether (DE) within 2 h by SiO2-nZVI/Pd (1.0 g L-1) and then DE was completely degraded by P. putida after 4 days in sequential aerobic biodegradation. All the possible intermediates in the whole process were identified by ultra performance liquid chromatography (UPLC) and gas chromatography-mass spectrometer (GC-MS) analyses. The detection of BDE17, BDE7, BDE1 and DE indicated that rapidly stepwise debromination preferentially occurred at para positions in the anaerobic stage. Moreover, during aerobic biodegradation by P. putida, a number of phenolic compounds, such as phenol, catechol and hydroquinone were generated via ring opening by dioxygenation and further mineralized through the tricarboxylic acid cycle (TCA). Importantly, this combined process achieved rapid mineralization of PBDEs and avoided the generation of some highly toxic products like bromophenols and HO-PBDEs, which might have promising application prospects in the remediation of halogenated POPs.

Ostopanic acid analogues and its preparation method and use

The invention relates to ostopanic acid, ostopanic acid analogues and their preparation method and use. The preparation method provided by the invention is characterized in that based on a characteristic that the reaction of a Weinreb amide and a Grignard reagent can selectively stay in a ketone stage so that the overreaction is avoided, two side chains of the ostopanic acid analogue can be constructed and thus a series of the ostopanic acid analogues can be synthesized fast. The preparation method provided by the invention adopts easily acquired raw materials, allows mild reaction conditions and has simple processes. The ostopanic acid and the ostopanic acid analogues obtained by the preparation method have obvious antitumor effects.