118316-02-2

Upstream product

• 79-21-0 peracetic acid 
• 64-19-7 acetic acid 
• 135-02-4 ortho-anisaldehyde 
• 25891-31-0 triformylamine 
• 90-05-1 2-methoxy-phenol 
• 90-02-8 salicylaldehyde 
• 18181-71-0 2-(2-methoxyphenoxy)ethanol 
• 203312-21-4 1-(4-ethoxy-3-methoxyphenyl)-2-(2-methoxy-phenoxy)propan-1,3-diol 
• 19513-80-5 2-(2-methoxyphenoxy)-1-(4-methoxyphenyl)ethan-1-one 
• 64-18-6 formic acid 
• 556-63-8 lithium formate 
• 100-66-3 methoxybenzene 
• 10535-17-8 1-(3,4-dimethoxyphenyl)-2-(methoxyphenoxy)propane-1,3-diol 
• 186581-53-3 diazomethane 

Downstream Products

• 90-05-1 2-methoxy-phenol 
• 940089-19-0 2-methoxyphenyl 2-methoxybenzoate 
• 6833-21-2 2-methoxy-N-phenylbenzamide 
• 1185237-14-2 3-benzylidene-5-(2-methoxyphenyl)furan-2(3H)-one 
• 2880-58-2 2-methoxy-1,4-benzoquinone 
• 121-33-5 vanillin 

Relevant academic research and scientific papers

Baeyer-Villiger oxidation of aromatic aldehydes catalysed by zirconium phosphates intercalated with ionic liquids

Crystalline α-zirconium phosphate intercalated with 1-ethyl-3-methylimidazolium chloride or 1-hexyl-3-methylimidazolium chloride, and crystalline γ-zirconium phosphate intercalated with 1-ethyl-3-methylimidazolium chloride were synthesised, characterized and evaluated as selective catalysts in the Baeyer-Villiger oxidation of p-methoxybenzaldehyde, o-methoxybenzaldehyde and 2,4,6-trimethylbenzaldehyde by hydrogen peroxide, in glacial acetic acid or without solvent. The best selectivities of p-methoxyphenol (100 %), o-methoxyphenol (95 %) and 2,4,6-trimethylphenol (55 %) were achieved without solvent and are explained by the properties and structure of each catalyst.

Urchin-like Nb2O5 hollow microspheres enabling efficient and selective photocatalytic C–C bond cleavage in lignin models under ambient conditions

Selective cleavage of robust C?C bonds to harvest value-added aromatic oxygenates is an intriguing but challenging task in lignin depolymerization. Photocatalysis is a promising technology with the advantages of mild reaction conditions and strong sustainability. Herein, we show a novel urchin-like Nb2O5 hollow microsphere (U-Nb2O5 HM), prepared by one-pot hydrothermal method, are highly active and selective for Cα?Cβ bond cleavage of lignin β-O-4 model compounds under mild conditions, achieving 94% substrate conversion and 96% C?C bond cleavage selectivity. Systematic experimental studies and density functional theory (DFT) calculations revealed that the superior performance of U-Nb2O5 HMs arises from more exposed active sites, more efficient free charge separation and the active (001) facet, which facilitates the activation of Cβ?H bond of lignin models and generate key Cβ radical intermediates by photogenerated holes, further inducing the Cα?Cβ bond cleavage to produce aromatic oxygenates. This work could provide some suggestions for the fabrication of hierarchical photocatalysts in the lignin depolymerization system.

Visible-light-induced oxidative lignin c-c bond cleavage to aldehydes using vanadium catalysts

Lignin is the largest carrier of aromatics on earth, and its depolymerization can afford value-Added aromatic products. Direct cleavage of the C-C bonds in lignin linkages is significant, but it is challenging to obtain low-molecular-weight aromatic monomers. Herein, using vanadium catalysts under visible light, we selectively cleave the C-C bonds in β-1 and β-O-4 interlinkages occluded in lignin models and extracts by an oxidative protocol. Visible light irradiation triggered single electron transfer between the substrate and the catalyst, which further induced the selective Cα-Cβ bond cleavage and generated the final aromatic products through radical intermediates. Using this photocatalytic chemistry, the reactivity of lignin models and the selectivity of Cα-Cβ bond cleavage were significantly improved. More importantly, this protocol affords aromatic monomers through the fragmentation of organosolv lignins even at room temperature, indicating the potential of photocatalytic C-C bond cleavage of lignin linkages under ambient conditions.

The formyloxyl radical: Electrophilicity, C-H bond activation and anti-Markovnikov selectivity in the oxidation of aliphatic alkenes

In the past the formyloxyl radical, HC(O)O, had only been rarely experimentally observed, and those studies were theoretical-spectroscopic in the context of electronic structure. The absence of a convenient method for the preparation of the formyloxyl radical has precluded investigations into its reactivity towards organic substrates. Very recently, we discovered that HC(O)O is formed in the anodic electrochemical oxidation of formic acid/lithium formate. Using a [CoIIIW12O40]5- polyanion catalyst, this led to the formation of phenyl formate from benzene. Here, we present our studies into the reactivity of electrochemically in situ generated HC(O)O with organic substrates. Reactions with benzene and a selection of substituted derivatives showed that HC(O)O is mildly electrophilic according to both experimentally and computationally derived Hammett linear free energy relationships. The reactions of HC(O)O with terminal alkenes significantly favor anti-Markovnikov oxidations yielding the corresponding aldehyde as the major product as well as further oxidation products. Analysis of plausible reaction pathways using 1-hexene as a representative substrate favored the likelihood of hydrogen abstraction from the allylic C-H bond forming a hexallyl radical followed by strongly preferred further attack of a second HC(O)O radical at the C1 position. Further oxidation products are surmised to be mostly a result of two consecutive addition reactions of HC(O)O to the CC double bond. An outer-sphere electron transfer between the formyloxyl radical donor and the [CoIIIW12O40]5- polyanion acceptor forming a donor-acceptor [D+-A-] complex is proposed to induce the observed anti-Markovnikov selectivity. Finally, the overall reactivity of HC(O)O towards hydrogen abstraction was evaluated using additional substrates. Alkanes were only slightly reactive, while the reactions of alkylarenes showed that aromatic substitution on the ring competes with C-H bond activation at the benzylic position. C-H bonds with bond dissociation energies (BDE) ≤ 85 kcal mol-1 are easily attacked by HC(O)O and reactivity appears to be significant for C-H bonds with a BDE of up to 90 kcal mol-1. In summary, this research identifies the reactivity of HC(O)O towards radical electrophilic substitution of arenes, anti-Markovnikov type oxidation of terminal alkenes, and indirectly defines the activity of HC(O)O towards C-H bond activation.

Amine-Mediated Bond Cleavage in Oxidized Lignin Models

Introducing amines/ammonia into lignin cracking will allow novel bond cleavage pathways. Herein, a method of amines/ammonia-mediated bond cleavage in oxidized lignin β-O-4 models was studied using a copper catalyst at room temperature, demonstrating the effect of the amine source on the selectivity of products. For primary and secondary aliphatic amines, lignin ketone models underwent oxidative Cα?Cβ bond cleavage and Cα?N bond formation to generate aromatic amides. For ammonia, the competition between oxygen and ammonia determined the selectivity between Cα?N and Cβ?N bond formation, generating amides and α-keto amides, respectively. For tertiary amines, the lignin models underwent oxidative Cα?Cβ bond cleavage to benzoic acids. Control experiments indicated that amines act as nucleophiles attacking at the Cα or Cβ position of the oxidized β-O-4 linkage to be cleaved. This study represents a novel example that the breakage of oxidized lignin model can be regulated by amines with a copper catalyst.

Kinetics and DFT Studies of Photoredox Carbon-Carbon Bond Cleavage Reactions by Molecular Vanadium Catalysts under Ambient Conditions

Visible light assisted photocatalytic organic reactions have recently received intense attention as a versatile approach to achieve selective chemical transformations, including C-C and several C-X (X = N, O, S) bond formations under mild reaction conditions. The light harvesters in previous reports predominantly comprise ruthenium or iridium photosensitizers. In contrast, selective, photocatalytic aliphatic C-C bond cleavage reactions are scarce. The present study focuses on rationally designing VV oxo complexes as molecular, photoredox catalysts toward the selective activation and cleavage of a C-C bond adjacent to the alcohol group in aliphatic alcoholic substrates. We have employed kinetics measurements and DFT calculations to develop a candidate for the catalytic C-C bond activation reaction that is up to 7 times faster than our original vanadium complex. We have also identified a substrate where the C-C bond cleaves at rates 2.5-17 times faster, depending on the catalyst used. In order to better understand the effects of ligand modification on the thermodynamics and catalysis, DFT calculations were employed to reveal the orbital energies, the electronic transitions during the C-C bond cleavage, and the activation barriers. Our combined kinetics and computational studies indicate that the incorporation of electron-withdrawing groups at select sites of the ligand is essential for the development of active and stable vanadium photocatalysts for our C-C bond cleavage reactions.

SELECTIVE CARBON-CARBON BOND CLEAVAGE BY EARTH ABUNDANT VANADIUM COMPOUNDS UNDER VISIBLE LIGHT PHOTOCATALYSIS

Provided herein a vanadium(V) complex of formula I, where R1 to R8 are as defined herein. Also provided herein are reactions making use of the vanadium(V) complex of formula I, such as selective sp3-sp3 carbon-carbon bond cleavage under visible light photocatalysis and photodegradation of lignin.

Selective photocatalytic C-C bond cleavage under ambient conditions with earth abundant vanadium complexes

Selective C-C bond cleavage under ambient conditions is a challenging chemical transformation that can be a valuable tool for organic syntheses and macromolecular disassembly. Herein, we show that base metal vanadium photocatalysts can harvest visible light to effect the chemoselective C-C bond cleavage of lignin model compounds under ambient conditions. Lignin, a major aromatic constituent of non-food biomass, is an inexpensive, accessible source of fine chemical feedstocks such as phenols and aryl ethers. However, existing lignin degradation technologies are harsh and indiscriminately degrade valuable functional groups to produce intractable mixtures. The selective, photocatalytic depolymerization of lignin remains underexplored. In the course of our studies on lignin model compounds, we have uncovered a new C-C activation reaction that takes place under exceptionally mild conditions with high conversions. We present our fundamental studies on representative lignin model compounds, with the aim of expanding and generalizing the substrate scope in the future. Visible light is employed in the presence of earth-abundant vanadium oxo catalysts under ambient conditions. Selective C-C bond cleavage leads to valuable and functionally rich fine chemicals such as substituted aryl aldehydes and formates. Isotope labeling experiments, product analyses, and intermediate radical trapping, together with density functional theory studies, suggest a unique pathway that involves a photogenerated T1 state during the C-C bond cleavage reactions. Our study demonstrates a sustainable approach to harvest sunlight for an unusual, selective bond activation, which can potentially be applied in organic transformations and biomass valorization.

ALDEHYDE CONVERSION METHOD USING A MOLECULAR SIEVE AND THE USE OF THE MOLECULAR SIEVE AS A CATALYST IN SAID METHOD

The inversion relates to an aldehyde conversion method comprising putting an aldehyde into contact with oxygenated water and with a catalyst, under oxidation conditions, wherein the catalyst is a molecular sieve with pores of a diameter of at least 0.52 nm and has an empirical formula in a calcined and dehydrated form of(SnxTiySi1-x-y-zGez) O2 wherein x is a molar fraction of the tin and has a value between 0.001 and 0.1; y is a molar fraction of titanium and has a value from zero to 0.1; and z is the molar fraction molar of the germanium and has a value from zero to 0.08.

Orthoamides, LVI [1]. A new method of wide scope for the preparation of aryl formates

Aryl formates 4a-u, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26 are prepared by formylation of hydroxyarenes 3a-u, 5, 7, 9, 11, 13, 15, 17, 19, 21, 23, 25 with N,N-diformylacetamide (1) or triformamide (2), respectively, in fairly good yields. The reactions can be catalyzed by sodium diformamide or praseodymium(III) triflate. The thiolformate 28 was obtained analogously from 1-thionaphthol (27).