56980-32-6

Upstream product

• 146780-46-3 2-(3-Methyl-cyclohex-3-enyl)-[1,3]dioxolane 
• 107-02-8 acrolein 
• 78-79-5 isoprene 
• 146780-45-2 2-(3-Methyl-4-phenylsulfanyl-cyclohex-3-enyl)-[1,3]dioxolane 
• 146780-44-1 3-Methyl-4-phenylsulfanyl-cyclohex-3-enecarbaldehyde 

Downstream Products

• 117015-83-5 2-Brom-1-methoxy-5-dimethoxymethyl-1-methyl-cyclohexan 
• 117015-82-4 2-Brom-1-methoxy-4-dimethoxymethyl-1-methyl-cyclohexan 
• 117015-88-0 (3R,4R)-4-Bromo-3-methoxy-3-methyl-cyclohexanecarboxylic acid methyl ester 
• 115664-07-8 3-Brom-4-methoxy-4-methyl-cyclohexan-1-carbonsaeuremethylester 
• 54385-25-0 (+/-)-3-methylcyclohex-3-ene-1-carboxylic acid 
• 6493-78-3 3-methyl-3-cyclohexene-1-carboxylic acid methyl ester 

Relevant academic research and scientific papers

Selective production of bio-based: Para -xylene over an FeOx -modified Pd/Al2O3catalyst

para-Xylene (PX) is a basic building block of polyethylene terephthalate, which is currently produced from petroleum resources. Developing a renewable route to PX is highly desirable to address both economic and environmental concerns. Several attempts used noble metal catalysts, e.g. Pd/Al2O3, to synthesize PX from biomass-derived 4-methyl-3-cyclohexene-1-carboxaldehyde (4-MCHCA), but suffered from a severe decarbonylation reaction, resulting in toluene as the main product. In this paper, we report an FeOx modification strategy to suppress the decarbonylation reaction on a Pd/Al2O3 catalyst, leading to a drastic shift in selectivity towards PX with a yield up to 81percent via a cascade dehydroaromatization-hydrodeoxygenation (DHA-HDO) pathway. Characterization and control experiments revealed that the electron density of Pd sites decreased in an FeOx-modified Pd/Al2O3 catalyst compared to Pd/Al2O3, thus tuning the preferential adsorption mode of the substrate from η2-(C,O), the key transition state of the decarbonylation reaction, to the η1-(O) mode that favors the hydrodeoxygenation process. Notably, this designed catalyst is highly stable and is readily applicable in the selective synthesis of a broad range of desired aromatic chemicals via the same DHA-HDO pathway from cyclohex-3-enecarbaldehyde derivatives. Overall, this work develops a controllable catalyst modification strategy that tailors an efficient catalyst for petroleum-independent bio-PX synthesis.

Selective Production of Renewable para-Xylene by Tungsten Carbide Catalyzed Atom-Economic Cascade Reactions

Tungsten carbide was employed as the catalyst in an atom-economic and renewable synthesis of para-xylene with excellent selectivity and yield from 4-methyl-3-cyclohexene-1-carbonylaldehyde (4-MCHCA). This intermediate is the product of the Diels–Alder reaction between the two readily available bio-based building blocks acrolein and isoprene. Our results suggest that 4-MCHCA undergoes a novel dehydroaromatization–hydrodeoxygenation cascade process by intramolecular hydrogen transfer that does not involve an external hydrogen source, and that the hydrodeoxygenation occurs through the direct dissociation of the C=O bond on the W2C surface. Notably, this process is readily applicable to the synthesis of various (multi)methylated arenes from bio-based building blocks, thus potentially providing a petroleum-independent solution to valuable aromatic compounds.

Selective Production of Toluene from Biomass-Derived Isoprene and Acrolein

Toluene is a basic chemical that is currently produced from petroleum resources. In this paper, we report a new route for the effective synthesis of toluene from isoprene and acrolein, two reactants readily available from biomass, through a simple two-step reaction. The process includes Diels–Alder cycloaddition of isoprene and acrolein in a Zn-containing ionic liquid at room temperature to produce methylcyclohex-3-enecarbaldehydes (MCHCAs) as intermediates, followed by M (M=Pt, Pd, Rh)/Al2O3-catalyzed consecutive dehydrogenation–decarbonylation of the MCHCAs at 573 K to generate toluene with an overall yield up to 90.7 %. Model reactions indicated that a synergistic inductive effect of the C=C double bond and the aldehyde group in MCHCA plays a key role in initiating the consecutive dehydrogenation–decarbonylation, and that methyl benzaldehydes are the key intermediates in the gas-phase transformation of MCHCAs. Microcalorimetric adsorption of CO on different catalysts showed that decarbonylation of the substrate occurs more likely on the strong adsorption sites. To the best of our knowledge, it is the first report of Pt/Al2O3-catalyzed consecutive dehydrogenation–decarbonylation of a given compound in one reactor. This work provides a highly efficient and environmental friendly route to toluene by utilizing two compounds that can be prepared from biomass.

Impact of carbon dioxide pressurization on liquid phase organic reactions: A case study on Heck and Diels-Alder reactions

Heck coupling reactions of methyl acrylate with various aryl bromides have been investigated using a Pd/TPP catalyst in toluene under pressurized CO 2 conditions up to 13 MPa. Although CO2 is not a reactant, the pressurization of the reaction liquid phase with CO2 has positive and negative impacts on the rate of Heck coupling depending on the structures of the substrates examined. In the case of either 2-bromoacetophenone or 2-bromocinnamate, the conversion has a maximum at a CO2 pressure of about 3 MPa; for the former, it is much larger by a factor of 3 compared with that under ambient pressure. For 2-bromobenzene, in contrast, the conversion is minimized at a similar CO2 pressure, being half compared with that at ambient pressure. In the other substrates, including the other isomers of these three aryl bromides, the conversion simply decreases or does not change so much with the CO2 pressure. To examine the factors responsible for the effects of CO2 pressurization, the phase behavior and the molecular interactions with dense phase CO2 have also been studied by visual observation and in situ high pressure FT-IR spectroscopy. In addition, impact of CO2 pressurization was also studied for the Diels-Alder reactions of isoprene with a few dienophiles like methyl acrylate, methyl vinyl ketone, and acrolein in the same solvent, toluene, but a heterogeneous silica-alumina catalyst was used (the reaction system was liquid-solid biphasic). When the CO2 pressure is raised, the conversion monotonously decreases for the three dienophiles; however, the product selectivity changes with the pressure, in particular for acrolein. The FT-IR spectroscopic measurements suggest that its reactivity is altered by interactions with CO2 molecules under pressurized conditions.

Ionic liquids and their use

Ionic compounds having a freezing point of no more than 50° C., formed by the reaction of at least one amine salt of the formula R1R2R3R4N+X? (I) with at least one hydrated salt, which is a chloride, nitrate, sulphate or acetate of Li, Mg, Ca, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Pb, Bi, La or Ce; wherein R1, R2 and R3 are each independently a C1 to C5 alkyl or a C6 to C10 cycloalkyl group, or wherein R2 and R3 taken together represent a C4 to C10 alkylene group, thereby forming with the N atom of formula (I) a 5 to 11 membered heterocyclic ring, and wherein R4 is hydrogen, or phenyl, or C1 to C12 alkyl or cycloalkyl group, optionally substituted with at least one group selected from OH, Cl, Br, F, I, phenyl, NH2, CN, NO2, COOR5, CHO, COR5 and OR5, wherein R5 is a C1 to C10 alkyl or cycloalkyl group, and X? is an anion capable of being complexed by the said hydrated salt. The compounds are useful as solvents, electrolytes, and catalysts, and have particular application in solvents/electrolytes for metal plating and electropolishing processes, in particular in chromium plating.

A cationic palladium(II) complex-catalyzed diels-alder reaction

A cationic palladium(II) complex, [PdL2(RCN)2](BF4)2, has been found to catalyze the Diels-Alder reaction of α, β-unsaturated carbonyl compounds with dienes, affording the corresponding cycloadducts in good yields. Excellent enanlioselectivity can be achieved in the reaction of N- acryloyloxazolidinone and cyclopentadiene by use of a chiral ligand, BINAP.

Macromolecular materials in heterogeneous catalysis: An aluminium silasesquioxane gel as active catalyst in Diels-Alder reactions of enones

A highly active, genuinely heterogeneous catalyst for liquid-phase Diels-Alder reactions of enones results from the silanol centred modification of an incompletely condensed silasesquioxane with trimethylaluminium, the resulting catalytic material being a gel that contains aluminium(III) siloxy functions (Al-O-Si) which are incorporated in a well defined, three-dimensional SiO framework.

On the role of hexafluoroisopropanol in Diels-Alder reactions of acid-sensitive reagents

1,1,1,3,3,3-Hexafluoro-2-propanol (HFIP) is described as an excellent solvent for those Diels-Alder reactions in which Lewis-acid-sensitive reagents are used, leading to high yields with good regio- and endo/exo selectivities under very mild conditions.

Diiodosamarium, a Catalyst Precursor for Diels-Alder and Hetero Diels-Alder Reactions.

SmI2 presents catalytic activity for Diels-Alder reactions between cyclopentadiene or isoprene and various dienophiles, and for hetero Diels-Alder reactions.