52251-19-1

Upstream product

• 5372-81-6 dimethyl aminoterephthalate 
• 77-78-1 dimethyl sulfate 
• 10312-55-7 3-aminoterephthalic acid 
• 1026076-51-6 1,4-dimethyl 2-(methylamino)benzene-1,4-dicarboxylate 
• 74-88-4 methyl iodide 
• 867-89-0 1-dimethylamino-1-methoxyethylene 
• 2166-24-7 pyridazine-3,6-dicarboxylic acid dimethyl ester 
• 67-56-1 methanol 
• 39617-00-0 2-(N,N-dimethylamino)terephthalic acid 

Downstream Products

• 39617-00-0 2-(N,N-dimethylamino)terephthalic acid 

Relevant academic research and scientific papers

Strong overcrowding in dimethyl 2-(dimethyl-amino)terephthalate

The mol-ecular structure of the title compound, C12H15NO4, has several features related to steric hindrance due to the ester and dimethyl-amine groups being located ortho with respect to one another. In particular, the carbonyl group of the ester is not coplanar with the ring, the amine N atom is in a pyramidal arrangement [the N atom is 0.2161 (12) A from the three C atoms to which it is bonded] and the C atom of the adjacent ester group lies 0.3784 (14) A out of the plane of the aromatic ring. The deformations found in the X-ray structure have been confirmed by ab initio quantum mechanical calculations.

Engineering Second Sphere Interactions in a Host-Guest Multicomponent Catalyst System for the Hydrogenation of Carbon Dioxide to Methanol

Many enzymes utilize interactions extending beyond the primary coordination sphere to enhance catalyst activity and/or selectivity. Such interactions could improve the efficacy of synthetic catalyst systems, but the supramolecular assemblies employed by biology to incorporate second sphere interactions are challenging to replicate in synthetic catalysts. Herein, a strategy is reported for efficiently manipulating outer-sphere influence on catalyst reactivity by modulating host-guest interactions between a noncovalently encapsulated transition-metal-based catalyst guest and a metal-organic framework (MOF) host. This composite consists of a ruthenium PNP pincer complex encapsulated in the MOF UiO-66 that is used in tandem with the zirconium oxide nodes of UiO-66 and a ruthenium PNN pincer complex to hydrogenate carbon dioxide to methanol. Due to the method used to incorporate the complexes in UiO-66, structure-activity relationships could be efficiently determined using a variety of functionalized UiO-66-X hosts. These investigations uncovered the beneficial effects of the ammonium functional group (i.e., UiO-66-NH3+). Mechanistic experiments revealed that the ammonium functionality improved efficiency in the hydrogenation of carbon dioxide to formic acid, the first step in the cascade. Isotope effects and structure-activity relationships suggested that the primary role of the ammonium functionality is to serve as a general Br?nsted acid. Importantly, the cooperative influence from the host was effective only with the functional group in close proximity to the encapsulated catalyst. Reactions carried out in the presence of molecular sieves to remove water highlighted the beneficial effects of the ammonium functional group in UiO-66-NH3+ and resulted in a 4-fold increase in activity. As a result of the modular nature of the catalyst system, the highest reported turnover number (TON) (19 ?000) and turnover frequency (TOF) (9100 h-1) for the hydrogenation of carbon dioxide to methanol are obtained. Moreover, the reaction was readily recyclable, leading to a cumulative TON of 100 ?000 after 10 reaction cycles.

PHOTO-REDOX TITANIUM CONTAINING ORGANIC FRAMEWORKS AND METHODS OF MAKING AND USE THEREOF

Disclosed herein are metal-organic frameworks and methods of making and use thereof.

Systematic variation of the optical bandgap in titanium based isoreticular metal-organic frameworks for photocatalytic reduction of CO2 under blue light

A series of metal-organic frameworks isoreticular to MIL-125-NH2 were prepared, where the 2-amino-terephthalate organic links feature N-alkyl groups of increasing chain length (from methyl to heptyl) and varying connectivity (primary and secondary). The prepared materials display reduced optical bandgaps correlated with the inductive donor ability of the alkyl substituent as well as high photocatalytic activity towards the reduction of carbon dioxide under blue illumination operating over 120 h. Secondary N-alkyl substitution (isopropyl, cyclopentyl and cyclohexyl) exhibits larger apparent quantum yields than the primary N-alkyl analogs directly related to their longer lived excited-state lifetime. In particular, MIL-125-NHCyp (Cyp = cyclopentyl) exhibits a small bandgap (Eg = 2.30 eV), a long-lived excited-state (τ = 68.8 ns) and a larger apparent quantum yield (Φapp = 1.80%) compared to the parent MIL-125-NH2 (Eg = 2.56 eV, Φapp = 0.31%, τ = 12.8 ns), making it a promising candidate for the next generation of photocatalysts for solar fuel production based on earth-abundant elements.

Charged functional group effects on a metal-organic framework for selective organic dye adsorptions

A quaternary N-alkyl ammonium salt-containing zinc-based metal-organic framework (MOF) was synthesized and tested for selective organic dye adsorption experiments. Through covalent post-synthetic modification (PSM), the tertiary amine-containing MOF was converted into a quaternary N-alkyl ammonium salt-containing MOF under solid-state methylation conditions. The positively charged MOF was found to exclusively adsorb the negatively charged organic dye, while the positively charged organic dyes were not adsorbed. This separation experiment revealed that functional group control is an important and critical factor for molecule separations using porous materials.

Synthesis of secondary and tertiary amine-containing MOFs: C-N bond cleavage during MOF synthesis

Secondary and tertiary amine-containing metal-organic frameworks (MOFs) have been synthesized, and unprecedented C-N bond cleavage phenomena were observed during MOF formation. Utilizing the secondary amine-containing ligand (BDC-NHMe), three new MOFs hav