38628-51-2Relevant articles and documents
Photoinduced Hydrocarboxylation via Thiol-Catalyzed Delivery of Formate across Activated Alkenes
Alektiar, Sara N.,Wickens, Zachary K.
supporting information, p. 13022 - 13028 (2021/09/03)
Herein we disclose a new photochemical process to prepare carboxylic acids from formate salts and alkenes. This redox-neutral hydrocarboxylation proceeds in high yields across diverse functionalized alkene substrates with excellent regioselectivity. This operationally simple procedure can be readily scaled in batch at low photocatalyst loading (0.01% photocatalyst). Furthermore, this new reaction can leverage commercially available formate carbon isotologues to enable the direct synthesis of isotopically labeled carboxylic acids. Mechanistic studies support the working model involving a thiol-catalyzed radical chain process wherein the atoms from formate are delivered across the alkene substrate via CO2?- as a key reactive intermediate.
Preparation method of organic carboxylic acid
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Paragraph 0050-0052, (2019/10/15)
The invention discloses a preparation method of organic carboxylic acid. The preparation method comprises the following steps that catalysts, olefins, water and solvents are added into a reaction container; CO is introduced; heating reaction is performed; after the reaction completion, separation is performed to obtain organic carboxylic acid; the catalysts comprise transition metal catalysts, ligands and catalysis assistants; the catalysis assistants comprise Lewis acid salt. The preparation method has the advantages that the dependency on protonic acid in the prior art is avoided; the Lewisacid salt is used as the catalysis assistant, so that the corrosion of a reaction system on equipment can be effectively prevented; the requirements on equipment are lowered. The preparation method has excellent substrate practicability; the operation steps are simple and fast; the reaction conditions are mild and are easy to control; the raw materials are cheap and can be easily obtained; the product yield and the product purity are high; the preparation method is suitable for large-scale industrial production; the normal/iso ratio of reaction products can be regulated and controlled throughthe catalysis assistants; the defects of regulating and controlling the normal/iso ratio of the reaction products by traditional phosphine ligands are overcome; the reaction progress of the reaction is simplified; the cost is favorably reduced.
Synthesis of Am80 (tamibarotene) prodrug candidates, congeners and metabolites
Muratake, Hideaki,Amano, Yohei,Toda, Takahiro,Sugiyama, Kiyoshi,Shudo
, p. 846 - 852 (2013/09/12)
Compound 1 (IT-M-07000) was previously reported as a candidate prodrug of Am80 (Tamibarotene; used to treat acute promyelocytic leukemia), and shown to be efficiently metabolized to Am80 via β-oxidation. Here, we describe in detail the synthesis of 1, together with another tetradeuterated candidate prodrug, IT-YA-00616 (2), as well as two congeners, and several metabolic intermediates of 1 previously detected in mouse plasma.
Control of interpenetration and gas-sorption properties of metal-organic frameworks by a simple change in ligand design
Prasad, Thazhe Kootteri,Suh, Myunghyun Paik
supporting information; experimental part, p. 8673 - 8680 (2012/08/28)
In metal-organic framework (MOF) chemistry, interpenetration greatly affects the gas-sorption properties. However, there is a lack of a systematic study on how to control the interpenetration and whether the interpenetration enhances gas uptake capacities or not. Herein, we report an example of interpenetration that is simply controlled by the presence of a carbon-carbon double or single bond in identical organic building blocks, and provide a comparison of gas-sorption properties for these similar frameworks, which differ only in their degree of interpenetration. Noninterpenetrated (SNU-70) and doubly interpenetrated (SNU-71) cubic nets were prepared by a solvothermal reaction of [Zn(NO3)2]·6 H2O in N,N-diethylformamide (DEF) with 4-(2-carboxyvinyl)benzoic acid and 4-(2-carboxyethyl)benzoic acid, respectively. They have almost-identical structures, but the noninterpenetrated framework has a much bigger pore size (ca. 9.0×9.0 A) than the interpenetrated framework (ca. 2.5×2.5 A). Activation of the MOFs by using supercritical CO 2 gave SNU-70' and SNU-71'. The simulation of the PXRD pattern of SNU-71' indicates the rearrangement of the interpenetrated networks on guest removal, which increases pore size. SNU-70' has a Brunauer-Emmett-Teller (BET) surface area of 5290 m2 g-1, which is the highest value reported to date for a MOF with a cubic-net structure, whereas SNU-71' has a BET surface area of 1770 m2 g-1. In general, noninterpenetrated SNU-70' exhibits much higher gas-adsorption capacities than interpenetrated SNU-71' at high pressures, regardless of the temperature. However, at P2 at 77 K and CO2 at 195 K are higher for noninterpenetrated SNU-70' than for interpenetrated SNU-71', but the capacities for H2 and CH4 are the opposite; SNU-71' has higher uptake capacities than SNU-70' due to the higher isosteric heat of gas adsorption that results from the smaller pores. In particular, SNU-70' has exceptionally high H2 and CO2 uptake capacities. By using a post-synthetic method, the C=C double bond in SNU-70 was quantitatively brominated at room temperature, and the MOF still showed very high porosity (BET surface area of 2285 m2 g -1). Copyright
