53389-56-3

Upstream product

• 487-68-3 mesytaldehyde 
• 67-64-1 acetone 
• 4643-20-3 (E)-4-chloro-3-buten-2-one 
• 108-67-8 1,3,5-trimethyl-benzene 
• 23586-57-4 2,4,6-trimethylphenylthallium(III) trifluoroacetate 
• 1896-62-4 (E)-benzalacetone 
• 125261-32-7 2,4,6-trimethylphenyl trifluoromethanesulfonate 
• 78-94-4 methyl vinyl ketone 
• 1423-60-5 methyl ethynyl ketone 
• 576-83-0 2,4,6-trimethylphenyl bromide 
• 41106-03-0 C-mesityl-N-methylnitrone 
• 1067-71-6 Diethyl (2-oxopropyl)phosphonate 
• 1439-36-7 1-triphenylphosphoranylidene-2-propanone 
• 92035-54-6 1-(2,4,6-trimethylphenyl)-3-buten-1-ol 

Downstream Products

• 75001-23-9 5-(2,4,6-trimethylphenyl)-3-methyl-2E,4E-pentadienal 
• 95414-50-9 (2Z,4E)-5-mesityl-3-methylpenta-2,4-dienal 
• 95414-48-5 ethyl 5-mesityl-3-methyl-2,4-pentadienoate 
• 95414-47-4 ethyl 5-mesityl-3-methyl-2,4-pentadienoate 
• 88311-79-9 5-(2,4,6-trimethyl-phenyl)-cyclohexane-1,3-dione 
• 87820-88-0 tralkoxydim 

Relevant academic research and scientific papers

Preparation method of tralkoxydim

The invention discloses a method for preparing tralkoxydim. The method comprises the following steps: preparing a first intermediate from 2,4,6-trimethylbenzaldehyde and acetone; preparing a second intermediate from the first intermediate, diethyl malonate and propionyl chloride; and preparing tralkoxydim by utilizing the second intermediate and ethoxyamine, wherein in the process of preparing the second intermediate, a condensation reaction and a rearrangement reaction are carried out at the same time, and after the first intermediate is prepared and before tralkoxydim is prepared, separation or purification treatment is not carried out. According to the invention, tralkoxydim is prepared by simultaneously carrying out condensation and rearrangement reactions and not carrying out a separation or purification process in the reaction process, so the steps of multiple times of separation, purification, transfer, feeding and the like in existing preparation methods are omitted, time and labor are saved, the consumption of reagents is reduced, a large amount of cost is saved, and the problems that a tralkoxydim preparation method is complex in step, product yield is low and layering emulsification is serious in an esterification reaction process in the prior art are solved.

Stereodivergent Pd/Cu Catalysis for the Dynamic Kinetic Asymmetric Transformation of Racemic Unsymmetrical 1,3-Disubstituted Allyl Acetates

A stereodivergent Pd/Cu catalyst system has been developed for the unprecedented dynamic kinetic asymmetric transformation (DyKAT) of racemic unsymmetrical 1,3-disubstituted allylic acetates with prochiral aldimine esters. A series of α,α-disubstituted α-amino acids bearing vicinal stereocenters were easily prepared with excellent enantioselectivities (up to >99% ee) and diastereoselectivities (up to >20:1 dr). Moreover, all four stereoisomers of the product can be readily obtained simply by switching the configurations of the two chiral metal catalysts. Furthermore, the present work highlights the power of synergistic Pd/Cu catalysis consisting of two common bidentate chiral ligands for stereodivergent synthesis.

Traceless OH-Directed Wacker Oxidation-Elimination, an Alternative to Wittig Olefination/Aldol Condensation: One-Pot Synthesis of α,β-Unsaturated and Nonconjugated Ketones from Homoallyl Alcohols

A new method for one-pot synthesis of β-substituted and β,β-disubstituted α,β-unsaturated methyl ketones from homoallyl alcohols by sequential PdCl2/CrO3-promoted Wacker process followed by an acid-mediated dehydration reaction has been developed. Remarkably, internal homoallyl alcohols delivered regioselectively nonconjugated unsaturated carbonyl compounds under the same protocol. A new starting material-based synthesis of α,β-unsaturated and nonconjugated methyl ketones is demonstrated.

Copper-catalyzed retro-aldol reaction of β-hydroxy ketones or nitriles with aldehydes: Chemo- and stereoselective access to (E)-enones and (E)-acrylonitriles

A copper-catalyzed transfer aldol type reaction of β-hydroxy ketones or nitriles with aldehydes is reported, which enables chemo- and stereoselective access to (E)-α,β-unsaturated ketones and (E)-acrylonitriles. A key step of the in situ copper(i)-promoted retro-aldol reaction of β-hydroxy ketones or nitriles is proposed to generate a reactive Cu(i) enolate or cyanomethyl intermediate, which undergoes ensuing aldol condensation with aldehydes to deliver the products. This reaction uses 1.2 mol% Cu(IPr)Cl (IPr denotes 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) as the catalyst in the presence of 6.0 mol% NaOtBu cocatalyst at room temperature or 70 °C. A range of aryl and heteroaryl aldehydes as well as acrylaldehydes are compatible with many useful functional groups being tolerated. Under the mild and weakly basic conditions, competitive Cannizzaro-type reaction of benzaldehydes and side reactions of base-sensitive functional groups can be effectively suppressed, which show synthetic advantages of this reaction compared to classic aldol reactions. The synthetic potential of this reaction is further demonstrated by the one-step synthesis of biologically active quinolines and 1,8-naphthyridine in excellent yields (up to 91%). Finally, a full catalytic cycle for this reaction has been constructed using DFT computational studies in the context of a retro-aldol/aldol two-stage mechanism. A rather flat reaction energy profile is found indicating that both stages are kinetically facile, which is consistent with the mild reaction conditions.

Organoselenium-catalyzed baeyer-villiger oxidation of α,β-unsaturated ketones by hydrogen peroxide to access vinyl esters

By carefully screening the organoselenium pre-catalysts and optimizing the reaction conditions, simple dibenzyl diselenide was found to be the best pre-catalyst for Baeyer-Villiger oxidation of (E)-α,β-unsaturated ketones with the green oxidant hydrogen peroxide at room temperature. The organoselenium catalyst used in this reaction could be recycled and reused several times. This new method was suitable not only for methyl unsaturated ketones, but also for alkyl and aryl unsaturated ketones. Therefore, it provided a direct, mild, practical, highly functional group-tolerant process for the chemoselective preparation of the versatile (E)-vinyl esters from the readily available (E)-α,β-unsaturated ketones. A possible mechanism was also proposed to rationalize the activity of the organoselenium catalyst in the presence of hydrogen peroxide in this Baeyer-Villiger oxidation reaction.

Organic synthesis via magnetic attraction: Benign and sustainable protocols using magnetic nanoferrites

Magnetic nano-catalysts have been prepared using simple modification of iron ferrites. The nm size range of these particles facilitates the catalysis process, as an increased surface area is available for the reaction; the easy separation of the catalysts by an external magnet and their recovery and reuse are additional beneficial attributes. Glutathione bearing nano-ferrites have been used as organocatalysts for the Paal-Knorr reaction and homocoupling of boronic acids. Nanoferrites, post-synthetically modified by ligands, were used to immobilize nanometals (Cu, Pd, Ru, etc.) which enabled the development of efficient, sustainable and green procedures for azide-alkynes-cycloaddition (AAC) reactions, C-S coupling, O-allylation of phenol, Heck-type reactions and hydration of nitriles.

Cyclohexane 1,3-diones and their inhibition of mutant SOD1-dependent protein aggregation and toxicity in PC12 cells

Amyotrophic lateral sclerosis (ALS) is a fatal neurodegenerative disease characterized by the progressive loss of motor neurons. Currently, there is only one FDA-approved treatment for ALS (riluzole), and that drug only extends life, on average, by 2-3 months. Mutations in Cu/Zn superoxide dismutase (SOD1) are found in familial forms of the disease and have played an important role in the study of ALS pathophysiology. On the basis of their activity in a PC12-G93A-YFP high-throughput screening assay, several bioactive compounds have been identified and classified as cyclohexane-1,3-dione (CHD) derivatives. A concise and efficient synthetic route has been developed to provide diverse CHD analogs. The structural modification of the CHD scaffold led to the discovery of a more potent analog (26) with an EC50 of 700 nM having good pharmacokinetic properties, such as high solubility, low human and mouse metabolic potential, and relatively good plasma stability. It was also found to efficiently penetrate the blood-brain barrier. However, compound 26 did not exhibit any significant life span extension in the ALS mouse model. It was found that, although 26 was active in PC12 cells, it had poor activity in other cell types, including primary cortical neurons, indicating that it can penetrate into the brain, but is not active in neuronal cells, potentially due to poor selective cell penetration. Further structural modification of the CHD scaffold was aimed at improving global cell activity as well as maintaining potency. Two new analogs (71 and 73) were synthesized, which had significantly enhanced cortical neuronal cell permeability, as well as similar potency to that of 26 in the PC12-G93A assay. These CHD analogs are being investigated further as novel therapeutic candidates for ALS.

A simple and facile Heck-type arylation of alkenes with diaryliodonium salts using magnetically recoverable Pd-catalyst

The Heck-type arylation of alkenes was achieved in aqueous polyethylene glycol using a magnetically recoverable heterogenized palladium catalyst employing diaryliodonium salts under ambient conditions. The benign reaction medium and the stability of the catalyst are the salient features of this simple and facile protocol.

Solvent-dependent reactivities of acyclic nitrones with β-diketones: Catalyst-free syntheses of endiones and enones

Reactions of the nitrones -O+N(Me)C(H)Ar 1 (Ar=phenyl 1a, 4-methylphenyl 1b, 2,4,6-trimethylphenyl 1c, and anthracen-9-yl 1d) with the cyclic β-diketones 1,3-indandione 2 or barbituric acid 3 in CH 2Cl2, afford the corresponding endiones 2′a-2′d or 3′a-3′d. In contrast, dimedone 4 reacts with 1a or 1b to give the endione 4′a or 4′b and the bis-adduct 4″a or 4″b. Nevertheless, reaction of 4 with 1c or 1d in CH 2Cl2 furnishes only the endione adducts 4′c or 4′d. However, the reaction of 4 with 1a or 1b in methanol gives only 4″a or 4″b, respectively. Among acyclic β-diketones only malonic acid 7 reacts with 1a-1c. Reaction of 7 with 1a in CH2Cl 2 forms cinnamic acid 7″a, whereas in the case of 1b, the endione 7′b and (E)-3-p-tolylacrylic acid 7″b are obtained. The nitrone 1c reacts with 7 in CH2Cl2 to afford the endione 7′c or with acetone yielding (E)-4-mesitylbut-3-en-2-one 8. X-ray analyses are reported for 4′c, 5, and 7″b. In addition, the calculated acidity of the hydrogen at the α-C atom is shown to correlate with the reactivity of the β-diketones with nitrones.

Metal-free hydroarylation of alkynes: A very convenient, simple procedure for substituted arylalkenes

Hydroarylation of aryl-substituted alkynes with simple and substituted arenes was conducted in the presence of trifluoroacetic acid in dichloromethane without any metal catalysts or additives. Electron-rich arenes coupled with aryl-substituted alkynes to give 1,1-diarylalkenes in good to high yields. Georg Thieme Verlag Stuttgart.