55444-18-3

Upstream product

• 64-17-5 ethanol 
• 871876-94-7 3,3'-(1,2-phenylene)dipropionic acid 
• 69403-16-3 2-[2-(2,2-bis-ethoxycarbonyl-ethyl)-benzyl]malonic acid diethyl ester 
• 3054-95-3 acrylaldehyde diethyl acetal 
• 615-42-9 1,2-Diiodobenzene 
• 91-13-4 α,α'-dibromo-o-xylene 
• 110795-28-3 3,3'-(1,2-phenylene)bisacrylic acid 

Downstream Products

• 871876-94-7 3,3'-(1,2-phenylene)dipropionic acid 
• 4444-24-0 1,2-benzenedipentanoic acid 
• 177429-63-9 1,2-bis-(3-bromopropyl)benzene 
• 143260-95-1 3-[2-(3-hydroxypropyl)phenyl]propanol 

Relevant academic research and scientific papers

Efficient synthesis and theoretical study of siloxy-benzocyclooctenes: 7,8,-Bis-trimethylsilanyloxy-5,6,9,10-tetrahydro-benzocyclooctene and 6,9-dimethyl-7,8-bis-trimethylsilanyloxy-5,6,9,10-tetrahydro-benzocyclooctene -6,9-dicarboxylic acid diethyl ester

2-[2-(2,2-Bis-ethoxycarbonyl-ethyl)-benzyl]malonic acid diethyl ester 2, 3-[2-(2-ethoxycarbonyl-ethyl)-phenyl]-propionic acid ethyl ester 3, 2-[2-(2,2-bis-ethoxycarbonyl-propyl)-benzyl]-2-methyl-malonic acid diethyl ester 4, 7,8-bis-trimethylsilanyloxy-5,6,9,10-tetrahydro-benzocyclooctene 5, and 6,9-dimethyl-7,8-bis-trimethylsilanyloxy-5,6,9,10-tetrahydro-benzocyclooctene -6,9-dicarboxylic acid diethyl ester 6 have been synthesised for study of their spectroscopic and structural features. The synthetic method involved is monoalkylation of malonic acid diethyl ester and 2-methyl-malonic acid diethyl ester with 1,2-bis-bromomethyl-benzene in DMSO, and yields esters 2 and 4, respectively. The decarboxylation of 2 by DMSO/LiCl in the presence of a very small amount of water yields diester 3. Compounds 3 and 4 undergo acyloin condensation to give siloxy-benzocyclooctenes 5 and 6, respectively. The calculated structures and parameters of bis-siloxy-benzocyclooctene 6 show the reason why cyclization of 4 was independent of the quantity of reagents used. (C) 2000 Elsevier Science Ltd.

EMM-31 MATERIALS AND PROCESSES AND USES THEREOF

The disclosure is related to EMM-31 materials, processes, and uses of the same as well as reagents used in the preparation of the EMM-31 materials, process and intermediates for preparing these reagents.

Chemoselective Heck arylation of acrolein diethyl acetal catalyzed by an oxime-derived palladacycle

A dimeric 4-hydroxyacetophenone oxime-derived palladacycle has been used as a very efficient precatalyst for the chemoselective arylation of acrolein diethyl acetal to give either cinnamaldehyde derivatives or 3-arylpropanoate esters by proper choice of the reaction conditions. The synthesis of cinnamaldehyde derivatives can be performed by Heck reaction of acrolein diethyl acetal with iodo-, bromo- or chloroarenes in N,N-dimethylacetamide (DMA) using K2CO3 as base at 120°C and tetra-n-butylammonium acetate (TBAA) and KCl as additives, followed by acid workup. In the case of 3-arylpropanoate esters the corresponding arylation of acrolein diethyl acetal with iodoarenes can be performed at 90°C in aqueous DMA using (dicylohexyl)methylamine as base, whereas for bromoarenes the reaction has to be performed at 120°C using tetra-n-butylammonium bromide (TBAB) as additive. Alternatively, this process can be performed under microwave irradiation. These couplings take place in good yields and with lower catalyst loading than with palladium(II) acetate as well as in shorter reaction times and with lower excess of acrolein diethyl acetal.

3-arylpropanoate esters through the palladium-catalyzed reaction of aryl halides with acrolein diethyl acetal

The reaction of aryl halides with acrolein diethyl acetal in the presence of Pd(OAc)2, n-Bu3N, and n-Bu4NCl in DMF at 90°C affords ethyl 3-arylpropanoates. A variety of functional groups are tolerated in the aryl halides, including ether, aldehyde, ketone, ester, nitrile, and nitro groups. ortho-Substituents do not hamper the reaction. 3-Arylpropanoate esters were isolated in good to excellent yields with many neutral, electron-rich and electron-poor aryl iodides and electron-poor aryl bromide. Neutral and electron-rich aryl bromides gave the desired ester in moderate yields.