6798-58-9

Upstream product

• 66379-84-8 2,2,2-trichloro-1-[4-(dimethylamino)phenyl]ethan-1-ol 
• 100-10-7 4-dimethylamino-benzaldehyde 
• 56-23-5 tetrachloromethane 
• 41463-93-8 4-N,N-dimethylaminobenzaldehyde hydrazone 
• 3167-62-2 diethyl (dichloromethyl)phosphonate 
• 6779-08-4 triphenylphosphonium dichloromethylide 

Relevant academic research and scientific papers

Efficient Multigram Approach to Acetylenes and CF3-ynones Starting from Dichloroalkenes Prepared by Catalytic Olefination Reaction (COR)

A novel approach to terminal acetylenes based on catalytic olefination reaction COR of arylaldehydes to form dichloroalkenes followed by treatment with nBuLi was elaborated. This method is atom economical and displays high yields and effectivity. The corresponding alkynes can be prepared in up to 97 % yield. One pot procedure towards CF3-ynones was elaborated to provide these products in up to 87 % yield starting from dichloroalkenes.

β-(Carbonatoxy)alkyl radicals: A new subset of β-(ester)alkyl radical fragmentation during copper(I)-mediated synthesis of 1,1-dichloro-1-alkenes

A new subset of β-(ester)alkyl radicals is presented. It is the first study on the chemistry of β-(alkoxycarbonyloxy)alkyl radicals that fill the gap in the spectrum of the migrating groups in β-(ester)alkyl radical reactions. The change from less nucleofugal (acetate) group to the more nucleofugal (carbonate) group in the spectrum of the migrating group changed the reaction path from rearrangement to fragmentation. This approach has been used for the synthesis of 1,1-dichloroalkenes in high yields. The formation of dichloroalkenes was accounted by the involvement of alkene radical cation and carbonate anion pair (a CIP) as a result of heterolysis of the CO bond of the carbonate at the β-position of the β-(alkoxycarbonyloxy)alkyl radical. The alkene radical cation was trapped by nucleophilic reaction with MeOH to form methyl ester.

Conversion of aromatic aldehydes into 1-aryl-2,2-dichloroethenes

A new general one-pot preparative method for the synthesis of 1-aryl(hetaryl)-2,2-dichloroethenes from aldehydes was developed. The method involves successive conversions of the latter into hydrazones followed by treatment with carbon tetrachloride in the

A novel synthetic approach to dichlorostyrenes

We found that N-unsubstituted hydrazones of aromatic aldehydes can be easily converted to the corresponding 1,1-dichlorostyrenes in the reaction with carbon tetrachloride using copper (I) chloride as catalyst. Factors affecting the route of the reaction and yields of the products were investigated. A proposed mechanism for the reaction is discussed. (C) 2000 Published by Elsevier Science Ltd.

Carbanions phosphonate prepares par voie electrochimique: formation et reactivite vis-a-vis d'un aldehyde

Reactivity towards p-methoxybenzaldehyde (ArCHO) of electrochemically generated phosphonate carbanions has been investigated.Electrolyses were carried out at a mercury cathode in DMF and two routes to the desired carbanion have been compared: (i) Deprotonation of phosphonates of general formula (EtO)2P(O)CHYW (Y = W = Cl; Y = H, W = Cl; Y = Cl, W = CO2Et; Y = H, W = CO2Et; Y = CH3, W = CO2Et; Y = Cl, W = CH3), by the bases resulting from the electroreduction of azobenzene; addition of the carbanion formed onto the carbonyl group takes place and leads to the adduct (EtO)2P(O)CYW(Ar)O-. (ii) Two-electron reduction of halophosphonates (EtO)2P(O)CXYW (X = Cl, Y and W as above; X = Br, W = CO2Et, Y = Cl, Br, or CH3); when no H atom is present on the carbon bearing the phosphonate group (Y and W no = H), the same evolution leading to the above adduct is observed, on the contrary, when Y = H, the electrogenerated carbanion deprotonates the substrate and the resulting carbanion (EtO)2P(O)CXW reacts with the aldehyde; giving the adduct (EtO)2P(O)CXW(Ar)O-.Evolution of the intermediate adduct depends on the substituents Y (or X) and W: when W = CO2Et, whatever the nature of Y (or X), diethyl phosphate is eliminated with formation of the ethylenic ArCH=CWY (or X) (Wittig-Horner reaction); the same evolution is observed when Y = W = Cl.When W = Cl and Y = H or CH3, the final product is the phosphonate epoxyde resulting from chloride elimination (Darzens reaction).Chemo- and stereoselectivity depend only on the nature of Y and W but are independent of the mode of generation of the carbanion.Yields are limited by side-protonation reactions, which are related to the basicity of the phosphonate carbanions.Analysis of the results permits selection of the optimal electrolysis conditions for purposes of synthesis.Key words: electrosynthesis, electrogenerated bases, phosphonates, Wittig-Horner.