67685-90-9

Upstream product

• 53856-98-7 4-phenyl-2-butanone dimethyl acetal 
• 617-86-7 triethylsilane 
• 67-56-1 methanol 
• 52755-38-1 1-phenyl-2-buten-1-ol 
• 24808-74-0 (+/-)-3-methoxy-1-phenyl-1-butene 
• 75-16-1 methylmagnesium bromide 
• 30076-98-3 (3,3-dimethoxypropyl)benzene 

Downstream Products

• 1294006-08-8 3-(4-fluorophenyl)1-methylpropyl methyl ether 
• 79-20-9 acetic acid methyl ester 
• 4830-94-8 (3-chlorobutyl)benzene 

Relevant academic research and scientific papers

Effects of phosphorus substituents on reactions of α- alkoxyphosphonium salts with nucleophiles

The effects of phosphorus substituents on the reactivity of α-alkoxyphosphonium salts with nucleophiles has been explored. Reactions of α-alkoxyphosphonium salts, prepared from various acetals and tris(o-tolyl)phosphine, with a variety of nucleophiles proceeded efficiently. These processes represent the first examples of high-yielding nucleophilic substitution reactions of α-alkoxyphosphonium salts. The reactivity of these salts was determined by a balance between steric and electronic factors, respectively, represented by cone angles θ and CO stretching frequencies ν (steric and electronic parameters, respectively). In addition, a novel reaction of α-alkoxyphosphonium salts derived from Ph3P with Grignard reagents was observed to take place in the presence of O2 to afford alcohols in good yields. A radical mechanism is proposed for this process that has gained support from isotope-labeling and radical-inhibition experiments. A dramatic change in the reactivity of an α-alkoxyphosphonium salt toward nucleophiles is observed due to the steric and electronic nature of the phosphine substituents. By changing the type of phosphorus substituents, the reaction pathway can be controlled to proceed selectively by substitution or a new radical reaction (see scheme; OTf=trifluoromethansulfonate, TMS=trimethylsilyl, o-tol=tolyl). Copyright

Chemoselective conjugate reduction of α,β-unsaturated ketones catalyzed by rhodium amido complexes in aqueous media

Although a notable feature of Noyori's Ru-TsDPEN complex is that the transfer hydrogenation reaction is highly chemoselective for the C-O functional group and tolerant of alkenes, our early report indicated that the chemoselectivity could be switched from C-O to C-C bonds in the transfer hydrogenation of activated α,β-unsaturated ketones. Now we have found that a variety of α,β-unsaturated ketones, even without other electron-withdrawing functional groups, could be reduced on the alkenic double bonds with high selectivities employing amido-rhodium hydride complex in aqueous media, and up to 100% chemoselectivity has been achieved. It is notable that the chemoselectivity was improved significantly on going from organic solvent to water. Moreover, a 1,4-addition mechanism has been proposed on the basis of the corresponding experimental details and computational analysis.

Pyrylium salt promoted substitution reactions of acetals with various silylated nucleophiles

Catalytic amounts of triarylpyrylium salts photochemically and thermally promoted the substitution reactions of dimethyl acetals with silylated nucleophiles.

MODEL REACTIONS FOR THE STUDY OF HYDROGENATION AND ACIDIC ACTIVITY OF PALLADIUM CATALYSTS

Palladium catalysts have been used to study the hydrogenation of 1-phenyl-2-butene-1-ol which is accompanied by several side reactions considered to be acid-catalysed.Another model reaction studied was dehydration and subsequent hydrogenation or hydrogenolysis of 1-phenyl-1,3-propanediol to 3-phenyl-1-propanol, accompanied by formation of propylbenzene.The dehydration and propylbenzene formation can be again classified as acid-catalysed reactions.Another one is methanolysis of styrene oxide taking place under conditions of liquid phase hydrogenation due to the acid properties of Pd-H systems.Hydrogenation activity of Pd catalysts was tested by hydrogenation of cyclohexene.Sixteen Pd catalysts on different supports and with different content of active component were used, their activity and selectivity was determined and the effect of variable parameters in the synthesis of these catalysts on the activity and selectivity is discussed.