22161-42-8

Upstream product

• 6262-58-4 Phenyl-p-tolyl-cyclopropenon 
• 103-82-2 phenylacetic acid 
• 17556-67-1 isopropyl-[(4-methylphenyl)meth-(E)ylidene]amine 
• 124-38-9 carbon dioxide 
• 3287-02-3 4-(phenylethynyl)toluene 
• 104-87-0 4-methyl-benzaldehyde 

Downstream Products

• 1657-45-0 (Z)-4-methylstilbene 
• 1142935-03-2 (2S)-3-(4-methylphenyl)-2-phenylpropanoic acid 

Relevant academic research and scientific papers

Palladium-Catalyzed Highly Regioselective Hydrocarboxylation of Alkynes with Carbon Dioxide

A Pd-catalyzed highly regioselective hydrocarboxylation of alkynes with carbon dioxide has been established. By the combination of Pd(PPh3)4 and 2,2′-bis(diphenylphosphino)-1,1′-binaphthalene (binap), a variety of functionalized alkynes, including aryl alkynes, aliphatic alkynes, propargylamines, and propargyl ethers, could be leveraged to provide a wide array of α-acrylic acids in high yields with high regioselectivity under mild reaction conditions. Experimental and DFT mechanistic studies revealed that this reaction proceeded via the cyclopalladation process of alkynes and carbon dioxide in the presence of binap to generate a five-membered palladalactone intermediate and enabled the formation of Markovnikov adducts. Moreover, this strategy provided an effective method for the late-stage functionalization of alkyne-containing complicated molecules, including natural products and pharmaceuticals.

Up to 96% enantioselectivities in the hydrogenation of fluorine substituted (E)-2,3-diphenylpropenoic acids over cinchonidine-modified palladium catalyst

The enantioselective hydrogenation of methoxy-and fluorine-substituted (E)-2,3-diphenylpropenoic acid derivatives was studied over cinchonidine- modified, supported palladium catalysts in the absence and presence of benzylamine as additive. The fluorine substituent in the appropriate position was even more efficient than the methoxy group in increasing the optical purity of the saturated product. High enantioselectivities, up to 96%, were obtained in the hydrogenation of some disubstituted derivatives, unprecedented in the hydrogenation of prochiral unsaturated carboxylic acids over modified heterogeneous catalyst. The best optical purities were reached in the hydrogenation of derivates bearing a para-substituent on the β phenyl and an ortho-substituent on the a phenyl ring, respectively. The influence of the substituent on the β phenyl ring was attributed to the increase in the efficiency of the modifier-substrate interaction by electronic effects or to a decrease in the adsorption strength of the substituted acid over modified surface sites. The beneficial effect of the ortho-substituent on the a phenyl ring was assumed to be due to the additional interaction of this substituent with the modifier on the surface, its steric hindrance contributing only in a small part to the observed effect. These suggestions were supported by results obtained in the hydrogenations of some methyl-substituted derivatives.

Pathways for the solvent-free condensation between schiff bases and methylenic compounds

Pathways for the solvent-free condensation between Schiff Bases and methylenic compounds are discussed taking into account the reported mechanistic purposes and new experimental data.

Reactions of carbonyl compounds in basic solutions. Part 34. The mechanism of the base-catalysed ring fission of 2,3-diphenylcycloprop-2-en-1-one

The rate coefficients for the base-catalysed ring fission of a series of 2-phenyl-3-(2-, 3-or 4-substituted phenyllcycloprop-2-en-1-ones to give the corresponding (E)-2,3-diphenylacrylic acids have heen determined in water at 30.0 °C, as well as for the unsubstituted compound at 40.0, 50.0 and 60.0 °C. The effects of meta-and para-substituents on the rates have been correlated using the Hammett equation to give a reaction constant, p, equal to ca 1.2 at 30 °C. For the unsubstituted compound, the activation parameters have been calculated and the kinetic solvent isotope effect has been studied. The effects of ortho-substituents on the rates appear to be mainly polar, rather than steric, in origin. The evidence indicates a mechanistic pathway which proceeds by addition of hydroxide anion to the ketone, which is rate-determining. The adduct suffers ring fission to give the final product via a carbanionic intermediate.

N-SUBSTITUTED HETEROCYCLIC DERIVATIVES USEFUL IN THE TREATMENT OF CARDIOVASCULAR DISORDERS

The present invention relates to N-substituted heterocyclic derivatives of formula: STR1 processes for their preparation, and pharmaceutical compositions which contain them. The compounds according to the invention are non-peptide compounds which oppose the action of angiotensin II. The compounds according to the invention are thus useful in the treatment of cardiovascular disorders such as hypertension and heart failure.

Metal Ion Effects in Wittig Reactions: A General Hypothesis for the Mechanism of the Wittig Reaction

To evaluate better the effects of N2p-P(IV) through-space interactions in Wittig reactions, a thorough study of metal ion effects in Wittig reactions lacking such interactions has been completed.As in the case of Wittig reactions with stabilized ylides, it has been determined that, with a moderated ylide, the stereochemistry (E:Z ratio) of alkene formation with an aldehyde is determined at the point that a new carbon-carbon bond has been formed to give a betaine or an oxaphosphetane intermediate.The observations that in most cases where lithium ion is present, theproduct mixture is enriched with the Z alkene, while when sodium or potassium ions are present, the E isomer predominates, are deemed to support the concept that a spin-paired diradical is formed as an unstable intermediate when sodium or potassium ions are present but that an ionic reaction occurs when lithium ions are present.The evidence that has been accumulated suggests that the reactions studied here (involving aromatic, heterocyclic, and aliphatic aldehydes and benzylidenediphenylmethylphosphorane or the preformed betaines, in THF at -78 deg C) occur under kinetic control and without any significant degree of equilibration or Wittig reversal.

Structural Effects of the Acidity of E-α-Phenyl-β-arylacrilic Acids

The dissociation equilibrium constants of some E-α-phenyl-β-arylacrilic acids (Ar=2-pyridyl, 3-pyridyl, 4-pyridyl, 1-naphthyl, 2-naphthyl, anthracen-9-yl) have been measured in 80percent aqeous 2-methoxyethanol at 25 deg C., The pKa values of these acids, together with those of p-substituted phenyl, 2-furyl, 2-thienyl and selenophen-2-yl derivitives, have been rationalized by an equation involving separate contributions of polar, conjugative and steric effects of heterocycles.The pKa values of some E-α-phenyl-β-alkylacrilic acids (alk=methyl; ethyl; n-propyl; i-propyl; n-butyl; i-butyl) are also reported.