What is the reason for the high boiling and melting point in carboxylic acids and amides?5 answersCarboxylic acids and amides exhibit high boiling and melting points due to strong intermolecular forces like hydrogen bonding. Primary and secondary amides show strong hydrogen bonding, leading to high melting points and low solubilities in most solvents. In contrast, tertiary amides have increased solubility and lower melting points as hydrogen bonding is not possible. Additionally, the enthalpies of solution of amides in aqueous-organic solvents increase with the hydrophobic properties of the molecules, resulting in positive enthalpic coefficients due to the endothermic interaction of alkyl groups with the solvent. These interactions contribute to the stability and high boiling points observed in carboxylic acids and amides, making them essential in various applications like lubricants, surfactants, and detergents.
What are the functions of carboxylic acids?3 answersCarboxylic acids have various functions in different fields. In medicine and crop protection, carboxylic acid derivatives are important components of many processes and molecules. They are present in approximately 25% of commercialized pharmaceuticals and agrochemicals. Carboxylic acids fulfill the criteria for optimal bioavailability in active ingredients due to their ability to act as hydrogen-bond donors and acceptors. In pharmacology, carboxylic acid compounds can be used in the treatment of diseases mediated by TLR7, such as various cancers and inflammatory conditions. In organic synthesis, carboxylic acids and their derivatives can serve as versatile building blocks without the need for additional activation steps. They can be used as synthetic equivalents of acyl, aryl, or alkyl halides, as well as organometallic reagents. Carboxylic acids also find applications in the production of copolymers, as catalysts, and in corrosion resistance and surface modification of metallic substrates.
What are the acidic conditions for carboxylic acid racemization?5 answersThe acidic conditions for carboxylic acid racemization vary depending on the method used. One method involves the treatment of the optically active carboxylic acid with an acid anhydride and its conjugate base. Another method involves the coexistence of a base (such as potassium hydroxide) and dimethyl sulfoxide at a temperature range of 60-130°C. Additionally, a method using whole resting cells of Lactobacillus spp. for biocatalytic racemization of α-hydroxycarboxylic acids was described, which occurs under mild (physiological) reaction conditions. The specific acidic conditions for this method were not mentioned in the abstract. It is important to note that different methods may have different optimal conditions for carboxylic acid racemization, and further details can be found in the respective papers.
Between esters and amides, which is more easily hydrolyzed? Why?3 answersEsters are more easily hydrolyzed than amides. The hydrolysis of esters is facilitated by the presence of a carbonyl group, which is more susceptible to nucleophilic attack by water molecules. In contrast, amides have a resonance-stabilized carbonyl group, which makes it less reactive towards hydrolysis. The reactivity difference between esters and amides can also be attributed to the electronic and steric effects of the substituents. Ortho-disubstituted benzoic acids, which form esters, are highly resistant to hydrolysis due to steric hindrances caused by the substituents. On the other hand, DNA catalysts have been found to hydrolyze esters and aromatic amides, suggesting that the hydrolysis of these compounds is facilitated by general acid-catalyzed elimination. Overall, the ease of hydrolysis of esters compared to amides can be attributed to the differences in their electronic and steric properties.
Can you show me papers which schow how industrially amides are made from nitriles?3 answersAmides can be industrially produced from nitriles using various methods. One approach is the use of solid metal oxides and transition metal supported catalytic systems, which have shown high catalytic activity and applicability to a wide range of substrates. Another method involves metal-catalyzed transfer hydration of nitriles using amides or aldoximes as water donors. Additionally, a greener chemo-enzymatic cascade has been developed to synthesize nitriles and amides from aldehydes, with moderate isolation yields achieved. Another efficient method involves the hydroboration of nitriles using an alkali metal catalyst, neosilyllithium, which has shown excellent functional group tolerance. Furthermore, a Cu-catalyzed aerobic oxidation process using supported copper oxide nanoparticles has been used to synthesize nitriles and primary amides from alcohols and ammonia. These methods provide cost-effective and environmentally friendly approaches for the industrial production of amides from nitriles.
Can you show me papers which schow how industrially amides threwhydrolysis are made from nitriles?5 answersAmides can be synthesized from nitriles through various methods. One approach is the hydroboration of nitriles using pinacolborane as a reagent, catalyzed by neosilyllithium, which leads to the formation of N-boryl amines, boryl ethers, and amine hydrochlorides. Another method involves the transfer hydration of nitriles to amides using amides or aldoximes as water donors, catalyzed by metal catalysts. Partial hydrolysis of nitriles can also be employed, either through traditional heating with solvent reflux or ultrasound, to obtain amides. Anhydrous hydrolysis of nitriles to amides can be achieved using acetaldoxime as the water source in the presence of a Rh catalyst. Additionally, the palladium-catalyzed coupling of nitriles and aryl bromides can be utilized to form aryl amides.