Amination, fine chemical synthesis

Although zeolites have been known for their adsorption properties for over a century, it was not until 1952, when the first synthetic zeolite was prepared, that their utility in chemical transformations was explored. Since that time, zeolites have been used for a multitude of purposes, and to this day, they are essential catalysts in the petroleum industry, converting large and small hydrocarbons into high-octane compounds. As an outgrowth of this work, zeolites have found utility in industrial fine chemical synthesis for the construction of aromatics, heterocycles, aliphatic amines, and ethers, and the photochemistry within zeolites has already grown out of its infancy. 

Catalytic behaviors of solid base catalysts for fine chemicals synthesis as well as the fundamental reactions are described. The reactions included are double bond isomerization of olefins, addition of hydrogen and amines to conjugated dienes, dehydration, dehydrogenation, reduction, alkylation, aldol addition and condensation, Wittig-Horner and Knoevenagel reactions, dehydrocyclodimerization, and ring transformation. The characteristic features of different types of solid base catalysts, zeolites, metal oxides, solid superbases and non metal-oxides, are summarized. 

Oxalyl Chloride. This diacid chloride [79-37-8], ClCOCOCl, mol wt 126.9, is produced by the reaction of anhydrous oxaUc acid and phosphoms pentachloride. The compound vigorously reacts with water, alcohols, and amines, and is employed for the synthesis of agrochemicals, pharmaceuticals, and fine chemicals. 

Many new sugar based products present the advantage of being non-toxic and biodegradable. The products resulting from the telomerization of 1 with appropriate nucleophiles such as alcohols, amines, water, or carbon dioxide serve generally as useful intermediates in the synthesis of various natural products and fine chemicals [60-63], as precursors for plasticizer alcohols [56, 64], components of diesel fuels [65], surfactants [11, 66], corrosions inhibitors, and non-volatile herbicides [67]. 

Copper-catalysts promoted with i) other group VIA or VIIIA metals and ii) alcaline or alcaline earth elements (IA or IIA) are used for selective hydrogenation of various organic compounds (1). Moreover Cu(Co) Zn-Al catalysts were extensively studied for the synthesis of methanol and of light alcohols (2,3). More recently, due to the development of fine chemical processes, detailed studies of copper catalysts were carried out in order to show, like for noble metals, the effect of supports (SMSI), of promoters and of activation-on metal dispersion or reduction, on alloy formation... For example modified copper catalysts are known for their utilization in the dehydrogenation of esters (4-6), in the hydrolysis of nitriles (7), in the selective hydrogenation of nitriles (8), in the amination of alcohols (9)... 

C - N bond formation is one of the most important transformations in organic synthesis. Amines are widely used as intermediates to prepare solvents, fine chemicals, agrochemicals, pharmaceuticals and catalysts for polymerization. The nucleophilic attack of alkyl halides by primary and secondary amines is useful for the preparation of tertiary amines but the reaction requires a longer reaction time and gives rise to a mixture of secondary and tertiary amines. 

Gompared to C-C bond forming reaction, the G-N bond formation is still immature. Moreover, new amination methodologies will have a direct impact on pharmaceutical and fine chemical industries for the synthesis of a variety of commercially interesting compounds. Since the pyrrolyl anion exhibits ambident behavior as a nucleophile, alkylation can occur at carbon as well as at nitrogen (Scheme 20). 

Since, for secrecy reasons, information on new processes and the state of their development is not always published, or only after long delays, the classification applied or recent developments may be misleading. For example, the potential of phase-transfer catalyzed processes may already be more important than the present literature indicates. The same statement could apply for areas such as amidocarbonylation, the synthesis of fine chemicals by means of metallocenes, the reductive/oxidative carbonylation of aromatic amines or nitro derivatives, Heck coupling using palladacycles and heterocyclic carbene complexes, catalytic McMurry coupling, or other proposed methods. Recent developments must therefore leave open the stage of development reached, perhaps signaling that at the time of publication no commercialized, licensable process is yet known to the scientific community. 

The ammoxidation of methyl aromatic and heteroaromatic compounds is a convenient route to many nitriles required for further synthesis of fine chemicals. For example, for the production of amines by hydrogenation or of carboxylic acids and amides by hydrolysis. 

Activated carbon supported palladium catalysts have been widely used in fine organic chemical synthesis. Some of the typical applications are debenzyiation, hydrogenation, reductive alkylation, reductive amination, etc. As an effective synthetic method, debenzyiation has been used commercially in organic synthesis to deprotect various functional groups. 

The amination reaction, forming primary, secondary, and tertiary amines, can be between alcohols, aldehydes, or ketones, and ammonia and hydrogen. Sabatier and Mailhe in 1909 [1] first reported the synthesis of amines from alcohols. Over the course of the 20 century the in jortance of these compounds has increased and amines are key intermediates and final products within the fine chemical, agrochemical, and pharmaceutical industries. The amination of alcohols to form amines has been the subject of a number of mechanistic studies [2-8] proposing a variety of mechanisms. In this study we have investigated the... 

Radical reactions are widely used for carbon-carbon bond formations. This has led to highly efficient novel synthetic methods that can be used in natural product synthesis as well as preparation of fine chemicals. Many of these processes involve a reductive final step (see for instance Volume 1, Chapter 1.3). Alternative methods that allow functionalization of carbon-centered radicals are highly desired. In this chapter, we will focus on oxygenation and amination reactions. 

Electrochemical oxidation and reduction of het-ero atom compounds, such as N, S, and P compounds, has been intensively studied and utilized for synthesis of many fine chemicals [1-4]. Electrooxidative S-S, S-N, S-P, and N-P bond formation is performed successfully by electrolysis of thiols, disulfide/amine, disulfide/phosphate, amine/ phosphate, and so on, affording useful chemicals, e.g., thiuram disulfide [17], sulfenamide [18], sulfenimides [19], phosphorothiolates [20], phosphoramidate [21], and so on. For instance, cross-coupling of phthalimide and dicyclohexy disulfide is performed by electrolysis in acetonitrile containing a catalytic amount of sodium bromide under a ccaistant apphed voltage (3 V, 0.7-0.9 V vs. SCE) to afford N-(cyclohexylthio)phthalimide, an important prevulcanization inhibitor in the rubber industry, in quantitative yield [19] (Fig. 4). 

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