Catalysts, copper salts

Continuous chlorination of benzene at 30—50°C in the presence of a Lewis acid typically yields 85% monochlorobenzene. Temperatures in the range of 150—190°C favor production of the dichlorobenzene products. The para isomer is produced in a ratio of 2—3 to 1 of the ortho isomer. Other methods of aromatic ring chlorination include use of a mixture of hydrogen chloride and air in the presence of a copper—salt catalyst, or sulfuryl chloride in the presence of aluminum chloride at ambient temperatures. Free-radical chlorination of toluene successively yields benzyl chloride, benzal chloride, and benzotrichloride. Related chlorination agents include sulfuryl chloride, tert-huty hypochlorite, and /V-ch1orosuccinimide which yield benzyl chloride under the influence of light, heat, or radical initiators. 

An alternative way to produce aniline is through ammonolysis of either chlorobenzene or phenol. The reaction of chlorobenzene with aqueous ammonia occurs over a copper salt catalyst at approximately 210°C and 65 atmospheres. The yield of aniline from this route is also about 96% ... 

Steam and silica gel to produce phenol from chlorobenzene, the Dow process with steam and a copper salt catalyst, etc. 

Deacon process. A method of converting hydrogen chloride to chlorine by oxidation of hydrogen chloride with oxygen at 400-500C over a copper-salt catalyst, 2HC1 + O —> + H20. It is a... 

Unless otherwise stated, reaction was carried out with la (0.18 mmol, 1 equiv), 2a (equiv shown), 3b (1.1 equiv), and a copper salt (catalyst amount shown) in 1,4-dioxane (3 mL) at 80 °C Yields of isolated products. The reaction was conducted on 1.25 mmol scale... 

The conversion of an aromatic diazonium compound into the corresponding arsonic acid by treatment with sodium arsenite in the presence of a catalyst, such as copper or a copper salt, is called the Bart reaction. A modification of the reaction employs the more stable diazonium fluoborate in place of the diazonium chlorid.i. This is illustrated by the preparation of />-nitrophenylarsonic acid ... 

Oxidation. Acetaldehyde is readily oxidised with oxygen or air to acetic acid, acetic anhydride, and peracetic acid (see Acetic acid and derivatives). The principal product depends on the reaction conditions. Acetic acid [64-19-7] may be produced commercially by the Hquid-phase oxidation of acetaldehyde at 65°C using cobalt or manganese acetate dissolved in acetic acid as a catalyst (34). Liquid-phase oxidation in the presence of mixed acetates of copper and cobalt yields acetic anhydride [108-24-7] (35). Peroxyacetic acid or a perester is beheved to be the precursor in both syntheses. There are two commercial processes for the production of peracetic acid [79-21 -0]. Low temperature oxidation of acetaldehyde in the presence of metal salts, ultraviolet irradiation, or osone yields acetaldehyde monoperacetate, which can be decomposed to peracetic acid and acetaldehyde (36). Peracetic acid can also be formed directiy by Hquid-phase oxidation at 5—50°C with a cobalt salt catalyst (37) (see Peroxides and peroxy compounds). Nitric acid oxidation of acetaldehyde yields glyoxal [107-22-2] (38,39). Oxidations of /)-xylene to terephthaHc acid [100-21-0] and of ethanol to acetic acid are activated by acetaldehyde (40,41). 

Trilialophenols can be converted to poly(dihaloph.enylene oxide)s by a reaction that resembles radical-initiated displacement polymerization. In one procedure, either a copper or silver complex of the phenol is heated to produce a branched product (50). In another procedure, a catalytic quantity of an oxidizing agent and the dry sodium salt in dimethyl sulfoxide produces linear poly(2,6-dichloro-l,4-polyphenylene oxide) (51). The polymer can also be prepared by direct oxidation with a copper—amine catalyst, although branching in the ortho positions is indicated by chlorine analyses (52). 

Rearrangement of dehydrolinalool (4) using vanadate catalysts produces citral (5), an intermediate for Vitamin A synthesis as well as an important flavor and fragrance material (37). Isomerization of the dehydrolinalyl acetate (6) in the presence of copper salts in acetic acid followed by saponification of the acetate also gives citral (38,39). Further improvement in the catalyst system has greatly improved the yield to 85—90% (40,41). 

Methyl violet [8004-87-3] Cl Basic Violet 1 (17), is made by the air oxidation of dimethyl aniline in the presence of salt, phenol, and a copper sulfate catalyst. Initially, some of the dimethyl aniline is oxidized to formaldehyde and /V-methyl aniline under those conditions. The formaldehyde then reacts with dimethyl aniline to produce N,N,]S7,1S7-tetramethyldiaminodiphenylmethane, which is oxidized to Michler s hydrol [119-58-4]. The hydrol condenses with... 

Salts of neodecanoic acid have been used in the preparation of supported catalysts, such as silver neodecanoate for the preparation of ethylene oxide catalysts (119), and the nickel soap in the preparation of a hydrogenation catalyst (120). Metal neodecanoates, such as magnesium, lead, calcium, and zinc, are used to improve the adherence of plasticized poly(vinyl butyral) sheet to safety glass in car windshields (121). Platinum complexes using neodecanoic acid have been studied for antitumor activity (122). Neodecanoic acid and its esters are used in cosmetics as emoUients, emulsifiers, and solubilizers (77,123,124). Zinc or copper salts of neoacids are used as preservatives for wood (125). 

Catalysts (eg, copper salts) may help with aryl haUdes of lower activity, but amination of chloroben2ene and l,4-dichloroben2ene is generally not... 

The main by-products of the Ullmaim condensation are l-aniinoanthraquinone-2-sulfonic acid and l-amino-4-hydroxyanthraquinone-2-sulfonic acid. The choice of copper catalyst affects the selectivity of these by-products. Generally, metal copper powder or copper(I) salt catalyst has a greater reactivity than copper(Il) salts. However, they are likely to yield the reduced product (l-aniinoanthraquinone-2-sulfonic acid). The reaction mechanism has not been estabUshed. It is very difficult to clarify which oxidation state of copper functions as catalyst, since this reaction involves fast redox equiUbria where anthraquinone derivatives and copper compounds are concerned. Some evidence indicates that the catalyst is probably a copper(I) compound (28,29). 

An example of the use of copper as a catalyst is Acid Blue 25 [6408-78-2] (Cl 62055) in which l-amino-2-sulfonic-4-bromoanthraquinone is condensed with aniline using copper salts (Ullmann reaction) (314). Another example is oxidation to the tria2ole of Direct YeUow 106 [12222-60-5] (Cl 40300) (315,316). 

Today the sulphonation route is somewhat uneconomic and largely replaced by newer routes. Processes involving chlorination, such as the Raschig process, are used on a large scale commercially. A vapour phase reaction between benzene and hydrocholoric acid is carried out in the presence of catalysts such as an aluminium hydroxide-copper salt complex. Monochlorobenzene is formed and this is hydrolysed to phenol with water in the presence of catalysts at about 450°C, at the same time regenerating the hydrochloric acid. The phenol formed is extracted with benzene, separated from the latter by fractional distillation and purified by vacuum distillation. In recent years developments in this process have reduced the amount of by-product dichlorobenzene formed and also considerably increased the output rates. 

A small portion of vinyl chloride is produced from ethane via the Transcat process. In this process a combination of chlorination, oxychlo-rination, and dehydrochlorination reactions occur in a molten salt reactor. The reaction occurs over a copper oxychloride catalyst at a wide temperature range of 310-640°C. During the reaction, the copper oxychloride is converted to copper(I) and copper(II) chlorides, which are air oxidized to regenerate the catalyst. Figure 6-1 is a flow diagram of the Transcat process for producing vinyl chloride from ethane. ... 

The action of a copper salt converts benzoic acid to phenol. The copper, reoxidized by air, functions as a real catalyst. The Lummus process operates in the vapor phase at approximately 250°C. Phenol yield of 90% is possible ... 

The situation has now changed and currently an area of considerable research interest is in heterogenizing homogeneous catalysts. One such instance is to be found in the ethylene based manufacture of vinyl acetate (11). A homogeneous catalytic process based on palladium and copper salts was first devised, but corrosion problems were made much less serious in a heterogeneous system based on the same chemical principles. 

The reaction with ammonia or amines, which undoubtedly proceeds by the SnAt mechanism, is catalyzed by copper and nickel salts, though these are normally used only with rather unreactive halides. This reaction, with phase-transfer catalysis, has been used to synthesize triarylamines. Copper ion catalysts (especially cuprous oxide or iodide) also permit the Gabriel synthesis (10-61) to be... 

From the several (not exhaustive) examples listed above, it is obvious that bis(oxazolines) associated to copper salts are efficient catalysts to perform Diels-Alder cycloadditions of numerous substrates, leading to highly valuable products with high diastereo- and enantioselectivity. Efforts have been moreover drawn towards the preparation of moisture- and air-stable systems... 

Copper-complexes prepared with other type of N-chelating ligands have been also prepared and evaluated as catalysts for the Diels-Alder reaction. Eng-berts et al. [103] studied enantioselective Diels-Alder reaction of 3-phenyl-l-(2-pyridyl)-2-propen-l-one with cyclopentadiene in water (Scheme 39). By using coordinating chiral, commercially available a-amino-adds and their derivatives with copper salts as catalysts, they obtained the desired product with yields generally exceeding 90%. With L-abrine (72 in Scheme 39) as chiral moiety, an enantiomeric excess of 74% could be achieved. Moreover, the catalyst solution was reused with no loss of enantioselectivity. 

The above-described structures are the main representatives of the family of nitrogen ligands, which cover a wide spectrum of activity and efficiency for catalytic C - C bond formations. To a lesser extent, amines or imines, associated with copper salts, and metalloporphyrins led to good catalysts for cyclo-propanation. Interestingly, sulfinylimine ligands, with the chirality provided solely by the sulfoxide moieties, have been also used as copper-chelates for the asymmetric Diels-Alder reaction. Amide derivatives (or pyridylamides) also proved their efficiency for the Tsuji-Trost reaction. 

The most active catalyst for this reaction is formed in situ from 125 (fig. 2.22), in the presence of copper salts. Interestingly, high conversions and ee are only observed with the precursor 125 but not 123 or 121 [101]. 

Copper salts may be replaced also by other catalysts . ... 

Copper salts such as CuS04 are potent catalysts of the oxidative modification of LDL in vitro (Esterbauer et al., 1990), although more than 95% of the copper in human serum is bound to caeruloplasmin. Cp is an acute-phase protein and a potent inhibitor of lipid peroxidation, but is susceptible to both proteolytic and oxidative attack with the consequent release of catalytic copper ions capable of inducing lipid peroxidation (Winyard and... 

In order to improve the selectivity toward the formation of 1,3-PDO, we studied the influence of metal salt additives. While the addition of calcium or copper salts exhibited a moderate influence, the presence of iron salts played a significant role on the rate and selectivity of the reaction (Figure 35.1). The metal additives reduced noticeably the activity of the rhodium catalysts suggesting that they acted as a surface poison, but they modified the selectivity of the glycerol hydrogenolysis, probably through selective diol chelation. 

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