Cupric products/yields

Crystalline benzimidazoles have been obtained from all aldonic acids so far tested with only one exception that is known to the writer. Lohmar and Link29 reported that the condensation of D-glucosaminic acid (= 2-amino-2-desoxy-D-gIuconic acid) with o-phenylenediamine under a variety of conditions failed to yield a crystalline product. The direct oxidative condensation of D-glucosamine hydrochloride with o-phenylenediamine in the presence of cupric acetate yielded only the known 2-(D-arofro-tetrahydroxybutyl)quinoxaline (III) and not the desired benzimidazole. 

Repas [631] has proved that addition of water to the system H3P04/Si02 increases the propylene oligomerization product yield. He has also proposed a mechanism for this reaction in which surface propylene phosphate esters are the catalytic centers for propylene oligomerization. This catalytic system is often modified with cupric [641-643], nickel [642,644], and calcium salts [641], manganese derivatives [645], and amines [646,647]. 

For reaction with hydrogen haUdes, the substitution reaction with haUde ion easily occurs when a cuprous or cupric compound is used as the catalyst (23) and yields a halogenated aHyl compound. With a cuprous compound as the catalyst at 18 °C, the reaction is completed in 6 h. Zinc chloride is also a good catalyst (24), but a by-product, diaHyl ether, is formed. 

The oxidation has also been accomplished with Claycop (montmorillonite K-10 clay supported cupric nitrate). The reaction of 96 to 102 was complete in 1.5-7 h with 81-93% yields. The time can be reduced to 5-10 minutes using ultrasound with minimal effect on yields. The major limitation of this protocol was the observation that only R = aryl gave product. Oxidation of 4-alkyl substituents was inert to these conditions with recovery of starting 96. 

As discussed in Section 10.3, the system consisting of a diazonium ion and cuprous ions can be used for hydroxy-de-diazoniation at room temperature in the presence of large concentrations of hydrated cupric ions (Cohen et al., 1977 see Schemes 10-7 to 10-9). With (Z)-stilbene-2-diazonium tetrafluoroborate under these conditions, however, the major product of ring closure of the initially formed radical was phenanthrene (64%). When the cupric nitrate was supplemented by silver nitrate the yield increased to 86% phenanthrene. Apparently, the radical undergoes such rapid ring closure that no electron transfer to the cupric ion takes place. 

Homocoupling of alkyl halides in aqueous media can be mediated by manganese/cupric chloride to give the dimerization products in good yield. Cross-coupling can also be controlled to give the desired... 

Disubstituted 1,2,3-triazoles are usually minor components in the product mixtures obtained from reactions of triazole with electrophiles (see Section 5.01.5). The few regioselective syntheses of such compounds include a reaction of aminoacetophenones 1235 with hydrazines. The reaction with methylhydrazine proceeds well without any catalysis, but that with phenylhydrazine requires cupric chloride as a catalyst. It is assumed that hydrazone 1236 that forms in the first step is in a tautomeric equilibrium with its azo form 1237. However, it is not clear how bond formation between the nitrogen atoms and oxidation to the triazole system occurs. 4-Aryltriazoles 1238 are obtained in 50-66% yield (Scheme 205) <2003SC3513>. 

Copper-catalyzed monoaddition of hydrogen cyanide to conjugated alkenes proceeded very conveniently with 1,3-butadiene, but not with its methyl-substituted derivatives. The most efficient catalytic system consisted of cupric bromide associated to trichloroacetic acid, in acetonitrile at 79 °C. Under these conditions, 1,3-butadiene was converted mainly to (Z )-l-cyano-2-butene, in 68% yield. A few percents of (Z)-l-cyano-2-butene and 3-cyano-1-butene (3% and 4%, respectively) were also observed. Polymerization of the olefinic products was almost absent. The very high regioselectivity in favor of 1,4-addition of hydrogen cyanide contrasted markedly with the very low regioselectivity of acetic acid addition (vide supra). Methyl substituents on 1,3-butadiene decreased significantly the efficiency of the reaction. With isoprene and piperylene, the mononitrile yields were reduced... 

Nucleophiles, when they are used in the presence of cupric perchlorate, capture the cation-radicals initially formed. Instead of benzidines, the para-substituted dialkylanilines were obtained. In this a manner, A,A-dialkylanilines with halo or thiocyanato moieties in para positions were prepared in good yields under the same (simple) conditions. Scheme 7.13 illustrates the sequence of the transformations observed. The products are useful intermediates in the synthesis of dyes, drugs, and color cinema formulations. 

The oxidation products of hydroxylamine depend upon the nature of the oxidizing agent and the conditions of oxidation. Acid solutions of hydroxylamine react with ferric oxide to give quantitative yields of nitrous oxide and water (Knorre and Arndt, 20 Bray et al., 21) alkaline solutions of hydroxylamine react with cupric hydroxide to give... 

A reactive intermediate may be responsible for the copper catalysis of the hydroxylamine reaction. The intermediate formed in the silver-catalyzed reaction, if it has any real existence, is not further oxidized but breaks down into nitrogen and water. Oxidation of hydroxylamine by cupric ion, on the other hand, yields predominately nitrous oxide. The intermediate formed by the removal of a single electron from the hydroxylamine in this reaction must be further oxidized to yield the final product. Such an intermediate may react readily with silver ions in solution. 

An alternate procedure used in a few specialty applications is the cuprammonium process. This involves stabilization of cellulose in an ammonia solution of cupric oxide. Solubilization occurs by complex formation of cupric ion with ammonia and the hydroxyl groups of cellulose. Regeneration of cellulose, after formation of the desired products, is accomplished by treatment with acid. The main application of the cuprammonium process is for the synthesis of films and hollow fibers for use in artificial kidney dialysis machines. The cuprammonium process yields products with superior permeability and biocompatibility properties compared to the xanthation process. Less than 1% of all regenerated cellulose is produced by the cuprammonium process. 

A variation of this procedure involves the use of a catalytic amount of palladium chloride with cupric chloride as a reoxidant.2 This method, however, generally gives lower yields and less pure products. 

In terms of A -substitution, Hartwig reported improved conditions for the Pd(0) catalyzed N-arylation of indoles and pyrrole <99JOC5575>. It was found that when commercially available P(<-Bu)3 was employed as ligand and cesium carbonate as base, the reaction between indoles 95 and unhindered aryl bromides 96 or chlorides occurred under milder conditions than the Pd(OAc)2/DPPF system previously reported yielding the A/-arylated products 97. Alternatively, it has been found that pyrrole- and indole-2-carboxylic acid esters can be selectively 7V-arylated with phenylboronic acids in the presence of cupric acetate and either tiiethylamine or pyridine <99T12757>. 

Nitration of 1-hydroxyquinolizinium nitrate affords only a 31% yield of the betaine nitrated at the 2-position (64JCS3030). With quinolizin-4-one (14), which may be regarded as the betaine of 4-hydroxyquinolizinium ion, nitration in acetic acid at room temperature gives a 43% yield of 1,3-dinitroquinolizone. Only by use of cupric nitrate in acetic anhydride is there some mononitration (a mixture of 1- and 3-isomers), but here again the major product is the dinitro compound (64T1051). 

In order to shorten the reaction time, various heavy metal salts (zinc, lead, and manganese acetates) of weak organic acids, zinc or cobalt and tin chlorides are added to the reaction mixture [11]. For example, refluxing an uncatalyzed mixture of 3 moles of isobutyl alcohol and urea for 150 hr at 108°-126°C gives a 49% yield of the carbamate. Adding lead acetate or cobalt chloride to the same reaction lowers the reaction time to 75 hr, at which point an 88-92 % yield is obtained. In another example, ethylene glycol (1 mole) and urea (2 moles) are heated for 3 hr at 135°-155°C with Mn(OAc)2 to give a 78% yield of the diurethane [11]. The commercial production of butyl carbamate uses catalytic quantities of cupric acetate [12]. 

On the other hand, in the presence of small amounts of metallic salts such as cupric chloride, the course of the reaction changes to produce good yields of azo compounds [70]. The reaction, unfortunately, is not quite general. Thus the toluidines and aminophenols, for example, produce copious amounts of tarry products while the nitroanilines, evidently, are smoothly converted into azo compounds. 

A solution of 2 gm (0.014 mole) of 3-nitroaniline in 40 ml of glacial acetic acid and 1.85 gm (0.028 mole) of peracetic acid is treated with 1 ml of an aqueous solution containing 5 mg of cupric chloride dihydrate. The reaction mixture is stirred for 16 hr at 17°C. After this time, the precipitated product is filtered off (0.8 gm). The mother liquor is added to 200 ml of a 3N sodium hydroxide solution, whereupon another 0.61 gm of product is precipitated. The crude products are combined yield 1.42 gm (72%), m.p. 140°-144°C. On recrystallization the melting point is raised to 144°-147°C. 

Reaction between a siloxycyclopropane and Cu(BF3)2 in ether gives a product due to symmetrical coupling of two homoenolate moieties (Eq. 53, Table 12) [51]. This is particularly noteworthy as a simple route to 1,6-ketones superior to classical approaches such as the Kolbe electrolysis [52], Several lines of evidence suggest the intermediacy of Cu(II) homoenolates. AgBF3 and CuF2 effect the same reaction albeit with lower yields. The reactions with cupric halides give... 

Phenyltrimethylammonium bromide perbromide (PhMe3N Br3) was introduced as a reagent for the bromination of cyclic ketals81 (see section IV) but it has also been utilized for the selective bromination of ketones containing double bonds.82 The same claim has been made for cupric bromide as a brominating agent 83 yields are not good, however, and in methanol, the solvent usually employed, the formation of methoxy-substituted products is a common side reaction (cf. ref. 84, 85). 

Even the comparatively unreactive phenoxazine and phenothiazine systems undergo halogenation and nitration with ease and it is normal to prepare monosubstituted derivatives by stepwise procedures rather than by direct electrophilic attack. Indeed, the nitration of phenoxazine is uncontrollable and even N-acylphenoxazines afford a mixture of di- and tetra-nitro products (03CB475). Similarly phenothiazine and nitric acid produce a complex mixture of nitrated sulfoxides and sulfones. Chlorine in DMSO at 40 °C reacts with phenothiazine to yield 3,7-dichlorophenothiazine, whereas cupric chloride gives the 1,7-isomer (76JPR353). Direct bromination of phenoxazine produces a mixture of 3-bromo- and 3,7-dibromo-phenoxazines, while thionyl chloride affords the 1,3,7,9-tetrachloro derivative (60ZOB1893). 

Cellulose dissolves in Schweitzer s reagent, an ammoniacal solution of cupric oxide. After treatment with an alkali, ibe addition of carbon disulfide causes formation of sodium xanihate. a process used in the production of rayon. Sec also Fibers. The action of acetic anhydride in the presence of sulfuric acid produces cellulose acetates, the basis for a line of synthetic materials. See also Cellulose Ester Plastics (Organic). Nitrocelluloses are produced hy ihc action of nitric acid and sulfuric acid on cellulose, yielding compounds that are highly flammable and explosive. See also Explosives. 

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