Methanol, copper salt

ACETYLENOGEN (75-20-7) Contact with water, moist air, steam, alcohols forms explosive acetylene gas, corrosive calcium hydroxide, and heat. Violent reaction with acid, acid fumes, copper salts, strong oxidizers (bromine, chlorine, iodine, etc.), iron trichloride, tin dichloride, silver nitrate. Incompatible with oxidizers, hydrogen chloride, methanol, copper salt solutions, lead fluoride, magnesium, selenium, sodium peroxide, stannous chloride, sulfur. 

Phthalimide (L ), succinimide (L ), glutarimide (L ), pyrid-2-ylcarboximide-N-toluene-p-sulphonyl (L ) and benzofur-2-ylcarboximide-A/ -toluene-p-sulphonyl (L ) react with copper salts at pH 8.5 in 70% aqueous methanol to form K2[Cu(L)4(MeOH)2] (L = L L or L"), Cu(L )2 and The... 

An alternate approach to the palladium catalyzed ethynylation of thiophene derivatives has been reported by Zeni and co-workers. They coupled 2-(butyltelluro)thiophenes with different acetylenes (6.48.), The reaction, which was effectively catalyzed by palladium dichloride, was run in the absence of copper salts. The choice of base (triethylamine) and solvent (methanol) were both crucial for the success of the coupling.70... 

Phthalocyanines or tetrabenzoporphyrazines are prepared by the Wyler-Riley process (37BRP464126, 37BRP476243) via condensation of phthalic anhydride and urea in the presence of copper(I) chloride or by reaction of phthalonitrile with copper salts. Metal-free phthalocyanine, no longer of commercial importance, is prepared by reaction of phthalonitrile with sodium amylate, followed by demetallization in methanol. 

Monosubstituted acetylenic compounds can be oxidatively dimerized by air at room temperature in the presence of copper salts in a pyridine-methanol solution. This method has been applied to a wide variety of acetylenic compounds and gives high yields in disubstituted diacetylenic compounds (equation 264).590... 

Dimethyl carbonate is an interesting material which can be used instead of toxic dimethyl sulfate as a multipurpose alkylating reagent.438-578 Its synthesis can be performed in one step from cheap methanol, CO and oxygen materials in the presence of copper salts (e.g. copper(ll) methoxychloride or CuCl/py) at ca. 100 °C and 15-70 atm (equation 290).578,62S This reaction is thought to proceed in two steps 578 (a) formation of copper(II) methoxychloride from the reaction of copper(I) chloride, 02 and methanol (equation 291) and (b) reduction of copper(II) methoxychloride with CO to form dimethyl carbonate and regenerate copper(I) chloride (equation 292).626... 

Figure 5-86. The transesterification of the chelating ligand diethyl picolinate is enhanced upon coordination to a metal. Reaction with methanolic copper(u) salts gives the methyl ester in a very rapid process.

Metallization. Bident ate formazans that are insoluble in water can be warmed with cobalt, nickel, and copper salts (preferably acetates) to form metal chelates in solvents such as methanol, ethanol, acetone, and dimethylformamide. Metal complexes of tri- and tetradentate formazans are much more stable. Metallization with divalent salts occurs rapidly at room temperature. On reaction with diazo-tized 2-aminophenols or 2-aminonaphthols, coupling and metallization with divalent metal salts can take place concurrently under the same conditions. When coupling is complete, the dye is usually fully metallized. 

It is worthwhile to cite the pioneering work of Brackman and Havinga, carried out in the 1950s and considered as early tyrosinase models [1,2,179], Here, conditions were found to effect the straightforward catalytic o-hydroxyla-tion of phenols to give substituted o-quinones. A most interesting case occurs when copper salts are reacted with phenol, 02, and morpholine (mp) in methanol, giving insoluble morpholino-substituted o-benzoquinone. The reaction is complicated, but a Cu(II)-peroxo-phenol-mp species is seen to be an important intermediate (Scheme 17). 

The [MSR 6] reactor type (see below) was applied for methanol steam reforming over Cu/Ce02/Al203 catalysts by Men et al. [34, 35], Wash coating of the alumina was performed, followed by subsequent impregnation steps with ceria and copper salt solutions. At 250 °C reaction temperature and a water/methanol molar ratio of 0.9, the copper/ceria atomic ratio was varied from 0 to 0.9, revealing the lowest conversion for pure ceria and a sharp maximum for a ratio of 0.1 (see Figure 2.13). 

Dimethyl terephthalate is manufactured from terephthalic acid or directly from p-xylene. Esterification of terephthalic acid with methanol occurs with sulfuric acid as the acid catalyst. Direct oxidation of p-xylcnc with methanol present also produced dimethyl terephthalate copper salts and manganese salt are catalysts for this reaction. The dimethyl terephthalate (boiling point 288°C, melting point 141°C) must be carefully purified via a five-column distillation system. 

Compounds with a terminal acetylenic function, RCsCH, react with 1-bromoalkynes, R CsCBr in the presence of an aliphatic amine and a catalytic amount of a copper salt to give the coupling products RCsCCsCR. This useful reaction, discovered by Cadiot and Chodkiewicz [195], gives a ready access to a number of poly-unsaturated systems. The usual procedure involves dropwise addition of the bromoacetylene R GsCBr to a mixture of the acetylene RCsCH, ethylamine, ethanol or methanol, a catalytic amount of copper chloride or bromide and a small amount of hydroxylamine.HCl. This reducing agent prevents the oxidation to copper ). The reaction is usually very fast at temperatures in the region of 30 C. Since much heat is evolved, the reaction can be monitored easily by temperature observation. 

After recrystallization from methanol or 95% ethanol the fluffy light blue copper salt melts at 157-158°. 

Reductive desulfurization of the dithioketals 5.14 and 5.15 is performed under the same conditions as for thioethers [G02] LAH in the presence of copper salts or borohydrides in the presence of nickel salts (Figure 5.8). The deoxygenation of tertiary amine-oxides such as 5.16 and 5.17 can be performed with borohydride exchange resin-copper sulfate in methanol at room temperature or under reflux. This reaction tolerates other functional groups such as carbon-carbon double bonds, chlorides, epoxides, esters, amides, nitriles, sulfoxides, and sulfones [SA4] (Figure 5.8). 

The catalytic effect of copper salts on the 0-arylation of alcohols has been observed, but its synthetic importance remains limited. 7 jhe formation of 2-iodo-2 -acetoxybiphenyl (30) by reaction of the biphenyleneiodonium sulfate (29) with sodium acetate in boiling glacial acetic acid was quantitative when the reaction was catalysed by copper salts.(see 5.1.4.2) In the case of phenols, the (9-arylation by diaryliodonium salts is preferentially performed in a weakly basic medium (generally triethylamine) in the presence of copper bronze in dichloromethane or methanol at room temperature or at mild temperatures (around 50 C). Under these conditions, the 0-aryl ethers are obtained easily in good yields. l ... 

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