Copper methoxide

Wang and co-workers have reported [Y2Cug02(hp)i2Cl2(N03)4(H20)2] and [Nd2Cug02-(hp)i2Cl2(0Me)4(H20)4], which are made from reaction of copper methoxide with Hhp in MeOH, followed by addition of either yttrium nitrate or neodymium chloride. The metal core is similar in both compounds, with a central M2CU4 octah ron (M = Y or Nd), with the... 

Costa E., Camus A., Marsich N.J. Copper methoxides formed by thermal decomposition of copper methyl in methanol. Inorg. Nucl. Chem. 1965 27 281 Daniele S., Hubert-Pfalzgraf L.G., Daran J.C. Building of lanthanide oxoalkoxides Synthesis and molecular structure of [Gd6(/i4-0)(/x3,77 -OR)4(R,/j -OR)6(/iv -OR)2(OR)4] (R= C2H40Me). Polyhedron 1996 15 1063... 

Copper methoxide, Cu(OMe)2 Blue powder, insoluble, decompose on heating IR, UV-vis, magnetic properties [77,78]... 

Terminal alkynes react with propargylic carbonates at room temperature to afford the alka-l, 2-dien-4-yne 14 (allenylalkyne) in good yield with catalysis by Pd(0) and Cul[5], The reaction can be explained by the transmetallation of the (7-allenylpailadium methoxide 4 with copper acetylides to form the allenyKalk-ynyl)palladium 13, which undergoes reductive elimination to form the allenyl alkyne 14. In addition to propargylic carbonates, propargylic chlorides and acetates (in the presence of ZnCb) also react with terminal alkynes to afford allenylalkynes[6], Allenylalkynes are prepared by the reaction of the alkynyl-oxiranes 15 with zinc acetylides[7]. 

The Guerbet reaction can be used to obtain higher alcohols 2-propyl-1-heptanol [10042-59-8] from 1-pentanol condensation and 6-methyl-4-nonanol from 2-pentanol (80—83). Condensations with alkah phenolates as the base, instead of copper catalyst, produce lower amounts of carboxyhc acids and requke lower reaction temperatures (82,83). The crossed Guerbet reaction of 1-pentanol with methanol in the presence of sodium methoxide catalyst afforded 2-heptanol in selectivities of about 75% (84). 

Direct Blue 218 had reported sales of 623 t valued at 4.4 million ia 1987. It is produced from Direct Blue 15 (76) by metallizing and elimination of methyl groups from the methoxide to form the copper complex. Direct Blue 15 (76) is prepared by coupling o-dianisidine [119-90-4] to two moles of H-acid (4-amiQO-5-hydroxy-2,7-naphthalenedisulfonic acid) under alkaline pH conditions. Other important direct blues iaclude Direct Blue 80 (74), (9-dianisidine coupled to two moles of R-acid (3-hydroxy-2,7-naphthalenedisulfonic acid [148-75-4]) followed by metallizing to form a bis copper complex, and Direct Blue 22 (77), an asymmetrical disazo dye, prepared by coupling o-dianisidine to Chicago acid [82-47-3] and 2-naphthol. Direct Blue 75 (78) is an example of a trisazo dye represented as metanilic acid — 1,6-Q.eve s acid — 1,6-Q.eve s acid — (alb) Ai-phenyl J-acid. 

Chloroquinoline (401) reacts well with potassium fluoride in dimethylsulfone while its monocyclic analog 2-chloropyridine does not. Greater reactivity of derivatives of the bicyclic azine is evident also from the kinetic data (Table X, p. 336). 2-Chloroquinoline is alkoxylated by brief heating with methanolic methoxide or ethano-lic potassium hydroxide and is converted in very high yield into the thioether by trituration with thiocresol (20°, few hrs). It also reacts with active methylene carbanions (45-100% yield). The less reactive 3-halogen can be replaced under vigorous conditions (160°, aqueous ammonia-copper sulfate), as used for 3-bromoquino-line or its iV-oxide. 4-Chloroquinoline (406) is substituted by alcoholic hydrazine hydrate (80°, < 8 hr, 20% yield) and by methanolic methoxide (140°, < 3 hr, > 90% yield). This apparent reversal of the relative reactivity does not appear to be reliable in the face of the kinetic data (Tables X and XI, pp. 336 and 338) and the other qualitative comparisons presented here. 

Chloro-6-methyl-l,5-naphthyridine reacts readily with methano-lic methoxide (65°, 7 hr, 75% yield), but more vigorous conditions (180°, 2-7 hrs, 30-85% yield) were used for various aminations. The 4-chlorodiazanaphthalene reacted with a sec-alkylamine under less vigorous conditions (95%, 36 hr, 85% yield) and with ammonia-phenol (180°, 3 hr, 50% yield) gave the phenoxy derivative which was also alkylaminated (200°, 3 hr, 90% yield).The 3-bromo and 3-bromo-2-ethoxy derivatives of428 were aminated with copper sulfate and concentrated ammonia (170°, 40 hr, 75% yield). 

One aspect of the copper catalytic system that has received attention is the identity of the active catalytic species. In the case of displacement of aryl bromides by methoxide ion in the presence of CuBr, it has been suggested that the active species is Cu(I)(OCH3)2, an anionic cuprate.153... 

A version of P.R.202 in a platelet form is obtainable by recrystallizing of the crude pigment from a polar solvent such as DMF in the presence of a thiol compound and sodium methoxide. The new form affords, for instance in PVC, the appearance of a lustrous copper bronze tone [27]. 

Better results can be obtained by generating the boronate species with the aid of sodium methoxide. In this case, satisfactory transmetalation occurs on treatment with Cul. Thus, the functionalized copper reagent 55 can be alkynylated with 1-bromo-l-hexyne at —40 °C, furnishing the enyne 56 in 75% yield (Scheme 2.15) [32]. 

The nonpolar copper ethoxide and methoxide may be substituted by more polar groups such as N,N-diethylethanolamine or butoxyethanol (16). The resulting alkoxides can be mixed with Y- and Ba-isopropoxides in tetrahydrofuran and hydrolyzed. Hydrolysis appears to be quite complete since the resulting precipitates are almost carbon-free. Thus, crystallization of the superconducting phase occurs at temperatures lower than 800°C. 

Nucleophilic substitution of (189b) with methoxide ion gave the methoxy substituted compound, which, however, reacted further to give deboronated thiophenes. Copper-promoted nucleophilic substitution of some 4-brominated thieno fused diazaborines can be carried out successfully (equations 13 and 14) <77CS<11)76). 

The cyclodehydration of o-phenoxybenzoic acids has been widely used to synthesize xanthones carrying variety of substituents. An Ullmann reaction provides a useful route to the required acids a 2-chlorobenzoic acid and a phenol react in an inert solvent such as nitrobenzene in the presence of copper bronze and potassium carbonate (53JCS1348). In a modified procedure sodium methoxide is used without solvent at 200 °C (79JA665). Cyclization is accomplished in concentrated sulfuric acid or in acetyl chloride containing a little sulfuric acid (61JCS2312). 

The direct electrochemical synthesis of metal alkoxides by the anodic dissolution of metals into alcohols containing conducting electrolytes was initially demonstrated by Szilard in 1906 for the methoxides of copper and lead.19 More recently the method has received some attention particularly in the patent literature.29-25 The preparation of the ethoxides of silicon, titanium, germanium, zirconium and tantalum by electrolysis of ethanolic solutions of NH Cl has been patented, although the production of the ethoxides was found to cease after several hours.24,25... 

Similar reactivity towards phenylisocyanate is found, while carbodiimide yields a 1 1 adduct in which insertion into the M—-OR bond has not taken place.250,251 Copper(II) methoxide undergoes the reversible insertion of C02 to yield the corresponding carbonate.252... 

Sodium hydrogen carbonate Thionyl chloride Copper iodide Diazomethane Imidazole Trifluoroacetic acid Sodium methoxide 7-Bromo-3a,8b-cis-3a,8b-dihydro-3H-5-cyclopenta[b] benzofurancarboxylic acid... 

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