Aldehydes copper® chloride

Wacker (1) A general process for oxidizing aliphatic hydrocarbons to aldehydes or ketones by the use of oxygen, catalyzed by an aqueous solution of mixed palladium and copper chlorides. Ethylene is thus oxidized to acetaldehyde. If the reaction is conducted in acetic acid, the product is vinyl acetate. The process can be operated with the catalyst in solution, or with the catalyst deposited on a support such as activated caibon. There has been a considerable amount of fundamental research on the reaction mechanism, which is believed to proceed by alternate oxidation and reduction of the palladium ... 

A rapid and high yielding synthesis of pyrazolo[3,4- pyrimidinones by reaction of aromatic aldehydes with 4-amino-l-methyl-3-propyl-177-pyrazole-5-carboxamide intermediates in the presence of copper chloride has recently been reported for the synthesis of Viagra analogues <2005H(65)1821>. 

An important recent advance in the area is the demonstration that allyl chlorides readily form allylcopper species upon exposure to highly activated copper ( Rieke copper ). The resultant allylcoppers have been shown to react with a fairly wide range of nucleophiles (ketones, aldehydes, acid chlorides, enones, epoxides [after conversion to the cuprate], imines, and allyl bromides)56. Regiochemical considerations in such substitutions depend upon the cases studied, and are fairly complex. The allylcoppers formed have, in all cases, the least substituted C—Cu bond allyl transfer from these reagents is selective from the imposition of the allyl (enone electrophiles excepted)(equations 41 and 42). The allyl chloride... 

The sonochemical conditions minimize p-elimination.274 Perfluoroalkylation of arene tricarbonyl-chromium aldehydes occurs without decomposition of the transition metal group used to induce stereoselectivity in the addition.275 l,l/l-Trifluoro-2-bromo-2-propene adds to an aldehyde function in the presence of zinc and copper chloride (Eq. 62).276 The adduct was used for the s3mthesis of steroid precursors via a ring opening of the benzocyclobutene to an ortho quino-dimethane, followed by an intramolecular Diels-Alder reaction. 

Wacker process 1. A catalytic process used to oxidize aliphatic hydrocarbons such as ethylene to ethanol, aldehydes, and ketones using oxygen. The process uses an aqueous solution of mixed palladium and copper chlorides either in solution or on a support of activated carbon through which the ethylene is bubbled. The process was invented in 1957 and is named after the chemical company. 2. A process used for the production of sodium salicylate through the reaction of sodium phenate and carbon dioxide. 

Using a number of other aldehydes, more compHcated products result. Stmcture (2) was also found to react with alkynes in the presence of copper(I) chloride to give furans ... 

Nonactivated terminal acetylenes have been added to enamines derived from aldehydes. A long reaction time or catalysis by copper(I) chloride is necessary. Thus the enamine (16) formed the adduct (72) on heating with phenylacetylene (64). 

Installation of a different side chain completely alters the pharmacological profile leading to a new class of muscle relaxants. The synthesis begins with copper(II)-promoted di-azonium coupling between furfural (j ) and 3,4-dichlorobenzene-diazonium chloride (15) to give bi aryl aldehyde Next, condensation with 1-aminohydantoin produces the muscle relaxant clodanolene (17). ... 

Oxy-aldehyd, n, hydroxy aldehyde, -ammo-niak, n, oxyammonia (hydroxylamine), -azoverbindung, /. hydroxyazo compound, -benzol, n, hydroxybenzene (phenol), -bem-steinsaure. /, hydroxysuccinic acid (malic acid). -biazol, n. oxadiazole, oxdiazole. -bitumen, n, oxidized bitumen, -carbon-s ure, /, hydroxycarboxylic acid, -chlnoltn, n. hydroxyquinoline, -clunon, n. hydroxy-quinone. -chlorid, n. oxychloride, -chlor-kupfer, n. copper oxychloride, -cyan, n. oxycyanogen. 

Reaction of the lithium enolate 2 with prochiral aldehydes at low temperature proceeds with little selectivity, producing all four possible diastereomers 3, 4, 5, and 6 in similar amounts50. Transmetalation of the lithium enolate by treatment with three equivalents of diethylaluminum chloride or with one equivalent of copper cyanide generates the corresponding cthylaluminum and copper enolates which react at — 100°C with prochiral aldehydes to produce selectively diastereomers 1 and 2, respectively50. The reactivity of tin enolates of iron- propanoyl complexes has not been described. 

In contrast, transmetalation of the lithium enolate at —40 C by treatment with one equivalent of copper cyanide generated a species 10b (M = Cu ) that reacted with acetaldehyde to selectively provide a 25 75 mixture of diastereomers 11 and 12 (R = CH3) which are separable by chromatography on alumina. Other diastereomers were not observed. Similar transmetalation of 10a (M = Li0) with excess diethylaluminum chloride, followed by reaction with acetaldehyde, produced a mixture of the same two diastereomers, but with a reversed ratio (80 20). Similar results were obtained upon aldol additions to other aldehydes (see the following table)49. 

The reaction of crotonaldehyde and methyl vinyl ketone with thiophenol in the presence of anhydrous hydrogen chloride effects conjugate addition of thiophenol as well as acetal formation. The resulting j3-phenylthio thioacetals are converted to 1-phenylthio-and 2-phenylthio-1,3-butadiene, respectively, upon reaction with 2 equivalents of copper(I) trifluoromethanesulfonate (Table I). The copper(I)-induced heterolysis of carbon-sulfur bonds has also been used to effect pinacol-type rearrangements of bis(phenyl-thio)methyl carbinols. Thus the addition of bis(phenyl-thio)methyllithium to ketones and aldehydes followed by copper(I)-induced rearrangement results in a one-carbon ring expansion or chain-insertion transformation which gives a-phenylthio ketones. Monothioketals of 1,4-diketones are cyclized to 2,5-disubstituted furans by the action of copper(I) trifluoromethanesulfonate. ... 

CHROMIUM TRIOXIDE-PYRIDINE COMPLEX, preparation in situ, 55, 84 Chrysene, 58,15, 16 fzans-Cinnamaldehyde, 57, 85 Cinnamaldehyde dimethylacetal, 57, 84 Cinnamyl alcohol, 56,105 58, 9 2-Cinnamylthio-2-thiazoline, 56, 82 Citric acid, 58,43 Citronellal, 58, 107, 112 Cleavage of methyl ethers with iodotri-methylsilane, 59, 35 Cobalt(II) acetylacetonate, 57, 13 Conjugate addition of aryl aldehydes, 59, 53 Copper (I) bromide, 58, 52, 54, 56 59,123 COPPER CATALYZED ARYLATION OF /3-DlCARBONYL COMPOUNDS, 58, 52 Copper (I) chloride, 57, 34 Copper (II) chloride, 56, 10 Copper(I) iodide, 55, 105, 123, 124 Copper(I) oxide, 59, 206 Copper(ll) oxide, 56, 10 Copper salts of carboxylic acids, 59, 127 Copper(l) thiophenoxide, 55, 123 59, 210 Copper(l) trifluoromethanesulfonate, 59, 202... 

The allylation of aldehydes can be carried out using stannous chloride and catalytic cupric chloride or copper in aqueous media." In-situ probing provides indirect (NMR, CV) and direct (MS) evidence for the copper(I)-catalyzed formation of an allyltrihalostannane intermediate in very high concentration in water (Scheme 8.6). Hydrophilic palladium complex also efficiently catalyzes the allylation of carbonyl compounds with allyl chlorides or allyl alcohols with SnCl2 under aqueous-organic... 

The group of Leadbeater reported a different type of Mannich reaction, which involved condensation of an aldehyde (1.5 equivalents) with a secondary amine and a terminal alkyne, in the presence of copper(I) chloride (10 mol%) to activate the... 

One example for the reaction of a 229-type copper reagent is shown in Equation (128). Neopentyl-substituted organocopper reagent 230, which bears aldehyde, is generated followed by treatment with acetyl chloride to provide coupling product 231 in 70% yield. Application of this method to the selective functionalization of polyhalogenated aromatics was also reported.497... 

Since the acetaldehyde cannot be separated by fractional distillation from the ether in which it has been collected, it is converted into the crystalline aldehyde-ammonia. The contents of the two receivers are transferred to a small filter jar which is cooled in a freezing mixture, and ammonia gas is led in from a cylinder. The delivery tube for the current of ammonia is a straight calcium chloride tube with its wide end deeply submerged in the liquid. To break up the crystalline mass which is formed, this tube is frequently moved to and fro. The jar is kept covered with a clock-glass (bored), piece of cardboard, or copper gauze. On account of the ether which evaporates, all flames in the vicinity must be extinguished. 

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