Cuprous chloride hydrocarbons

By passing a mixture of carbon monoxide and hydrogen chloride into the aromatic hydrocarbon in the presence of a mixture of cuprous chloride and aluminium chloride which acts as a catalyst (Gattermann - Koch reaction). The mixture of gases probably reacts as the equivalent of the unisolated acid chloride of formic acid (formyl chloride) ... 

An analogous mechanism was proposed for the conversion of the triflate 416 to the vinyl-, allyl- and allenyl-A2-cephems 448 in yields of 47-71% by the respective tributyltin compounds in the presence of cuprous chloride (Scheme 6.91) [176]. Accordingly, the cyclic allene 417 should be liberated from 416 in the first step. Then, the organocopper species would transfer a hydrocarbon group to the central allene carbon atom of 417, leading to an allyl anion derivative, which is protonated during the workup. These reactions of 416 and 443 indicate that the cyclic allenes 417 and 444 behave toward nucleophiles as 1,2-cyclohexadiene (6) (Schemes 6.11— 13) and its non-polar derivatives such as 215 (Scheme 6.51), 221 (Scheme 6.52), 311 (Scheme 6.67) and 333 (Schemes 6.71 and 6.73), that is, they interact with nucleophiles at the central carbon atom of the allene system exclusively. 

For preparative purposes the method of obtaining aldehydes from the primary alcohols is preferable by far, at least in the aliphatic series. The simple aromatic aldehydes can be obtained by alkaline hydrolysis of the arylidene chlorides, R.CHC12, which are produced from the hydrocarbons by substitution with chlorine (technical method for the preparation of benzaldehyde). In addition to these methods the elegant synthesis of Gattermann and Koch should be mentioned here. This synthesis, which proceeds like that of Friedel-Crafts, consists in acting on the aromatic hydrocarbon with carbon monoxide and hydrogen chloride in the presence of aluminium chloride and cuprous chloride. 

GATTERMANN-KOCH REACTION. Formulation of hen/cne, alkyl-betuenes. or polycyclic aromatic hydrocarbons with carbon monoxide and hydrochloric acid in the presence of aluminum chloride al high pressure. Addition of cuprous chloride allows Ihe reaction to proceed at atmospheric pressure. 

Aromatic aldehydes are prepared by passing carbon monoxide and dry hydrogen chloride through an ether or nitrobenzene solution of an aromatic hydrocarbon in the presence of a catalyst, commonly aluminum chloride with cuprous chloride as a carrier. The process is illustrated by the synthesis of p-tolualdehyde (51%). A convenient procedure for obtaining an equimolar mixture of anhydrous hydrogen chloride and carbon monoxide consists in dropping chlorosulfonic acid on formic acid, viz.,... 

Cuprous chloride forms crystalline complexes with numerous unsaturated hydrocarbons, of which one has already been mentioned. In several of these Cu(i) forms two bonds to Cl and a third to a multiple bond of the hydrocarbon, the three bonds from Cu being coplanar. In the 1,5-cyclooctatetraene complex, CuCl. the Cu and Cl atoms form an infinite chain (Fig. 25.5(a)), while in... 

Photolytic rearrangement. Irradiation of the w-complex of s cyclo-octadiene with cuprous chloride produces tricyclo[3.3.0.02- ]octane, a remarkably stable hydrocarbon. ... 

Since the Friedel-Crafts reaction, when applied to phenol ethers, yields the corresponding aldehydes far more easily than the same reaction applied to the hydrocarbons, it is remarkable that the Gattermann-Koch method cannot be used with phenol ethers. If it be desired to obtain aldehydes from them, hydrocyanic acid is used in place of carbon monoxide in these cases the presence of cuprous chloride is unnecessary. The action takes place, due to the union of hydrocyanic and hydrochloric adds to form the chloride of imidoformic add ... 

In the early sixties, a redox catalyst system for the addition of halogenated hydrocarbons to olefins was discovered at Dow (3). The addition was carried out in the presence of a mixture of cuprous chloride and an amine such as piperidine or cyclohexylamine (Scheme II). Essentially quantitative yields of the one-to-one adducts could be obtained and the new catalyst system worked as well with carbon tetrachloride as bromotrichloromethane. Independently, M. Asscher and D. Vofsi (4) found a similar catalyst system. 

The addition takes place according to Markownikoff s rule. The addition of carbo lic acida to the double bonds of isobutylene and trimethyl-ethylene gives tertiary esters. A true equilibrium independent of sulfuric acid concentrations is established in the exothermic reaction. The addition does not go well with ethylene, but goes well with many of the higher alkenes, particularly with some of the terpenes. To avoid the polymerizing effects of sulfuric acid, various other catalysts, such as sulfonic acids, triethylamine, hydrofluoric acid, boron trifluoride, and cuprous chloride have been used. The addition may take place at room temperature or higher and is aided by pressure. The vapors of the acid and hydrocarbon may be passed over catalysts, such as activated carbon, heteropoly acids, or metal phosphates. ... 

The reactions of acetylene which have been mentioned are analogous to those of the unsaturated hydrocarbons containing a double bond. Acetylene and other compounds which contain a carbon atom in combination with hydrogen and joined to a second atom in the manner which is represented by a triple bond, that is, those containing the group H —C =, show characteristic properties which serve to distinguish them from other substances. Such compounds are converted into metallic derivatives when they are treated with an ammoniacal solution of cuprous chloride or of silver chloride. If acetylene is passed into a solution of cuprous chloride in ammonia, a red precipitate is formed which has the composition C2CU2. This compound, which is a carbide of copper, is usually called copper acetylide. It explodes, when dry, if it is struck or is heated to 100°-120°. When treated with hydrochloric acid or with a solution of potassium cyanide, acetylene is formed. 

Traugott Sandmeyer (Wettingen, 15 September 1854-Zurich, 9 April 1922) was Victor Meyer s lecture assistant and participated in the discovery of thiophen (see p. 810). He discovered the Sandmeyer reaction for the preparation of halogen derivatives of aromatic hydrocarbons by warming a solution of a diazonium compound with cuprous chloride and hydrochloric acid, or cuprous bromide and hydrobromic acid, or with hydriodic acid or potassium... 

A second commercial route to acrylonitrile used by DuPont, American Cyanamid, and Monsanto was the catalytic addition of HCN to acetylene (46). The reaction occurs by passing HCN and a 10 1 excess of acetylene into dilute HCl at 80° C in the presence of cuprous chloride as the catalyst. These processes use expensive C2 hydrocarbons as feedstocks and thus have higher overall acrylonitrile production costs compared to the propylene-based process technology. The last commercial plants using these process technologies were shutdown by 1970. 

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