Gatterman method

The catalytic action of the cuprous salts is assumed to depend on the formation of addition compounds which aid in the elimination of nitrogen and direct the halogen to the nucleus. In the Sandmeyer method the diazonium salt solution is added to a freshly prepared solution of the cuprous halide at a temperature below 10°. The mixture is then warmed until the evolution of nitrogen ceases. In some cases better yields are obtained if the diazonium solution is added slowly to a boiling solution of the cuprous salt. In the Gatterman method the desired diazonium salt is prepared. In the case of bromide and iodide, the diazonium sulfate is prepared and is mixed with an excess of potassium bromide or iodide. Finely divided copper is added and the mixture is warmed until the evolution of nitrogen ceases. The finely divided copper may be prepared by adding zinc dust to copper sulfate solution. The object of this experiment is to illustrate both methods. For semimicro work either chlorobenzene or o-chlorotoluene may be used. 

All attempts to prepare selenazole derivatives by the Gatterman (for-mylation) or Friedel-Crafts (alkylation) methods failed (19, 26). indicating that the electrophilic reactivity of the 5-position is less than that of benzene or toluene. 

Another method, formylation with CO and HCl in the presence of AICI3 and CuCl (the Gatterman-Koch reaction), is limited to benzene and alkylbenzenes. ... 

A useful method for the synthesis of 5-chloro-l,2,4-thiadiazoles (206) is the reaction of amidines with trichloromethylsulfenyl chloride (see Equation (30)). 3-Halo derivatives (349) (X = Cl, Br, I) (Equation (57)) have been obtained in moderate yields from the corresponding amines (348) via the Sandmeyer-Gatterman reaction <84CHEC-I(6)463>. 3-Chloro-l,2,4-thiadiazolin-5-ones (350) and (351) can be prepared by reacting chlorocarbonylsulfenyl chloride with carbodiimides or cyanamides respectively (Scheme 79) <84CHEC-I(6)463>. 

The Gatterman aldehyde synthesis employs hydrogen cyanide and unlike the Gatterman-Koch procedure, this method is successful in the case of phenols and phenolic ethers, although only the more reactive hydrocarbons are formylated... 

Gatterman, Practical Methods of Organic Chemistry, trans. by Schober and llabasinian, p. 202, The Macmillan Company, New York, 1921. 

Gatterman and Wieland, Laboratory Methods of Organic Chemistry. The Macmillan Co, Ne-w York, 1938. 

The electrophilic formylation of arenes with CO in the presence of acids (Gatterman-Koch conditions) is an efficient method for preparing aromatic aldehydes. HF-SbFs-SO2CIF is the most active system for this reaction [82]. It has been demonstrated that even diformylation can be achieved on polymeric aromatics such as biphenyl with the use of fluoroantimonic acid (Eq. 36) [83]. 

Introduction. The diazo group, N2X, is easily replaced by a number of other functional groups, such as OH, Cl, Br, I and CN. This affords a convenient method for the preparation of such derivatives as cannot be obtained by other methods except with great difficulty. The replacement of N2X by a halogen group is accomplished by heating the solution of diazonium salt with cuprous halide (Sandmeyer reaction) or with finely divided copper (Gatterman reaction). In the preparation of iodides the catalytic effect of copper is not required it is necessary only to pour the diazonium salt into a solution of potassium iodide and then to acidify the solution ... 

Introduction. In the preceding experiment it was shown that an aqueous solution of a diazonium salt treated with a solution of an alkali iodide gives iodobenzene. The replacement of the diazo group, N2X, by chlorine or bromine atoms involves the catalytic action of copper salts. Thus, benzenediazonium chloride warmed with a solution of cuprous chloride and hydrochloric acid gives chlorobenzene with cuprous bromide, bromobenzene is formed. The use of the cuprous salt is known as the Sandmeyer method. Instead of cuprous salts, finely divided copper may be used according to Gatterman s method. 

The Cohen s method for performing the Gatterman synthesis of symmetrical biaryls Preparation of 4,4 -dinitrobiphenyl (61) [94]... 

Aldehydes cannot be synthesized by the Friedel-Crafts reaction using methanoyl chloride (formyl chloride) because it is an unstable compound. However, a gaseous mixture of carbon monoxide and hydrogen chloride reacts like formyl chloride. The formylation of an aromatic compound using this gaseous mixture and aluminum trichloride is called the Gatterman—Koch synthesis. Like the Friedel-Crafts reaction, this method is limited to activated aromatic compounds. 

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