Aryl derivatives reactions

C. Alkyl and Aryl Derivatives.—Reactions of organometallic reagents, such as methyl-lithium, with fluorocyclophosphazenes are, in general,... 

With the exception of the nuclear amination of 4-methylthiazole by sodium amide (341, 346) the main reactions of nucleophiles with thiazole and its simple alkyl or aryl derivatives involve the abstraction of a ring or substituent proton by a strongly basic nucleophile followed by the addition of an electrophile to the intermediate. Nucleophilic substitution of halogens is discussed in Chapter V. 

Ai lepiesents an aiyl group. Diaiyl products are obtained after long reaction times. Other Friedel-Crafts catalysts, eg, ZnCl2, FeCl2, FIF, and BF, can also be used. In most cases, stoichiometric amounts of the catalyst ate requited. Flowever, strong complexation of the phosphine by the catalyst necessitates separation by vacuum distillation, hydrolysis, or addition of reagents such as POCl to form more stable aluminum chloride complexes. Whereas yields up to 70—80% are possible for some aryl derivatives, yields of aliphatic derivatives are generally much less (19). 

Thiophene [110-02-1] and a number of its derivatives are significant in fine chemical industries as intermediates to many products for pharmaceutical, agrochemical, dyestuffs, and electronic appHcations. This article concentrates on the industrial, commercial, and economic aspects of the production and apphcations of thiophene and thiophene derivatives and details the main synthetic schemes to the parent ring system and simple alkyl and aryl derivatives. Functionalization of the ring and the synthesis of some functional derivatives that result, not from the parent ring system, but by direct ring cyclization reactions are also considered. Many good reviews on the chemistry of thiophene and thiophene derivatives are available (1 7). 

The aldol-like reaction of an aromatic aldehyde 1 with a carboxylic anhydride 2 is referred to as the Perkin reaction. As with the related Knoevenagel reaction, an o ,/3-unsaturated carboxylic acid is obtained as product the /3-aryl derivatives 3 are also known as cinnamic acids. 

By application of the Schmidt reaction, the conversion of a carboxylic acid into an amine that has one carbon atom less than the carboxylic acid, can be achieved in one step. This may be of advantage when compared to the Curtius reaction or the Hofmann rearrangement, however the reaction conditions are more drastic. With long-chain, aliphatic carboxylic acids yields are generally good, while with aryl derivatives yields are often low. 

The Suzuki reaction97 allows tire coupling of two aromatic rings by reaction of an arylboronic compound with a iodo or bromo aryl derivative. The tetrakis (U iphenylphosphine) Pd is the catalyst working in the basic medium. This reaction was recently used98 in aqueous media for the preparation of different isomers of diphenyldicarboxylic acids (Fig. 5.21) but also for the synthesis of soluble rodlike polyimides99 by coupling the 3,6-diphenyl- V, V,-bis(4-bromo-... 

This chapter covers recent information on the preparation, physical properties, and reactions of quinoxaline and its C-alkyl, C-aryl, iV-alkyl, and A-aryl derivatives as well as their respective ring-reduced analogs. In addition, it includes methods for introducing alkyl or aryl groups (substituted or otherwise) into quinoxalines already bearing substituents and the reactions specific to the alkyl or aryl groups in such compounds. For simplicity, the term alkylquinoxaline in this chapter is intended to include alkyl-, alkenyl-, alkynyl-, and aralkylquinoxalines likewise, arylquino-xaline includes both aryl- and heteroarylquinoxalines. 

The reaction of 1-amino-1-deoxyketoses, and their N-alkyl and N-aryl derivatives, with alkyl or aryl isothiocyanates (Huber et al, 1960) was studied in more detail, and new 4-(alditol-l-yl)-l-alkyl(aryl)-3-alkyl(aryl)-l,3-dihydro-2H-imidazole-2-thiones were obtained. These compounds were used as starting materials for the synthesis of OL-histidines, DL-histidine-2-thiol, and other imidazole derivatives of biological interest. 

B. Aryl Derivatives.—The Ph3P=N group imparts high nucleophilic reactivity to the tervalent phosphorus atom in A -(diphenylphosphino)tri-phenylphosphazene, Ph3p=N PPha- Ready reactions occur with methyl iodide, phosphorus(in) halides, and bromine ... 

Organoboranes can also be made using organocopper reagents. One route to methyl and aryl derivatives is by reaction of a dialkylborane, such as 9-BBN, with a cuprate reagent.4... 

The same authors also observed that 25 underwent a Grignard reaction which provided a new route for synthesizing various 5-alkyl or 5-aryl derivatives of benzo[6]thiepin (27) 22). 

As for the regioselectivity of the nitrone cycloaddition to MCP and its alkyl or aryl derivatives, a tendency of the three-membered ring to end up at the 4-position of the final isoxazolidine ring clearly emerges from the experimental findings. This result is particularly noteworthy if compared to regiospecific formation of the 5,5-disubstituted isoxazolidines in the reactions of nitrones, not... 

Another multicomponent synthesis giving N-3-substituted compounds 28 consisted of the sequential reaction of metallated phosphonoacetates, in one pot, with a nitrile then an aldehyde and finally an isocyanate. This was an extensive study of the scope and limitations of the different substituents on all the components. The most important feature was that, for good yields, the isocyanate should bear an electron-withdrawing group - tosyl was the most successful. However, an exchange reaction could be carried out by reaction of the tosyl products with aryl isocyanates under microwave irradiation, giving the N-3-aryl derivatives 29 <06CEJ7178>. 

Aryl derivatives of the heavier group 6 derivatives can also serve for the synthesis of arylmercury compounds.52 For instance, treatment of the diaryltellurium complex 30 with HgCl2 leads to the formation of a coordination complex which undergoes a slow dismutation reaction to afford the arylmercury chloride derivative 31 and the corresponding tellurium species (Scheme 3).53... 

Addition of Alkyl and Aryl Derivatives To illustrate stereoselective syntheses in nucleophilic reactions of nitrones, the synthesis of (+ )-lentiginosine... 

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