Selenazoles, preparations

Diethylamino-4-methy]-5 -phenyiazao selenazole, preparation, by diazo coupling, 246... 

Diethylamino-4-methyl-5-phenvi carbinyi-selenazole, preparation, melting point. 250... 

Ary lamino-4-phenyl-5-phenyl azo selenazoles, preparation, by diazotization, 248 2-Ary lamino-5-phenyIselenazole, N-nitrosamino derivatives, 247 2-Arylaminoselenazoies, nitrosation, 246 table of products, 226. 230 2-Arylhexahydrobenzosdenazoles, by... 

In the first chapter, devoted to thiazole itself, specific emphasis has been given to the structure and mechanistic aspects of the reactivity of the molecule most of the theoretical methods and physical techniques available to date have been applied in the study of thiazole and its derivatives, and the results are discussed in detail The chapter devoted to methods of synthesis is especially detailed and traces the way for the preparation of any monocyclic thiazole derivative. Three chapters concern the non-tautomeric functional derivatives, and two are devoted to amino-, hydroxy- and mercaptothiazoles these chapters constitute the core of the book. All discussion of chemical properties is complemented by tables in which all the known derivatives are inventoried and characterized by their usual physical properties. This information should be of particular value to organic chemists in identifying natural or Synthetic thiazoles. Two brief chapters concern mesoionic thiazoles and selenazoles. Finally, an important chapter is devoted to cyanine dyes derived from thiazolium salts, completing some classical reviews on the subject and discussing recent developments in the studies of the reaction mechanisms involved in their synthesis. 

Hofmann (1), of the Zurich School, was the first to have tried unsuccessfully to prepare the unsubstituted parent compound, selenazole much later, in 1955, Metzger and Bailly (2) were equally unsuccessful in trying to prepare selenazole from 2-aminoselenazole by reduction of the diazo compound,... 

This chapter is an attempt to present the important results of studies of the synthesis, reactivity, and physicochemical properties of this series of compounds. The subject was surveyed by Bulka (3) in 1963 and by Klayman and Gunther (4) in 1973. Unlike the oxazoles and thiazoles. there are few convenient preparative routes to the selenazoles. Furthermore, the selenium intermediates are difficult to synthesize and are often extremely toxic selenoamides tend to decompose rapidly depositing metallic selenium. This inconvenience can be alleviated by choice of suitable reaction conditions. Finally, the use of selenium compounds in preparative reactions is often complicated by the fragility of the cycle and the deposition of metallic selenium. 

The different functional categories of the selenazoles have been classed in according to the functional priority or to the quantity of prepared compounds. 

Amino-4-aryl-5-acetic acid selenazoles were used by Knott (2l i as intermediates in the preparation of T.2, 4.6-naphthoselenazoles (21. 30, 31). 

The preparation of substituted selenazole thioethers (Scheme 22) has already been described (35. 36). These compounds are obtained by the action of a haloketothioether on. for example, selenoacetamide. selenobenzamide, and A -ethylselenourea. These selenazoles have not been characterized, but they have been used as intermediates in the preparation of cyanine dyes. 

The general formula of the 2-(2- or 4-furyl. thienyl, or selenienyljselenazoles is shown in Scheme 24 (40, 105. 106). (Selenienyl-2), (furyl-2), (thienyl-2), and (chloromethyi-4)selenazoles may be prepared by Hantzsch s reaction from selenoamides as described in Scheme 25. Hydrolysis give hydroxymethyl derivatives. 

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. 

Much of the development of the chemistry of sulfanilamidoselenazole derivatives is a result of the important role played by sulfonamides in chemotherapy and more particularly the good activity of sulfathiazoie against bacterial infections. Backer and De Jonge (441 prepared these derivatives by reaction of 2-amino-4-methyl- and 2-aminO-4-phenyl-selenazoles with A -acetylsulfanilic acid chloride in pyridine.. Alkaline... 

The dyes prepared in this way show a positive solvatochromism as the dielectric constant of the solvent increases, indicating that they possess a predominantly nonpolar structure. Substituents on the phenyl group in the 4-position of the selenazole ring have little influence on the absorption spectra. 

Carbocyanine or merocyanine dyes prepared from selenazole or selenazoline rings have a particular interest in photography. 

This reaction may also be used to introduce other substituents into the thiazole ring, and examples are described in Chapter 4.19 and in (69CC818) and (72MI40300). In contrast, this reaction sequence has not been used to prepare selenazole derivatives, these being more readily available by the reactions described in Section 4.03.2.2.2. 

Although the first reported preparations of selenazoles go back to the year 1889, for decades after this no further details were found in... 

Attempts to prepare selenazole derivatives were first described by Hofmann,2 a student of Hantzsch, in connection with investigations in the thiazole series. By reaction of selenobenzamide with a-halogeno compounds corresponding to the general reaction (2, R" = CeHg), he synthesized a series of 2-phenylselenazoles. In the same way, several... 

The difficulties encountered in the synthesis of 2-alkyl- and 2-aryl-substituted selenazoles lie principally in the preparation of the corresponding selenoamides. In this respect, a method is worthy of note in which the use of selenoamides is dispensed with. For this, a nitrile, a hydrogen selenide, and an a-halogenoketone are reacted together in the presence of a condensation catalyst. Phosphorus oxychloride, alone or mixed with zinc chloride or phosphorus trichloride, is specially suitable. The yields of the corresponding 2-alkylseIenazoles are up to a maximum of 25%,... 

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