Pyrroles 2- amination

The l//-pyrrol-2-amine 1387 reacted in dry CH2CI2 with 0.5 equiv of l//-pyrrole-2,5-dicarbonyl dichloride 1388 in the presence of Et3N, to give compound 1389, a new heterocyclic anion receptor, which was isolated in 47% yield (Equation 294) <20060L1593>. The moderate yields for this reaction are ascribed to the inherent instability of compound 1388 and to the formation of the three-ring dimer species 1390. Structural proof for receptor 1389 came from a single-crystal X-ray diffraction analysis. 

When heated with acidic oxide catalysts, mixtures of butynediol with ammonia or amines give pyrroles (66) (see Pyrrole AND PYRROLE DERIVATIVES). 

Hantzsch and Feist Syntheses. The Hant2sch synthesis of pyrroles iavolves condensation of an a-haloketone (10) with a p-keto ester (6) ia the presence of ammonia or an amine (22). 

Paal-Knorr Synthesis. The condensation of a 1,4-diketone, for example, with ammonia or a primary amine generally gives good yields of pyrroles many syntheses have been reported (24). The lack of avaHabitity of the appropriate 1,4-diketone sometimes limits the usefiilness of the reaction. 

Pyrrohdine [123-75-1] (tetrahydropyrrole) (19) is a water-soluble strong base with the usual properties of a secondary amine. An important synthesis of pyrrohdines is the reaction of reduced furans with excess amine or ammonia over an alumina catalyst in the vapor phase at 400°C. However, if labde substituents are present on the tetrahydrofurans, pyrroles may form (30). 

Pyrrohdines also can be obtained by reaction of 1,4-dihydroxyaLkanes with amines in the presence of dehydrating agents at elevated temperatures or by reaction of primary amines with 1,4-dihaloaLkanes. The dry distillation of 1,4-butanediamine dihydrochloride also generates pyrrohdine. Pyrroles can also be catalyticahy hydrogenated to pyrrohdines. 

The light-induced rearrangement of 2-phenyl- to 3-phenyl-thiophene may occur by a similar mechanism an equilibrium between the bicyclic intermediate (26) and the cyclopro-penylthioaldehyde (27) has been suggested (Scheme 2). The formation of IV-substituted pyrroles on irradiation of either furans or thiophenes in the presence of a primary amine supports this suggestion (Scheme 3). Irradiation of 2-phenylselenophene yields, in addition to 3-phenylselenophene, the enyne PhC=C—CH=CH2 and selenium. Photolysis of 2-phenyltellurophene furnishes solely the enyne and tellurium (76JOM(108)183). 

The classical structures of pyrrole, furan and thiophene (31) suggest that these compounds might show chemical reactions similar to those of amines, ethers and thioethers (32) respectively. On this basis, the initial attack of the electrophile would be expected to take place at the heteroatom and lead to products such as quaternary ammonium and oxonium salts, sulfoxides and sulfones. Products of this type from the heteroaromatic compounds under consideration are relatively rare. 

The palladium-promoted conversion of 1,3-dienes to pyrroles proceeds via 4-acetoxy-2-alkenylpalladium complexes (Scheme 50g) (81CC59), and a similar pathway may be involved in the palladium mediated reaction of but-2-ene-l,4-diol with primary amines to give A-substituted pyrroles (74CC931). 

Some examples of ring opening reactions with carbanions leading to five-membered heterocyclic ring formation are shown in Scheme 85. Pyrrole syntheses from functionally substituted oxiranes and amines are often described and typical examples are shown in Scheme 86. 

PAAL - KNORR Pyrrole Synthesis Pyrrole synthesis from 1,4-butanedlone and amines. 

Pyrrolines and pyrroles by (4+1) annulation of 2,3-bis(phenylsullony0-1.3-butadlene and amines. 

Treatment of acyl pyrroles with primary and secondary amines affords amides. ... 

Sulfonamides (R2NSO2R ) are prepared from an amine and sulfonyl chloride in the presence of pyridine or aqueous base. The sulfonamide is one of the most stable nitrogen protective groups. Arylsulfonamides are stable to alkaline hydrolysis, and to catalytic reduction they are cleaved by Na/NH3, Na/butanol, sodium naphthalenide, or sodium anthracenide, and by refluxing in acid (48% HBr/cat. phenol). Sulfonamides of less basic amines such as pyrroles and indoles are much easier to cleave than are those of the more basic alkyl amines. In fact, sulfonamides of the less basic amines (pyrroles, indoles, and imidazoles) can be cleaved by basic hydrolysis, which is almost impossible for the alkyl amines. Because of the inherent differences between the aromatic — NH group and simple aliphatic amines, the protection of these compounds (pyrroles, indoles, and imidazoles) will be described in a separate section. One appealing proj>erty of sulfonamides is that the derivatives are more crystalline than amides or carbamates. 

Two new sections on the protection for indoles, imidazoles, and pyrroles, and protection for the amide — NH are included. They are separated from the regular amines because their chemical properties are sufficienth different to affect the chemistry of protection and deprotection. The Reactivity Charts in Chapter 8 are identical to those in the first edition. The chart number appears beside the name of each protective group when it is first discussed. 

The aldehyde functionality present in 3-phenyl-2H-azirine-2-carbox-aldehyde reacts selectively with amines and with Qrignard and Wittig reagents to give a variety of substituted azirines. These azirines have been used, in turn, to prepare a wide assortment of heterocyclic rings such as oxazoles, imidazoles, pyrazoles, pyrroles, and benzazepins. ... 

Dimethoxytetrahydrofuran forms pyrrole derivatives with primary amines, these derivatives then condense with 4-dimethylaminobenzaldehyde in acid milieu to yield colored products [1] ... 

Dimethylaminocinnamaldehyde reacts with primary amines to form colored or fluorescent Schiff s bases (I). Pyrroles react with the reagent to form colored or fluorescent condensation products (II) ... 

Discovered more than a century ago, the Knorr and Paal-Knorr (PK) pyrrole syntheses are similar intermolecular condensations of amines with carbonyl compounds to give pyrroles. 

The Knorr pyrrole synthesis involves the reaction between an a-amino ketone 1 and a second carbonyl compound 2, having a reactive a-methylene group, to give a pyrrole 3. The amine 1 is often generated in situ by reduction of an oximino group. 

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