Alkylation 3- pyrrolyl derivatives

Electropolymerization represents a useful method to control precisely the deposition of thin films of conducting polymers. These thin films have a wide variety of applications in optical devices [29]. Walder and coworkers showed that photocurrents could be generated using a trilayer thin film. The three different electropolymerized polymers were cleverly prepared from a common precursor, 4-methyl-4 -(2-pyrrolyl-1 -ethyl)-2,2 -bipyridine 7 two were alkylated, diquat derivatives and one was the Ru metal complex of this ligand, which acted as a sensitizer. The appropriate ordering of the triad in terms of their redox potentials led to the maximizing of the photocurrent (Scheme 7.2) [30],... 

Although the synthesis of multiple-pyrrolyl compounds can be achieved by SnAt reactions of perfluoroaromatics with pyrrolylsodium at ambient temperature <96JOC9012>, deleterious side reactions are often observed during attempted A-alkylations of the alkali salts of pyrrole. A protocol has therefore been developed for the preparation of N-arylmethylenepyrroles by reduction of the corresponding AT-acyl derivatives by treatment with sodium borohydride/boron trifluoride etherate in a sealed tube <96S457>. ... 

The patent literature covers many pyridazine derivatives claimed as blood platelet aggregation inhibitors and antithrombotic agents. The interest has been focused mainly on 6-aryl-4,5-dihydro-3(2//)-pyridazinones. In these compounds the aryl substituent has been varied within a wide range. Thus, dihydro-pyridazinones bearing a substituted or heterocycle-fused phenyl group at C-6 (60, R R2,R3 = H, alkyl Ar = substituted Ph) [34, 110-112,205-233] as well as various heteroaryl substituted congeners (61, R1, R2, R3 = H, alkyl Ar = pyridyl, thienyl, pyrrolyl, pyrazolyl) [234-241] have been prepared in search of novel antithrombotics. 

Pyrroles can be converted into alkali metal salts (with NaNH2/NH3 or K/toluene) (see also Section 2.3.3.1). The use of pyrrolyl or indolyl sodium or potassium salts under ionizing conditions favors the formation of A-acyl or IV-alkyl derivatives (Scheme 4) (740S(54)58,74OS(54)60). 

The formation of 3-pyrrolylcarbinols (280) from the photochemically induced reaction of pyrrole, or its 1-alkyl derivatives, with aliphatic aldehydes and ketones is thought to proceed via an oxetane intermediate (279) (79JOC2949). In contrast, the analogous reaction of 1 -phenylpyrrole with benzophenone leads to the formation of the diphenyl(2-pyrrolyl)car-binol, whilst the oxetane (281) has been isolated from the photoaddition of 1-benzoylpyrrole and benzophenone (76JHC1037, B-77MI30500). 2-Benzoyl-1-methylpyrrole undergoes a normal Paterno-Buchi photocyclization with 2,3-dimethylbut-2-ene, via the n -> v triplet... 

In a boiling mixture of nitric (d 1.50) and concentrated sulfuric acids 2-chloroben-zimidazole gives 2-chloro-5,6-dinitrobenzimidazole in a 75-80% yield [67], In analogous conditions, benzimidazole and 2-alkyl substituted benzimidazoles are also transformed into 5,6-dinitro derivatives however, in this case simultaneous formation of 4,6-dinitro isomers, which can be separated by fractional crystallization, has been fixed [48, 68], 5(6)-Nitro-2-heterylbenzimidazoles (thiazolyl-4-, furyl-4-, and pyrrolyl-4-) having antihelminthic activity were obtained by nitration with sulfuric-nitric mixture on cooling [69],... 

As expected from simple MO considerations, the radical cations of five-membered heterocycles, e.g. the blue species formed from furan, pyrrole, thiophene, and their alkyl derivatives, are n ions. The semi-occupied orbital is the n orbital with the heteroatom in the nodal plane (ai), see Scheme 2, structure 1. In radical cations of a,ca-bis-(l-pyrrolyl) alkanes the charge remains localized on a single ring, rather than being delocalized over both units [5, 10, 11]. 

A-Alkylation or acylation of 3(2//)-pyridazinones by standard procedures afforded derivatives with unambiguous structure, whereas pyri-dazines can yield either Ar or (V2-substituted products. Pyridazine-4-carboxamide, when alkylated with 5-iodovaleric acid or related acids, yielded a mixture of both Nr and A -regioisomers in the ratio of 1 1.25 or 1 1. They were not separated (95AP307 96PHA76). Alkylation of 3-(2-pyrrolyl)pyridazine afforded the A -alkylated product, as evidenced from X-ray analysis [96AX(C)1002]. 

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