Fused quinoline heterocycles VI: Synthesis of 5H‐1‐thia‐3,5,6‐triazaaceanthrylenes and 5H‐1‐thia‐3,4,5,6‐tetraazaaceanthrylenes

Ethyl 3‐amino‐4‐chlorothieno[3,2‐c]quinoline‐2‐carboxylate ( 4 ) is a versatile synthon, prepared by reacting an equimolar amount of 2,4‐dichloroquinoline‐3‐carbonitrile ( 1 ) with ethyl mercaptoacetate ( 2 ). Ethyl 5‐alkyl‐5H‐1‐thia‐3,5,6‐triazaaceanfhrylene‐2‐carboxylates 9a‐c , novel perianellated tetracyclic heteroaro‐matics, were prepared by refluxing 4 with excess of primary amines 7a‐c to yield the corresponding amino‐thieno[3,2‐c]quinolines 8a‐c . Subsequent reaction with an excess of triethyl orthoformate (TEO) furnished 9a‐c . Reaction of 4 with TEO in Ac₂O at reflux, gave the simple acetylated compounds, thieno[3,2‐c]‐quinolines 12 and 13 . Refluxing 4 with benzylamine ( 7d ) gave 10 , and subsequent treatment with TEO gave the tetracyclic compound 11 . Refluxing 13 with an excess of alkylamines 7a‐d gave the fhieno[3,2‐c]quino‐lines 15 . Refluxing the aminothienoquinolines 8b with an excess of triethyl orthoacetate gave thieno[3,2‐c]quinoline 17 , while heating with Ac₂O gave 18 and 19 , with small amounts of 16 . Reaction of 8a,b with ethyl chloroformate and phenylisothiocyanate generated the new 1‐thia‐3,5,6‐triazaaceanthrylenes 20a,b and 21a,b , respectively. Diazotization of 8a‐c afforded the novel tetracyclic ethyl 5‐alkyl‐5H‐1‐fhia‐3,4,5,6‐tetraazaaceanthrylene‐2‐carboxylates 22a‐c in good yields.     

Synthesis of 1‐methyl‐, 4‐nitro‐, 4‐amino‐and 4‐iodo‐1,2‐dihydro‐3H‐pyrazol‐3‐ones

4‐Aminopyrazole‐3‐ones 4b, e, f were prepared from pyrazole‐3‐ones 1b‐d in a four‐step reaction sequence. Reaction of the latter with methyl p‐toluenesulfonate gave 1‐methylpyrazol‐3‐ones 2b‐d . Compounds 2b‐d were treated with aqueous nitric acid to give 4‐nitropyrazol‐3‐ones 3b‐d. Reduction of compounds 3b‐d by catalytic hydrogenation with Pd‐C afforded the 4‐amino compounds 4b, e, f. Using similar reaction conditions, nitropyrazole‐3‐ones derivatives 2c, d were reduced into aminopyrazole‐3‐ones 5e, f. 4‐Iodopyrazole‐3‐ones 7a, 7c and 8 were prepared from the corresponding pyrazol‐3‐ones 2a, 2c and 6 and iodine monochloride or sodium azide and iodine monochloride.     

Studies with Functionally Substituted Methylbenzotriazoles: Novel Synthesis of Functionally Substituted Pyrazolo[5,1‐c]‐1,2,4‐Triazines Benzotriazol‐1‐yl, 1‐Pyrazol‐4‐yl Benzotriazoles and 1‐Isoxazol‐4‐yl Benzotriazoles

1‐Benzotriazolylacetophenone 1 couples with aromatic diazonium salts to yield the corresponding coupling products 2 . Reaction of 1 with diazotized aminopyrazole afforded the benzotriazolylpyrazolo[5,1‐c][1,2,4]triazine 6 . Compound 1 condensed with DMFDMA to yield the enaminone 7 which reacted with hydrazines to yield the pyrazoles 8a,b . Isomeric pyrazoles 10 were synthesized via condensing 1 with phenyl‐hydrazine and subsequent condensation of the formed phenylhydrazone 9 with DMFDMA. Reaction of 7 with hydroxylamine afforded the isoxazole 11 which was converted into the nitrile 13 on reflux in dioxane in the presence of sodium hydride. Compound 13 was also directly obtained from reaction of 1 with 1‐cyanobenzo‐triazole. The reaction of 1 with hippuric acid and arylidenemalononitriles 18a‐c afforded the pyranone 17 and pyridine derivatives 23a‐c , respectively.     

Chemoselective reaction of formalin with 2‐(5‐substituted‐2‐hydroxybenzylamino)phenols: Synthesis of 6‐substituted 3‐(2‐hydroxyphenyl)‐3,4‐dihydro‐2H‐benzo[e][1,3]oxazines

Reaction of 2‐(5‐substituted‐2‐hydroxybenzylamino)phenols ( 2 ) with formalin in ethanol under reflux has chemoselectively led to 2‐(6‐substituted‐2H—benzo[e][1,3]oxazin‐3(4H)‐yl)phenols ( 3 ) in good yield involving the ring closure of the hydroxyl group of the C‐aryl ring and not that of the N‐aryl ring.     

Studies with enamines and azaenamines: Synthesis and reactivity of 3‐dimethylamino‐2‐[(3‐indolyl) carbonyl]propenonitrile

2‐Oxo‐3‐(indol‐3‐yl)propanonitrile 2 condensed with dimethylformamide dimethylacetal to yield the enaminonitrile 3 . The latter reacted with 4‐chloroaniline to yield the 4‐chlorophenylaminoacrylonitrile 5 . Reaction of 3 with hydrazine hydrate led to formation of pyrazole‐4‐carbonitrile 6 . Compound 3 reacted with ethyl acetoacetate in refluxing acetic acid and in presence of ammonium acetate to yield the indolylpyridine 10 . Enamine 3 reacted with 5(1H)‐aminotriazole 13 and 3(5)‐aminopyrazole 17 to yield the pyrimidine derivatives 15 and 19 , respectively.     

Synthesis of heterocyclic compounds using amidines as their ene‐1,1‐diamine tautomers. II. Synthesis of 2,3‐dihydropyridine, 3,4‐dihydropyridine and 3,4‐dihydropyrrol‐2‐one derivatives by the reaction of amidines with α, β‐unsaturated carbonyl compounds

N‐t‐Butylacetamidines 1 on heating with methyl vinyl ketone, acrolein or crotonaldehyde gave the 2,3‐dihydropyridine derivatives 4,5 or 6 via N‐alkylation of the acetamidines 1 . Reaction of amidines 1 with phenyl 1‐propenyl ketone, benzalacetone or chalcone gave 3,4‐dihydropyridine derivatives 8, 9 or 10 . These were obtained by C‐alkylation, achieved by Michael addition of the acetamidines 1 as their N,C‐tautomers ene‐1,1‐diamines 1 ′ to α,β‐unsaturated carbonyl compounds, and subsequent cyclodehydration of adducts. Reaction of 1 with ethyl 3‐benzoylacrylate gave 3,4‐dihydropyrrol‐2‐one derivatives 13 .     

Diels‐alder reactions of 2‐(2‐nitroethenyl)‐1H‐pyrroles and their oxygen and sulfur analogs with quinones

Diels‐Alder reaction of 2‐(E‐2‐nitroethenyl)‐1H‐pyrrole ( 2a ) with 1,4‐benzoquinone gave the desired benzo[e]indole‐6, 9(3H)‐dione ( 4a ) in 10% yield versus a 26% yield (lit. 86% [5]) of the known N‐methyl compound ( 4b ) from the N‐(or 1)‐methyl compound ( 2b ). Protection of the nitrogen of 2a with a phenylsul‐fonyl group ( 2c ) gave a 9% yield of the corresponding N‐(or 3)‐phenylsulfonyl compound ( 4c ). The reaction of 2b with 1,4‐naphthoquinone gave in 6% yield (lit. 64% [5]) the known 3‐methylnaphtho[2,3‐e]‐indole‐6, 9(3H)‐dione ( 6 ). The reaction of 2‐(E‐2‐nitroethenyl)furan ( 8a ) gave a small yield of the desired naphtho[2,1‐b]furan‐6, 9‐dione ( 9a ), recognized by comparing its NMR spectrum with that of 4b. The corresponding reaction of 2‐(E‐2‐nitroethenyl)thiophene ( 8b ) gave a 4% yield of naphtho[2,1‐ b ]thiophene‐6,9‐dione ( 9b ), previously prepared in 24% yield [12] in a three‐step procedure involving 2‐ethenylthiophene. Introducing an electron‐releasing 2‐methyl substituent into 8a and 8b gave 12a and 12b , which, upon reaction with 1,4‐benzoquinone, gave 2‐methylnaphtho[2,1‐b]furan‐6, 9‐dione ( 13a ) and its sulfur analog ( 13b ) in yields of 4 and 8%, respectively.     

Synthesis of 2‐alkyl‐4,5‐aryl‐2H‐[1λ6,2,3,6]‐thiatriazine‐1,1‐dioxides

Sulphamoyl chlorides and chlorosulphonyl isocyanate react with monosubstituted hydrazones and alkylhydrazonates to sulphamoyl hydrazones and sulphamoyl hydrazonates respectively. Reaction of benzil monoalkylhydrazones with chlorosulphonyl isocyanate results in formation of 2‐alkyl‐4,5‐aryl‐2H‐ [1λ⁶,2,3,6]‐thiatriazine‐1,1‐dioxides.     

Novel Bis(2‐(5‐((5‐phenyl‐1H‐tetrazol‐1‐yl)methyl)‐4H‐1,2,4‐triazol‐3‐yl)phenoxy)Alkanes: Synthesis and Characterization

In this study, 10 different substituted aromatic bis‐benzaldehydes were synthesized by treating hydroxy benzaldehydes with various dihaloalkanes. Bis aldehydes 5a , 5b , 5c , 5d , 5e , 5f , 5g , 5h , 5i , 5j were treated with 2‐(5‐phenyl‐1H‐tetrazole‐1‐yl)acetohydrazide ( 3 ) in acidic medium and in the presence of ammonium acetate to yield a series of new isomeric bis(2‐(5‐((5‐phenyl‐1H‐tetrazol‐1‐yl)methyl)‐4H‐1,2,4‐triazol‐3‐yl)phenoxy)alkanes ( 6a , 6b , 6c , 6d , 6e , 6f , 6g , 6h , 6i , 6j ) in excellent to good yield. The newly synthesized compounds were characterized by the available spectroscopic analysis.     

Syntheses of New Unsymmetrical 2,5‐Disubstituted‐1,3,4‐oxadiazoles and 1,2,4‐Triazolo[3,4‐b]‐1,3,4‐thiadiazoles Bearing Thieno[2,3‐c]pyrazolo Moiety

New series of (thieno[2,3‐c]pyrazolo‐5‐yl)‐[1,2,4]triazolo[3,4‐b][1,3,4]thiadiazoles 10a , 10b , 10c and (thieno[2,3‐c]pyrazol‐5‐yl)‐1,3,4‐oxadiazol‐3(2H)‐yl)ethanones 6a , 6b , 6c has been synthesized from thieno[2,3‐c]pyrazole‐5‐carbohydrazide 3 by multistep reaction sequence. (5‐Aryl‐1,3,4‐oxadiazol‐2‐yl)‐1H‐thieno[2,3‐c]pyrazoles 4a , 4b , 4c were also synthesized from thieno[2,3‐c]pyrazole‐5‐carbohydrazide 3 by cyclization with various aromatic carboxylic acids. The hydrazide 3 was obtained by reaction of thieno[2,3‐c]pyrazole‐5‐carboxylate 2 with hydrazine hydrate in good yield, and compound 2 was obtained by the reaction of 5‐chloro‐3‐methyl‐1‐phenyl‐1H‐pyrazole‐4‐carbaldehyde 1 and 2‐ethyl thioglycolate in presence of sodium alcoholate in good yield.     

Studies with 3‐functionally substituted 2‐arylhydrazononitriles: A new route to 3‐substituted‐2‐arylhydrazononitriles, 4‐amino‐pyrazole‐5‐carbonitriles,azadienes and cinnolines

3‐Amino‐3‐phenyl‐2‐phenylazoacrylonitrile 6 is obtained in good yield via reaction of 5 with phenyl magnesium bromide. The compound 6 is readily converted into 4a . The so formed alkanenitrile reacted with phenylmagnesium bromide to yield 8 . Compound 8 could be also obtained from reaction of 9 with phenylmagnesium bromide. The arylhydrazononitriles 8 and 4a reacted with chloroacetonitrile to yield the 4‐aminopyrazoles 12a,b . Compound 12a reacted with acetic anhydride to yield the 15a and with benzoyl chloride to yield the pyrazole 16 which was converted into 15b . Refluxing 10 in acetic acid gave a mixture of the azadiene 21 and the cinnoline 22 is obtained. The azadiene 21 is converted into 22 either thermally or photochemically.     

Transformation of 4‐oxo‐4H‐[1]‐benzopyran‐3‐carboxaldehydes into pyrazolo[3,4‐B]pyridines

Reaction of 6‐methyl‐4‐oxo‐4H‐[1]‐benzopyran‐3‐carboxaldehyde 1 with 5‐amino‐3‐methyl‐1‐phenylpyrazole 2 in alcoholic reaction media in the presence of 4‐toluenesulfonic acid as catalyst afforded 5‐(2‐hydroxy‐5‐methylbenzoyl)‐3‐methyl‐1‐phenyl‐1H‐pyrazolo[3,4‐b]pyridine 3 and 2‐methoxy‐6‐methyl‐3‐(3‐methyl‐1‐phenylpyrazol‐5‐ylaminomethylene)chroman‐4‐one 7 . We explain the mechanism of formation of both products on the basis of kinetic study of individual reaction steps.     

Regioselective synthesis of pentacyclic polyheterocycles: Sequential [3,3] sigmatropic rearrangement of 4‐(4′‐aryloxybut‐2′‐ynyloxy)‐1‐phenyl‐1,8‐naphthyridin‐2(1H)‐ones

A number of 4‐aryloxymethyl‐6‐phenyl‐2H‐pyrano[3,2‐c][1,8]naphthyridin‐5(6H)‐ones ( 4a‐f ) are regioselectively synthesized in 72‐78% yield by the Claisen rearrangement of 4‐(4′‐aryloxybut‐2′‐ynyloxy)‐1‐phenyl‐1,8‐naphthyridin‐2(1H)‐ones ( 3a‐f ) in refluxing chlorobenzene for 4‐6 h. These products are then subjected to a second Claisen rearrangement catalyzed by anhydrous AlCl₃ at room temperature for 2 h to give hitherto unreported pentacyclic heterocycles ( 5a‐f ) in 78‐85% yield.     

Reaction of 6‐Methyl‐2‐Thiouracil and 6‐Phenyl‐2‐Thiouracil with Chloro‐β‐Dicarbonyl and Bromo‐β‐Dicarbonyl Compounds and Their Nitrile Analogs

Derivatives of 2‐methylidene‐1,3‐dihydropyrimidin‐4‐ones 2a , 2b , 2c , 2d , 2e , 2f , 2g were synthesized by interaction of 6‐methyl‐2‐thiouracil and 6‐phenyl‐2‐thiouracil 1a , 1b with some activated halogenides: diethyl bromomalonate, ethyl 2‐chloro‐3‐oxobutanoate, ethyl 2‐bromocyanoacetate, 2‐bromo‐5,5‐dimethylcyclohexan‐1,3‐dione, and bromomalononitrile. The boiling of 1a with ethyl 2‐bromocyanoacetate in mixture of ethanol and EtONa results in intramolecular cyclization and formation of thiazolo[3,2‐a]pyrimidin‐5‐one 3 . Interaction of 1a with 3‐chloropentane‐2,4‐dione and 2‐bromo‐1,3‐diphenylpropane‐1,3‐dione yielded corresponding S‐substituted thiopyrimidines 4a , 4b . In general, the products of 1b S‐alkylation are less prone to sulfur extrusion. Reaction of 1b with diethyl bromomalonate in the absence of EtONa stops at the S‐alkylation step, while in the presence of EtONa in ethanol or PPh₃ in dioxane 2‐(ethoxycarbonylmethyl)thio‐6‐phenyl‐1,3‐dihydropyrimidin‐4(1H)‐one 6 is formed exclusively. Molecular structure and crystal structure of 2‐(1,1‐diethoxycarbonylmethyliden)‐6‐methyl‐1,3‐dihydropyrimidin‐4(1H)‐one 2a are discussed.     

Studies with Heterocyclic β‐Enaminoniriles: A Simple Route for the Synthesis of Polyfunctionally Substituted Thiophene,Imidazo[1,2:1′,6′]pyrimido[5,4‐b]thiophene and Thieno[3,2‐d]pyrimidine Derivatives

Reaction of 3,5‐diaminothiophene‐2‐carbonitrile derivatives 3a‐c with ethoxycarbonylmethyl isothiocyanate and/or N‐[bis(methylthio)methylene]glycine ethyl ester led to formation of 7‐substituted‐8‐amino‐5‐thioxo‐6H‐imidazo[1,2:1′,6′]pyrimido[5,4‐b]thiophene‐2(3H)‐one derivatives 6a‐c and 7‐substituted‐8‐amino‐5‐(methylthio)imidazo[1,2:1′,6′]pyrimido[5,4‐b]thiophene‐2(3H)‐one 7a‐c , respectively. Also, the synthetic potential of the β‐enaminonitrile moiety in 3a‐c has been explored; it proved to be a promising candiate for the synthesis of 1,6‐disubstituted‐2,4‐diamino‐7,8‐dihydro‐8‐oxopyrrolo[1,2‐a]thieno[2,3‐e]pyrimidine derivatives 10a‐f and pyrido[2′,3′:6,5]pyrimido[3,4‐a]benzimidazole derivatives 12a,b .     

Chloroformamidinium salts: Efficient reagents for preparation of 2‐aminobenzoimidazole, 2‐aminobenzoxazole,and 2‐aminobenzothiazole derivatives

A Reaction involving chloroformamidinium salts (TCFH 1a , BTCFH 1b , DmCFH 1c , DmPCFH 1d , BPCFH 1e ) and 2‐aminophenol 9a , benzene‐1,2‐diamine 9b , and 2‐aminothiophenol 9c afforded 2‐aminobenzoxazole 13 , 2‐aminobenzoimidazole 14 , and 2‐aminobenzothiazole 15 derivatives, respectively as major products, due to the in situ heterocyclization with dimethylamine acting as the better leaving group. Attempts for preparation of 13‐15 from the reaction of N,N‐dimethyl carbomyl chloride 16 with 2‐aminophenol 9a , benzene‐1,2‐diamine 9b , and 2‐aminothiophenol 9c were unsuccessful, and gave the unexpected products benzoxazol‐2‐ol 18a , benzoimidazol‐2‐one 18b , and S‐(2‐amino‐phenyl) N,N‐dimethylthiocarbamate 19 respectively. On the other hand reaction of chloroformamidinium salts 1a‐e with 3‐benzyl‐2‐hydrazinoquinoxaline 3 and 1‐hydrazinophthalazine hydrochloride 4 in the presence of triethylamine as a base, afforded the [1,2,4]triazolo derivatives 6 and 7 respectively in good yield and purity. These triazole derivatives were formed due to the strong tendency towards heterocyclization and substitution of dimethylamine group as a better leaving group.     

Studies with enamines: Reactivity of N,N‐dimethyl‐N‐[(E)‐2‐(4‐nitrophenyl)‐1‐ethenyl]amine towards nitrilimine and aromatic diazonium salts

In the presence of triethylamine, cycloaddition reaction of enamine 1 with hydrazonoyl halides 2 followed by dimethylamine elimination was achieved, yielding the corresponding 1,3,4‐trisubstituted pyrazoles 4 . Coupling of enamine 1 with aromatic diazonium salts afforded 2‐(arylhydrazono)‐2‐(4‐nitrophenyl)acetaldehyde 9 in good yield. Refluxing the phenyl hydrazone 9a with chloroacetone in ethanol in the presence of triethylamine afforded 1,3,5‐trisubstituted pyrazole 12a , formed via intermediate 11a. Reaction of 9a with hydroxylamine hydrochloride in ethanol in the presence of anhydrous sodium acetate yielded oxime 13a which was irradiated in a microwave oven in the presence of acetic acid to afford a mixture of 15a and 16a.     

N,O‐chelate aluminum and zinc complexes: synthesis and catalysis in the ring‐opening polymerization of ε‐caprolactone

Reaction between 2‐(1H‐pyrrol‐1‐yl)benzenamine and 2‐hydroxybenzaldehyde or 3,5‐di‐tert‐butyl‐2‐hydroxybenzaldehyde afforded 2‐(4,5‐dihydropyrrolo[1,2‐a]quinoxalin‐4‐yl)phenol (HOL¹NH, 1a) or 2,4‐di‐tert‐butyl‐6‐(4,5‐dihydropyrrolo[1,2‐a]quinoxalin‐4‐yl)phenol (HOL²NH, 1b). Both 1a and 1b can be converted to 2‐(H‐pyrrolo[1,2‐a]quinoxalin‐4‐yl)phenol (HOL³N, 2a) and 2,4‐di‐tert‐butyl‐6‐(H‐pyrrolo[1,2‐a]quinoxalin‐4‐yl)phenol (HOL⁴N, 2b), respectively, by heating 1a and 1b in toluene. Treatment of 1b with an equivalent of AlEt₃ afforded [Al(Et₂)(OL²NH)] (3). Reaction of 1b with two equivalents of AlR₃ (R = Me, Et) gave dinuclear aluminum complexes [(AlR₂)₂(OL²N)] (R = Me, 4a; R = Et, 4b). Refluxing the toluene solution of 4a and 4b, respectively, generated [Al(R₂)(OL⁴N)] (R = Me, 5a; R = Et, 5b). Complexes 5a and 5b were also obtained either by refluxing a mixture of 1b and two equivalents of AlR₃ (R = Me, Et) in toluene or by treatment of 2b with an equivalent of AlR₃ (R = Me, Et). Reaction of 2a with an equivalent of AlMe₃ afforded [Al(Me₂)(OL³N)] (5c). Treatment of 1b with an equivalent of ZnEt₂ at room temperature gave [Zn(Et)(OL²NH)] (6), while reaction of 1b with 0.5 equivalent of ZnEt₂ at 40 °C afforded [Zn(OL²NH)₂] (7). Reaction of 1b with two equivalents of ZnEt₂ from room temperature to 60 °C yielded [Zn(Et)(OL⁴N)] (8). Compound 8 was also obtained either by reaction between 6 and an equivalent of ZnEt₂ from room temperature to 60 °C or by treatment of 2b with an equivalent of ZnEt₂ at room temperature. Reaction of 2b with 0.5 equivalent of ZnEt₂ at room temperature gave [Zn(OL⁴N)₂] (9), which was also formed by heating the toluene solution of 6. All novel compounds were characterized by NMR spectroscopy and elemental analyses. The structures of complexes 3, 5c and 6 were additionally characterized by single‐crystal X‐ray diffraction techniques. The catalysis of complexes 3, 4a, 5a–c, 6 and 8 toward the ring‐opening polymerization of ε‐caprolactone was evaluated. Copyright © 2008 John Wiley & Sons, Ltd.     

Synthesis of carbazole,acridine, phenazine, 4H‐benzo[def]carbazole and their derivatives by thermal cyclization reaction of aromatic amines

A variety of nitrogen‐containing heterocycles were synthesized by passing vapors of aromatic amines over calcium oxide at 450–650 °C under nitrogen carrier gas. Reaction of 2‐aminobiphenyl 3a at 560 °C gave carbazole 4 in 80% yield. Reaction of 2, 2′‐diaminobiphenyl 3b afforded a mixture of carbazole 4 and 4‐aminocarbozole 6b. In the case of 2‐amino‐2′‐nitrobiphenyl 3c, benzo[c]cinnoline 7 was obtained along with carbazole 4. Reaction of 2‐amino‐2′‐methoxybiphenyl 3d gave four products of carbazole 4,4‐hydroxycarbazole 6e, phenanthridine 8 and dibenzofuran 9. Reaction of 2‐aminodiphenylmethane 5a afforded acridine 10. In the case of 2‐aminobenzophenone 5b, acridone 11 was obtained as a major product. Reaction of 2‐aminobenzhydrol 5c gave acridine 10. When 2‐aminodiphenylamine 5d was reacted, phenazine 12 was obtained in good yield. In contrast, reaction of 2‐aminodiphenyl ether 5e produced only 2‐hydroxydiphenylamine 13. Reaction of 4‐aminophenanthrene 14 produced 4H‐benzo[def]carbazole 15 in 61% yield.     

An Innovative Protocol for the Synthesis of 3‐(Pyridin‐2‐yl)‐5‐sec‐aminobiphenyl‐4‐carbonitriles and 9,10‐Dihydro‐3‐(pyridine‐2‐yl)‐1‐sec‐aminophenanthrene‐2‐carbonitriles

Herein, we present an innovative, novel, and highly convenient protocol for the synthesis of 3‐(pyridin‐2‐yl)‐5‐sec‐aminobiphenyl‐4‐carbonitriles ( 6a , 6b , 6c , 6d , 6e , 6f , 6g ) and 9,10‐dihydro‐3‐(pyridine‐2‐yl)‐1‐sec‐aminophenanthrene‐2‐carbonitriles ( 10a , 10b , 10c , 10d , 10e ), which have been delineated from the reaction of 4‐sec‐amino‐2‐oxo‐6‐aryl‐2H‐pyran‐3‐carbonitrile ( 4a , 4b , 4c , 4d , 4e , 4f , 4g ) and 4‐sec‐amino‐2‐oxo‐5,6‐dihydro‐2H‐benzo[h]chromene‐3‐carbonitriles ( 9a , 9b , 9c , 9d , 9e ) with 2‐acetylpyridine ( 5 ) through the ring transformation reaction by using KOH/DMF system at RT. The salient feature of this procedure is to provide a transition metal‐free route for the synthesis of asymmetrical 1,3‐teraryls like 3‐(pyridin‐2‐yl)‐5‐sec‐aminobiphenyl‐4‐carbonitriles ( 6a , 6b , 6c , 6d , 6e , 6f , 6g ) and 9,10‐dihydro‐3‐(pyridine‐2‐yl)‐1‐sec‐aminophenanthrene‐2‐carbonitriles ( 10a , 10b , 10c , 10d , 10e ). The novelty of the reaction lies in the creation of an aromatic ring from 2H‐pyran‐2‐ones and 2H‐benzo[h]chromene‐3‐carbonitriles via two‐carbon insertion from 2‐acetylpyridine ( 5 ) used as a source of carbanion.