The chemistry of polycyclic arene imines. V. Reactions of phenanthrene 9,10-imine with nucleophiles under phase transfer conditions

Reactions of phenanthrene 9,10-imine (1) with alkyl halides, sodium azide and ammonium thiocyanate in two liquid phase systems were investigated. In the presence of aqueous sodium hydroxide and alkyl halides triethylbenzylammonium (TEBA) salts promote N-alkylation of 1 with preservation of the aziridine ring. Tetrabutylammonium (TBA) salts catalyze nucleophilic substitutions in which the three membered ring is cleaved. Aqueous sodium azide reacts with 1 to give trans-10-azido-9,10-dihydro-9-phenanthrenamine (2) . Ammonium and potassium thiocyanate cause expansion of the aziridine ring; while the unsubstituted imine 1 yields the 2-thiazolamine derivative 4 , N-butylphenanthrene 9,10-imine (8) froms trans-3a,11b-dihydro-3-butylphenanthro[9,10-d]thiazol-2-imine (9) with an exocyclic CN bond. The structure of 9 was established by X-ray crystal analysis.     

The chemistry of polycyclic arene imines. VII. Reactions of phenanthrene 9,10-imine with aromatic carboxaldehydes,carboxylic acids and acetylenic esters

The reactions of phenanthrene 9,10-imine ( 1 ) with aromatic aldehydes, benzoic acids and acetylenedi-carboxylic esters were investigated. The aldehydes were shown to give 1-[N-(arylmethylidene)-9-phenanthreneamine-10-yl]-1a,9b-dihydrophenanthro[9,10-b]azirine 2. The ‘dimeric’ structure of these products was established by X-ray diffraction analysis. The carboxylic acids proved to form in the presence of dicyclohexylcarbodiimide, N-aroylphenanthrene 9,10-imines 7 , that readily undergo rearrangement to N-aroyl-9-phenanthrenamines 8. Esters of acetylenedicarboxylic acid gave the corresponding esters of (Z)-2-(1a,9b-dihydrophenanthro[9,10-b]azirine-1-yl)-2-butendioic acid 10 .     

1a,11b-dihydrobenz[5,6]anthr[1,2-B]azirine. A non k-region polycyclic arene imine

The synthesis of the title compound 9 is described. Benz[a]anthracene 8,9-oxide (6) was reacted with sodium azide in aqueous acetone and the trans-9-azido-8,9-dihydrobenz[a]anthr-8-ol (7), so formed, was cyclized by tri-n-butylphosphine. Attempts to dehydrogenate 10,11-dihydrobenz[a]anthracene 8,9-imine (4) with DDQ or by allylic bromination followed by base assisted dehydrobromination was unsuccessful. The N-tosyl derivative of 4, prepared from the free imine, N,O-bis(trimethylsilyl)acetamide and tosyl chloride underwent rapid aziridine-ring cleavage by the silylating agent to give trans-8,9,10,11-tetrahydro-8-(4-methyl)benzensulfon-amido-9- [(trimethyl)oxy]benz[a]anthracene (10).     

The chemistry of polycyclic arene imine. VI. 1-[N,N-di-(2-propenyl)-9-phenanthreneamine-10-yl]-1a,9b-dihydrophenanthro[9,10-b]azirine an unusual allylation product of phenanthrene 9,10-imine

Phenanthrene 9,10-imine (1) was shown to react with allyl bromide and 50% aqueous sodium hydroxide under phase transfer catalysis conditions to give the title compound 3 as the only product. The starting imine 1 is assumed to undergo initially bis alkylation to form an N,N-di-(2-propenyl)phenanthrene 9,10-iminium salt (4) which, in turn, is attacked by a deprotonated phenanthrene imine anion (5). The structure of 3 has been determined by a single crystal X-ray diffraction analysis.     

Adducts of phenanthrene 9,10-imine and of benz[a]anthracene 5,6-imine to some nitrogen heterocycles

N-4-Pyridinyl-, N-2-quinolinyl-, and 2-pyrazinylphenanthrene 9,10-imines 4–6 , as well as N-4-pyridinyl- and N-2-pyrazinylbenz[a]anthracene 5,6-imines 12 and 13 were prepared by sodium hydride-mediated interaction of the parent arene imines, 1 and 10 , and the respective chloropyridine, chloroquinoline or chloropyrazine. N-Nicotynoyl-, N-2-pyridinoyl- and N-6-quinolinoylphenanthrene 9,10-imines 7–9 were obtained by interaction of N-trimethylsilylphenanthrene 9,10-imine ( 2 ) and the appropriate pyridine- or quinolinecarbonyl chlorides. Reaction of N-methylsulfonylphenanthrene 9,10-imine with thymine, cytosine, 5-fluorocytosine, purine, 6-chloropurine and adenine afforded, in the presence of either potassium carbonate or 1,5-diazabicyclo[3.4.0]non-5-ene, adducts 16–22 , respectively. The structures of the adducts were conformed by multinuclear nmr and by NOESY and C-H correlation 2D nmr spectrometry.     

The chemistry of polycyclic arene imines. III. N-alkylation of phenanthrene 9,10-imineN-alkylation of phenanthrene 9,10-imine

Phenanthrene 9,10-imine ( 1 ) was shown to undergo N-alkylation without aziridine ring cleavage by (a) metallation with sodium methylsulfinylmethide followed by addition of an alkyl halide at −20° (b) reaction of 1 , sodium hydride and the halide in dimethylformamide at 40° (c) treatment of a dichloromethane solution of 1 , the halide and triethylbenzylammonium chloride with aqueous sodium hydroxide under phase transfer conditions. The syntheses of N-isopropyl-, N-butyl-, N-pentyl-, N-allyl- and N-benzylphenanthrene 9,10-imine ( 2–6 ) are described.     

Reactions of pyridinium or isoquinolinium ketene dithioacetals with aromatic N-imines and S-imines

Reactions of ketene dithioacetals, 1-[1-substituted 2,2-bis(methylthio)ethenyl]pyridinium 1a-i or -isoquinolinium 2a,b iodides with aromatic N-imines, 1-aminopyridinium 3a-1,1 -aminoquinolinium ( 4 ), and 2-amino-isoquinolinium ( 5 ) mesitylene sulfonates gave the corresponding 2-methylthioimidazo[1,2-a]pyridines 9a-k , 2-methylthiopyrazolo[1,5-a]pyridines 11a-q , 2-methylthioimidazo[2,1-a]isoquinoline derivatives 10a,b and 2-methylthiopyrazolo[1,5-a]quinoline ( 12 ). The benzoyl compounds, 1-[1-benzoyl-2,2-bis(methylthio)ethenyl]-pyridinium iodides 1g,h,i reacted with N-imine 3a to give the 3-benzoyl-2-methylthioimidazo[1,2-a]pyridines 9h-k . The reaction of pyridinium ketene dithioacetals 1a,f,g (R¹ = COOE_t, COPh, and CN) with substituted pyridinium N-imines having an electron-withdrawing group on the pyridine ring afforded only the corresponding pyrazolo[1,5-a]pyridine derivatives 11j-r in good yields. Reactions of ketene dithioacetals with various S-imines are also described. Possible mechanisms for the formation of 9 and 11 are described.     

Emulsion copolymerization of vinyl acetate and butyl acrylate in the presence of fluorescent dyes

This article describes our first experiments for preparing dye‐labeled latex particles by the emulsion copolymerization of a 4/1 (w/w) mixture of vinyl acetate‐butylacrylate (VAc‐BA). We discuss the synthesis of acrylate derivatives of phenanthrene, anthracene, and pyrene [9‐acryloxymethyl phenanthrene ( 7 ), 9‐acryloxymethyl‐10‐methyl anthracene ( 8 ), and 1‐acryloxymethyl pyrene ( 10 )] and an allyl ether derivative of anthracene [9‐allyoxymethyl‐10‐methyl anthracene ( 9 )]. Although the phenanthrene derivative 7 gave latex particles with high monomer conversion and good dye incorporation, the pyrene acrylate and both anthracene comonomers strongly inhibited the free‐radical reaction. To assist our search for a dye that would serve as a useful energy acceptor for phenanthrene and without suppressing VAc‐BA polymerization, we also examined batch emulsion polymerization in the presence of a variety of dye derivatives—substituted anthracenes, acridines, a coumarin, and two benzophenone derivatives. All of the anthracene derivatives, as well as acridine, strongly inhibited monomer polymerization. The coumarin dye 7‐hydroxy‐4‐methyl coumarin ( 22 ) that had only limited solubility allowed more than 90% monomer conversion. Most promising were 2‐hydroxy‐5‐methyl benzophenone ( 23 ) and 4‐N,N‐dimethylamino benzophenone ( 24 ) that at 1 mol % in the monomer mixture permitted virtually quantitative monomer conversion to latex. 4′‐Dimethylamino‐2‐acryloxy‐5‐methyl benzophenone ( 25 ) copolymerized well with the VAc‐BA mixture, yielding latex particles in high yield and with a narrow size distribution. These dyes appear to be useful acceptor dyes for energy‐transfer experiments with phenanthrene. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1594–1607, 2002     

The chemistry of polycyclic arene imines. I. Substitution at the nitrogen atom of 1a,9b-dihydro-1H-phenanthro[9,10-b]azirine

Chlorides of carboxylic, sulfonic and phosphoric acids proved to convert phenanthrene-9,10-imine into the corresponding rearranged acet- sulfon- and phosphonamidophenanthrene. Trimethylchlorosilane and N,O-bis(trimethylsilyl)acetamide reacted with the imine without destruction of the aziridine ring. The silylated compound could be transferred into the respective N-substituted phenanthrene-9,10-imines when treated with acetyl-, methanesulfonyl-, 4-tosyl- and diethylphosphoryl chloride. A remarkably stable N-chlorophenanthrene-9,10-imine was obtained from the unsubstituted compound and N-chlorosuccinimide.     

The chemistry of arene imines. IV. An unusual silver promoted transformation of N-chlorophenanthrene 9,10-imine into 9,10-phenanthrenequinone dialkyl acetals

Methanolic silver nitrate and perchlorate convert N-chlorophenanthrene 9,10-imine (1) into 10,10-dimethoxy-9(10H)-phenanthrone (2) in 60% yield. Substitution of the mthanol by ethanol, 1- and 2-propanol gives phenanthrenequinone diethyl-, di-1-propyl- and di-2-propylacetals (3-5) , respectively. Silver acetate promotes these transformations only in the presence of a protic acid. The reaction mechanism is assumed to involve the generation of a cyclic nitrenium ion, nucleophilic ring opening by methanol, hydrolysis of the imine function and silver ion promoted oxidation.     

Imino-Bridged heterocycles. V . Synthesis of 6,11-dimethyl-1 1H-benzo[5,6]cyclohepta[1,2-c]pyridin-6,11-imine by a regiospecific amide to olefin cyclization

Attempted utilization of sulfenimines 6a,b to prepare tertiary carbinamines as intermediates to the desired 6,11-dimethyl-11H-benzo[5,6]cyclohepta[1,2-c]pyridin-6,11-imine system ( 10 ) instead gave products resulting from nitrogen-sulfur bond cleavage. The preparation and use of the corresponding sulfonimine 8 , however, led to 10 through a regiospecific base-catalyzed reaction.     

Effect of the chemical structure of a tetradentate equatorial ligand on the spin-crossover properties of the Fe (III) complexes chain structures: Electron paramagnetic resonance study

The effect of the chemical structure of the equatorial ligand on the spin state of the Fe (III) ion in a series of 1-D chain complexes of the general formula [Fe(L)(tvp)]BPh₄·nCH₃OH, where L = dianions of Schiff base containing a different number of aromatic groups: N,N′-ethylenebis (salicylaldimine) (salen) 1 , N,N′-ethylenebis (acetylacetone)2,2′-imine (acen) 2 , N,N′-ethylenebis (benzoylacetylacetone)2,2′-imine (bzacen) 3 , and tvp = 1,2-di(4-pyridyl)ethylene, was studied by ultraviolet–visible (UV–vis) and electron paramagnetic resonance (EPR) methods. The values of exchange interactions, thermodynamic parameters of spin-crossover, and electronic structure features of the Fe (III) complexes were estimated from the EPR data. The substitution of a fragment of the equatorial ligand L in the series salen–acen–bzacen changes the local symmetry of the complex in the 1-D chain, thereby affecting the spin variable properties.     

Synthesis of pteridine derivatives related to folic acid and methanopterin from pyrazine-2,3-dicarbonitrile

Pteridine derivatives related to folic acid and methanopterin were synthesized by two methods. The first synthesis is initiated by the radical substitution of 5-methylpyrazine-2,3-dicarbonitrile (3) with the (N-acylanilino)alkyl radical to give 6-methyl-5-(N-acylanilino)alkylpyrazine-2,3-dicarbonitrile (9) and was followed by the substitution of the 2-carbonitrile with methylamine and further conversion to 1-methyl-2-amino-6-(N-acylanilino)-alkyl-7-methylpteridin-4(1H)-imine 11 by the action of guanidine. The second method is initiated by radical hydroxymethylation of 5-methylpyrazine-2,3-dicarbonitrile (3) to give 5-hydroxy-methyl-6-methylpyrazine-2,3-dicarbonitrile (15), followed by oxidation of the hydroxymethyl group, N-phenylimination, and the substitution of the 2-carbonitrile with methylamine to give 6-methyl-2-methyl-arnino-5-(N-phenylimino)methenylpyrazine-3-carbonitrile (18). The reduction of the imino group and the final cyclization with guanidine gives 2-amino-6-anilinomethyl-1,7-dimethylpteridin-4(1H)-imine (20).     

Novel one‐ and two‐dimensional ZnII coordination polymers based on a versatile 3,6‐bis(pyridin‐4‐yl)phenanthrene‐9,10‐dione ligand

Two new Zn^II coordination polymers, namely, catena‐poly[[dibromidozinc(II)]‐μ‐[3,6‐bis(pyridin‐4‐yl)phenanthrene‐9,10‐dione‐κ²N:N′]], [ZnBr₂(C₂₄H₁₄N₂O₂)]_n, (1), and poly[[bromido[μ₃‐10‐hydroxy‐3,6‐bis(pyridin‐4‐yl)phenanthren‐9‐olato‐κ³N:N′:O⁹]zinc(II)] hemihydrate], {[ZnBr(C₂₄H₁₅N₂O₂)]·0.5H₂O}_n, (2), have been synthesized through hydrothermal reaction of ZnBr₂ and a 60° angular phenanthrenedione‐based linker, i.e. 3,6‐bis(pyridin‐4‐yl)phenanthrene‐9,10‐dione, in different solvent systems. Single‐crystal analysis reveals that polymer (1) features one‐dimensional zigzag chains connected by weak C—H...π and π–π interactions to form a two‐dimensional network. The two‐dimensional networks are further stacked in an ABAB fashion along the a axis through C—H...O hydrogen bonds. Layers A and B comprise left‐ and right‐handed helical chains, respectively. Coordination polymer (2) displays a wave‐like two‐dimensional layered structure with helical chains. In this compound, there are two opposite helical –Zn–HL– chains [HL is 10‐hydroxy‐3,6‐bis(pyridin‐4‐yl)phenanthren‐9‐olate] in adjacent layers. The layers are packed in an ABAB sequence and are further connected through O—H...Br and O—H...O hydrogen‐bond interactions to form a three‐dimensional framework. In (1) and (2), the mutidentate L and HL ligands exhibits different coordination modes.     

Transition metal complexes with bidentate ligands spanning trans-positions. VI. The preparation of some diaryl- and dialkyl derivatives of 2,11-bis (phosphinomethyl)benzo [c]phenanthrene

The preparation of the ditertiary phosphines 2,11-bis (di-m-tolylphosphinomethyl)benzo [c]phenanthrene ( 1b ), 2,11-bis (di-p-anisylphosphinomethyl)benzo-[c]phenanthrene ( 1c ), 2,11-bis (di-m-trifluoromethylphenylphosphinomethyl) benzo-[c]phenanthrene ( 1d ), 2,11-bis (dicyclohexylphosphinomethyl)benzo [c]phenanthrene ( 1e ) and 2,11-bis [di-(t-butyl)phosphinomethyl]benzo [c]phenanthrene ( 1f ), by a combination of synthetic routes is described.     

Transition-Metal Complexes with Bidentate Ligands Spanning trans-Positions. I. The synthesis of 2,11-bis(diphenylphosphinomethyl)benzo[c]-phenanthrene,a ligand promoting the formation of square planar complexes

The bidentate ligand 2,11-bis(diphenylphosphinomethyl)benzo[c]phenanthrene ( 1 ) was synthesized from 2,11-dimethyl-benzo[c]phenanthrene ( 3 ) via the corresponding bromomethyl derivative 9. 3 was obtained from the cyclization with boron trifluoride etherate of 1,1-di-(p-methylphenethyl)-epoxyethane ( 7 ), which was prepared from 1,5-di(p-tolyl)-pentan-3-one ( 6 ).     

Ring transformations of heterocyclic compounds. XVI. Spiro[cyclohexadiene-dihydroacridines]. A novel class of spirodihydroacridines by ring transformation of pyrylium salts with 9-methylacridine and its quaternary salts

2,4,6-Triarylpyrylium salts 1 react with the in situ generated anhydrobase of 9,10-dimethylacridinium methosulfate ( 2a ) in the presence of anhydrous sodium acetate in ethanol by a 2,5-[C₄+C₂] pyrylium ring transformation to give the hitherto unknown 6-aroyl-3,5-diaryl-10′-methylspiro[cyclohexa-2,4-diene-1,9′-9′,10′-dihydro-acridines] 3 . When the pyrylium perchlorate 1a is treated under the same conditions with the N-ethyl, N-allyl or N-benzyl substituted acridinium salts 2b-d a dealkylation of these salts occurs and the N-unsubstituted spiro[cyclohexadiene-dihydroacridine] 4a is formed. The same compounds 4 can also be obtained by transformation of the pyrylium salts 1 with 9-methylacridine ( 7 ) and triefhylamine/acetic acid in ethanol. Structure elucidation is performed by an X-ray crystal structure determination of the spiro[cyclohexadiene-dihydroacridine] 3a . Spectroscopic data of the transformation products and their mode of formation are discussed.     

Furopyridines. XVII . Cyanation,chlorination and nitration of furo[3,2-b]pyridine N-oxide

The N-oxide 2 of furo[3,2-b]pyridine ( 1 ) was cyanated by the Reissert-Henze reaction with potassium cyanide and benzoyl chloride to give 5-cyano derivative 3 , which was converted to the carboxamide 4 , carboxylic acid 5 , ethyl ester 6 and ethyl imidate 8 . Chlorination of 2 with phosphorus oxychloride yielded 2-9a , 3- 9b , 5- 9c and 7-chloro derivative 9d . Reaction of 9d with sodium methoxide, pyrrolidine, N,N-dimethylformamide and ethyl cyanoacetate afforded 7-methoxy- 10 , 7-(1-pyrrolidyl)- 11 and 7-dimethylaminofuro[3,2-b]pyridine ( 14 ) and 7-(1-cyano-1-ethoxy-carbonyl)methylene-4,7-dihydrofuro[3,2-b]pyridine ( 12 ). Nitration of 2 with a mixture of fuming nitric acid and sulfuric acid gave 2-nitrofuro[3,2-b]pyridine N-oxide ( 15 ).     

Studies on the synthesis of heterocyclic compounds. Part IV. Further investigation of the pschorr reaction with some pyrazole derivatives

Thermal decomposition of the diazonium sulfate derived from N-methyl-(1-phenyl-3-methylpyrazol-5-yl)-2-aminobenzamide afforded products formulated as 1-phenyl-3-methyl[2]benzopyrano[4,3-c]pyrazol-5-one (yield 10%), 1,4-dimethyl-3-phenylpyrazolo[3,4-c]isoquinolin-5-one (yield 10%), N-methyl-(1-phenyl-3-methylpyrazol-5-yl)-2-hydroxybenzamide (yield 8%) and 4′-hydroxy-2,3′-dimethyl-1′-phenylspiro[isoindoline-1,5′-[2]-pyrazolin]-3-one (yield 20%). Decomposition of the diazonium sulfate derived from N-methyl-(1,3-diphenylpyrazol-5-yl)-2-aminobenzamide gave products formulated as 7,9-dimethyldibenzo[e,g]pyrazolo[1,5-a][1,3]-diazocin-10-(9H)one (yield 8%), 4-methyl-1,3-diphenylpyrazolo[3,4-c]isoquinolin-5-one (yield 7%) and 4′-hydroxy-2-methyl-1′,3′-diphenylspiro[isoindoline-1,5′-[2]pyrazolin]3-one (yield 10%). The spiro compounds 6a,b underwent thermal and acid-catalysed conversion into the hitherto unknown 2-benzopyrano[4,3-c]pyrazole ring system 7a,b in good yield. Analytical and spectral data are presented which supported the structures proposed.     

Cycloaddition of norbornadiene to fluorine-containing heteroaddends

Cycloaddition reactions of norbornadiene with fluorinated heteroaddends (hexafluoro-acetone, dichlorotetrafluoroacetone, trifluoroacetonitrile, and N-trifluoroacetylhexafluoro-propan-2-imine) were studied. As a rule, the reactions follow the concerted mechanism. The reaction with bis(trifluoromethyl)ketene gave a mixture of tricyclene [2+2]- and [2+2+2]-cyclo-adducts formed along different pathways. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 1013–1015, April, 2005.