Synthesis of 3H[1,2]diazepino[5,6-b]indole and 3H[1,2]diazepino[4,5-b]indole derivatives

The synthesis of two new derivatives of 3H[1,2]diazepino[5,6-b]indole, 5 and 11 , and one new derivative of 3H[1,2]diazepino[4,5-b]indole, 16 , are described. Compound 5 was obtained by the reaction of methyl 2-(3-methoxycarbonyl-1-methylindole)acetate 2 , with hydrazine. Compound 11 was obtained in two ways from ethyl 2-(1-methylindole)acetate ( 8 ) by formylation and reaction with hydrazine. Compound 16 was obtained treating 3-(2-ethoxycarbonylindole)acetonitrile ( 14 ) with hydrazine.     

CRYSTAL STRUCTURE OF [Cu(NH3)2]2[{Cu(NH3)}2{Cu(NH3)(OH)}Re6Se8(CN)6]

Journal of Structural Chemistry - Chain coordination polymer [Cu(NH3)2]2[{Cu(NH3)}2{Cu(NH3)(OH)}Re6Se8(CN)6] (1) is obtained by a reaction of Cs2.75K1.25[Re6Se8(CN)4(OH)2]·H2O with CuCN in the...     

Novel neutral hexacoordinate benzamidinatosilicon(IV) complexes with SiN3OF2, SiN3OCl2, SiN3OBr2, SiN5O and SiN3O3 skeletons

The neutral pentacoordinate monoamidinatosilicon(IV) complex 1 (SiN(2)Cl(3) skeleton) and the neutral hexacoordinate monoamidinatosilicon(IV) complexes 2-9 (SiN(3)OF(2), SiN(3)OCl(2), SiN(3)OBr(2), SiN(5)O and SiN(3)O(3) skeletons) were synthesised and characterised by elemental analyses, single-crystal X-ray diffraction (except for 1) and NMR spectroscopy in the solid state and in solution. Compounds 2-9 contain one bidentate monoanionic N,N'-diisopropylbenzamidinato ligand, one bidentate monoanionic ligand derived from 8-hydroxyquinoline and (i) two identical monoanionic ligands (F, Cl, Br, N(3), NCO, NCS, OSO(2)CF(3)) or (ii) one bidentate dianionic benzene-1,2-diolato ligand. The dynamic behavior of 2-4 (SiN(3)OX(2) skeleton; X = F, Cl, Br) and 9 (SiN(3)O(3)) in solution was studied by multinuclear variable-temperature NMR experiments. Compound 1 was synthesised by reaction of SiCl(4) with the corresponding lithium amidinate, and compound 2 was obtained by reaction of 1 with 8-hydroxyquinoline and triethylamine. Compound 2 served as the starting material in the syntheses of 3-9, in which the two chloro ligands of 2 were substituted by two identical (pseudo)halogeno ligands, two trifluoromethanesulfonato ligands or one benzene-1,2-diolato ligand. Compounds 3 and 4 contain the novel SiN(3)OBr(2) and SiN(3)OF(2) skeletons, while compounds 5-7 are the first neutral hexacoordinate silicon(IV) complexes with an SiN(5)O skeleton.     

Cyclization of ylidenemalononitriles. X. Synthesis of benzazapropellane derivatives from α-Cyano-β-chloroalkylcinnamonitriles

The reaction of nucleophilic and non-nucleophilic bases wtih 2-carbamoyl-3-(γ-chloropropyl)-1-indenone ( 5 ) have been investigated. Condensation of γ-chlorobutyrophenone with malono-nitrile afforded α-cyano-β-(3-ehloropropyl)cinnamonitrile which was cyclized in concentrated sulfurie acid to produce 5 . Two other products obtained from the cyclization reaction were 2-carbamoyl-3-(γ-ehloropropylidene)-1-indanone ( 4 ) and α-carbamoyl-β-(3-chloropropyl)cinnam-amide. Treatment of a solution of 4 in ethyl acetate with piperidine resulted in cyclization of the γ-chloropropyl side chain to give 2-carbamoyl-3-cycIopropyl-1-indanone. The same compound was obtained in improved yield by the treatment of 4 or 5 with sodium hydroxide solution. The reaction of dirnethylamine with 5 in benzene gave initial Michael addition of the amine followed by internal alkylation of the carbanion so formed to yield 3a-dimethylamino-2,3,3a,8-tetrahydro-8-oxoeyclopent[a]indene-8a(lH)earboxamide ( 7a ). Similarly addition of ammonia, pyrrolidine, piperidine, benzenethiol, p-toluenethiol, 2-naphthalenethiol and nitromethane to the indenone I gave respective analogs of type 7 . Treatment of 5 with sodium cyanide in aqueous t-butyl alcohol resulted in a similar Michael addition followed by internal alkylation. In addition, cyclization between the nitrile and the carbamoyl functions occurred in the same step to give 2-oxo-4-imino-7,8-benzo-3-aza[3.3.3]-propellan-6-one ( 13a ). Hydrolysis of the iminopyrrolido ring in 13a to the corresponding suecin-irnide gave 2,4-dioxo-7,8-benzo-3-aza[3.3.3]propellan-6-one ( 13b ). Reactión of 13b with methyl iodide, allyl bromide, benzyl bromide, and diethyluminoethyl chloride afforded the corresponding N-alkylated products. A similar sequence starling with δ-ehlorovalerophenone led to 5,6-fused ring systems, including a [4.3.3]propellane. 2,9-Dioxo-4-methyl-7,8-benzo-3-aza[4.3.3]propell-4-ene was obtained by the reaction of 5 with acetone in dilute alkali.     

Selenium dioxide oxidations of dialkyl-3H-azepines: the first synthesis of 2-azatropone from oxidation of 2, 5-Di-tert-butyl-3H-azepine

Oxidation reactions of 2,5- and 3,6-di-tert-butyl-3H-azepines (1 and 2) with selenium dioxide (SeO(2)) were performed. The oxidation of 1 with SeO(2) gave 3-tert-butyl-7,7-dimethyl-4-oxo-octa-2,5-dienal 3 in 36% yield, 4-tert-butyl-5-(3,3-dimethyl-2-oxo-butylidene)-1, 5-dihydro-pyrrol-2-one 4 in 13% yield, 2, 6-di-tert-butyl-2-pyridinecarbaldehyde 5 in 12% yield, and 4, 7-di-tert-butyl-2H-azepin-2-one (2-azatropone) 6 in 6% yield, respectively. Oxidation of 2 with SeO(2) gave 2, 2-dimethyl-1-[2-(5-tert-butyl)-pyridyl]propanol 7 in 55% yield, and 3,6-di-tert-butyl-2H-azepine 8 in 5% yield, respectively. We found that selenium dioxide oxidation of 1 affords 4-oxo-octa-2,5-dienal 3 by a new ring cleavage reaction of 1, and we described the first synthesis of 2-azatropone 6 from this oxidation of 1. In the case of 2, pyridylpropanol 7 was obtained as the major product. We now report in detail result of these oxidation reactions, which have led to the synthesis of a novel azatropone derivative.     

Pyrimidine derivatives XII. A convenient preparation of 6-formylpyrimidinedione and 2- and 3-formylpyridine derivatives from corresponding nitrooxymethyl derivatives

The convenient preparation of 6-fomylpyrimidinedione derivatives and 2- and 3-formylpyridine are described. Thus, 5-bromo-1,3-dimethyl- ( 1a ), 5-bromo-3-methyl-1-(2-nitrooxyethyl)- ( 1b ), and 5-bromo-3-methyl-1-(3-nitrooxypropyl)-2,4(1H,3H)-pyrimidine-dione ( 1c ) were converted to the corresponding 6-formyl compounds 2a, 2b , and 2c , respectively, in excellent yields by the reaction with triethylamine and 1,4-diazabicyclo[2.2.2]octane. These 6-formylpyrimidinedione derivatives are key intermediates for the preparation of 6-carbon-carbon substituted compounds, which are expected to be potential antitumor and antiviral agents. Similarly, 2-(and 3-)formylpyridine ( 9a (and 9b )) were obtained by the reaction of 2-(and 3)nitrooxymethylpyridine ( 8a (and 8b )) with 1,4-diazabicyclo[2.2.2]octane.     

Unexpected Disproportionation of Tetramethylethylenediamine-Supported Perchlorodisilane Cl(3)SiSiCl(3)

The addition compound Cl(3)SiSiCl(3)·TMEDA was formed quantitatively by treatment of Cl(3)SiSiCl(3) with tetramethylethylenediamine (TMEDA) in pentane at room temperature. The crystal structure of Cl(3)SiSiCl(3)·TMEDA displays one tetrahedrally and one octahedrally bonded Si atom (monoclinic, P2(1)/n). (29)Si CP/MAS NMR spectroscopy confirms this structure. Density functional theory (DFT) calculations have shown that the structure of the meridional isomer of Cl(3)SiSiCl(3)·TMEDA is 6.3 kcal lower in energy than that of facial coordinate species. Dissolving of Cl(3)SiSiCl(3)·TMEDA in CH(2)Cl(2) resulted in an immediate reaction by which oligochlorosilanes Si(n)Cl(2n) (n = 4, 6, 8, 10; precipitate) and the Cl(-)-complexed dianions [Si(n)Cl(2n+2)](2-) (n = 6, 8, 10, 12; CH(2)Cl(2) extract) were formed. The constitutions of these compounds were confirmed by MALDI mass spectrometry. Additionally, single crystals of [Me(3)NCH(2)CH(2)NMe(2)](2)[Si(6)Cl(14)] and [Me(3)NCH(2)CH(2)NMe(2)](2)[Si(8)Cl(18)] were obtained from the CH(2)Cl(2) extract. We found that Cl(3)SiSiCl(3)·TMEDA reacts with MeCl, forming MeSiCl(3) and the products that had been formed in the reaction of Cl(3)SiSiCl(3)·TMEDA with CH(2)Cl(2). X-ray structure analysis indicates that the structures of [Me(3)NCH(2)CH(2)NMe(2)](2)[Si(6)Cl(14)] (monoclinic, P2(1)/n) and [Me(3)NCH(2)CH(2)NMe(2)](2)[Si(8)Cl(18)] (monoclinic, P2(1)/n) contain dianions adopting an "inverse sandwich" structure with inverse polarity and [Me(3)NCH(2)CH(2)NMe(2)](+) as countercations. Single crystals of SiCl(4)·TMEDA (monoclinic, Cc) could be isolated by thermolysis reaction of Cl(3)SiSiCl(3)·TMEDA (50 °C) in tetrahydrofuran (THF).     

Synthesis and Some Transformations of Ethyl 5-Alkoxymethyl-3-(2-methyl-3-oxobutyl)-2-oxotetrahydrofuran-3-carboxylates

Michael reaction of ethyl 5-alkoxymethyl-2-oxotetrahydrofuran-3-carboxylates with 3-methyl-3-buten-2-one gave ethyl 5-alkoxymethyl-3-(2-methyl-3-oxobutyl)-2-oxotetrahydrofuran-3-carboxylates. Alkaline hydrolysis of the latter, followed by decarboxylation afforded 5-alkoxymethyl-3-(2-methyl-3-oxobutyl)tetrahydrofuran-2-ones. The bromination of ethyl 5-alkoxymethyl-3-(2-methyl-3-oxobutyl)-2-oxotetrahydrofuran-3-carboxylates provides a convenient method for the preparation of 3-acetyl-8-alkoxymethyl-3-methyl- and 8-alkoxymethyl-3-bromoacetyl-3-methyl-2,7-dioxaspiro[4.4]nonane-1,6-diones in high yields.     

Syntheses based on 8-substituted 3-bromoacetyl-3,8-dimethyl-2,7-dioxaspiro[4,4]nonane-1,6-diones

By reaction of 8-substituted 3-bromoacetyl-3,8-dimethyl-2,7-dioxaspiro[4,4]nonane-1,6-diones with thiourea and substituted thioureas under Hansch reaction conditions, we have obtained the novel heterocycles 3-[2′-amino(arylamino)thiazol-4-yl]-3,8-dimethyl-2,7-dioxaspiro[4,4]nonane-1,6-diones. By reacting the above-indicated bromoacetyl spirodilactones with 5-aryl-3-mercapto-1,2,4-triazoles, we obtained 8-substituted 3-(aryl-3,8-dimethyl-1′,2′,4′-triazol-3′-yl)thioacetyl-2,7-dioxaspiro[4,4]nonane-1,6-diones. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 123–129, January, 2006.     

Transformations of 2-(3-Hydroxy-3-methyl-1-butynyl)adamantan-2-ol >Catalyzed by Acids

Reaction of 2-(3-hydroxy-3-methyl-1-butynyl)adamantan-2-ol with acetonitrile under Ritter reaction conditions is accompanied by isomerization and partial hydration where the water addition to the triple bond occurs nonselectively. As a result of reaction carried out in the presence of 8 equiv of sulfuric acid a mixture was obtained of N ²-[4-(1-acetylamino-2-adamantyl)-2-methyl-3-butyn-2-yl]acetamide, N ³-[1-(1-acetylamino-2-adamantyl)-3-methyl-2-oxo-3-butyl]-acetamide, and N ³-[1-(1-acetylamino-2-adamantyl)-3-methyl-1-oxo-3-butyl]acetamide in ~10:3:2 ratio. In the presence of 2 equiv of the acid the mixture obtained consisted of N ²-[4-(1-acetylamino-2-adamantyl)-2-methyl-3-butyn-2-yl]acetamide, N ³-[1-(1-acetylamino-2-adamantyl)-3-methyl-2-oxo-3-butyl]acetamide, and 1-(1-acetylamino-2-adamantyl)-3-methyl-2-buten-1-one in the same ratio. In Rupe reaction conditions we obtained instead of the expected ,-unsaturated ketones a mixture of 1-(1-hydroxy-2-adamantyl)-3-hydroxy-3-methylbutan-1-one and 1-(1-hydroxy-2-adamantyl)-3-hydroxy-3-methylbutan-2-one in a 5:3 ratio.     

Reaction of 2-(2-oxoethylidene)furan-3(2H)-ones with isopropylidenehydrazides of aromatic carboxylic acids: Synthesis of 3-hydroxy-3-(2-oxoethyl)-2,3-dihydropyridazin-4(1H)-ones

3-Hydroxy-3-(2-oxoethyl)-6-phenyl-2,3-dihydropyridazin-4(1H)-ones were obtained by the reaction of methyl 3-oxo-5-phenylfuran-2(3H)-ylideneacetate or 2-[2-(4-chlorophenyl)-2-oxoethylidene]-5-phenylfuran-3(2H)-one with benzoic or p-nitrobenzoic isopropylidenehydrazides. Equilibrium C₍₅₎H and C₍₅₎H₂ tautomeric forms were detected in solutions of the 4-chlorophenyl derivatives in DMSO-d₆. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1156–1158, August, 2007.     

Addition of Pt(PBut3) to osmium-tin cluster complexes

The reactions of the osmium-tin cluster complexes Os3(CO)12(mu3-SnPh)Ph, 9, and Os4(CO)16(mu4-Sn), 10, with Pt(PBut3)2 have been investigated. Two products, PtOs3(CO)12(Ph)(PBut3)(mu3-SnPh), 11, and Pt2Os3(CO)12(mu2-Ph)(PBut3)2(mu3-SnPh), 12, were obtained from the reaction of 9 with Pt(PBut3)2. These are mono- and bis-Pt(PBut3) adducts of 9 formed by the addition of a Pt(PBut3) group to the Os-Os bond in 11 and the Os-Os bond and Os-C bond to the sigma-bonded phenyl group in 12. A PBut3 derivative of 11, Os2(CO)8(mu3-SnPh)Os(CO)3(PBut3)Ph, 13, was obtained by treating 12 with PBut3. The reaction of 10 with Pt(PBut3)2 provided the bis-Pt(PBut3) adduct Os4(CO)16[Pt(PBut3)]2(mu4-Sn), 14, that was formed by the addition of a Pt(PBut3) group across the Os-Os bond of both Os2(CO)8 groups in 10. All four new compounds 11-14 were characterized by single-crystal X-ray diffraction analysis.     

3-Furylchromones

-[2-(5-Methoxycarbonyl)furyl]-2,4-dihydroxy- and 2,4,6-trihydroxyacetophenones were obtained by the condensation of polyphenols with (2-methoxycarbonyl-5-furyl)acetonitrile. 7-Acetoxy- and 5,7-diacetoxy-2-methyl-3-[2-(5-methoxycarbonyl)furyl]chromones were obtained from them by reaction with acetic anhydride in the presence of triethylamine and were subsequently deacylated to 7-hydroxy and 5,7-dihydroxy compounds. 7-Hydroxy- and 5,7-dihydroxy-2-ethoxycarbonyl-3-[2-(5-methoxycarbonyl)furyl]chromones were obtained from the indicated acetophenones by reaction with ethoxalyl chloride.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1317–1320, October, 1972.     

An Improved Preparation of Polymer-Type η3-Allylpalladiumchlorides

Five polymer-type new compounds-(η³-cyclopentadienyl)palladiumchloride ( 6 ), (η³-indenyl) palladiumchloride ( 7 ), (η³-cycloheptatrienyl)palladiumchloride ( 8 ), (η³-phenalenyl)palladiumchloride ( 9 ) and (1,2,3-η³-4,5,6,7-η⁴-cyclopheptatrienyl)(palladium-chloride)(tricarboryl Iron) ( 10 ) have been prepared from the reaction of Na₂PdCl₄ with 1-trimethylsilylcyclopentadiene ( 1 ), 1-trimethylsilylindene ( 2 ), 1-trimethylsilyl cycloheptatriene ( 3 ), 1-trimethylsilylphenalene ( 4 ) and 1-trimethylsilylcycloheptatriene tricarbonyl Iron ( 5 ) respectively. All the complexes( 6 )-(10) are obtained in excellent yield using the improved preparation route. Furthermore, a reaction mechanism is proposed.     

2, 3-二氯-5-取代-5, 8-二氢-8-氧-吡啶并[2, 3-b)吡嗪-7-羧酸乙酯的合成

3, 5, 6-哌嗪三酮-2-甲酰胺(5)经与PCl5-POCl3反应制得3, 5, 6-三氯-2-氰基吡嗪(6)。6经转化为甲酯(7)再水解为3, 5, 6-三氯-2-吡嗪甲酸(8)。由8出发合成了两个2, 3-二氯-5-取代-5, 8-二氢-8-氧-吡啶并[2, 3-b]吡嗪-7-羧酸乙酯(11a~b)。其中5, 7~11均为新化合物, 其组成和结构经元素分析、IR、^1H NMR、MS证实。     

Access to the 2,3-dihydropyridazin-3-one and as-triazino[3,4-a]phthalazine ring systems from 4-aryl-2-oxo-butanoic acids

A novel series of 2,3-dihydropyridazin-3-ones 15 were synthesized via condensation between hydrazines and 4-(p-chlorophenyl)-2-hydroxy-2-(2-oxo-2-substituted ethyl)butanoic acids 8 which in turn were prepared by the reaction of substituted benzylpyruvic acids 6 with methyl alkyl(aryl) ketones 7. Dehydration of 8b-d by a mixture of glacial acetic acid and hydrochloric acid afforded 4-(p-chorophenyl)-2-(substituted phenacyl)-2-butenoic acids 10. Condensation reaction of 10 with hydrazines gave type 15 compounds in good yields. Also, a new series of as-triazino[3,4-a]phthalazines 20 was obtained from the reaction of substituted benzylpyruvic acids 6 with hydralazine to give the hydralazones 19 which underwent dehydrative cyclization reaction with PPA to afford 20. Structure assignments are based on ¹H, ¹³C nmr and ir spectra.     

The stepwise formation of mixed-metal coordination networks using complexes of 3-cyanoacetylacetonate

The complexes [Cu(L(1))2] 1, [Fe(L(1))3] 3 and [Al(L(1))3] 4 [L(1) = CH(3)C(O)C(CN)C(O)CH(3)] have been prepared for use as metallo-ligands in mixed-metal coordination networks. Surprisingly, the nature of the copper precursor is important in the synthesis of 1, with the reaction between Cu(NO3)2.3H2O, HL(1) and NEt3 giving [Cu6(micro(3)-OMe)4(micro-OMe)2(L(1))6] 2 instead of the anticipated 1, which was obtained with CuCl2.2H2O under the same conditions. Compound 1 reacts with AgNO3 to form [Cu(L(1))2.AgNO3](infinity) 5, the structure of which contains one-dimensional chains in which Ag+ ions bridge between molecules of 1. These chains are cross-linked into ladders by bridging nitrates. The product obtained from the reaction of 3 and AgNO3 is crucially dependent on the solvent used. The reaction in methanol-acetone gives [Fe(L(1))3.AgNO3](infinity) 6, {[Fe2(micro-OMe)2(L(1))4.2AgNO3].CH(3)C(O)CH(3)}(infinity) 7 and [Fe2(micro-OMe)2(L(1))4.AgNO3](infinity) 8. Compounds 6 and 8 both have one-dimensional chain structures, whereas 7 has a two-dimensional layer structure. The reaction in methanol gives 6 and 8 as the major products and, in addition, small quantities of {[AgFe2(micro-OMe)2(L(1))4]OH.0.4H2O](infinity) 9. Compound 9 has a three-dimensional structure based on doubly interpenetrated PtS nets. Compounds 7-9 contain Fe2(micro-OMe)2(L(1))4 dimers, but the coordination properties of the dimers differ, with all the cyanides coordinated in 7 and 9 but one uncoordinated in 8. The orientation of the cyanide groups depends on the relative chirality of the iron centres. A transmetallation reaction occurs between 4 and AgNO3 to give [Ag(L(1))](infinity) 10, which has a two-dimensional layer structure. Compounds 2, 3 and 5-10 have been characterised by X-ray crystallography.     

Synthesis of 3'-fluoro-2',3'-dideoxy-2',3'-didehydro-4'-ethynyl-D- and -L-furanosyl nucleosides

An efficient procedure has been developed for the synthesis of 3'-fluoro-2',3'-dideoxy-2',3'-didehydro-4'-ethynyl D- and L-furanosyl nucleosides (1 and 2) starting from 2,3-O-isopropylidene-d-glyceraldehyde. The key intermediate 1-O-benzoyl-3E-fluoro-3,4-unsaturated-5,6-di(tert-butyldimethylsilyloxy)-2-hexanone 8 was obtained in nine steps with the overall yield of 22%. The alpha,beta-unsaturated ketone 8 was then treated with ethynylmagnesium bromide in a typical Grignard reaction procedure to afford the two intermediates 9 and 10, which after deprotection, oxidation, and acetylation gave the corresponding 4-ethynyl-substituted D- and L-sugar moieties 15 and 16, respectively. A series of D- and L-pyrimidine and purine nucleosides were prepared by the coupling of the sugar moieties with various silylprotected bases. The anomeric mixtures were obtained after condensation. After separation, the beta-isomers were further deprotected to yield the target nucleosides. All the newly synthesized 4'-substituted nucleosides were tested for their activities against HIV, among which the D-adenine derivative showed moderate anti-HIV activity (EC(50) = 25.1 microM) without significant cytotoxicity.     

In situ photolysis of CD3I in solid orthodeuterium

Photochemical reactions of molecules in solid orthodeuterium (o-D2) have been studied by high-resolution infrared spectroscopy and compared with previous results obtained in solid parahydrogen (p-H2). Ultraviolet photolysis of CD3I molecules in solid o-D2 yielded CD3 radicals and iodine atoms efficiently, which indicates a small cage effect in solid o-D2, as in the case of solid p-H2. The Fourier transform infrared spectrum of the nu3 vibrational band of CD3 showed a rotational structure with additional splitting due to crystal field interactions. The magnetic dipole transition (2P1/2<--2P3/2) of the I atom isolated in solid o-D2 was observed together with a strong rotational satellite of deuterium molecules through the electron-roton coupling in solid hydrogen. The tunneling reaction between CD3 and D2 was not observed in a time scale of a few days, which gives the upper limit of the tunneling reaction rate of 10(-8) s(-1) at 4.2 K.     

Substituted γ-lactones. XXX. Reactions of α-Keto-β-Subtituted-γ-butyrolactones with diamines

The condensation reaction between α-keto-β-aroyl (or acyl) -γ-butyrolactones, 4a-4e and o-phenylenediamine or 2, 3-diaminonaphthalene leads under retrograde aldol condensation involving loss of formaldehyde to formation of 3-substituted-3, 4-dihydro-2 (1H) quinoxalinones or benzo [g] quinoxalinones, 7a-7g , respectively as a new convenient synthesis of this type of heterocyclic systems. The reaction of type 4 compound with 4, 5-diaminopyromidine, 8 , was found to proceed differently. 2-[(4-Amino-5-pyrimidinyl)amine]-4-oxo-3-(hydroxymethyl)-4-phenyl-2-butenoic acid 9 was the only product formed when the reaction between 4a and 8 was run in ethanol. The same reaction in glacial acetic acid proceeds with loss of formaldehyde, to afford 7-phenacylidene-7,8-dihydro-6 (1H)-pteridione 10 . The reaction between type 4 compounds and ethylenediamine or 1, 4-phenylenediamine leads to the formation of the bis-condensation products 13–15 , respectively.