Reaction of benzyne with cycloheptatriene preparation and thermolysis of some benzo(C9H10) hydrocarbons

The title reaction gave a 2+2 cycloadduct, 8,9-benzo-cis-bicyclo[5.2.0]nona-2,4,8-triene 7, together with ene product, 7-phenylcycloheptatriene. The structure of 7 was confirmed by catalytic reduction to give 8,9-benzo-cis-bicyclo[5.2.0]non-8-ene, which was also obtained in the reaction of benzyne with cycloheptene, and by reduction of the known 8,9-benzobicyclo[5.2.0]nona-1,8-diene. Other benzo(C₉H₁₀) hydrocarbons which have been synthesised are 7,8-benzobicyclo[4.2.1]nona-2,4,7-triene 5, 2,3-benzobicyclo[6.1.0]nona-2,4,6-triene 28 and 4,5-benzobicyclo[6.1.0]nona-2,4,6-triene 29. The thermolysis of 7, 28, 29 and of 3,4-benzo-exo-endo-tetracyclo[4.3.1.0^3,4.0^7,9]dec-3-en-10-one, 25, is described.     

Addition reactions of nucleophiles to dibenzoylacetylene

Several enamine diones have been prepared through the nucleophilic addition of different amines to dibenzoylacetylene (DBA). Thus, the reaction of aniline, piperidine, o-aminophenol and N-phenylbenzylamine with DBA gave the corresponding 1:1 adducts namely, 1,4 - diphenyl - 2 - (N - phenylamino)but - 2 - ene -1,4 - dione (1), 1,4 - diphenyl - 2 - piperidinobut - 2 - ene - 1,4 - dione (2), 2 - (N - 2 - hydroxyphenylamino)1,4 - diphenylbut - 2 -ene - 1,4 - dione (3) and 1,4 - diphenyl - 2 - (N - phenylbenzylamino)but - 2 - ene - 1,4 - dione (4). UV absorption data reveal that the adducts 1 and 3, formed from aniline and o-aminophenol, respectively, are the E-isomers, arising through a trans-mode of addition whereas the adducts 2 and 4, formed from piperidine and N-phenyl-benzylamine are the Z-isomers, formed through a cis-mode of addition.The reaction of N-phenaeylaniline with DBA gave 2,3 - dibenzoyl - 1,4 - diphenylpyrrole (5), whereas the reaction of 1,8 - diaminonaphthalene with DBA gave a mixture of products consisting of 2 - benzoyl - 2 - phenacyl -2,3 - dihydroperimidine (11) and 2 - benzoylperimidine (12). The reaction of 2-aminopyridine with DBA gave a mixture of two 1:1-adducts, 2 - (2 - imino - 1(2H) - pyridyl) - 1,4 - diphenylbut - 2 - ene - 1,4 - dione (14) and 1,4 -diphenyl - 2 - (N - 2 - pyridylamino)but - 2 - ene - 1,4 - dione (15).     

Reaction of 3,6-diphenyl-1,2,4,5-tetrazine with cis,cis-1,5-cyclooctadiene : An attempt at preparing some dihydropyridazine derivatives

The reaction of 3,6-diphenyl-1,2,4,5-tetrazine 1 with cis,cis-cycloocta-1,5-diene 7 has been studied with a view to preparing some interesting dihydropyridazine derivatives. Refluxing a mixture of 1 with excess of 7 in benzene solution for 8hr resulted in the formation of a mixture of products consisting of 1,4-diphenyl-10a-hydroperoxy-4a, 5,6,9,10,10a-hexahydrocycloocta[d]pyridazine (8, 27%) and 2,4a,5,6,8,10a,11,12-octahydro-1,4,7,10-tetraphenyldipyridazo[4,5-a:4',5'-e]cyclooctene ( However, when the reaction of 1 with 7 was carried out in refluxing benzene for nearly 40 hr, the products formed were a 14% yield of 8, a 17% yield of 9 and a 37% yield of 1,4-diphenyl-5,6,9,10-tetrahydrocycloocta[d]pyridazine (10). Neat heating of 1 with 7 around 150° for 10 hr, on the other hand, gave a 20% yield of 9, as the only isolable product. Thermolysis of 8 around 155° gave a mixture of products consisting of 2-oxocyclooct-5-enyl phenyl ketone N-benzoylhydrazone (15,30%) and 1H-3-phenyl-4,5,8,9-tetrahydrocycloocta[d]pyrazole (16, 22%). Nickel peroxide-oxidation of the adduct 9 gave a 67% yield of 1,4,7,10-tetraphenyldipyridazo[4,5-a:4',5'-e]cyclooctene (27). Acetylation of 9, on the other hand, gave a 70% yield of 2,3,8,9-tetraacetyl-2,3,5,6,8,9,11,12-octahydro-1,4,7,10-tetraphenyldipyridazo[4,5-a:4',5'-e]cyclooctene(28).     

Isolation,tentative identification,and synthesis studies of the volatile components of the hairpencil secretion of the monarch butterfly

The major volatile components of the hairpencil secretion of the male monarch butterfly have been identified as benzyl caproate and either 1, 5, 5, 9-tetramethyl-10-oxabicyclo[4.4.0]-3- decen-2-one(1), or 2, 2, 6, 8-tetramethyl-7-oxabicyclo[4.4.0]-4-decen-3-one(2). One sequence designed to synthesize 1 yielded two isomeric products of structure 1 whose spectra are very similar to each other but distinctly different from those of the natural product; this sequence also yielded a tricyclic ketal (9). A second sequence gave two epimeric spiro compounds (12) and a third sequence gave a [4.3.0] ring system (14).     

A unique peroxide formation based on the Mn(III)-catalyzed aerobic oxidation

The autoxidation of a mixture of 1,1-diarylsubstituted alkenes 4 and 4-hydroxy-1H-quinolin-2-ones 5 in the presence of a catalytic amount of manganese(III) acetate dihydrate in air gave 3,3-bis(2-hydroperoxyethyl)-1H-quinoline-2,4-diones 6 in 31-91% yields together with [4.4.3]propellane-type cyclic peroxides 7 (10-34%). A similar aerobic oxidation of 3-substituted quinolinones 8 yielded cyclic peroxide derivatives 9 and/or 3-hydroperoxyethylated quinolinediones 10 depending on the substituent. The structures of the bis(hydroperoxide) 6 (R¹=Me, Ar=4-ClC₆H₄) and the [4.4.3]propellane 7 (R¹=Me, Ar=Ph) have been corroborated by X-ray crystallography.     

Acetolysis of the trifluoromethanesulphonates of syn-12-hydroxyaldrin and syn-12-hydroxyisodrin and their dihydro derivatives : Reduction in neighbouring double bond participation effected by chlorine substituents

Acetolysis rates of the trifluoromethanesulphonates of two geometric isomers of hexachlorotetracyclo[6.2.1.1^3,6.O^2,7]dodeca-4,9-dien-12-ol (6, 8; syn-12-hydroxyaldrin, syn-12-hydroxy-isodrin) and of two geometric isomers of hexachlorotetracyclo[6.2.1.1^3,6.O^2,7dodec-9-en-12-ol (7,9; syn-12-hydroxy-4, 5-dihydroaldrin, syn-12-hydroxy-4,5-hydroisodrin) have been determined. The results show that neighbouring double bond participation by a —ClCCCl— grouping that is juxtaposed to an incipient secondary carbenium ion (> CH·OSO₂CF₃ is negligible compared with that seen in the non-chlorinated prototypes containing an analogously-situated —CHCH— grouping (e.g.4). The products of acctolysis of 8 and 9 were acetates of the original carbocyclic ring system, but the acctolysis of 6 at 64° yielded, as the sole rearranged product, a hexachloropentacyclo[7.2.1.O^2,8.O^3,5.O⁴]dodecen-6-yl acetatc10. The major products of acetolysis at 64° of 7 were a mixture of two isomeric hexachlorotetracyclol[6.3.1.O^2,9.O^3,7]dodecen-11-yl acetates(17,18) and a hexachloropentacyclo[6.4.0.O^2,10.O^3,7.O^9,11 dodec-4-ene 15; these were each formed via an initial bridging reaction and subsequent rearrangement steps. The factors that dictate the nature of products formed from each compound are discussed, and probable pathways to each are delineated.     

Structures of the tricyclododecenes prepared by the catalytical intramolecular cyclisation of 1,5,9-cyclododecatriene

The internal cyclisation of 1,5,9-cyclododecatriene, induced by a catalytical amount of Cp₂TiCl₂-LAHδ, leads to a mixture of cis, anti, cis-tricyclo[7.3.0.0^2,6]-7-dodecene (1), cis,syn,trans-tricyclo[7.3.0.0^2,6]-7-dodecene (2), trans,syn-tricyelop[7.3.0.0^2,6]-6-dodecene (3) and 5,6,7,8,9,10-hexahydrobenzocyclooctene (4). The structures of the main products were determined from the spectra of a number of derivatives taking into account symmetry properties and configurational flexibility.     

Thiocarbonyl ylides : Reactions and stereochemical properties of some 4-t-butylcyclohexyl derivatives

The azine from 4-t-butylcyclohexanone on treatment with hydrogen sulfide under pressure is converted to a mixture of stereoisomeric 1,3,4-thiadiazolidines. Dehydrogenation of this mixture with an alkyl azodicarboxylate afforded in quantitative yield (based on azine) a mixture of the three possible Δ³-1,3,4-thiadiazolines. These three isomers have been isolated and their structures have been established as trans,trans-3,11-di-[1,1-dimethylethyl]-14,15-diaza-7-thiadispiro[5.1.5.2]pentadeca-14-ene(5); the cis,cis-isomer (6), and the cis,trans-isomer (7). Pyrolysis of either 5 or 6 leads in quantitative yield to cis,trans-3,10-di-[1,1-dimethylethyl]thiadispiro[5.0.5.2]tridecane (8), the formation of which is rationalized by conrotatory ring closure of the same thiocarbonyl ylide (24) formed from either 5 or 6. Pyrolysis of 7 leads exclusively to a thiirane isomeric with 10 and which is assigned the cis,cis-structure (9). The thiiranes 8 and 9 are desulfurized by tri-n-butylphosphine to the anti- and syn-1-(1,1-dimethylethyl)-4-[4-(1,1-dimethylethyl)cyclohexylidene]cyclohexanes (11 and 12), respectively. The cycloadditions of the thiocarbonyl ylides derived from 5–7 with dimethyl acetylenedicarboxylate and dimethylazodicarboxylate have been examined but stereochemistries have not been assigned to these products. Cis additions to the olefins (11 and 12) have been investigated with the most attention having been paid to the reactions with osmium tetroxide. The configurations of the glycols expected from these reactions have been correlated by comparison with the three possible glycols (16–18) obtained from pinacol reduction of 4-t-butylcyclohexanone. These three glycols have been separated and their configurations assigned from PMR and IR data. A discussion of the stereochemical implications of the various results is given.     

Photochemical and thermal rearrangements of a benzoylnaphthobarrelene-like system

8-Benzoyl-9-deuterionaphtho[de-2.3.4]bicyclo[3.2.2]nona-2,6,8-triene (12a)rearranges in a photochemical di-π-methane-type process to the l-benzoylatho[de-[2.3.4]tricyclo[4.3.0.0^2,9]nona-3,7-dienes 14a-c.The dihydro derivate 13a and the hydroxypheoylmethyl analogs 21a and 22a undergo similarly regioselective rearrangements to 15a+c, 23a-c, and 24a, respectively. At 298 K the primary photoreaction directly occus from the S₁(n,π^*) and T₂(n,π^*) states, and it proceeds from T₁(π,π^*) and from S₂(π,π^*) either directly or via T₂. At lower temperature on direct irradiation. S₁→T intersystem crossing and triplet reaction compete with reaction from the singlet. The rearrangement 12a→14a-c proceeds along three reaction paths evolving from the two primary photochemical processes of naphthyl-vinyl and vinyl-vinyl bonding in β-position to the CO (12→25+29). Two ground-state triplet diradical intermediates such as 25 and 27 have been shown to intervene consecutively—for the first time in di-π-methane photochemistry. Each has been characterized by ESR and IR, and the second one additionally by fluorescence and fluorescence excitation, and by laser flash photolysis.The failure of products 14a-c to interconvert photochemically is ascribed to efficient energy dissipation through thermally reversible pbotocleavage of the 3-membered ring.Compounds 12 and 14 thermally interconvert in the dark which constitutes the first example of a ground-state counterpart of a di-π-methane photorearrangement. The thermal reaction includes a path with highly regioselective (and possibly concerted) product formation competing with a stepwise process causing positional scrambling. The sequence 12→14 (photochemically; Φ = 1.0 at 366 nm and 298 K) and an electrophile-catalyzed reversal 14→12 in the dark is a model of a chemical light energy storage cycle which can be conducted without loss of reactants.     

The diels-alder dimerisation of 2,3-dichlorocyclopentadienone and of 2,3,8,9-tetrachlorobicyclo[4.3.0]nona-2,4,8-trien-7-one

The Diels-Alder dimer of 2,3-dichlorocyclopentadienone, shown to be endo-4,5,7,8-tetrachlorotricyclo[5.2.1.0^2,6]deca-4,8-dien-3,10-dione 1, forms 2,3,8,9-tetrachlorobicyclo[4.3.0]nona-2,4,8-trien-7-one 3 on thermal extrusion of carbon monoxide. The trienone 3 itself dimerises at ca. 160°, with loss of hydrogen chloride, affording two stereoisomeric aromatic derivatives 8 and 9.     

Protonation of methane(tri-α-diazoacetone) in acid softening solvents : Acid and base-induced intramolecular cyclizations OM methane(tri-chloroacetone) to trioxaadamantane and triasterane derivatives

Controlled protonation of methane(tri-α-diazoacetone) (1) leads to open-chain tricarbonyl compounds 2, which can be cyclized by acids to 2,4,9-trioxaadamantanes 3. On the other hand, the base-induced cyclization of methane(tri-chloroacetone) (2, X  Cl) leads to a triasterane derivative: 1-hydroxymethyltetracyclo-[3.3.1.0^4,6]nona-3, 7-dione (4).     

Heterohomoconjugation versus heterobicycloconjugation in 9-thiabicyclo[4.2.1]nona-2,4,7-triene

The bridged heterocycles, 9-thiabicyclo[4.2.1]nonane (3), 9-thiabicyclo[4.2.1]non-7-ene (4), 9-thiabicyclo[4.2.1]nona-2,4-diene (5) and 9-thiabicyclo[4.2.1]nona-2,4,7-triene (2), were examined by photoelectron spectroscopy and the various MO levels theoretically located in each case by CNDO/S calculation. The combined information is best interpretable in terms of localized π interaction between sulfur and ethylene but not butadiene. The conclusion therefore is that thiabicyclotriene 2 is not a heterobicycloconjugated molecule but rather one best described as heterohomoconjugated.     

Studies on hetero-cage compounds—VI : Transannular cyclizations in pentacyclo[6.2.1.0.2,70.4,1005,9]undecan-3,6-dione system

Several 4-oxa- and -aza-bird-cage compounds were prepared by transannular cyclizations of pentacyclo[6.2.1.0.^2,70.^4,100^5,9]undecan-3,6-dione (3). Diol derivatives of 3 cyclized to afford the corresponding 4-oxa-bird-cage derivatives such as 9, 16a and 16b. The corresponding 3-keto-6-ol derivatives (6, 10a and 10b) did not cyclize transannularly, while 3-imino-6-ol, 3-keto-6-amino, and 3- imino-6-amino type derivatives cyclized to afford 3-substituted 4-oxa- and -aza-bidr-cage compounds such as 12, 14 and 18. The transannular cyclization reactivity in the 3 system has been compared with that in the bicyclo[3.3.1]nona-3,7-dione system (1).     

In vitro microbial studies of new pyrazolyl quinazolin-4(3H) ones

A series of new 2-[2-(2,6-dichlorophenyl)amino]phenyl methyl-3-[(5-substituted phenyl)-1,5-dihydro-1H-pyrazol-3-yl-amino]-6-iodoquinazolin-4(3H) ones (6a–m) have been synthesized by the reaction of 2-[2-(2,6-dichlorophenyl)amino]phenyl methyl-3-substituted phenyl acryl amido-6-iodoquinazolin-4(3H) ones with hydrazine hydrate in the presence of glacial acetic acid. The chalcone (5a–m) have been prepared by the condensation of 2-[2-(2,6-dichlorophenyl)amino]phenyl methyl-3-acetamido-6-iodoquinazolin-4(3H) one with different substituted aromatic aldehyde. The compound 1 on treatment with 5-iodoanthranilic acid in pyridine undergoes cyclisation gave 2-[2-(2,6-dichlorophenyl)amino]phenyl methyl-6-iodo-3,1-benzoxazin-4(3H) one (2). Treatment on benzoxazine with hydrazine hydrate gave 3-amino-2-[2-(2,6-dichlorophenyl)amino]phenyl methyl-6,8-dibromo quinazolin-4(3H) one (3) followed by acetylation synthesized 2-[2-(2,6-dichlorophenyl)amino]phenyl methyl-3-acetamido-6,8-dibromoquinazolin-4(3H)-one (4). The structure of synthesized compounds has been elucidated by IR, ¹H NMR, ¹³C NMR and elemental analysis. The products were screened for antibacterial and antifungal activity. Among the series containing some of the compounds showed promising results against standard drugs.     

Electrochemical reduction of heterocyclic enammonium salts

Four N,N-disubstituted 2-cyano-Δ⁷-hexahydroindolium salts, 1, have been reduced at a mercury cathode in aqueous buffered solutions at intermediate pH-values. From the catholyte the following products were isolated and identified: 2-(β-cyanoethyl)-cyclohexanone, 5, a secondary amine, 4, and a mixture of cis-trans isomeric tertiary 2-(β-cyanoethyl) cyclohexylamines, 6. A reaction path via the protonated enamine 3 is proposed based on the pH-dependence of the composition of the product mixture and a few reductions in DMF solution.     

Ketene-S,S,-acetals—VI : Synthesis of 3,3-bis-(methylthio)-2-propene-2-alkyl-1-aryl-1-ones and their reaction with guanidine: A novel route for pyrimidine synthesis

The α-ketoketene-S,S,-acetals 2a–h have been synthesized from the appropriate ketones 1a–f in good yields by extending the established method. The acetals 2a–d react with guanidine in the presence of sodium ethoxide to give pyrimidines 4a–d in 35–59% overall yields (Scheme 1). Treatment of 2e with guanidine similarly gave 5a in 23% yield. However, the reaction of 2e with guanidine in the presence of sodium n-propoxide gave a mixture of three products from which 5a was isolated as major product (20%) with 6a (7%) and 7a (5%). Under similar reaction conditions, 2f gave 5b, 6b and 7b in identical yields. Treatment of 2g–h with guanidine in the presence of sodium n-propoxide gave only 8a (28%) and 8b (23%) respectively. The formation of these pyrimidines involves base induced 1,3-proton migration in 2a–h to give intermediate olefins 10a–h.     

On the mechanism of the reductive cleavage of anti-9-phenyl-cis-bicyclo[6.1.0]nona-2,4,6-triene

Treatment of the title compound (1a) with potassium in liquid ammonia at ca ?33° immediately afforded the benzylcyclooctatetraene dianion (4a) which, upon quenching with iodine-pentane, gave benzylcyclooctatetraene (5) as the only isolable product. In contrast, treatment of1a with potassium amide in liquid ammonia at ?69° initially afforded the 9-phenylmethylenecyclooctatrienyl anion (6a) as a short-lived intermediate which was then converted to the α-aminobenzylcyclooctatetraene dianion (7a). These results, coupled with the observation that cis-bicyclo[6.1.0]nona-2,4-diene (12) in potassium amide-liquid ammonia affords the cis-bicyclo[6.1.0]nonadienyl anion (8b) which then slowly opens to the methylcyclooctatetraene dianion (4b) at ?12°, lead to the conclusion that4a is produced by a reductive cleavage of1avia a radical anion or dianion.     

Photorearrangement of homobenzobarrelenes,interference of cyclopropyl rings in the di-π-methane rearrangement

Acetone-sensitized irradiation of homobenzobarrelenes, exo- and endo-4a causes the di-π-methane rearrangement (Φ = 3.9 × 10^?1 and 9.5 × 10^?2 respectively), whereas direct irradiation was ineffective. The products formed were exo- and endo-homobenzosemibullvalenes. On the other hand, irradiation of the dicarbomethoxy derivatives exo- and endo-4b leads (directly or acetone-sensitized) to dimethyl 7,8- benzotricyclo [4.3.0.0.^2,9] nona-4,7-diene-2,4-dicarboxylate 12 by cyclopropylcarbinyl-homoallyl isomerization (exo-4b: Φ_dir. = 1.8 × 10^?2, Φ_sens. = 6.9 × 10^?2). Herkstroeter- Hammond plots make probable that the same triplet state is photoreactive in all cases.     

Synthesis and diastereoselective functionalisation of tricarbonyl[(3a,7a)-octahydro-3-substituted-2-(η-phenyl)benzoxazole]chromium(0) complexes

Two novel tricarbonyl[(3a,7a)-octahydro-3-substituted-2-(η⁶-phenyl)benzoxazole]chromium(0) complexes have been synthesised in excellent yield and characterised by X-ray crystallography. Treatment of complex 1 with butyllithium followed by electrophile quench (MeI, MeSSMe, Me₃SiCl, Me₃SnCl, Ph₂PCl, PhCH₂Br, PhCHO) gave 1,2-disubstituted (η⁶-arene)Cr(CO)₃ complexes in excellent yield, by completely diastereoselective ortho-deprotonation. The structures of the products 5 and 10 have been established by X-ray crystallographic analyses.     

Photochemistry of bridged cycloheptadienes. Multiplicity dependent pericyclic rearrangements of excited bicyclo[4.2.1]nona-2,4-diene-7,7,8,8-tetracarbonitrile

Bicyclo[4.2.1]nona-2,4-diene-7,7,8,8-tetracarbonitrile rearranges selectively under direct irradiation in acetonitrile to tricyclo[3.2.2.0^2,4]non-6-ene-8,8,9,9-tetracarbonitrile, and upon acetone sensitization to bicyclo[3.2.2]nona-2,6-diene-8,8,9,9-tetracarbonitrile. Both products are derived from sigma bond cleavage, in contrast to the parent unsubstituted diene where only the π-bonds react.