The improved synthesis,Diels‐Alder reactions,and desulfuration of trithio‐1,8‐naphthalic anhydride

In the presence of a strong Lewis base, such as Et₃N, trithio‐1,8‐naphthalic anhydride (3) is easily oxidized. Two improved syntheses of trithio‐1,8‐naphthalic anhydride (3) are described. Trithio‐1,8‐naphthalic anhydride (3) undergoes Diels‐Alder reactions with electron‐deficient alkenes to give novel fused heterocyclic compounds (6–11) that then can undergo a novel, gradual desulfuration dimerization with triethyl phosphite to afford 12 and its analogs 13 and 14. The structures of 6–14 are confirmed by microanalysis, IR, and NMR spectroscopy, and MS. © 1999 John Wiley & Sons, Inc. Heteroatom Chem 10: 141–146, 1999     

Research on perinone compounds

11-Substituted 14H-benz[4,5]isoquinolino[2,1-a]perimidin-14-ones were synthesized, and their spectra were studied. In contrast to electron-acceptor substituents, electron-donor substituents have little effect on the shift of the absorption maxima. In the reactions of 1,8-naphthalenediamine with various 4-substituted naphthalic anhydrides, electron-donor substituents have little effect on the shift of the absorption maxima. In the reactions of 1,8-naphthalenediamine with various 4-substituted naphthalic anhydrides, electron-donor substituents lead primarily to 10-substituted naphthaloperinones, whereas electron-acceptor substituents lead primarily to 11-substituted naphthaloperinones. An assumption regarding the mechanism of the formation of 10- and 11-substituted naphthaloperinones is expressed.See [1] for communication IV.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1649–1654, December, 1974.     

Synthesis and luminescence properties of 4-(2-methyl-5-oxazolyl)naphthalic anhydride and the products of its condensation with aromatic amines

4-(2-Methyl-5-oxazolyl)naphthalic anhydridewas synthesized by heating -aminomethyl 5-acenaphthyl ketone hydrochloride with acetic anhydride and subsequent oxidation of the resulting 2-methy1-5-(5-acenaphthyl)oxazole. 4-(2-Methyl-5-oxazolyl)-naphthalic acid phenylimide and 4(3)-(2-methyl-5-oxazolyl)-7-oxo-7H-benzimidazo-[1,2-b]benzo[de]isoquinoline were obtained by condensation of 4-(2-methy1-5-oxazo-lyl)naphthalic anhydride with aniline and o-phenylenediamine. The coincidence of the directions of polarization of the C=N bond of the oxazole ring and the electronic shifts in the system of the anhydride and phenylimide molecules leads to an increase in the quantum luminescence yield.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1613–1615, December, 1977.     

Acylation of 3,4-Dihydropyrrolo[1,2-a]pyrazines

The direction of trifluoroacetylation with trifluoroacetic anhydride of 3,4-dihydropyrrolo[1,2-a]pyrazines containing an alkyl or aralkyl substituent in position 1 depends on both the structure of the 3,4-dihydropyrrolo[1,2-a]pyrazine starting materials and on the ratio of reagent:substrate. It may lead to both mono- and disubstituted products. Trifluoroacetylation of 1-methyl-3,4-dihydropyrrolo[1,2-a]pyrazines occurs at the methyl group. Acetylation of 3,4-dihydropyrrolo[1,2-a]pyrazines leads only to N-acetyl-substituted reaction products.     

Investigation of H-Complex Formation of Derivatives of Naphthalimide with Phenol by IR Spectroscopy

The H-complex-forming reaction of naphthalimide derivatives with phenol has been investigated by IR spectroscopy. It was shown that for the majority of compounds studied the carbonyl group is the main center of basicity. In the case of amino-substituted imides of naphthalic acid transfer is possible of the reaction center from the carbonyl group to the nitrogen atom of the substituent introduced into the naphthalene ring. However because of steric hindrance this occurs only for amino- and methylamino-substituted naphthalimide.     

Acid-catalyzed transannular cyclization of 3aH-cyclopentene[8]annulene-1,4-(5H,9aH)-diones and some proposed mechanisms

Bicyclic 3aH-cyclopentene[8]annulene-1,4-(5H,9aH)-diones underwent three types of acid-induced transannular reactions, Michael cyclization, [3 + 2] cycloaddition, and Friedel-Crafts ipso-alkylation, depending on the cyclopentenone ring substituent (Me or Ph) and the position of [8]annulenone substituent as well as the nature of acids (BF3, MeSO3H, CF3SO3H). The Me-substituent permitted the Michael reaction for all acids used to give tricyclic diones by the activation of cyclopentenone carbonyl group. However, the Ph-substituent inhibited the Michael reaction for BF3 and MeSO3H but allowed the [3 + 2] cycloaddition and Friedel-Crafts reaction for CF3SO3H depending on the position of annulenone substituent. These CF3SO3H reactions exhibited the following novel rearrangements, affording 2-naphthalenone and 7-acenaphthylene derivatives, respectively. The factors that control the reaction mode of these transannular cyclizations were discussed in view of the constraint twist-boat conformation of [8]annulenone ring as well as the ring substituent effects on the intramolecular cyclization. In addition, these [8]annulenone rings were found to easily undergo the intramolecular [2 + 2] photocyclization to provide the tetracyclic cage compounds which exhibited the facile cycloreversion under the influence of acid.     

Direct iodination of indanone and tetralone derivatives by elemental iodine activated by Selectfluor™ F-TEDA-BF4

Derivatives of indan-1-one and 3,4-dihydronaphthalen-1(2H)-one bearing hydroxy or methoxy substituent on the aromatic ring were efficiently iodinated regioselectively at the α carbonyl position using elemental iodine activated by 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate) (Selectfluor™ F-TEDA-BF₄) in methanol.     

1,8—萘酐和1,8—萘酰亚胺中硝基和卤素基团的亲核取代反应

研究了１，８－萘酐和１，８－萘酰亚胺萘环上硝基和卤素原子的亲核取代反应，讨论了影响亲核取代反应的因素，根据２，４－二硝基苯酚与脂胺肪的亲核取代机理，提出了４－硝基－１，８－萘酐及４－硝基－１，８－萘酰亚胺与脂肪胺发生亲核取代反应可能的反应机理。     

57Fe NMR spectroscopy of ferrocenes bearing pi-acceptor substituents

Ferrocene derivatives bearing pi-acceptor substituents in 1- or 1,1'-positions such as carbonyl group(s) (1, 2), a sulfinyl group (4) or boryl group(s) (5, 6, 9) and related [3]ferrocenophanes (3, 7, 10, 12, 13) and a [4]ferrocenophane (8) were studied by 57Fe NMR spectroscopy. The deshielding effect of the respective pi-acceptor substituent can be partially or fully compensated by distortion of the ferrocene geometry. Both aspects become apparent by comparing delta57Fe data of the [n]ferrocenophanes with those of related non-cyclic derivatives.     

Trifluoroacetylation of pyrrolo[1,2-<Emphasis Type="Italic">a</Emphasis>]pyrazines

A study was carried out on the reaction of pyrrolo[1,2-a]pyrazines containing an alkyl, aryl, or aralkyl substituent at C-1 with trifluoroacetic anhydride. Trifluoroacetylation products may be formed either by reaction in the pyrrole ring or at the aryl or aralkyl groups at C-1. Products of electrophilic substitution at C-6 are formed in the trifluoroacetylation of pyrrolo[1,2-a]pyrazines containing at C-1 a substituent bulkier than a methyl group but lacking substituents at C-6 (the α-position of the pyrrole ring). __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1226–1233, August, 2007.     

Research of naphthyridines

It is shown by means of the UV spectra that a singly charged ion due to protonation at the N₍₄₎ atom develops when benzo[b]-1,8-naphthyrid-10-ones are dissolved in dilute mineral acids. The oxygen of the carbonyl group is also protonated in 96% sulfuric acid. Salts of the phenoxide type are formed in the reaction of these compounds with aqueous sodium hydroxide solutions. The pK_a values of benzo[b]-1,8-naphthyrid-10-ones determined spectrophotometrically in a sulfuric acid-water system range from –4.69 to –5.69, depending on the substituent in the 8 position, and correlate with the Hammett _p constants.See [1] for communication VIII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No, 9, pp. 1241–1244, September, 1977.     

Synthetic approaches to phomactins: Late stage stereochemical and reactivity issues

Oxidation of a 15-methylenebicyclo[9.3.1]pentadeca-3,7-dien-14-ol with a 10-phenylsulfonyl substituent provided a 14-oxobicyclo[9.3.1]pentadeca-1(15),3,7-triene-15-carbaldehyde that on reduction with DIBAL-H was converted into a 15-hydroxymethylbicyclo[9.3.1]pentadeca-1(15),3,7-triene-14-ol with the relative configuration at C14 required for incorporation into a synthesis of phomactin A. The oxidation and reduction of an analogous 3,4-epoxide that lacked the 10-phenylsulfonyl group gave a diol with the opposite relative configuration at C14. However, the TPAP oxidation and DIBAL-H reduction of a 14-hydroxy-15-methylene-3,4-epoxide that still had the 10-phenylsulfonyl group gave a diol with the required configuration at C14 although the expected spontaneous participation of the 14-hydroxyl group in an intramolecular epoxide ring-opening was only observed under Lewis acidic conditions.     

Stereochemistry of Nitrogen Heterocycles. Transformations of Stereoisomeric 1-chloro-2-methyl-4-keto-trans-decahydroquinolines in an acidic medium

It is shown that epimeric [with respect to the C(₂) atom] 1-chloro-2-methyl-4-keto-trans-decahydroquinolines in an acidic medium undergo intermolecular monochlorination in the position relatve to the carbonyl group with the formation of epimeric [with respect to the C(₂) atom] 3e-chloro- and 10a-chloro-2-methyl-4-keto-trans-decahydroquinolines and 2-methyl-4-keto-10-chloro-cis-decahydroquinolines. The mechanism of the transformations is examined, and an assumption regarding the possibility of cis-trans isomerization of the intermediately formed -chloronium complex is expressed.See [1] for Communication 66.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1100–1108, August, 1988.     

Selective synthesis and optical properties of diimidazo[1,2-a:5′,1′-c]quinoxaline derivatives

Novel diimidazo[1,2-a:5′,1′-c]quinoxaline derivatives were synthesized by a Pd-catalyzed intramolecular coupling reaction of 1,2-bis(2-iodo-1H-imidazol-1-yl)benzene. This method was applied to the selective introduction of an aryl substituent at the 10 position by the addition of a boronic ester. Moreover, a stepwise introduction of the aryl substituent could be achieved by the further coupling reaction at the 3 position. Focused on the optical properties, a more efficient substituent effect at the 10 position was obtained compared with the analogous structure, diimidazo[1,2-a:2′,1′-c]quinoxaline derivatives. In addition, we revealed that the diimidazo[1,2-a:5′,1′-c]quinoxaline skeleton potentially has an electron-donating character on the optical properties by introducing an electron-withdrawing substituent.     

The syn-anti isomerism of adducts of 1,2,3,4,5-pentamethylcyclopentadiene with maleic anhydride

Conclusions The dienic condensation of 1,2,3,4,5-pentamethylcyclopentadiene with maleic anhydride proceeds stereospecifically in relation to the configuration of the substituent in position 7 (the bridge) forming bicyclo[2.2.1] heptene derivatives: the ratio of the 7-syn-methyl- and 7-anti-methyl isomers (in relation to the double bond) corresponds to 3.5:1, respectively.Translated from Izvestiya Akademiii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 423–425, February, 1968.     

Synthesis of 4-(3-methylpyrazolyl-1)naphthalic anhydride

Heating 4-nitronaphthalic anhydride in an excess of 3(5)-methylpyrazole gives only 4-(3-methylpyrazolyl-1)naphthalic anhydride, which is converted by butylamine into the known N-butylimide of 4-(3-methylpyrazolyl-1)naphthalic acid.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, p. 194, February, 1992.     

Reduction of 4-oxo-4,6,7,8(5H)-tetrahydropyrrolo[3,2-c]azepines

1,2-Diaryl-4,6,7,8(5H)-tetrahydropyrrolo[3,2-c]azepines are obtained via the reduction of 1,2-diaryl-4-oxo-4,6,7,8(5H)-tetrahydropyrrolo[3,2-c]azepines with lithium aluminum hydride. In the case of a bromophenyl substituent reduction of the bromine atom occurs as well; similarly, in the case of a nitroaryl-substituted lactam, reduction of the amide carbonyl function is accompanied by reduction of the nitro group to an azo group.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 63–65, January, 1985.     

Synthesis and luminescence properties of anhydrides and N-phenylimides of substituted 4-(5-phenyl-2-oxazolyl)-naphthalic acids

Anhydrides and N-phenylimides of 4-(5-phenyl-2-oxazolyl)naphthalic acids with various substituents in the para position of the phenyl ring were synthesized. Electron-donor substituents, particularly the dimethylamino group, induce an appreciable long-wave shift of the absorption maxima and the luminescence due to their interaction with the carbonyl group of the peri-anhydride grouping. A large Stokesian shift and a high photoluminescence quantum yield are characteristic for the dimethylamino-substituted anhydrides.     

Preparation and characterization of tetraaza[14]annulene and its nickel(ii) and copper(II) complexes with crown ether functionalities

Three new organic hosts are described that contain a tetraaza[14]annulene core to which two crown ether voids are attached. These hosts include a free base tetraaza[14]annulene and/or its complexes with benzo-15-crown-5 rings. The crown tetraaza[14]annulene is synthesized from tetraaza[14]annulene and 4′-chloroformylbenzo-15-crown-5. Its nickel(II) and copper(II) complexes are prepared in a similar manner as above. In solution the compounds do not tend to form aggregates. However, aggregation is affected by the presence of alkali-metal salts, which coordinate to the crowns. Li⁺ and Na⁺ cations with diameters that match the diameters of the crown ether rings form 1:2 host-guest complexes. Complexes with 2:2 host-guest stoichiometry are formed when the diameters of K⁺ and Cs⁺ cations exceed that of the crown ether rings. Nevertheless, it is weak for the present macrocycle and its complexes to be inclined to form dimers owing to the steric hindrance of the substituent groups and owing to restraining the rotation of the carbonyl bond connecting the crown ether group.     

PREPARATION OF SOLUBLE SUBSTITUTED POLYACETYLENE OPTICAL LIMITING MATERIAL

Two novel polyacetylenes bearing nonlinear optical chromophoric group poly（3-（4-[4-（n-butyloxy） phenylazophenyl]carbonyl）oxy-1-propyne） （poly（1a）） and poly（3-（4-[4-（n-heptyloxy）phenylazophenyl]carbonyl）-oxy-l- propyne） （poly（lb）） were synthesized with [Rh（nbd）Cl]2-EtaN as catalysts. These polyacetylenes are soluble by using an alkyl spacer and an alkyloxyl group as a substituent. They were characterized by FTIR, NMR, GPC and UV-Vis and their optical limiting and nonlinear optical properties were investigated using 8 ns pulse at 532 nm wavenumber. The results show that these soluble functional polyacetylenes possess optical limiting properties and large nonlinear optical properties and poly（1b） possesses better optical limiting and nonlinear optical properties than poly（ 1 a）.