3-Hydroxyphenalenones 3, react by electrophilic halogenation to 2-chlorophenalenediones 4 or 2-iodophenalenone 5. The chloro group of 4 was exchanged against azide by reaction with sodium azide to give 2-azidophenalenediones 6. Nucleophilic chlorination of 3 furnishes 3-chlorophenalenones 7, which were converted to 3-azidophenalenones 8. Staudinger reaction of 8 with triphenylphosphane gave phosphazenes 9 which hydrolyzed to 3-aminophenalenones 10. Amines 10 can also be obtained directly from 3-hydroxyphenalenones 3 and ammonium acetate, or by catalytic hydrogenolysis of azides 8. Nitration of 3-hydroxyphenalenone 3 with nitric acid forms 2-nitrophenalenone 11, which was converted to 3-chloro-2-nitrophenalenone 12. Azidation, however, formed 2,3-diazidophenalenone 13. 2-Amino-3-hydroxyphenalenone 14 or 3-azidophenalenone 8 cyclize with carboxylic acid derivatives to oxazolo-phenalenones 15. 2-Acetylphenalenone 21 leads via the intermediate oxime 22 to an isomer mixture of isoxazolophenalenone 23 as main product and oxazolophenalenone 15 as by-product.
3-Hydroxyphenalenones 3, synthesized from 1,8-naphthalic anhydride 1 and malonates 2, react by electrophilic halogenation to 2-chlorophenalenediones 4 or 2-iodophenalenone 5. The chloro group of 4 was exchanged against azide by reaction with sodium azide to give 2-azidophenalenediones 6. Nucleophilic chlorination of 3 furnishes 3-chlorophenalenones 7, which were converted to 3-azidophenalenones 8. Staudinger reaction of 8 with triphenylphosphane gave phosphazenes 9 which hydrolyzed to 3-aminophenalenones 10. Amines 10 can also be obtained directly from 3-hydroxyphenalenone s 3 and ammonium acetate, or by catalytic hydrogenolys is of azides 8. Nitration of 3-hydroxyphenalenone 3a with nitric acid forms 2-nitrophenalenone 11, which was converted to 3-chloro-2-nitrophenalenone 12. Attempts to introduce the 3-azido group in 12, however, resulted in an exchange of both, the nitro group and the chl oro group, to form 2,3-diazidophenalenone 13. 2-Amino-3-hydroxyphenalenone 14 cyclizes with carboxylic acid derivatives to oxazo lo-phenalenones 15, which were also obtained from 3-azidophenalenone 8a and a carboxylic acid involving an azirine interme diate 16. This allows to move the position of the N-atom. A nother cyclization reaction leads via the intermedi ate oxime 22 of 2-acetylphenalenone 21, which gives an isomer mixture of isoxazolophenale one 23 as main product and oxazolophenalenone 15 as by-product, because of a parallel reaction via a Beckmann rearrangement.
Am 26. Januar 2005 hat das Bundesverfassungsgericht das Studiengebuhrenverbot aufgehoben. Damit ist es den einzelnen Bundeslandern freigestellt, ob sie Gebuhren erheben oder nicht. Wahrend in der Literatur zum Thema Studiengebuhren deren Finanzierungsfunktion im Vordergrund steht, widmet sich der vorliegende Beitrag der Funktion von Studiengebuhren zur Verringerung von Informationsa- symmetrien auf Hochschulmarkten: Ebenso wie Studienbewerber uber die Qualitat der Hochschulen nur unzureichend informiert sind, konnen Hochschulen die Begabung der Studienbewerber nicht ausreichend beurteilen. Basierend auf einem Modell von Bac (2002) wird untersucht, ob Universitaten ihre Qualitat glaubhaft durch die Hohe der Studiengebuhren signalisieren und hierdurch einen Selbstselektionsmechanismus auf Seiten der Studienbewerber induzieren konnen. Die Studienplatzvergabe wird hierbei als einmaliges, nicht-kooperatives Matching-Spiel modelliert, in dem von je zwei Universitatstypen und zwei Studienbewerbertypen ausgegangen wird. In Abhangigkeit von den Anteilen der begabten Studienbewerber und der Studienplatze an Universitaten hoher Qualitat, dem Verhaltnis aus Studienplatzen zu Studienbewerbern sowie den Erwartungen der Studienbewerber konnen sich in einem System mit variablen Studiengebuhren funf verschiedene perfekte Bayesianische Gleichgewichte einstellen: ein Pooling/Nonscreening-, ein Separating/Semiscreening-, ein Pooling/Screening- sowie zwei Varianten eines Separating/Screening-Gleichgewichts. Entgegen der allgemeinen Vermutung wird dabei deutlich, dass die Einfuhrung von Studiengebuhren keinesfalls immer zu einer Verbesserung des Matchings zwischen Studienbewerbern und Universitaten unterschiedlicher Qualitat fuhren muss.
Obwohl Studiengebühren an staatlichen Universitäten in einigen Bundesländern in Deutschland bereits eingeführt wurden, ist bislang unklar, ob Studiengebühren als Signalling-und Screening-Instrument Informationsasymmetrien auf Hochschulmärkten verringern können. Basierend auf einem Modell von Bac (2002) wird die Studienplatzvergabe als einmaliges, nicht-kooperatives Matching-Spiel modelliert. Entgegen der allgemeinen Vermutung wird deutlich, dass die Einführung von Studiengebühren keinesfalls immer zu einer Verbesserung des Matchings zwischen Studienbewerbern und Universitäten unterschiedlicher Qualität führen muss, selbst eine Verschlechterung ist denkbar. Die Betrachtung realer Bildungssysteme mit variablen Studiengebühren gibt Hinweise darauf, dass sich in der Realität tatsächlich unterschiedliche Gleichgewichte unterschiedlicher Effizienz eingestellt haben: Während sich die Bildungssysteme Italiens und Portugals in einem effizienten Separating/Screening-Gleichgewicht befinden dürften, wurde in den Bildungssystemen Spaniens und der Schweiz offenbar ein Separating/Semiscreening-Gleichgewicht erreicht. In Großbritannien scheint sich hingegen ein Pooling/Nonscreening-Gleichgewicht eingestellt zu haben. Für Deutschland ließe sich nach Einführung variabler Studiengebühren ein Separating/Semiscreening-oder ein Separating/Screening-Gleichgewicht II erwarten.
AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
3-Azido-2-phenylindan-1-one (4), which was obtained from 3-chloro-2-phenylindan-1-one (3), cyclizes on thermolysis to 5H-indeno[1,2-b]indol-10-one (5). Reaction of 3-azido-2-phenylindan-1-one (4) with triphenylphosphane gives 2-phenyl-3-(triphenylphosphoranylideneamino)-indan-1-one (6), which can be hydrolyzed to 3-amino-2-phenylindan-1-one (7). Attempts to perform a similar cyclization sequence with 3-chloro-2-pyridylindan-1-ones failed.
4-Azidopyridines such as 3-acetyl-4-azido-2-pyridones 3 or 4-azido-3-ethoxycarbonylpyridine 7 with reactive ortho-acyl substituents were obtained from the 4-hydroxy-2-pyridones 1, resp. 5 via 4-tosyloxy-2-pyridones 2 or the 2,4-dichloropyridine 6. DSC-assisted thermolysis of the azides 3 and 7 resulted in electrocyclization and elimination of nitrogen to the isoxazolo[4,3-c]pyridines 4 and 8.
4-Azidopyridines such as 3-acetyl-4-azido-2-pyridones 3 or 4-azido-3-ethoxycarbonylpyridine 7 with reactive ortho-acyl substituents were obtained from the 4-hydroxy-2-pyridones 1, resp. 5 via 4-tosyloxy-2-pyridones 2 or the 2,4-dichloropyridine 6. DSC-assisted thermolysis of the azides 3 and 7 resulted in electrocyclization and elimination of nitrogen to the isoxazolo[4,3-c]pyridines 4 and 8.
4-Chloro-3-nitro-2-pyridines 3 and 10, obtained from 4-hydroxy-2-pyridones 1 and 8 after nitration and chlorination, gave with sodium azide 4-azido-3-nitropyridines 4 and 11, which cyclized on thermolysis to furoxans 6 and 12. Desoxygenation of the furoxan 6 with triphenylphosphane gave the furazan 7. Thermal decomposition conditions of the azide 4 and the desoxygenation reaction of 6 to 7 were studied by differential scanning calorimetry (DSC).
Abstract1‐Azido‐3‐phenalenones 5 with acyl substituents in position 2, obtained by acylation and azidation of 1‐hydroxy‐3‐phenalenones 1, cyclized by thermolysis to give phenaleno[1,2‐c]isoxazol‐7‐ones 9. The thermolysis conditions were studied by differential scanning calorimetry.
AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
3-Azido-1-phenalenones 4 with aryl- or hetarylsubstituents in position 2 cyclized by thermolysis to give naphtho[8,1-ab]carbazolones 5 or naphtho[8,1-ab]-8a-azonia-9-lambda(2)-azafluorenes 7. Reduction of the azides 4 gave the corresponding amino derivatives 9. The thermolysis conditions were studied by differential scanning calorimetry.
5-Arylaminomethylene compounds such as 5-arylaminomethylenepyrimidine-2,4,6-triones 2 or 2-phenylaminomethylenephenalene-1,3-dione 13 cyclize by thermolysis via migration of the arylamino group to pyrimido[4,5-b]quinoline-2,4-diones 6 or 7-oxo-7H-naphtho[1,8-bc]acridine 15, respectively. 2-Phenylaminomethylenecyclohexane-1,3-dione 8 cyclizes to 9,9-dimethyl-9,10-dihydrophenanthridin-7(8H)-one 11 without rearrangement.
The genome of the Chilo iridescent virus (CIV) was analyzed for existence of repetitive DNA sequences by DNA-DNA hybridization using a defined and complete gene library of the viral genome (209 kbp) and by heteroduplex mapping. These experiments revealed the presence of repetitive DNA elements in the CIV genome, which are located in theEcoRI fragment H and in theEcoRI DNA fragment C at the coordinates 0.535 to 0.548 (EcoRI/Pstl DNA fragment, 2.7 kbp) and 0.920 to 0.944 (Pvull CIV DNA fragment L, 5.1 kbp), respectively. The DNA nucleotide sequence (2708 bp) of theEcoRI/Pstl subfragment was determined. The comparative analysis of the DNA sequences of this particular region of the viral genome with the DNA sequences of thePvull DNA fragment L (5064 bp) revealed the presence of several DNA sequences within theEcoRI/Pstl subfragment of theEcoRI CIV DNA fragment H which show homology to DNA sequences of thePvull DNA fragment L. For example, a DNA element (☐ A, 91 bp) is located at nucleotide positions 1981 to 2072 of theEcoRI CIV DNA fragment H which are complementary (>90%) to the nine regions of thePvull DNA fragment L (L-☐es 1 to 9). Furthermore heteroduplex mapping revealed the existence of a stem-loop structure (stem, 65 ± 10 by and loop, 652 ± 80 bp) at the genome coordinates 0.571 to 0.582 (2.5 kbp,HindIII/EcoRI subfragment of theEcoRI CIV DNA fragment H). This indicates that an inverted repeat sequence is located at this region of the viral genome. The DNA nucleotide sequence of this subfragment was determined (2555 bp) which confirmed the data obtained from electron microscopy. An inverted repeat DNA sequence located at nucleotide positions 304 and 1011 is able to form this type of stem-loop structure.
The DNA nucleotide sequence of the PvuII DNA fragment L (0.920 to 0.944 map units (m.u.] of the genome (209 kbp) of insect iridescent virus type 6 was determined. The size of this DNA fragment was 5064 bp with a base composition of 39.79% G + C and 60.21% A + T. The DNA sequence contained many perfect direct repeats of sizes up to 145 bp. In addition to these repetitions, a cluster of four imperfect repetitive DNA elements (R1 to R4) with a complex structural arrangement was detected. R1, R2, and R3 existed in duplicate (two boxes (B] between nucleotide positions 271 and 3466) and their size were as follows: R1-B1/B2 (567/568 bp), R2-B1/B2 (917/931 bp), and R3-B1/B2 (92/88 bp). The R4 repetitive element was found in 12 boxes (between bases 1301 and 4417), which were interrupted at nucleotide positions 1883 to 2236 and 3341 to 3587. These interruptions define three segments (S) harboring boxes B1 to B3 (S1), B4 to B8 (S2), and B9 to B12 (S3). The size of the individual boxes was found to be 239, 233, 107, 244, 222, 242, 242, 148, 240, 242, 242, and 102 bp for R4-B1 to B12, respectively. Five open reading frames (ORFs of 118 to 333 amino acid (AA) residues) were detected. The analysis of the amino acid sequences of the largest ORF revealed that the deduced amino acid sequence of the putative gene product contained two repetitions TR1 (three domains of 50 AA) and TR2 (two domains of 74 AA). Sequences of 43 amino acid residues of ORF 5 (160 to 202 AA) were homologous within the majority of ORFs. A consensus sequence-MANL(X)6 IGSSST(X)6 L(X)1 LGS(X)1 LQISG(X)2 L(X)1 VN- was found in all five ORFs. Although classical canonical and noncanonical transcriptional start signals were detectable, polyadenylation signals were not observed.
SUMMARY The physical map of the genome (209 kbp) of insect iridescent virus type 6, also known as Chilo iridescent virus (CIV), which is circularly permuted and terminally redundant, was constructed for the restriction enzymes ApaI, Asp718, PvuII and SphI using a gene library of viral DN A containing the complete viral genome. Although the CIV genome is linear, it was found that the restriction maps were circular, because of the unique structure of the genome of this virus.
A defined and complete gene library of the Chilo iridescent virus (CIV) genome was established. The CIV DNA was cleaved with restriction endonucleases EcoRl, Ncol, Sphl, and BamHl or double digested with BamHI Sal and the resulting DNA fragments were inserted into the corresponding sites of the bacterial vectors pACYC184, pKm2, pLES-C3, and pAT153 using T4 DNA ligase. All cloned fragments were identified by digestion of the recombinant plasmids with different restriction enzymes and checked by hybridization of recombinant plasmid to viral DNA. This analysis revealed that sequences representing 100% of the viral genome were cloned into the EcoRl site of pACYC184. Although the CIV genome is linear, all 32 EcoRl fragments have been cloned directly. This suggests that the CIV genome is circularly permuted. In addition, Ncol(72%), Sphl(40.7%), BamHl (11.6%), and BamHI Sal(39.7%) DNA fragments of the viral genome were inserted into the corresponding sites of pKm2, pL-ES-C3, and pAT153, respectively. The physical map of the viral genome was constructed using the established gene library for restriction enzymes Apal, BamHl, EcoRl, Ncol, Sall, and Smal. Although the CIV genome is linear, this analysis revealed that the restriction maps of the viral genome are circular. This finding supports the hypothesis that the CIV genome is circularly permuted.